WO2002057335A1

WO2002057335A1 - Polymerization catalyst for polyester, polyester, and process for producing the same

Info

Publication number: WO2002057335A1
Application number: PCT/JP2002/000266
Authority: WO
Inventors: Takahiro Nakajima; Ken-Ichi Tsukamoto; Shoichi Gyobu; Mitsuyoshi Kuwata; Nobuo Moriyama
Original assignee: Toyo Boseki Kabushiki Kaisha
Priority date: 2001-01-18
Filing date: 2002-01-17
Publication date: 2002-07-25
Also published as: CN100480300C; KR20080021165A; CN101412805A; TWI309246B; TW200526706A; KR100872634B1; CN101412805B; KR20030094236A; KR100905831B1; CN1486336A

Abstract

A polyester which is produced with a polymerization catalyst containing metals other than antimony and germanium as major metallic ingredients and which is reduced in filter clogging during molding, etc. The polyester contains at least one member selected from the group consisting of alkali metals, alkali metal compounds, alkaline earth metals, and alkaline earth metal compounds and at least one member selected from the group consisting of aluminum and compounds thereof, the contents of these satisfying the following relationships (1) and (2). [M] < 0.05 (1) [M] / [Al] ≤ 20 (2) ([M] and [A] indicate the total content of the alkali metal atoms and alkaline earth metal atoms and the content of the aluminum atoms, respectively, both in terms of mol% based on the acid ingredient(s) contained in the polyester.) The polyester is usable in a fiber, film, hollow molding, etc.

Description

• Description Title of the invention

Polyester polymerization catalyst, polyester, and polyester production method

[Technical field]

TECHNICAL FIELD The present invention relates to a polyester polymerization catalyst, a method for producing polyester and polyester, and more particularly, to a polyester polymerization catalyst which gives a polyester having improved filter clogging during molding, and a method for producing polyester and polyester. It is about the method.

'[Background technology]

Polyesters, especially polyethylene terephthalate (hereinafter abbreviated as PET), have excellent mechanical and chemical properties, and are suitable for a wide variety of applications, such as textiles for clothing and industrial materials, packaging, and the like. It has been applied to various films and sheets for magnetic tapes and molded products such as bottles and engineering plastics.

PET industrially produces bis (2-hydroxyethyl) terephthalate by esterification or transesterification of terephthalic acid or dimethyl terephthalate with ethylene glycol, which is then polycondensed using a catalyst at high temperature and under vacuum. This is obtained. Antimony trioxide is widely used as a catalyst for polycondensation. Antimony trioxide is a catalyst that is inexpensive and has excellent catalytic activity, but has the problem of darkening and foreign matter in PET due to the precipitation of metal antimony during polycondensation. Under such circumstances, a polyester containing no antimony or containing no antimony as a main component of the catalyst is desired. The above foreign matter in the polyester causes the following problems, for example.

(1) In polyester for film, the precipitation of antimony metal becomes a foreign substance in the polyester, which not only causes stains on the die at the time of melt extrusion, but also causes a surface defect of the film. Also, when used as a raw material for hollow molded products, etc. However, it is difficult to obtain a hollow molded product that is transparent.

(2) Foreign matter in polyester for fibers is a foreign matter that reduces the strength of the fiber and causes stains in a spinneret during spinning and an increase in filtration pressure of a filter. In the production of polyester fibers, a polyester polymerization catalyst free of foreign matter is required mainly from the viewpoint of operability.

Attempts have been made to use antimony trioxide as a polycondensation catalyst to suppress the occurrence of blackening and foreign matter in PET. For example, in Japanese Patent No. 2666502, generation of black foreign matter in PET is suppressed by using a compound of antimony trioxide, bismuth and selenium as a polycondensation catalyst. Japanese Patent Application Laid-Open No. 9-291141 states that the use of antimony trioxide containing sodium and iron oxides as a polycondensation catalyst suppresses the deposition of antimony metal. However, these polycondensation catalysts cannot achieve the purpose of reducing the content of antimony after all.

As polycondensation catalysts other than antimony compounds, titanium compounds and tin compounds have already been proposed.However, polyesters produced using these compounds are susceptible to thermal degradation during melt molding, and the polyesters are markedly colored. In an attempt to overcome such problems when a titanium compound is used as a polycondensation catalyst, for example, Japanese Patent Application Laid-Open No. 55-116722 discloses that tetraalkoxy titanate is A method has been proposed which is used simultaneously with salt and calcium salt. Also, JP-A-8-73581 proposes a method in which a tetraalkoxy titanate is used simultaneously with a cobalt compound as a polycondensation catalyst, and a fluorescent whitening agent is used. However, with these techniques, although the coloring of PET is reduced when tetraalkoxy titanate is used as a polycondensation catalyst, it has not been achieved to effectively suppress the heat of PET.

It is known that phenolic compounds generally have poor catalytic activity. Among aluminum compounds, chelating compounds of aluminum have been reported to have higher catalytic activity as polycondensation catalysts than other aluminum compounds, but they have sufficient catalytic properties compared to the above-mentioned antimony compounds and titanium compounds. Although it has In addition, polyesters polymerized over a long period of time using an aluminum compound as a catalyst have a problem that thermal stability and thermal oxidation stability are poor. In addition, the polyester polymerized using the aluminum disulfide compound as a catalyst generates a large amount of foreign matter insoluble in the polyester, which causes clogging of the filter due to the foreign matter during molding of the polyester, and when the polyester is used for fibers. There has been a problem that yarn breakage or the like frequently occurs during spinning, and when used in a film, the physical properties of the film deteriorate.

On the other hand, Japanese Patent Publication No. 46-41031 discloses that excellent catalytic activity is exhibited when an alkali metal or a compound thereof and a chelate compound of aluminum coexist. Polyester polymerized according to the method described in the publication has a problem that the thermal stability is excellent, but the thermal oxidation stability is still inferior, and that many foreign matters insoluble in the polyester are generated. However, when the polyester is molded, the filter is clogged due to the foreign matter, and when used for fibers, thread breakage frequently occurs during spinning, and when used for a film, the physical properties of the film are deteriorated. It was not suitable for practical use. ·

There is also a technology to add an alkaline earth metal compound to an aluminum-palladium compound to provide a catalyst with sufficient tactility. To achieve practical catalytic activity, the amount of alkaline earth metal compound is large. Necessary, the resulting polyester has reduced thermal stability and thermo-oxidative stability, is greatly colored by heating, and increases the amount of foreign matters insoluble in polyester.

Germanium compounds have already been put into practical use as catalysts which provide polyesters which have excellent catalytic activity and do not have the above-mentioned problems except for antimony compounds, but this catalyst is very expensive. Also, there is the problem that the concentration of catalyst in the reaction system changes due to the distilling out of the reaction system during polymerization, making it difficult to control the polymerization, and there is a problem in using it as the main component of the catalyst. .

Further, as a method of suppressing thermal deterioration during melt molding of polyester, there is a method of removing a catalyst from polyester. As a method for removing a catalyst from polyester, for example, Japanese Patent Application Laid-Open No. H10-251,394 discloses a method in which a polyester resin is brought into contact with an extractant which is a supercritical fluid in the presence of an acidic substance. Disclosed . However, such a method using a supercritical fluid is not preferable because it is technically difficult and leads to an increase in product cost.

Due to the above-mentioned circumstances, it is a polymerization catalyst that uses a metal component other than antimony germanium as the main metal component of the catalyst, and has excellent catalytic activity and thermal stability that causes almost no thermal deterioration during gas-melt molding. There is a demand for a polymerization catalyst that gives a polyester excellent in performance.

The decrease in molecular weight due to heat during the melt molding of polyester not only causes the heat resistance and mechanical properties of the melt molded product to deteriorate, but also lowers the quality of the molded product derived from by-products due to thermal decomposition, for example. It leads to an increase in coloring. Known antimony-catalyzed germanium-catalyst catalysts provide polyesters with relatively good thermal stability during melt molding compared to other titanium catalysts, but still have a complete thermal degradation during melt molding. I can't prevent it. Under such circumstances, a polyester polymerization catalyst that gives a polyester that can minimize the thermal deterioration during melt molding of the polyester has been desired.

WO 98/42769, Japanese Patent Publication No. 11-507694, etc., have proposed techniques using an aluminum compound as a polymerization catalyst. Examples of the aluminum compound include an aluminum chelate compound such as aluminum-dimethyl acetylacetonate, an inorganic acid salt such as aluminum chloride and aluminum hydroxide, an aluminum salt of a carboxylic acid, and an aluminum alkoxide. Have been. Of these, chelating compounds of aluminum such as luminium dimethyl acetylacetonate are generally expensive, and the aluminum content in the compound is low, leading to increased costs. There is a problem that the solubility is low and the addition method is limited. Aluminum hydroxide and aluminum alkoxide have the problem of low melt penetration into the system and low catalytic activity. (1) There is a problem that insoluble foreign matter is generated in polyester. Chlorine-containing inorganic acid salts such as aluminum chloride are relatively excellent in catalytic activity, but have a problem of high corrosiveness to the apparatus and a problem of large coloring of the obtained polymer.

On the other hand, examples of aluminum salts of carboxylic acids include aluminum acetate, basic aluminum acetate, aluminum lactate, aluminum benzoate and the like. However, these are generally inexpensive and have a low corrosion property to the apparatus, but have low solubility in the polyester, so that they have poor touch properties and have a problem that turbidity occurs in the obtained polyester. There was a problem. For example, Japanese Patent Application Laid-Open No. 10-324741 describes that polyester using aluminum acetate as a catalyst tends to form insoluble foreign matters and has a problem of poor spinning properties.

An object of the present invention is to provide a polyester produced using a polymerization catalyst containing a metal component other than antimony and germanium as a main metal component of the catalyst, and having improved filter clogging during molding and the like. It also provides a method of manufacturing the same.

Another object of the present invention is to provide a method for producing a polyester using a novel polyester polymerization catalyst other than an antimony compound and a germanium compound, and to provide a polyester produced by the method. is there.

It is another object of the present invention to provide an anti-catalyst that does not contain an antimony compound or a germanium compound as a main component of the catalyst, has excellent catalytic properties, and does not deactivate or remove the catalyst. An object of the present invention is to provide a polyester polymerization catalyst which gives a polyester having excellent thermal stability by effectively suppressing thermal deterioration.

The present invention also provides improved heat stability when performing melt molding of hollow molded articles such as finolems and bottles, fibers, and engineering plastics using the catalyst. An object of the present invention is to provide a polyester capable of obtaining a high-quality product even if waste generated during molding is reused, and a method for producing a polyester using the polyester polymerization catalyst.

Another object of the present invention is a polyester polymerization catalyst which gives a polyester capable of minimizing thermal degradation during melt molding, using the catalyst to form a hollow molded article such as a film or a bottle, or a fiber. The thermal stability of melt molding of engineering plastics and the like has been remarkably improved, and high quality products can be obtained even if virgin resin is used and waste generated during molding is reused. And a method for producing a polyester using the polyester heavy medium. Another object of the present invention is to provide an inexpensive, excellent catalytic activity, less corrosion to equipment, and a foreign substance that is insoluble in polyester without using an antimony compound or a germanium compound as a main component of the catalyst and using aluminum as a main metal component. An object of the present invention is to provide a polyester polymerization catalyst which gives a polyester with reduced generation of polyester and a method for producing the same. The present invention also provides a polyester in a method for producing a polyester using the catalyst.

[Disclosure of Invention]

The present inventors have conducted intensive studies aiming at solving the above-mentioned problems, and as a result, when polymerized using a catalyst in which an alkali metal compound or an alkaline earth metal compound and an aluminum hydride are coexisted, The foreign matter insoluble in the resulting polyester is found to be mainly caused by alkali metal compounds or alkaline earth metal compounds. Furthermore, the alkali metal compounds in polyesters It has been found that by setting the content of the aluminum and polyimide to a specific range, the generation of this insoluble foreign matter can be effectively suppressed, and problems such as filter clogging during polyester molding can be improved. The present invention has been completed.

That is, the present invention provides, as a solution to the above problems, at least one kind selected from the group consisting of alkali metals and their compounds, and at least one selected from the group consisting of alkaline earth metals and their compounds; A polyester characterized by containing at least one selected from the group consisting of compounds, and having them satisfying the following formulas (1) and (2).

(1) suke <0. 0 5

(2) << M >> Z << A 1 >> ≤2 0

(In the formula (1), (2), "M" represents the mole ^_0/0 of the total alkali metal atom and Al force Li earth metal atom to the acid component in the polyester, "A 1" is in the polyester Shows mol% of aluminum atom to acid component.)

In addition, the present inventors have conducted intensive studies aiming at solving the above problems, and as a result, when polymerized using a catalyst in which an aluminum metal compound or an aluminum earth compound and an aluminum compound coexist. Foreign substances insoluble in polyester are mainly produced As a result of finding out that it is caused by the alkali metal compound or the alkaline earth metal compound, and further studying it, the coexistence of the phosphorus compound effectively reduces these foreign substances. By setting the content of the phosphorus compound within the specified range, it is possible to effectively suppress the generation of foreign matters insoluble in the polyester and to improve problems such as filter clogging when molding the polyester. The invention has been reached.

That is, the present invention provides, as a solution to the above problems, at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds, and at least one selected from the group consisting of aluminum and its compounds Contains at least one kind and at least one kind selected from the group consisting of phosphorus compounds.

And a polyester containing them in an amount satisfying the following formulas (4) to (6).

(4) 0. 1≤ [M] ≤ 1 5 0

(5) [M] / [A1] ≤ 40

(6) [P] / [A 1≥0.0 1

(In the formulas (4) to (6), [M] indicates the total amount (ppm) of alkali metal atoms and alkaline earth metal atoms contained in the polyester, and [A1] and [P] indicate The amounts (ppm) of aluminum and phosphorus atoms contained in the ester are indicated.)

Further, the present inventors have conducted intensive studies aiming at solving the above-mentioned problems, and as a result, when polymerized using a catalyst in which an aluminum metal compound or an aluminum metal compound and an aluminum compound coexist. The foreign matter that is insoluble in the polyester formed during the process was found to be mainly caused by alkali metal compounds and alkaline earth metal compounds, and as a result of further investigation, it was found that the alkali metal compounds and alkaline earth compounds Among the metal compounds, at least one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium and their conjugates is used, and their content in the polyester is adjusted to a specific range. In addition, the coexistence of a phosphorus compound effectively suppresses the formation of foreign matter insoluble in polyester, The present invention found that the problems of the filter one clogging at the time of molding is improved Reached SI.

That is, the present invention provides, as a solution to the above-described problems, at least one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium, and their conjugates, and a group consisting of aluminum and compounds thereof. At least one, and at least selected from the group consisting of phosphorus compound Bareru more selected - containing species, and lithium, sodium, potassium, beryllium, Maguneshiu beam, calcium and total polymer 1 content of the compounds 0 ⁶ g The present invention provides a polyester characterized in that the amount is 7.0 mol or less per metal atom conversion, and a method for producing the same.

The present inventors have conducted intensive studies with the aim of solving the above problems, and as a result, a polyester produced using a polymerization catalyst containing aluminum as a main metal component, and a polyester made from a group consisting of phosphorus compounds. Polyesters containing at least one selected from the group consisting of phenolic compounds and at least one selected from the group consisting of phenolic compounds, and a polyester with a specific ratio of phosphorus atoms to aluminum atoms in a specific range, have problems such as filter clogging at the time of molding. The inventors have found that the thermal oxidation stability has been improved, and have reached the present invention.

That is, the present invention provides, as a solution to the above-mentioned problems, at least one selected from the group consisting of aluminum and its conjugates, and at least one selected from the group consisting of phosphorus compounds; The selected polyester contains at least one kind, and the ratio of the amount of phosphorus atoms (ppm) to the amount of aluminum atoms (ppm) contained in the polyester is in the range of 0.01 to 50. And a method for producing the same.

In addition, the present inventors have conducted intensive studies aiming at solving the above-mentioned problems, and as a result, foreign matters insoluble in polyesterol generated when polymerized using an aluminum compound as a catalyst are mainly caused by aluminum compounds. As a result of further investigation, it was found that by coexisting aluminum compound and phosphorus compound in polyester, and by setting the content ratio of aluminum compound and phosphorus compound to a specific ratio, these foreign substances can be effectively reduced. The present invention was found to reduce the problem and to improve the problems such as filter clogging when molding polyester. That is, the present invention provides, as a solution to the above-mentioned problem, a polyester containing at least one selected from the group consisting of aluminum and its conjugates and at least one selected from the group consisting of phosphorus compounds. providing a polyester ratio to the amount _(PP m) of the aluminum atoms of the amount of phosphorus atoms (ppm) is characterized in that it is in the 0.5 to 2 range 0 contained.

The present invention also provides the polyester produced using the metal and / or the compound as a catalyst, and a method for producing the polyester.

In addition, the present inventors have conducted intensive studies with the aim of solving the above problems, and as a result, although aluminum compounds originally have poor catalytic activity, by combining them with a specific amount of phosphorus compounds, they can be used as polymerization catalysts. The present inventors have found that the present invention has an excellent activity and reached the present invention. The use of the polymerization catalyst of the present invention makes it possible to obtain inexpensively a high-quality polyester that does not use an antimony compound.

That is, the present invention provides, as a solution to the above-mentioned problem, adding at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds, and adding the phosphorus atom and the aluminum atom to each other. A method for producing a polyester, wherein the molar ratio is in the range of 0.5 to 20; and a polyester produced by the method. The present invention also relates to a polyester polymerization catalyst comprising at least one selected from the group consisting of aluminum and its conjugates and at least one selected from the group consisting of phosphorus compounds, wherein the catalyst comprises a mole of phosphorus atom and aluminum atom. Provided are a polyester polymerization catalyst having a ratio in the above range, a polyester produced using the same, and a method for producing a polyester.

In addition, the present inventors have conducted intensive studies with the aim of solving the above-mentioned problems. As a result, even if the metal or the metal compound itself has low catalytic activity, it is possible to combine the metal or the metal compound with the phosphorous compound. It becomes a polyester polymerization catalyst that improves the catalytic activity, and such a polyester polymerization catalyst composed of a metal or a metal compound and a phosphorus compound has excellent tactility, without deactivating or removing the catalyst. However, the present inventors have found that heat deterioration during melt molding is effectively suppressed, and the resulting polymer catalyst is a polyester polymerization catalyst that gives a polyester having excellent heat stability. Thus, the present invention has been completed. . That is, the present invention provides, as a solution to the above-mentioned problem, a polyester polymerization catalyst comprising a metal or a metal compound and a phosphorus conjugate, wherein an activity parameter (AP) satisfies the following formula (10). A polyester polymerization catalyst is provided.

(10) AP (min) <APX (min)

(In the above formula, AP is the time required to polymerize polyethylene terephthalate (PET) with an intrinsic viscosity of 0.65 d1 Zg at a pressure of 275 ° C and a pressure of 0.1 l Torr using a predetermined amount of catalyst. A PX indicates the time (min) required to polymerize PET using the same amount of metal or metal compound of the above catalyst and the same conditions as above. Shown.)

Another aspect of the present invention is a polyesterlene polymerization catalyst, wherein the thermal stability parameter (TS) of polyethylene terephthalate (; PET) polymerized by using the catalyst satisfies the following equation (9). The thermal stability of melt molding of films, bottles and other hollow molded articles, fibers, engineering plastics, etc. made of polyesters polymerized using the polyester polymerization catalyst has been significantly improved. Good quality products can be obtained even when used or when the waste generated during molding is reused.

(9) TS <0.20

(In the above formula, TS is the intrinsic viscosity ([eco!:! Is 64 to 0.66 dl / g.) 1 g of PET is placed in a glass test tube, vacuum-dried at 130 ° C for 12 hours, and then placed in a non-circulating nitrogen atmosphere. It is a numerical value calculated from the intrinsic viscosity ([IV] _f ) after maintaining the molten state at 300 ° C for 2 hours below.

TS = 0.245 {[IV] _f1 ¹ ^'47 ^-1 [IV] i- ¹ · ⁴⁷ }

In the case of PET with an intrinsic viscosity of 0.64 to 0.66 dlZg, in practice, the correlation between the stirring torque of the PET polymerization reaction vessel and the intrinsic viscosity is measured in advance, and the polymerization state is controlled using this stirring torque. It can be obtained by stopping the polymerization when the stirring torque reaches a predetermined value.

In addition, the present inventors have conducted intensive studies with the aim of improving the feel of aluminum salts of carboxylic acids, and as a result, it has been found that a catalyst obtained by dissolving aluminum carboxylate in water or an organic solvent in advance is used as a catalyst. To improve catalytic activity The present invention has been proposed. 'That is, the present invention provides water and z or an organic solvent as a solution to the above problem.

And a method for producing a solution of a polyester heavy carrier comprising a solution in which at least one selected from the group consisting of aluminum carboxylate is dissolved.

[Best Mode for Carrying Out the Invention]

The polyester of the present invention comprises at least one selected from the group consisting of alkali metal and their compounds, and at least one selected from the group consisting of alkaline earth metals and their compounds, and a carboxylic acid such as a dicarboxylic acid of a polyester or a polycarboxylic acid. must be contained in an amount of less than 0.05 mole ^_0/0 in total metal atoms relative to the number of moles of all the structural Interview two Tsu City of acid component. Further, the content is preferably 0.005 mol% or more. If the content is 0.05 monole% or more, a large amount of foreign matter insoluble in the polyester is generated, and as a result, there is a problem that yarn breakage during spinning and filter clogging during molding frequently occur. In addition, the coloring of the resin becomes remarkable, and the appearance of the molded article is impaired. The problem that the hydrolysis resistance of the resin is lowered occurs. With a problem that content is poor in thermal stability less and Le emissions Ri good 0.005 mole ^_0/0 occurs, is not preferable because the catalytic activity is significantly decreased in the case of using as the catalyst. More preferred range of the content is 0.03 mol% to 0.008 mol%, still more preferably from 0.02 mole ^_0/0 from 0.01 mol ^_0/0.

The polyester of the present invention is selected from the group consisting of aluminum and its compounds in addition to at least one selected from the group consisting of the above alkali metals and their compounds and alkaline earth metals and their conjugates. Must contain at least one of the following: In addition, the content of at least one selected from the group consisting of alkaline earth metals and their compounds and the content of at least one selected from the group consisting of aluminum and their compounds for alkali metals and their compounds, It is necessary that the molar ratio of the sum of the aluminum metal atoms and the aluminum metal atoms to the aluminum metal atoms be 20 or less. This ratio is preferably 0, 1 or more. If the ratio exceeds 20, a large amount of foreign matter is insoluble in the polyester, resulting in frequent thread breakage during spinning and filter clogging during molding. Problems arise. In addition, when used as a catalyst, there is a problem that the tactility is significantly reduced. If the ratio is less than 0.1, a large amount of foreign matter insoluble in the polyester resulting from the aluminum compound is generated, and the thermal stability of the polyester is also undesirably reduced. A more preferred range of the ratio is in the range of 0.5 to 10. In the polyester, at least one selected from the group consisting of alkali metal and their compounds and alkaline earth metals and their compounds, and at least one selected from the group consisting of aluminum and their compounds By adjusting the content to the above range, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

Further, the content of aluminum and the compound thereof of the present invention is 0.001 mole as aluminum atom with respect to the total number of moles of the carboxylic acid component such as dicarboxylic acid and polycarboxylic acid of the polyester. it is preferred that from ^_0/0 is in the range of 0.05 mol ^_0/0. If the content of aluminum atoms is more than 0.05 mole ^_0/0, undesirable because heat stability of poly ester is reduced to produce. If the content of the aluminum atom is less than 0.001 mol / ₀ , the contact property is remarkably reduced when used as a catalyst, which is not preferable. More preferably, in the range of 0.005 mole ^_0/0 of 0.04 mol%, even more preferably from 0.01 mol ^_0/0 0 - 03 mol ^_0/0.

It is preferable that the polyester of the present invention contains a total of 25 ppm or less of metallic alkali metal and alkaline earth metal atoms from the viewpoint of reducing foreign matters. This content is more preferably 20 ppm or less, and even more preferably 15 p or less.

As described above, the polyester of the present invention needs to contain at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds. Of these, polyesters containing an alkaline earth metal or a compound thereof have lower thermal stability, are more colored by heating, and have a relatively large amount of foreign substances. It is preferable that the alkaline metal is contained without containing the alkaline earth metal.

Further, the polyester of the present invention preferably contains a phosphorus compound. Phosphorization By containing the compound, the effect of suppressing the generation of foreign substances derived from Alri metal or Al earth metal is obtained, and the thermal stability of the polyester is also improved.

As described above, polyesters containing aluminum or its compounds and alkaline earth metals or their compounds tend to have poor thermal stability and relatively large amounts of foreign substances are generated. By containing a class of metals within the scope of the present invention and further containing a phosphorus compound, the problems of heat stability and foreign matters of the polyester are improved. It is preferable to add a phosphorus compound when producing the polyester according to the method of the present invention, since the generation of foreign matters insoluble in the polyester is effectively suppressed. Further, the addition of a phosphorus compound is preferable because the thermal stability and the like of the polyester can be improved.

The amount of the phosphorus compound of the present invention, the polymerization to ⁵ X10- 5 mole% versus the moles of all the structural Yunitto carboxylic acid component such as deer Rupon acid Ya polycarboxylic acid polyester obtained 1 it is preferably in the range of mole ^_0/0, more preferably

1 Xicr is from ⁴ mole ^_0/0 in a range of 0.5 mol ^_0/0.

Further, another polyester of the present invention is obtained by adding at least one kind selected from the group consisting of alkali metal and their compounds and at least one selected from the group consisting of alkaline earth metals and their compounds as a total of metal atoms in the polyester. 0. It must be contained in lppm or more and 150ppm or less. If the content is more than 150 ppm, many foreign matters insoluble in the polyester are generated, and as a result, there is a problem that yarn breakage during spinning and filter clogging during molding frequently occur. In addition, coloring of the resin becomes remarkable, causing a problem that ^ II of the molded article is impaired and a problem that the thermal stability 熱 hydrolysis resistance ^ of the resin is reduced. If the content is less than 0.1 ppm, there is a problem that the thermal stability of the resin is poor, and a problem that the catalytic activity is remarkably reduced when used as a catalyst. A more preferable range of the content is lppm or more and 100ppm or less, more preferably 5ppm or more and 50ppm or less.

The polyester of the present invention is selected from the group consisting of aluminum and its compounds in addition to at least one selected from the group consisting of the above alkaline metals and their compounds, in addition to the alkaline earth metals and their compounds. At least one Must be contained. In addition, for alkali metals and their compounds, the content of at least one selected from the group consisting of alkaline earth metals and their compounds and the content of at least one selected from the group consisting of aluminum and their compounds On the other hand, it is necessary that the ratio of the total content (ppm) of the aluminum metal atoms and the aluminum earth metal atoms (ppm) to the aluminum atom content ( _P pm) in the polyester be 40 or less. This ratio is preferably not less than 0.05.If the ratio exceeds 40, a large amount of foreign matter insoluble in the polyester is generated, and as a result, thread breakage during spinning and filter clogging during molding frequently occur. In addition, when used as a catalyst, there is a problem that the catalytic activity is remarkably reduced, and the ratio is smaller than 0.05, which is caused by the aluminum compound. It is not preferable because a large amount of foreign matter insoluble in the polyester is generated, and the thermal stability of the polyester is also deteriorated .. A more preferable range of the ratio is 0.1 to 20 and more preferably 0.5. It is 10 or less.

The polyester of the present invention includes, in addition to at least one member selected from the group consisting of alkali metal and their compounds, and alkaline earth metal and their compounds, and at least one member selected from the group consisting of aluminum and its compounds At least one selected from the group consisting of phosphorus compounds. Further, the content of at least one selected from the group consisting of phosphorus compounds and aluminum and at least one selected from the group consisting of the compounds is defined as the content of phosphorus atoms (ppm) and the content of aluminum atoms in the polyester. (ppm) ratio must be 0.01 or more. This ratio is preferably 30 or less. If the ratio is less than 0.01, there arises a problem that a large amount of insoluble foreign matter is generated in the polyester due to the aluminum conjugate, and a problem that the thermal stability of the polyester is reduced. If the ratio exceeds 30, a large amount of foreign matter insoluble in the polyester is generated, and if the catalyst activity is significantly reduced for use as a catalyst, a problem arises, which is not preferable. A more preferable range of the ratio is 0.1 or more and 20 or less, and more preferably 1 or more and 10 or less.

In the polyester, at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds By setting the content of at least one selected from the group consisting of minimium and its compounds, and at least one selected from the group consisting of phosphorus compounds within the above ranges, the generation of foreign matters insoluble in polyester is effectively suppressed, Problems such as yarn breakage during spinning and filter clogging during molding are improved. .

In the present invention, the aluminum and the compound thereof are preferably contained in the polyester in an amount of 0.5 ppm or more and 500 ppm or less as an aluminum atom. If the content of the aluminum atom exceeds 500 ppm, it is not preferable because a large amount of foreign matter insoluble in the polyester caused by the aluminum-palladium compound is generated and the thermal stability of the polyester is deteriorated. When the content of the aluminum atom is less than 0.5 ppm, a large amount of foreign substances due to the alkali metal compound or the alkaline earth metal compound is generated, or the catalytic activity is significantly reduced when used as a catalyst, which is preferable. Absent. More preferably, it is in the range of 5 ppm or more and 70 ppm or less, and still more preferably in the range of 10 ppm or more and 30 ppm or less.

Further, the phosphorus compound in the present invention is preferably contained in the polyester in a range of lppm to lOOppm as a phosphorus atom. If the phosphorus atom content is less than lp pm, the effect of suppressing the formation of foreign matter insoluble in the polyester is poor, and the thermal stability of the polyester is undesirably reduced. If the content of the phosphorus atom exceeds 100 ppm, it is not preferable because a large amount of foreign matter insoluble in the polyester is generated. More preferably, it is in the range of 10 ppm to 200 ppm, and still more preferably in the range of 20 ppm to 100 ppm.

The polyester of the present invention needs to contain at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds. Among these, lithium, It is preferable to contain at least one selected from the group consisting of sodium, potassium, magnesium, calcium, and compounds thereof from the viewpoint of reducing foreign matters in the polyester ゃ coloring of the polyester. Among these, it is preferable to contain at least one selected from the group consisting of lithium, calcium and compounds thereof because the polyester has excellent thermal stability. Furthermore, it contains at least one selected from the group consisting of calcium and their compounds from the viewpoint of reducing the coloring of the polyester. Is preferred.

The present invention also relates to a polyester produced using the above-mentioned metal and Z or a compound as a catalyst, and a method for producing the same. The amount of the metal and z or the compound to be added needs to be such that the content of the metal atom in the finally obtained polyester is as described above. In the polyester produced by this method, the generation of foreign matters insoluble in the polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

The alkali metals and their compounds and the alkaline earth metals and their compounds used as the polymerization catalyst in the present invention include Li, Na, K, Rb, Cs, Be, Mg, and Ca. It is preferable that at least one metal selected from the group consisting of, Sr, and Ba or a compound thereof is used. Among them, the use of Alkyri metal or a compound thereof reduces foreign matters insoluble in polyester and reduces the heat stability of polyester. It is more preferable because of excellent properties. When an alkali metal or a compound thereof is used, use of L i, N a, K or a compound thereof is preferable. Among them, use of L i or a compound thereof is particularly preferable because foreign matters insoluble in polyester are further reduced.

Further, another polyester of the present invention comprises at least one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium and compounds thereof, and at least one selected from the group consisting of aluminum and compounds thereof. kind, as well as at least one of a free selected from the group consisting of phosphorus compounds, forces one lithium, sodium, potassium, beryllium, magnesium, Cal Shiumu and total polymer 1 content of the compounds O ^e g per metal atom It is characterized by being 7.0 mol or less in conversion. If the content is more than 7.0 mol, a large amount of foreign matter insoluble in the polyester is generated, and as a result, there is a problem that yarn breakage during spinning and filter clogging during molding frequently occur. In addition, the coloring of the resin becomes remarkable, causing a problem that the appearance of the molded article is impaired, and a problem that the thermal stability and the hydrolysis resistance of the resin are reduced. The content is preferably at least 0.05 mol, and if less than this, the thermal stability of the resin may be poor, and when used as a catalyst, the catalytic activity may be significantly reduced. Said content The amount is more preferably from 0.1 to 4.0 mol, even more preferably from 0.2 to 2.5 mol, and particularly preferably from 0.2 to 1.2 mol. With such a polyester, the generation of foreign matters insoluble in the polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

The content of aluminum and its compound in the polyester of the present invention is preferably 0.5 to 500 ppm as aluminum atoms. If the content of the aluminum atom exceeds 500 ppm, it is not preferable because a large amount of foreign matter insoluble in the polyester due to the aluminum conjugate is formed and the thermal stability of the polyester is deteriorated. If the content of aluminum atoms is less than 0.5 ppm, a large amount of foreign substances due to the alkali metal compound or alkaline earth metal compound is generated, or the catalytic activity is significantly reduced when used as a catalyst, which is not preferable. . It is more preferably in the range of 5 to 70 ppm, further preferably in the range of 10 to 40 ppm, and particularly preferably in the range of 15 to 25 ppm.

Further, the content of the phosphorus compound in the polyester of the present invention is preferably 1 to 100 ppm as a phosphorus atom. If the phosphorus atom content is less than Slppm, the effect of suppressing the generation of foreign matter insoluble in the polyester is poor, and the thermal stability of the polyester is undesirably reduced. If the phosphorus atom content exceeds 100 ppm, it is not preferable because a large amount of foreign matter insoluble in the polyester is generated. More preferably, it is in the range of 10 to 200 ppm, even more preferably in the range of 20 to 100 ppm.

The polyester of the present invention needs to contain at least one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium, and compounds thereof. Among these, lithium, sodium, It is preferable to contain at least one selected from the group consisting of magnesium, calcium and their conjugates from the viewpoint of reducing foreign matter in the polyester, reducing coloring of the polyester and improving thermal stability. Among these, it is preferable to contain at least one selected from the group consisting of lithium, sodium and their compounds.

The present invention relates to at least one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, potassium, and their conjugates; And at least one selected from the group consisting of phosphorus compounds such that the content thereof is in the range described above with respect to the finally obtained polyester. The present invention also relates to a method for producing a polyester using the catalyst. In the polyester obtained by this method, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

Further, another polyester of the present invention is at least one selected from the group consisting of aluminum and its compounds, and at least one selected from the group consisting of phenol compounds at least one selected from the group consisting of phosphorus compounds. And the amount of phosphorus atoms contained in the polyester

(ppm) and the amount of aluminum atoms (ppm) are in the range of 0.01 to 50. If the ratio of the amount of phosphorus atoms (ppm) to the amount of aluminum atoms (ppm) (the amount of phosphorus atoms / the amount of aluminum atoms) is less than 0.01, a large amount of foreign matters insoluble in the polyester resulting from the aluminized product. As a result, there is a problem that yarn breakage during spinning and filter clogging during molding frequently occur. In addition, coloring of the resin becomes remarkable, causing a problem that ^ II of a molded article is impaired and a problem that thermal stability and thermal oxidation stability of the resin are reduced. When the ratio exceeds 50, a large amount of foreign matter insoluble in the polyester is generated, and as a result, there is a problem that yarn breakage during spinning and filter clogging during molding frequently occur. In addition, when used as a catalyst, there is a problem that the tactility is significantly reduced. The preferred range of the ratio is 0.1-20, more preferably 0.5-10.

The content of aluminum and its compound in the polyester of the present invention is preferably 0.5 to 500 ppm as aluminum atoms. If the content of the aluminum atom exceeds 500 _{PPm, it} is not preferable because a large amount of foreign matter insoluble in the polyester due to the aluminum compound is generated and the thermal stability and the thermo-oxidative stability of the polyester are reduced. If the content of the aluminum atom is less than 0.5 ρηη, the catalytic activity is remarkably reduced when used as a catalyst, which is not preferable. More preferably, it is in the range of 5 to 70 ppm, still more preferably in the range of 10 to 40 ppm, and particularly preferably in the range of 15 to 25 ppm. The polyester of the present invention has a phosphorus compound that improves the catalytic activity of the aluminum compound, suppresses the generation of foreign substances, and improves the thermal stability and thermal oxidation stability of the polyester. It is. Further, by containing a phenolic compound, the thermal acid stability of the polyester is further improved, and as a result, thermal degradation and yellowing of the polyester are suppressed.

Further, another aspect of the present invention is a polyester containing at least one selected from the group consisting of phosphorus compounds and at least one selected from the group consisting of phenolic conjugates, and wherein the polyester It is characterized in that the total amount of contained metal atoms is 100 ppm or less with respect to polyester. The polyester has improved the problem of filter clogging at the time of molding, has improved thermal stability and thermal acid stability, and has a small amount of metal atoms. The extract from polyester is also reduced. If the total amount of metal atoms exceeds 100 ppm, it is not preferable because foreign matters in the polyester increase and the quality of the polyester is impaired. Metal atoms are preferably contained in the polyester in a total amount of 1 ppm or more. When the metal species is used as a catalyst, the catalytic activity is effectively exhibited, which is preferable. The total amount of metal atoms is preferably from 3 to 50 ppm, particularly preferably from 5 to 30 ppm. The metal species is not particularly limited, but is preferably at least one selected from alkali metals, alkaline earth metals, and aluminum.

The content of the phosphorus compound in the polyester of the present invention is preferably from 1 to 1000 ppm as a phosphorus atom. If the phosphorus atom content is less than lppm, the effect of suppressing the formation of foreign matter insoluble in polyester is poor, and the thermal stability and thermal oxidation stability of polyester are undesirably low. If the phosphorus atom content exceeds 100 ppm, it is not preferable because a large amount of foreign matter insoluble in polyester is generated. More preferably, it is in the range of 10 to 200 ppm, more preferably in the range of 20 to 100 ppm. On the other hand, when the polyester of the present invention contains at least one selected from the group consisting of alkali metals and their compounds, and alkaline earth metals and their compounds, physical properties such as thermal stability of the polyester are obtained. Preferred, because it improves. Of these, lithium, sodium, potassium, magnesium, calcium It is preferable to contain at least one member selected from the group consisting of a polymer and a compound thereof from the viewpoint of reducing foreign matter in the polyester ゃ coloring of the polyester. Among these, it is preferable to include at least one selected from the group consisting of lithium, calcium, and compounds thereof because the polyester has excellent thermal stability. Further, it is preferable to contain at least one selected from the group consisting of calcium and a compound thereof from the viewpoint of reducing coloring of the polyester.

When the polyester of the present invention contains an alkaline metal, an alkaline earth metal, or a compound thereof, the content thereof is 1 X based on the number of moles of the entire polycarboxylic acid unit constituting the polyester. 1 0 ⁶ or 0.1 mole ^_0/0 less than the it is rather preferable, more preferably 5 X 1 0 ⁶ ~0. 0 5 mol ^_0/0, more preferably IX 1 0 ⁵ ~ 0. 0 a 3 mole ^_0/0, particularly preferably ^{1 X 1 0- 5 ~0. 0} 1 Monore ^_0/0. Since the content of alkali metals and alkaline earth metals is small, problems such as a decrease in thermal stability, a decrease in hydrolysis resistance, generation of foreign matter, and coloring are reduced. When the content of alkali metals, alkaline earth metals and their compounds exceeds 0.1 mol%, thermal stability is reduced, foreign matter is generated, coloring is increased, and hydrolysis resistance is reduced. May occur. When the content is less than 1 X 1 0- ⁶ mol%, it is clear that the effect also contain! / ,,.

The present invention also relates to a method for producing a polyester as described above using the compound described as a catalyst.

Further, another polyester of the present invention is a polyester containing at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds, and the amount of phosphorus atoms contained in the polyester. It is necessary that the ratio of (ppm) to the amount (ppm) of aluminum atoms be in the range of 0.5 to 20. If the ratio is less than 0.5, a large amount of insoluble foreign matter is generated in the polyester due to the aluminum compound. As a result, there is a problem that yarn breakage during spinning and filter clogging during molding frequently occur. In addition, the coloration of the resin becomes remarkable, causing a problem that the appearance of the molded article is impaired and a problem that the thermal stability of the resin is reduced. When the ratio exceeds 20, a large amount of insoluble foreign matter is generated in the polyester, resulting in thread breakage during spinning and filter clogging during molding. A problem that occurs frequently occurs. In addition, when used as a catalyst, there is a problem that the catalytic activity is significantly reduced. The preferred range of the ratio is from 1 to 15, more preferably from 3 to 10.

By setting the content of at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds in the polyester within the above range, the generation of foreign matters insoluble in the polyester is effective. The problems such as yarn breakage during spinning and filter clogging during molding are improved. Further, the anoreminium and the compound thereof of the present invention are preferably contained in the polyester in an amount of 1 ppm to 100 ppm as aluminum atoms in the polyester. If the content of aluminum atom exceeds 100 ppm, it is not preferable because a large amount of foreign matter insoluble in the polyester caused by the aluminum compound is generated and the thermal stability of the polyester is deteriorated. If the content of aluminum atoms is less than Slppm, the catalytic activity is significantly reduced when used as a catalyst, which is not preferable. More preferred details, in the range of less 5p _P m or more 70 ppm, more preferably from 30ppm less range of LOppm.

Further, it is preferable that the phosphorus compound of the present invention is contained in the polyester in a range of 5 ppm or more and 200 ppm or less as a phosphorus atom. If the phosphorus atom content is less than ⁵ ppm, the effect of suppressing the formation of foreign matter insoluble in polyester is poor, and the thermal stability of the polyester is undesirably low. If the phosphorus atom content exceeds 200 ppm, it is not preferable because a large amount of foreign matter insoluble in polyester is generated. More preferably, it is in the range of 10 ppm to 100 ppm, and even more preferably, it is in the range of 20 ppm to 80 ppm.

The form in which the phosphorus compound of the present invention is present in the polymer is not particularly limited. Examples of the polyester polymerization catalyst include phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, and phosphinous acid compounds. It is preferable to use the compound in any form of a phosphine compound. By using a phosphorus compound having such a structure in coexistence with the aluminum-dimethyl conjugate during the polymerization of the polyester, an effect of improving the catalytic activity can be obtained. Among these, when the phosphonic acid-based conjugate is used, the effect of improving the catalytic activity when used as a catalyst is improved. Large and preferred. Among phosphonic acid-based compounds, a form having an aromatic ring structure is particularly preferable because the effect of improving tactility when used as a catalyst is particularly large.

On the other hand, when the polyester of the present invention contains at least one kind selected from the group consisting of alkali metal and their hydrated compounds and alkali metal and their compounds, the polyester It is preferable because physical properties such as thermal stability are improved. Among these, it is preferable to contain at least one selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, and compounds thereof from the viewpoint of reducing foreign matters in the polyester and reducing the coloring of the polyester. .

When the polyester of the present invention contains an alkaline metal, an alkaline earth metal, and a compound thereof, the content is 1 X with respect to the number of monoles of all the polycarboxylic acid units constituting the polyester. 1 0 ⁶ or 0.1 mole ^_0/0 less than the it is rather preferable, more preferably ^{5 X 1 0- s ~0. 0} 5 mol ^_0/0, more preferably IX 1 0 ⁵ ~ 0. 0 a 3 mole ^_0/0, particularly preferably ^{1 X 1 0- 5 ~0. 0} 1 mol ^_0/0. Since the content of alkali metals and alkaline earth metals is small, problems such as a decrease in thermal stability, a decrease in hydrolysis resistance, generation of foreign matter, and coloring are reduced. When the content of alkali metals, alkaline earth metals and their compounds is over 0.1 mol%, thermal stability decreases, foreign matters are generated and coloration increases, hydrolysis resistance decreases, and so on. Cases occur. In less than 1 X 1 0- ⁵ mole% content, the effect is not clear also contain.

The present invention also relates to a polyester produced using the above-described metal and compound as a catalyst, and a method for producing the same. The amount of the metal and the compound to be added needs to be such that the content of the metal atom to the phosphorus atom in the finally obtained polyester is as described above. By this method, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

It is preferable that the polyester of the present invention is not produced using a heavy vehicle such as an antimony compound, a germanium compound, a titanium compound, a tin compound, or the like. On the other hand, the polyester of the present invention has a polymerization catalyst such as an antimony compound, a germanium compound, a titanium compound, and a tin compound, and the addition of these components causes problems in the above-described products such as the properties, processability, and color tone of the polyester. When they are used as a polymerization catalyst, they are effective in improving productivity by shortening the polymerization time, and are preferred.

The polyester of the present invention is preferably adjusted to have an antimony atom content of 50 ppm or less with respect to the polyester, since the occurrence of darkening and foreign matters of the polyester is suppressed. It is more preferably 30 ppm or less, and further preferably lOppm or less. On the other hand, the polyester of the present invention preferably does not contain an antimony atom.

In addition, the polyester of the present invention is preferred to have a germanium atom content of 20 ppm or less with respect to the polyester, so that it is not disadvantageous in cost. More preferably, it is 10 ppm or less, and still more preferably, 5 p or less. On the other hand, the polyester of the present invention preferably does not contain a germanium atom.

Further, it is preferable that the content of the titanium atom of the polyester of the present invention is 5 m or less with respect to the polyester, since the heat stability and the color tone of the polyester are excellent. It is more preferably 3 ppm or less, and still more preferably 1 ppm or less. On the other hand, the polyester of the present invention preferably does not contain a titanium atom.

It is preferable that the polyester of the present invention further contains cobalt or a compound thereof from the viewpoint of reducing coloring of the polyester. However, the content of cobalt or its conjugate in the polyester is preferably less than 10 ppm with respect to the polyester as a cobalt atom. It is more preferably less than 5 ppm, and still more preferably 3 ppm or less.

It is known that cobalt compounds themselves have a certain degree of tactility.However, if they are added to such an extent that they exhibit a sufficient catalytic effect, the resulting polyester polymer will have reduced brightness and reduced thermal stability. Occur. In the present invention, a cobalt compound Can be more effectively eliminated without reducing the brightness and thermal stability of the resulting polyester by adding a small amount of . The purpose of the cobalt compound in the present invention is to eliminate coloration, and it may be added at any stage of the polymerization or after the end of the polymerization reaction.

On the other hand, it is preferable that the polyester of the present invention does not contain a copartite atom because the polyester polymer has excellent thermal stability and brightness. Further, another polyester polymerization catalyst of the present invention comprises at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds, and has a monolithic ratio of phosphorus atoms to aluminum atoms. 0.5 to 20. Further, the method for producing a polyester of the present invention is characterized in that the polyester is produced by adding at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds in the above range. And If the molar ratio is less than 0.5, the catalytic activity is remarkably reduced, and it takes a long time to polymerize a polyester having a predetermined viscosity. In addition, the generation of foreign matter insoluble in the polyester, the coloring of the resin becomes remarkable, and the thermal stability of the resin is reduced. When the molar ratio exceeds 20, the catalytic activity is remarkably reduced, and it takes a long time to polymerize a polyester having a predetermined viscosity. The preferred range of the molar ratio is 2 to 15, more preferably 3 to 10, and particularly preferably 4 to 8.

The addition amount of the aluminum and the compound of the present invention is in the range of 0.001 lmo 1% to 0.1 mo 1% as aluminum atoms, based on the total number of moles of the polycarboxylate unit constituting the obtained polyester. Is preferred. 0 added

If the content exceeds 1 mo 1%, the thermal stability and thermo-oxidative stability of the polyester may be reduced, foreign matter insoluble in the polyester may be generated, and the coloration of the resin may be increased. If the addition amount is less than 0.001 mo 1%, the catalytic activity may not be sufficiently exhibited. A more preferable range of the addition amount is 0.003 mol% to 0.005 mol 1%, still more preferably 0.005 mol ⁰ / o to 0.02 mol%, and 0.007 mol% to 0.005 mol%. 015mo 1% is particularly preferred. Aluminum- ゥ like this The polymerization catalyst of the present invention has a great feature in that it exhibits a sufficient catalytic activity even when the amount of the system component is small. As a result, thermal stability and thermal oxidation stability are excellent, and foreign substances and coloring due to aluminum are reduced.

The addition amount of the phosphorus compound of the present invention is preferably in the range of 0.005 mol% to 0.2 mol 1% as a phosphorus atom, based on the number of moles of all the polycarbonate units constituting the obtained polyester. . If the addition amount is less than 0.005 mo 1%, the effect of addition may not be exhibited. If the addition amount exceeds 0.2 mo 1%, on the contrary, the catalysis as a polyester polymerization catalyst may decrease. A more preferred range of addition ^{_{amount, 0. 007mo l o / 0 ~0}} . 05 is a mo 1%, rather more preferably is 0. 01ηαο 1% ~0. 02mo l %.

This technology uses an aluminum compound as the main catalyst component without using a phosphorus compound.This reduces the amount of aluminum compound used, and reduces the thermal stability when a cobalt compound is added and the aluminum compound is used as the main catalyst. Although there is a technology to prevent coloration due to heat, adding a copartite compound to such an extent that it has a sufficient catalytic activity will soon lower the thermal stability. Therefore, it is difficult to achieve both with this technology. According to the present invention, the use of a phosphorus compound in a specific amount does not cause problems such as a decrease in thermal stability and the generation of foreign matter, and furthermore, a metal-containing component. A polymerization catalyst having a sufficient catalytic effect can be obtained even when the amount of aluminum added is small, and by using this polymer, melt molding of polyester films, bottles and other hollow molded articles, fibers and engineering plastics, etc. Thermal stability at the time is improved. Of the phosphorus compounds of the present invention, the addition of a phosphate ester such as phosphoric acid-trimethylphosphoric acid is not preferable because almost no effect is observed. Further, the phosphorus compound of the present invention may be used in combination with a conventional metal-containing polyester polymerization catalyst such as an antimony conjugate, a titanium compound, a tin compound, and a germanium compound within the range of the addition amount of the present invention. However, the effect of accelerating the melt polymerization reaction is not recognized.

Another feature of the present invention is that a polyester polymerization catalyst, wherein the thermal stability parameter (TS) of polyethylene terephthalate (PET) polymerized using this catalyst satisfies the following formula (9): Features. (9) TS <0.20

However, for TS, put PE Tlg with intrinsic viscosity ([IV],) of 0.64 to 0.66 dl / g in a glass test tube, vacuum-dry at 130 ° C for 12 hours, and then place in a non-circulating nitrogen atmosphere. It is a numerical value calculated from the intrinsic viscosity ([IV] _f ) after maintaining the molten state at 300 ° C for 2 hours below.

TS = 0.245 {[IV] _f - ^{1 47-} [IV] i- ¹ · ⁴⁷ }

A non-circulating nitrogen atmosphere means a nitrogen atmosphere that does not flow.For example, a glass test tube containing a resin chip is connected to a vacuum line, and the pressure is reduced to O OTorr after 5 times or more of pressure reduction and nitrogen filling. And sealed. The use of a catalyst with a powerful structure provides remarkably excellent melting heat stability against heating and melting when producing molded products such as films, bottles, fibers, etc., and gives molded products with reduced molecular weight, less coloring and less generation of foreign matter. A polyester is obtained.

TS is more preferably 0.17 or less, particularly preferably 0.15 or less.

Hitherto, a polyester polymerization catalyst that provides PET such that T S falls within the above range has not been known. In the present invention, a polyester polymerization catalyst that gives PET having a TS within the above range is found, and a film made of a polyester polymerized using the polyester polymerization catalyst, a hollow molded article such as a bottle, a fiber, an engineering plastic, etc. It has been found that the thermal stability during melt-molding has been significantly improved, and that high-quality products can be obtained even if virgin resin is used and the waste generated during molding is reused. That is another characteristic.

The above-mentioned polyester polymerization catalyst preferably contains at least one selected from the group consisting of phosphorus compounds as a catalyst component.

Another polyester polymerization catalyst of the present invention comprises a metal or a metal compound and a phosphorus compound, and is characterized in that the activity parameter (AP) satisfies the following expression (10).

(10) AP (min) <APX (min)

However, AP polymerizes polyethylene terephthalate (PET) with an intrinsic viscosity of 0.65 dl "g at a pressure of 275 ° C and a pressure of 0.1 l Torr using a predetermined amount of catalyst. APX is the AP when only the metal or metal compound is used in the same amount as above.

The AP measurement method is specifically as follows.

1) (B HET manufacturing process) Mixture of bis (2-hydroxyethyl) terephthalate (BHET) and oligomers using terephthalic acid and 2 times the molar amount of ethylene glycol with an esterification rate of 95% Hereinafter, referred to as BHET mixture). .

2) (Catalyst addition step) Add a predetermined amount of catalyst to the above BHET mixture, stir at 245 ° C for 10 minutes at normal pressure under a nitrogen atmosphere, and then heat up to 275 in 50 minutes And gradually lower the pressure of the reaction system of the mixture of oligomers to 0.1 Torr.

3) (Polycondensation step) A polycondensation reaction is performed at 275 ° C and 0. ITorr, and polymerization is performed until the intrinsic viscosity (IV) of polyethylene terephthalate reaches 0.65 d 1 g.

4) The polymerization time required for the polycondensation step is defined as A P (min).

These are performed using a batch-type reactor.

1) The production of the BHET mixture in the (BHET production process) is performed by a known method. For example, terephthalic acid and twice the amount of ethylene glycol are charged into a patch-type autoclave equipped with a stirrer, and the esterification reaction is performed while distilling water out of the system at 245 under a pressure of 0.25 MPa. It is manufactured by

By setting the activity parameter AP within the above range, in addition to improving the thermal stability due to the coexistence of the phosphorus compound, the reaction rate is faster, and the time for producing polyester by polycondensation is further reduced. The AP is more preferably 0.9 APX or less, further preferably 0.8 APX or less, and particularly preferably 0.7 APX or less.

2) “Predetermined amount of catalyst” in the (catalyst addition step) means the amount of catalyst that is used in a variable amount according to the activity of the catalyst, and is small for high-activity catalysts and low for low-activity catalysts. The amount increases.

In general, phosphorus compounds are known as stabilizers for polyesters. It is known that the thermal polymerization can be suppressed.However, conventionally, a polyester polymerization catalyst comprising a metal or a metal compound and a phosphorus compound such that the active parameter AP force falls within the above range has been known. Was not known. In fact, when a polyester is polymerized using an antimony compound, a titanium compound, or a germanium compound, which is a typical catalyst for polyester polymerization, as a polymerization catalyst, the addition of a phosphorus compound promotes the polymerization to a substantially useful level. Is not allowed. In the present invention, an activity parameter AP force S, a polyester polymerization catalyst comprising a metal or a metal compound and a phosphine compound having the above-mentioned range is obtained, and a catalyst activity is excellent by using the polymerization catalyst. It is characterized by the fact that without deactivating or removing the catalyst, thermal degradation during melt molding is effectively suppressed and a polyester having excellent ripening stability is provided.

(2) In the above-mentioned polyester polymerization catalyst, the thermal stability parameter (TS) of polyethylene terephthalate (PET) polymerized by using the catalyst preferably satisfies the following expression (9).

(9) TS <0.20

The use of a powerfully structured catalyst results in excellent catalytic activity, remarkably excellent melting heat stability against heat melting when manufacturing molded products such as films, bottles, and fibers, and a reduction in molecular weight and coloration. A polyester that gives a molded article with less generation of foreign matter is obtained.

TS is more preferably 0.18 or less, particularly preferably 0.15 or less.

In the polyester polymerization catalyst of the present invention, the thermal oxidation stability parameter (TOS) of polyethylene terephthalate (PET) polymerized using the catalyst preferably satisfies the following formula (11).

(11) TOS <0.10

In the above formula, TOS has a melt-polymerized IV of 0.64-0.66 dl / g] PET resin chip is freeze-ground and dried as a powder of 20 mesh or less under vacuum at 130 ° C for 12 hours 0.3 g is placed in a glass test tube, dried under vacuum at 70 for 12 hours, and then heated at 230 ° C for 15 minutes under air dried with silica gel. TOS = 0. 245 {[IV] t '1 - 47 one [IV] _s

[IV] i and [IV] „indicate the IV (d 1 / g) before and after the heating test, respectively.

As a method of heating under air dried with silica gel, for example, a method of connecting a drying tube containing silica gel to the upper part of a glass test tube and heating under dry air can be exemplified.

By using the polyester polymerization catalyst having the above-described structure, a polyester which gives a molded article such as film-pottle which is excellent in heat resistance and aging resistance can be obtained.

TOS is more preferably 0.09 or less, still more preferably 0.08 or more Byeon.

In the present invention, a PET resin chip used for measuring TS and TOS is prepared by quenching from a molten state after the above steps 1) to 3). As the shape of the resin tip used for these measurements, for example, a cylinder-shaped resin tip with a length of about 3 mni and a diameter of about 2 mm is used.

The polyester polymerization catalyst of the present invention preferably has an activity parameter (AP) satisfying the following formula (12).

(12) AP (min) <2T (min)

T is an AP when 0.05% by mol of antimony is added to the acid component in the polyethylene terephthalate produced by using the acid catalyst as a catalyst.

In the present invention, antimony trioxide used for comparison uses antimony trioxide having a purity of 99% or more. For example, use commercially available Antimony (III) oxide (ALDRICH CHEMICAL, purity 99.999%).

It is preferable to set the activity parameter AP within the above range, since the reaction rate is high and the time for producing the polyester by polycondensation is increased. AP is more preferably 1.5T or less, further preferably 1.3T or less, and particularly preferably 1.0T or less.

The metal component constituting the polyester polymerization catalyst of the present invention is not particularly limited as long as it is other than antimony, titanium, and germanium. Examples include potassium earth metals, Group IV elements such as aluminum and gallium, Group IV elements such as silicon, various transition metals, and lanthanoid elements. Of these, Group III elements are preferred, and among them, aluminum is particularly preferred. The compounds of these metals are not particularly limited, but specific examples thereof include saturated aliphatic carboxylate salts such as formic acid, acetic acid, propionic acid, butyric acid, and oxalic acid, atalylic acid, and methacrylic acid. Aromatic salts such as unsaturated aliphatic carboxylate, benzoic acid, etc.Halogen-containing carboxylate such as trichloroacetic acid, lactic acid, cunic acid

, Salicylic acid and other hydroxycanoleponates, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromine Inorganic acid salts such as acid, 1-propanesulfonic acid, 1-pentanesulfonic acid, organic sulfonate such as naphthalenesulfonic acid, organic sulfate such as lauryl sulfate, methoxy, ethoxy, n-propoxy, iso-propoxy, n — Alkoxides such as butoxy and tert-butoxy; chelate compounds such as acetinoleacetonate; hydrides, oxides, and hydroxylated compounds.

The preferred amount of the metal component used in the production of the polyester varies depending on the type of metal used.However, it is 1 × 10− as a metal atom based on the total number of moles of the polycarboxylic acid cut constituting the polyester. ⁶ or more 0.5 mol. / ₀ laid preferred that less, more preferably ⁵ X 1 0- 5 ~0. 1 mol ^_0/0. If the amount is 0. Exceeds 5 mol ^_0/0, the quality such as thermal stability and color tone of the resulting polyester is undesirably lowered. If the amount is less than 1 X 1 0- ⁶ mol%, the effect is not clear also be added.

The polyester polymerization catalyst of the present invention preferably contains at least one selected from the group consisting of aluminum and compounds thereof as a catalyst component.

The amount of the aluminum or aluminum compound to be used in the present invention is 0.001 to 0.05 with respect to the number of monoles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. preferably the molar ^_0/0, rather more preferably is 0. 0 0 5 to 0. 0 2 mol ^_0/0. Usage to zero. 0 0 1 mole ^_0/0 less der Rutosawa ^ properties are sufficiently exhibited it! /, May, if the amount used is 0.0 to 5 mol%, Ya thermostability Deterioration of thermal oxidation stability, generation of foreign matter due to aluminum, In some cases, the addition of coloring becomes a problem. As described above, the polymerization catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity even when the addition amount of the aluminum component is small. As a result, thermal stability and thermal oxidation stability are excellent, and foreign substances and coloring caused by aluminum are reduced.

The amount of the phosphorus compound of the present invention, preferably from 0.0001 to 0.1 mole ^_0/0 with respect to the number of moles of all the structural Yunitto polycarboxylic acid component of the polyester obtained, 0.00 5..0. More preferably, it is 05 mol%. If the amount of the phosphorus compound is less than 0.0001 mol%, the effect of the addition may not be exhibited.If the amount exceeds 0.1 mol%, the catalytic activity as a polyester polymer may be reduced. .

A technology that uses an aluminum compound as the main catalyst component without using a phosphorus compound.This technology reduces the amount of aluminum compound used, and further adds a cobalt compound to make the aluminum catalyst a main catalyst. Although there is a technology to prevent coloring due to a decrease in the properties, adding a copanoleto compound to such an extent that it has sufficient catalytic activity will soon reduce the thermal stability. Therefore, it is difficult to achieve both with this technology. According to the present invention, the use of the above-mentioned Lynch compound does not cause problems such as a decrease in thermal stability and the generation of foreign matter, and furthermore, the metal-containing component aluminum A polymerization catalyst having a sufficient catalytic effect can be obtained even with a small addition amount as a rubber. By using this polymerization catalyst, hollow molded products such as polyesterolefinolem and pottle, fibers and engineered plastics can be obtained. The thermal stability during melt molding of sticks and the like is improved. Of the phosphorus compounds of the present invention, the addition of a phosphoric acid ester such as phosphoric acid trimethylphosphoric acid is not preferred because no catalytic activity improving effect is observed. Further, even when the phosphorus compound of the present invention is used in combination with the conventional antimony compound, titanium compound, or germanium compound within the range of the addition amount of the present invention, the effect of promoting the melt polymerization reaction is not recognized. .

It is preferable to include at least one selected from aluminum salts of phosphorus compounds as components constituting the polyester polymerization catalyst of the present invention. It is also preferable to use a combination of an anoreminium salt of a phosphorus compound with another anoreminium compound or a phosphorus compound.

The amount of the aluminum salt of the Lynch compound of the present invention used may be All configuration Interview polycarboxylic acid component Le -.. 0.1 with respect to the number of moles of Tsu bets 0001-0 is preferably 2 mol ^_0/0, 0.005 to 0 1 further preferably Monore%.

Another aspect of the present invention is characterized in that an aluminum carboxylate dissolved in water and / or an organic solvent in advance is used as a catalyst.

Specific examples of the aluminum carboxylate of the present invention include aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate aluminum laurate, aluminum stearate, and aluminum benzoate. And aluminum triacetate, aluminum lactate, aluminum citrate, aluminum tartrate, and aluminum salicylate. Of these, those having a structure of an acetic acid anolemminium salt, such as aluminum acetate and basic anolemminium acetate, and sulfuric acid. Aluminum is preferred from the viewpoint of solubility in the system and catalytic activity.

Examples of the use of an aluminum salt of a carboxylic acid as a polyester polymerization catalyst include aluminum acetate, basic aluminum acetate, aluminum lactate, and aluminum benzoate. Low solubility in water, it has poor catalytic activity and has problems when insoluble foreign matter is formed in the obtained polyester, and there is a problem in using these conjugates as catalysts as they are. . The present invention is characterized in that it has been found that sufficient catalytic activity can be imparted by using a catalyst obtained by dissolving these in water and Z or an organic solvent in advance.

Before the aluminum carboxylate of the present invention is added to the polymerization system of the polyester, it must be dissolved in water, Z or an organic solvent in advance and added to the polymerization system. As the organic solvent, glycols are preferably used, and in the case of producing PET, ethylene dalicol is preferably used.

Examples of those having the structure of an aluminum salt of acetic acid include basic aluminum acetate, anolemme-triacetate, and aluminum acetate solution. Among these, from the viewpoint of solubility and stability of firewood night. Therefore, the use of basic aluminum acetate is preferred. Of the basic aluminum acetates, the use of aluminum monoacetate or aluminum diacetate is preferred. Any basic aluminum acetate is water And those dissolved in z or an organic solvent must be used as the catalyst. By using a catalyst having such a configuration, it is possible to obtain a polyester having excellent catalytic activity and excellent quality. As the solvent, water diols are preferably used, and when PET is produced, water and Z or ethylene glycol are preferably used.

In another aspect of the present invention, when a carboxylate aluminum salt stabilized with boric acid or the like is used as a catalyst, the solubility and solution stability are excellent, the catalyst activity is excellent, and the quality is excellent. It is characterized by finding that polyester can be obtained. As the aluminum salt of carboxylic acid, those having a structure of an aluminum salt of acetic acid are preferable, and among them, use of basic aluminum acetate is preferable. Examples of the stabilizer include urea and thiourea in addition to boric acid, but use of boric acid is preferred. When a material stabilized with boric acid is used, it is preferable to use a material stabilized with boric acid in an amount equal to or less than equimolar to aluminum, and in particular, from 1/2 to 1/3 mol of boric acid. It is preferable to use an aluminum compound stabilized with an acid. When the aluminum salt of lipoic acid stabilized with boric acid or the like is used as a catalyst, these must be dissolved in water and / or an organic solvent in advance and added to the polymerization system. It is preferable from the viewpoint of. As the organic solvent, glycols are preferably used. In the case of producing PET, ethylene glycol is preferably used. '

The use of, as a catalyst, a mixture of basic aluminum acetate in advance with an alkali compound such as tetraethylammonium hydroxide is disclosed in WO98 / 42969. Although it is described that the formation of insoluble foreign matter is suppressed by this method, the use of an alkali compound is essential in this technique, and thus, there is a problem of coloring of polyester and generation of foreign matter caused by the alkali compound. In the present invention, since it is not essential to previously mix the aluminum compound described in the patent and the aluminum-dimethyl conjugate of the present invention, it is possible to obtain a polyester in which the above-described problems of coloring and foreign matter are reduced. it can.

In order to produce a solution of the aluminum sulfonate salt of the present invention in water or Z or an organic solvent, a solution in which an aluminum carboxylate is previously dissolved in water is used. Preferably. It is preferable to add an organic solvent such as a diol to the aqueous solution as needed. The aqueous solution may be added to the polymerization system as it is, but in order to reduce the heat shock at the time of addition, a solution obtained by diluting the aqueous solution with a diol such as ethylene dalicol is added to the polymerization system, or It is preferable to add water to the polymerization system by distilling water by replacing the solution diluted with the diol with one solution.

When the aqueous solution of the aluminum carboxylate is diluted with a diol such as ethylene glycol, it is preferable to dilute the aqueous diol with a diol having a volume ratio of 0.5 to 50 times the volume of water. When the concentration of the aluminum carboxylate solution to be added to the polymerization system is 0.01 to 1 monore / liter in terms of anolemmi-atom atom, it is insoluble in the obtained polyester. This is preferable because generation of foreign matter is particularly suppressed. When dissolving aluminum carboxylate in water and / or an organic solvent, or by adding a stabilizer such as boric acid or an acid such as citric acid, lactic acid, or oxalic acid to the dissolved solution, the solubility or solution It is preferable because the stability is enhanced.

Hereinafter, specific examples of a method for preparing a solution in which basic aluminum acetate used in the present invention is dissolved in water and / or an organic solvent will be described.

Preparation example of aqueous solution of basic aluminum acetate>

Water is added to the basic alcohol acetate, and the mixture is stirred at room temperature for several hours or more. The stirring time is preferably 12 hours or more. Then, stir at 60 ° C or more for several hours or more. The temperature in this case is preferably in the range of 60 to 80 ° C. The stirring time is preferably 3 hours or more. The concentration of the 7_ solution is preferably from 5 g / l to 100 g / l, and particularly preferably from 1 Og / 1 to 3 Og / 1.

Ethylene glycol is added to the above aqueous solution. The amount of ethylene glycol to be added is preferably 1 to 5 times the volume of the aqueous solution. More preferably, the amount is 2 to 3 times. The ^ S is stirred at room temperature for several hours to obtain a homogeneous mixed solution of water and ethylene glycol. Thereafter, the solution is heated and water is distilled off, whereby ethylene glycol can be obtained. The temperature is preferably at least 80 ° C, more preferably at most 120 ° C. More preferably, stirring is carried out at 90 to 110 ° C. for several hours to distill off water. Hereinafter, a specific example of a method for preparing an ethylene daricol solution of aluminum lactate used in the present invention will be described.

Prepare an aqueous solution of aluminum lactate. The preparation may be performed at room temperature or under heating, but preferably at room temperature. The concentration of the 7_R solution is preferably 20 g Zl to 100 g / l, and 50 to

80 g / 1 is particularly preferred. Ethylene glycol is added to the aqueous solution. The amount of ethylene glycol added is preferably 1 to ₅ times the volume of the aqueous solution. More preferably, the amount is 2-3 times. The solution is stirred at room temperature to obtain a uniform mixed solution of water / ethylene glycol, and then the mixture is heated and the water is distilled off to obtain an ethylene glycol solution. The temperature is preferably at least 80 ° C, more preferably at most 120 ° C. More preferably, stirring is performed at 90 to 110 ° C. for several hours to distill off water.

When at least one selected from the group consisting of phosphorus compounds is added to a solution in which aluminum carboxylate, which is the polyester polymerization catalyst of the present invention, is dissolved in water Z or an organic solvent, the stability of the solution is improved. However, it is preferable because the formation of foreign matter is suppressed. When preparing a solution in which aluminum carboxylate is dissolved in water and / or an organic solvent, at least one selected from the group consisting of phosphorus compounds may be allowed to coexist. The amount of the phosphorus compound added is preferably such that the molar ratio of phosphorus atoms to aluminum atoms is in the range of 0.1 to 10. As a method of adding the phosphorus compound, the phosphorus compound may be added to a previously prepared solution of the aluminum compound, or the aluminide may be dissolved in the previously prepared solution of the phosphorus compound. Alternatively, both solutions may be prepared by mixing them, or both may be dissolved in a solvent at the same time. As the solvent, water diols are preferably used, and in the case of producing PET, water or ethylene glycol is preferably used.

The amount of the aluminum compound used in the production of the polyester according to the method of the present invention is such that the aluminum atom is used for the number of moles of all constituent units of the carboxylic acid component such as dicarboxylic acid or polycarboxylic acid of the obtained polyester. 0.0 0 1 to 0.0 5 moles ^_0/0 is preferred as, more preferably 0. 0 0 5 to 0.0 2 mol ^_0/0. Usage to zero. 0 0 might 1 tactile properties is below mol% is not sufficiently exhibited, the amount used is 0.0 to 5 mol ^_0/0 greater than, the thermal stability and thermal acid I instability Low In some cases, the generation of foreign matters and the increase in coloring caused by aluminum may cause problems. As described above, even when the addition amount of the aluminum component is small, the polymerization catalyst of the present invention has a great feature in that it exhibits sufficient catalytic activity. As a result, thermal stability and thermal oxidation stability are excellent, and foreign substances and coloring due to aluminum are reduced.

When producing polyester according to the method of the present invention, it is preferable to use at least one member selected from the group consisting of phosphorus compounds, because the effect of improving physical properties such as thermal stability of polyester can be obtained.

The amount of the phosphorus compound used in the production of the polyester according to the method of the present invention is preferably 0.001 to 0.1 with respect to the total number of moles of the constituent polyester of the polycarboxylic acid component of the obtained polyester. preferably 1 mole ^_0/0, 0. 0 0 5 to 0.0 5 Monore ^_0/0 der Rukoto further preferred les. When a catalyst obtained by adding a phosphorus compound to the carboxylic acid carboxylic acid salt of the polyester polymerization catalyst of the present invention is used as the catalyst, the amount of the catalyst added may be adjusted so that the amount of the phosphorus compound falls within the above range. I like it. When the phosphorus compound is added separately from the catalyst solution, it is preferable that the total amount of the phosphorus compound added to the polymerization system be within the above range.

By using the phosphorus compound of the present invention in combination, it is possible to obtain a catalyst which exhibits a sufficient catalytic effect even when the amount of aluminum added in the polyester polymerization catalyst is small. If the amount of the phosphorus compound is less than 0.001 mol%, the effect of the addition may not be exhibited. If the amount exceeds 0.1 mol%, the catalyst as a polyester polymerization catalyst may be produced. The activity may decrease, and the tendency of the decrease varies depending on the amount of aluminum used.

When the polyester is produced according to the method of the present invention, it is preferable not to add an alkali metal, an alkaline earth metal, or a mixture thereof.

On the other hand, in a preferred embodiment of the present invention, in addition to aluminum or its compound, a small amount of at least one element selected from the group consisting of an aluminum metal and an alkaline earth metal and a compound thereof is added as the second metal-containing component. It is. In a preferred embodiment, the second metal-containing component coexists as the polyester heavy vehicle of the present invention. Also, the polyester polymerization catalyst solution of the present invention is preliminarily containing at least one selected from alkali metals, alkaline earth metals and compounds thereof. May be added during the polymerization, or at least one selected from alkali metals, alkaline earth metals and compounds thereof may be added separately from the catalyst solution. The addition of a strong second metal-containing component is effective in suppressing the production of diethylene glycol and increasing the catalytic activity, and therefore, a catalyst component with a higher reaction rate is obtained, which is effective in improving productivity. .

It is well known that a catalyst having sufficient catalytic activity is obtained by adding an alkali metal compound or an alkaline earth metal compound to an aluminum compound. Use of such a known catalyst provides a polyester having excellent thermal stability.However, a known catalyst using an alkali metal compound or an alkali earth metal compound in an attempt to obtain practical catalytic activity. Then, it is necessary to add a large amount of them, and when the metal compound is used, the amount of foreign substances caused by the metal compound increases, and when used for fibers, the spinning properties and yarn properties are increased. Physical properties, transparency, thermal stability, thermal oxidation stability, hydrolysis resistance, etc. are bad. Furthermore, the color tone of melt-formed products such as fibers and films deteriorates. In addition, when an alkaline earth metal compound is used in combination, the obtained polyester has low thermal stability and thermal oxidative stability in order to obtain practical activity, and is greatly colored by heating. Also increase.

When adding an alkali metal, alkaline earth metals and their compounds, its amount M (mol ⁰ /.), To the number of moles of all the polycarboxylic acids units constituting the polyester, 1 X 1 0- ⁶ or more 0.1 mole ⁰ / preferably less than ₀ and is, more rather preferably is ^{5 X 1 0- 6 ~0. 0} 5 mol ^_0/0, more preferably 1 X 1 0- ⁵ ~0. 0 a 3 mole ^_0/0, particularly preferably ^{1 X 1 0- 5 ~0. 0} 1 mol ^_0/0. Since the addition amount of alkali metal and alkaline earth metal is small, the reaction rate can be increased without causing problems such as a decrease in thermal stability, generation of foreign matter, and coloring. Further, the reaction rate can be increased without causing a problem such as a decrease in water resistance. When the amount M of Al-Li metal, Al-earth metal and its compound is more than 0.1 mol%, thermal stability decreases, foreign matter is generated and coloration increases, and hydrolysis resistance decreases. A problem may occur in processing. M is 1 X 1 0- ⁶ mol% Not Mitsurude, the effect is not clear also be added.

In producing the polyester according to the method of the present invention, a cobalt compound In a preferred embodiment, the compound is added as a cobalt atom in an amount of less than 10 ppm to the polyester. It is more preferably less than 5 ppm, and still more preferably 3 ppm or less. Further, the solution of the polyester polymerization catalyst of the present invention containing the Coparty conjugate in advance may be added at the time of polymerization, or the Coparty conjugate may be added separately from the catalyst solution.

On the other hand, when producing a polyester according to the method of the present invention, it is preferable not to use a connort compound.

When a polyester is produced according to the method of the present invention, other polymerization catalysts such as an antimony compound, a titanium compound, a germanium compound, and a tin compound, and the addition of these components can be used as described above for the properties, processability, and color tone of the polyester. Coexistence within the range of the addition amount that does not cause a problem in the product is advantageous and preferable in improving productivity by shortening the polymerization time.

However, the antimony compound can be added in an amount of 50 ppm or less as an antimony atom to the polyester obtained by polymerization. More preferably, it is added in an amount of 30 ppm or less. If the added amount of antimony is more than 50 ppm, metal antimony precipitates, and blackening or foreign matter is generated in polyester, which is not preferable. ,

The titanium compound can be added to the polymer obtained by polymerization in a range of ΙΟρρπι or less. More preferably, it is added in an amount of 5 ppm or less, more preferably 2 ppm or less. If the added amount of titanium is more than 10 ppm, the thermal stability of the obtained resin is significantly reduced.

The germanium compound can be added to the polyester obtained by polymerization in an amount of 20 ppm or less as a germanium atom. More preferably, it is added in an amount of 10 ppm or less. If the amount of germanium added is more than 20 ppm, it is not preferable because it is disadvantageous in terms of cost.

When polymerizing the polyester according to the method of the present invention, one or more of an antimony compound, a titanium compound, a germanium compound, and a tin compound can be used. The metal and metal compounds of the present invention and the earth metal and the compounds thereof are not particularly limited, but include, for example, formic acid and vinegar of these metals. Saturated aliphatic carboxylate such as acid, propionic acid, butyric acid and oxalic acid; unsaturated aliphatic carboxylate such as acrylic acid and methacrylic acid; aromatic carboxylic acid salt such as benzoic acid; Gen-containing carboxylate, hydroxy carboxylate such as lactic acid, cunic acid, salicylic acid, carbonic acid, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen carbonate, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, Inorganic acid salts such as hydrobromic acid, chloric acid, and bromic acid, 1-propanesulfonic acid, 1-pentanesulfonic acid

, Organic sulfonates such as naphthalenesulfonic acid, organic sulfates such as lauryl sulfate, alkoxides such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, tert-butoxy, and acetyl acetate. Chelate compounds, hydrides, oxides, hydroxides and the like.

Among these compounds, when highly alkaline ones such as hydroxylamine are used, they tend to be difficult to dissolve in an organic solvent such as diol or alcohol such as ethylene dalicol. Must be added to the polymer, which may be a problem in the polymerization process. In addition, when a highly alkaline substance such as a hydroxylamine product is used, the polyester is liable to undergo side reactions such as hydrolysis during the polymerization, and the polymerized polyester tends to be colored, Also tends to decrease. Accordingly, the alkali metal or the compound thereof or the alkaline earth metal or the compound thereof according to the present invention is preferably a saturated aliphatic carboxylate, an unsaturated aliphatic carboxylate, or an aromatic carboxylate of these metals. , From halogen-containing sulfonic acids, hydroxycarboxylates, sulfuric acid, nitric acid, phosphoric acid, phosphonic acid, hydrogen phosphate, hydrogen sulfide, sulfurous acid, thiosulfuric acid, hydrochloric acid, hydrobromic acid, chloric acid, bromate The selected inorganic acid salt, organic sulfonate, organic sulfate, chelate compound, and oxide. Among these, the use of saturated aliphatic carboxylate, especially acetate, is preferred from the viewpoint of easy handling and availability.

The aluminum of the present invention or its compound is not particularly limited, but in addition to metal aluminum, for example, aluminum formate, aluminum acetate, basic aluminum acetate, aluminum propionate, aluminum oxalate, aluminum acrylate, Aluminum laurate, aluminum stearate, aluminum benzoate, aluminum triacetate, aluminum lactate, aluminum tartrate Aluminum, carboxylates such as aluminum citrate, aluminum salicylate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, polychlorinated aluminum, ethanol nitrate, aluminum sulfate, ethanol carbonate, aluminum phosphate, Inorganic acid salts such as aluminum phosphonate, aluminum methoxide, aluminum ethoxide, aluminum _n -propoxide, aluminum iso-propoxide, aluminum n-poxide, aluminum ptoxide, and other aluminum alkoxides, anolemminium acetate Anorate such as acetonate, aluminum acetyl acetate, aluminum ethynoleacetoacetate, aluminum dimethylenoacetoacetate di-isopropoxide Organic aluminum compounds such as aluminum chelates, trimethylaluminum, and triethylaluminum or their partial hydrolyzates, reaction products consisting of alkanolides of aluminum and aluminum chelates and hydroxycarboxylic acids, aluminum oxide, ultrafine particles Examples include aluminum oxide, aluminum silicate, and composite oxides of aluminum and titanium, silicon, zirconium, alkali metals, alkaline earth metals, and the like. Of these, carboxylate and inorganic acid salt chelate compounds are preferable, and among these, basic aluminum acetate, aluminum chloride, aluminum hydroxide, aluminum hydroxide chloride, and aluminum dimethyl acetonoleacetonate are further preferable. Particularly preferred. As the basic aluminum acetate, one stabilized with an additive such as boric acid may be used.

The phosphorus compound of the present invention is not particularly limited. For phosphoric acid, phosphate esters such as trimethylphosphoric acid, triethylphosphoric acid, phenylphosphoric acid, triphenylphosphoric acid, phosphorous acid, trimethylphosphite, and triethylphosphoric acid. Phosphite such as phosphite, triffe-nole phosphite, tris (2,4-di-tert-butynolephenyl) phosphite, tetrakis (2,4-di-tert-butyl phenyl) 4,4'-biphenylenediphosphite Esters and the like.

More preferred phosphorus compounds of the present invention are at least one selected from the group consisting of phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds. It is a lindani compound. Polyester which is an object of the present invention by containing these phosphorus compounds The effect of improving the physical properties of tellurium is enhanced, and the use of these phosphorus compounds in combination with the aluminum-dimethyl compound of the present invention during the polymerization of polyester has an effect of improving corrosion resistance. . Among these, the use of a phosphonic acid-based compound is preferable because the effect of improving the physical properties and the effect of improving the catalytic activity are large. Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is highly preferable because the effect of improving the physical properties and the effect of improving the catalytic activity are greatly enhanced. By using such a phosphorus compound at the time of producing the polyester of the present invention, a catalyst exhibiting a sufficient catalytic effect can be obtained even when the addition amount of the alkali metal compound or the alkaline earth metal compound is small. .

The phosphonic acid compounds, phosphinic acid compounds, phosphinoxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds referred to in the present invention are represented by the following formulas (Iridai 1) to (I), respectively. The compound having the structure represented by dani 6).

[Formula 1]

o

II

-0-P-0-

[Formula 2]

o

-P-0-

[Formula 3]

o

P-one

One four [Formula 4]

One O— P—〇一

[Formula 5]

-P-0-

[Formula 6]

-P

Examples of the phosphonic acid type conjugate of the present invention include: Is mentioned. Examples of the phosphinic acid-based compound of the present invention include diphenylphosphinic acid, methinole dipheninolephosphinate, feninole diphenylinolephosphinate, feninolephosphinic acid, methyl feninolephosphinate, Phenyl phosphinate and the like. Examples of the phosphoxide compound of the present invention include diphenylphosphinoxide, methyldiphenylinolephosphinoxide, and triphenylphosphinoxide.

Among the phosphinic acid compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds, the phosphorus compounds of the present invention are represented by the following formulas (i7) to (i7) The compound represented by dani 12) is preferred.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

[Formula 12]

[(CH ₃ ) (CH ₂ ) 7] a P Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

In addition, when the compounds represented by the following general formulas (Formula 13) to (Formula 15) are used as the phosphorus compound of the present invention, the effect of improving the physical properties and the effect of improving the catalytic activity are particularly preferred.

[Formula 13]

P (= 0) R ¹ (OR ² ) (OR ³ )

P (= 0) ¹ R ⁴ (OR ² )

P (= 0) R ¹ R ⁵ R ⁸

(Wherein, R ¹ , R ⁴ , R ⁵ and R ⁶ are each independently hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, 7j <acid group or halogen group) Or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group, and R ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group. Represents a hydrocarbon group having 1 to 50 carbon atoms, provided that the hydrocarbon group may contain an alicyclic structure such as cyclohexyl or an aromatic ring structure such as phenyl-naphthyl. As the compound, a compound in which R ¹ , R ⁴ , R ⁵ , and R ⁶ are groups having an aromatic ring structure in the above formulas (Dani 13) to (Dani 15) is particularly preferable. The phosphorus compounds of the present invention include, for example, dimethyl methionolephosphonate, dipheninole methylphosphonate, dimethinole pheninolephosphonate, ethyl pheninolephosphonate, dipheninole pheninolephosphonate, dimethyl benzylphosphonate, and benzylphosphonate. Getinole, dipheninolephosphinic acid, methinole diphenolenophosphinate, feninole dipheninolephosphinate, feninolephosphinic acid, methinole pheninolephosphine, feninolephosphinate feninolephosphinate, dipheninolephosphine Oxides, methinoresifeninolephosphine oxides, triffee-norephosphine oxides, and the like. Of these, dimethyl phenylphosphonate and getyl benzinolephosphonate are particularly preferred! / ,.

Among the phosphorus compounds arrested above, in the present invention, a metal chloride of phosphorus is particularly preferable as the phosphorus compound. The metal salt compound of phosphorus is not particularly limited as long as it is a metal salt of a phosphorus compound. However, when a metal salt of a phosphonic acid compound is used, the effect of improving the physical properties of polyester and the effect of improving catalytic activity, which are the objects of the present invention, are large. preferable. The metal salts of phosphorus compounds include monometal salts, dimetal salts, trimetal salts, and the like. Further, among the phosphorus compounds described above, the metal part of the metal salt is selected from L i, N a, K :, Be, M g, S r, B a, M n, N i, Cu, and Zn. The use of such a material is preferable because the catalyst activity is greatly improved. Of these, Li, Na, and Mg are particularly preferred.

As the phosphorus metal salt compound of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (I-dani 16) because the effect of improving physical properties and the effect of improving tactility are large.

[Formula 1 6]

M (R ^J Q ") _m

Wherein R ¹ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a 7-carbon group containing an acid group, a halogen group, an alkoxyl group, or an amino group. Represents a hydrogen group, ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a 7-acid group or an alkoxylate group, and R ³ represents hydrogen or carbon. Represents a hydrocarbon group having a carbon number of 1 to 50 including a carbon number of 1 to 50, a hydroxyl group or an alkoxyl group or a canolepodinole, wherein 1 is an integer of 1 or more, and m is 0 or an integer of 1 or more. And 1 + m is 4 or less, M represents a (1 + m) -valent metal cation, n represents an integer of 1 or more, and the hydrocarbon group is an alicyclic structure such as cyclohexyl or a branch. It may contain a structure or an aromatic ring structure such as phenylnaphthyl.)

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-thrill, 4-biphenyl, 2-biphenyl, and the like. The above; R ² includes, for example, hydrogen, methynole group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, Examples include a naphthyl group, a substituted phenol group, a naphthyl group, and a group represented by CH ₂ CH ₂ OH. Examples of R ³ O— include a hydroxide ion, an alcohol ion, an acetate ion and acetylacetone ion. It is preferable to use at least one selected from the compounds represented by the following general formula (Iridani 17) among the compounds represented by the above general formula (Iridani 16). [Formula 17]

M (R ³ 0 ") m

(In the formula, R ¹ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halogen group, or a hydrocarbon group having 1 to 50 carbon atoms including an alkoxyl group or an amino group. ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxy group or a hydrocarbon group having 1 to 50 carbon atoms including carbonyl, wherein 1 is an integer of 1 or more, and m is 0 or 1 or more. Represents an integer, 1 + m is 4 or less, M represents a (1 + m) -valent metal cation, and the hydrocarbon group is an alicyclic structure or a branched structure such as cis-hexyl or a phenylnaphthyl. And the aromatic ring structure may be included.)

Examples of R ¹ include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl, 2-biphenyl and the like. Examples of R ³ O— include hydroxide ion, alcohol ion, acetate ion and acetylacetonion.

Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the physical properties and the effect of improving the catalytic activity are large.

In the above formula (I-Dai 1'7), it is preferable that M is selected from L, Na, K :, Be, Mg, Sr, Ba, Mn, Ni, Cu, and Zn. The effect of improving sex is greatly preferred. Of these, Li, Na, and Mg are particularly preferred.

Examples of the phosphorus metal salt compound of the present invention include lithium [(1-naphthyl) methylphosphonate], sodium [(1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], potassium [(2-naphthyl) methylphosphonate], magnesium bis [(2-naphthyl) methylphosphonate], lithium [pentylphosphonate], sodium Pem [ethyl benzinolephosphonate], magnesium bis [benzyl phosphonate], beryllium bis [benzyl phosphonate], strontium bis [benzyl phosphonate], manganese bis [benzyl phenyl phosphonate], benzyl / Sodium Rephosphonate, Magnesium Bis [benzylphosphonic acid], Sodium [(91-anthryl) methylphosphonate], Magnesium bis [(9-1-anthryl) methylphosphonate], Sodium [4-hydroxybenzinolephosphonate], Magnesium Bis [4-hydroxybenzinolephosphonate], Sodium [4-cyclophenylene benzoylphosphonate], Magnesium bis [4-1-chlorobenzylphosphonate ethyl] · ', Sodium [4-aminobenzinolephos] Phosphate Mechinore], magnesium bis [4 Amino base Njiruhosuhon methyl], sodium Fueniruhosuhon acid, magnesium bis [Fueniruhosuho phosphate Echiru], zinc bis [Fueniruhosuhon acid Echiru] and the like. Of these, lithium [(1-naphthyl) methylphosphonate], sodium [(1-naphthyl) methylphosphonate], magnesium bis [(1-naphthyl) methylphosphonate], lithium [benzyl-ethylphosphonate] ], Sodium [ethynole benzinolephosphonate], magnesium bis [ethynole benzylphosphonate], sodium benzinolephosphonate, and magnesium bis [benzinolephosphonate] are particularly preferred.

Among the phosphorus compounds described above, in the present invention, a phosphorus compound having at least one P—OH bond is particularly preferred as the phosphorus compound. Including these phosphorus compounds not only enhances the effect of improving the properties of polyester (I), which is an object of the present invention, but also allows the phosphorus compounds of the present invention to be used during the polymerization of polyester. When used in combination with a compound, the effect of improving the catalytic activity is greatly seen.

The phosphorus compound having at least one P-0H bond is not particularly limited as long as it is a phosphorus compound having at least one P-OH in the molecule. Among these phosphorus compounds, the use of a phosphonic acid-based compound having at least one P—OH bond is preferred because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are large. -Among the above-mentioned phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving physical properties and the effect of improving touch properties are large. As the phosphorus compound having at least one P—OH bond of the present invention, when at least one selected from compounds represented by the following general formula (Ich 18) is used, the effect of improving physical properties and the effect of improving catalyst activity are obtained. Is preferred.

[Formula 1 8]

0

II

R ~ (CH ₂ ) _n- • P-

OR 2

(In the formula (Ig 18), R ¹ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group, a halogen group, an anoRECOXINOLE group or an amino group. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a 7_K acid group or an alkoxy group, and η is an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cycloalkylhexyl, a branched structure, or an aromatic ring structure such as phenyl-naphthyl.

Examples of R1 include phenyl, 1-naphthyl, 2-naphthyl, 9-anthryl, 4-biphenyl-2-biphenyl, and the like. Examples of R2 include hydrogen, methynole, ethyl, propynole, isopropyl, η-butyl, sec-butyl, fert-butyl, long-chain aliphatic groups, phenyl groups, Examples include a naphthyl group, a substituted phenyl group, a naphthyl group, and a group represented by one CH ₂ CH ₂ OH.

Examples of the phosphorus compound having at least one P—OH bond according to the present invention include (1-naphthyl) methylphosphonate, (1-naphthyl) methylphosphonic acid, (2-naphthyl) methylphosphonate, ethylbenzyl, and benzylphosphonate. Honic acid, (9-anthryl) methyl ethyl phosphonate, 4-hydroxybenzyl Examples include ethynolephosphonate, 2-ethylmethynolebenzinolephosphonate, phenyl 4-methylbenzinolephosphonate, methyl 4-aminobenzylphosphonate, and ethyl 4-methoxybenzylphosphonate. Of these, (1-naphthyl) methylethyl phosphonate and benzylphosphonic acid ethyl are particularly preferred.

As a preferred phosphorus compound of the present invention, a phosphorus compound represented by a chemical formula (Formula 19) can be mentioned. '

[Formula 1 9]

R ¹ -CH ₂ -P (= 0) (OR ² ) (OR ³ )

(In the formula (Ich 19), R ¹ represents a hydrocarbon group having ¹ to 49 carbon atoms, or a hydrocarbon group having ¹ to 49 carbon atoms including a hydroxyl group, a halogen group, an alkoxyl group, or an amino group; ² and R ³ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, or a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. It may contain a branched structure or an aromatic ring structure.)

More preferably, the compound is a compound in which at least one of R ¹ , R ² , and R ^{3 in} the chemical formula (Fig. 19) contains an aromatic ring structure.

Specific examples of these phosphorus compounds are shown below.

[Formula 20]

〇

BPADE [Formula 21]

A

[Formula 22]

2 A

[Formula 23]

AMPA [Formula 2 4]

4PBPADE

[Formula 2 5] H ₅

2PBPADE

In addition, the phosphorus compound of the present invention having a large molecular weight has a large effect and is preferred because it is difficult to be distilled off at the time of bonding.

As the phosphorus compound of the present invention, it is preferable to use a phosphorus compound having a phenol moiety in the same molecule. Further, the phosphorus compound and the phenolic compound of the present invention are preferably compounds bonded to each other, that is, a phosphorus compound having a phenol moiety in the same molecule. By containing a phosphorus compound having a phenol moiety in the same molecule, the effect of improving the physical properties of the polyester, which is an object of the present invention, is enhanced.In addition, a phosphorus compound having a phenol moiety in the same molecule during polymerization of the polyester is improved. When used, the effect of enhancing the touch is greater, and therefore, the productivity of polyester is excellent. When a phosphorus compound having a phenol moiety in the same molecule is used, its content is determined by the content of the aluminum atom and the phosphorus atom in the polyester. It is necessary to be within the required range.

The phosphorus compound having a phenol moiety in the same molecule is not particularly limited as long as it is a phosphorus-containing compound having a phenol structure, but a phosphonic acid compound or a phosphinic acid having a phenol moiety in the same molecule The properties of polyester are improved by using one or more compounds selected from the group consisting of phosphine oxide compounds, phosphine oxide compounds, phosphonous acid compounds, phosphinous acid compounds, and phosphine compounds. The effect and the effect of improving the catalytic activity are large and preferable. Among these, the use of a phosphonic acid compound having one or more phenol moieties in the same molecule is particularly preferred because the effect of improving the physical properties of the polyester and the effect of improving the catalytic activity are particularly large. The phosphorus compound having a phenol moiety in the same molecule preferably has a hindered phenol structure.

As the phosphorus compound having a phenol moiety in the same molecule of the present invention, the following general formula

Preferred are the iris conjugates represented by (ii dan 26) to (ii dan 28).

[Dani 26], '

P (= 0) R ¹ (OR ² ) (OR ³ )

P (= 0) R ¹ R ⁴ (OR ² )

P (= 0) R ¹ R ⁵ R ⁶

Wherein R ¹ is a substituent such as a hydrocarbon group having 1 to 50 carbon atoms, including a phenolic moiety, a hydroxyl group, a halogen group, an alkoxyl group or an amino group. And represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrogen atom, and R ⁴ , R ⁵ and ⁶ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a halo group. Represents a hydrocarbon group having 1 to 50 carbon atoms including a substituent such as a halogen group, an anorecoxyl group, or an amino group. ² and R ³ each independently represent hydrogen, a hydrocarbon group having a carbon number of 1 to 50, a carbon number including a substituent such as a hydroxyl group or an alkoxyl group: a hydrocarbon group having a carbon number of! To 50. However, the hydrocarbon group may contain an alicyclic structure such as a branched structure ゃ cyclohexyl or an aromatic ring structure such as phenyl ゃ naphthyl. The ends of R ² and R ⁴ may be linked. )

Examples of the phosphorylated compound having a phenol moiety in the same molecule of the present invention include: p-hydroxyphenylphosphonate phosphonate; -hydroxyphenylphosphonate dimethinole, p-hydroxyphenylphosphonate phospholipid, p-hydroxyphenylenephosphonate Doxy-phenoxy diphosphonate, bis (p-hydroxyphenyl) phosphinic acid, bis (ρ-hydroxyphenyl phenol) methinolate phosphinate, bis (p-hydroxyphenyl phenol) phosphinic acid, ρ- Hydroxyphen-norrefinolephosphinic acid, p-Hydroxypheninolepheninolephosphinic acid Methinole, p-Hydroxyphenylpheninolephosphinic acid Phenolate, ρ-Hydroxypheninolephosphinic acid, Metinole ninole phosphinate, p-hydroxyfif Phenylinodiphosphinic acid, bis (p-hydroxyphenyl) phosphine oxide, tris (p-hydroxyphenylinole) phosphine oxide, bis (p-hydroxyphenylinole) methylphosphine oxide, and the following formula Compounds represented by (I-29) to (I-32) are exemplified. Among these, a compound represented by the following formula (Ichi 31) and dimethyl p-hydroxyphenylphosphonate are particularly preferred.

[Formula 2 9]

[Formula 30]

[Formula 31]

[Formula 32]

Examples of the compound shown by the above formula (I-Dani 31) include S-Rin 0-220 (manufactured by Sanko Co., Ltd.), which can be used.

Among the phosphorus conjugates having a phenol moiety in the same molecule according to the present invention, at least one selected from the specific metal salt compounds of phosphorus represented by the following general formula (III) is particularly preferred. [Formula 33]

((In the formula (Formula 3 3), 1 ^, 1 ² each independently represents hydrogen, Sumyi匕hydrogen group having 1 to 30 carbon atoms. R ³ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or an alkoxyl group, or carbon. R ⁴ O— includes, for example, hydroxide ion, alcoholate ion, acetate ion, acetylacetone ion, etc. 1 is an integer of 1 or more, and m is Represents an integer of 0 or 1 or more, and 1 + m is 4 or less

. M represents a (1 + m) -valent metal cation. n represents an integer of 1 or more. The hydrocarbon group may contain an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl-naphthyl. )

Among them, at least one selected from compounds represented by the following general formula (Formula 34) is preferable.

[Formula 34]

(Wherein, Mn + represents an n-valent metal cation; n is 1, 2, 3 or 4 Represents )

In the above formulas (I-Dani 33) or (I-Dani 34), M is Li, Na, K, Be, Mg, Sr, Ba, Mn, Ni, Cu, Z It is preferable to use one selected from n because the effect of improving the catalyst activity is large. Of these, L i, N a, and M g are particularly preferred.

Specific metal salt compounds of phosphorus according to the present invention include lithium [3,5-di-tert-butynole 4-hydroxybenzylphosphonate ethyl], sodium [3,5-di-tert-butyne-hydroxybenzylphosphonic acid] Ethyl], Sodium [3,5-di-tert-butynole 4-hydroxybenzinolephosphonic acid], Potassium [3,5-Di-tert-butyl-4-hydroxybenzylphosphonate], Magnesium bis [3,5] —Di-tert-butyl—4-hydroxyethylphosphonate], magnesium bis [3,5—di-tert-butyl_ / le 4-hydroxybenzylphosphonic acid], beryllium bis [3,5—di-tert-butyl] Methyl 4-hydroxybenzylphosphonate], strontium bis [3,5-di-tert-butyl-4-hydroxybenzylphosphonate] ), Barium bis [3,5-di-tert-butyl-1-hydroxy-4-benzyloxy-phosphonate], manganese bis [3,5-di-tert-butyl-4-ethyl benzylphosphonate] ], Eckenolevis [3,5-Diethyl tert-butyl / ethyl-4-hydroxybenzylphosphonate], Copper Bis [3,5-diethyltert-butyl-4-hydroxybenzylphosphonate], Zinc bis [3,5] 5 — G tert-Putinole_4-hydroxybenzinole phosphonate etinole]. Among these, lithium [3,5-di-tert-butyl-1-ethylhydroxylphosphonate], sodium [3,5-di-tert-butyl-4-hydroxyethyl phosphonate], magnesium bis [3,5] Tert-butyl-4-hydroxyethylbenzylphosphonate] is particularly preferred.

Among the phosphorus compounds having a phenol moiety in the same molecule of the present invention, the following general formula

At least one selected from specific phosphorus compounds having at least one P—OH bond represented by (Chemical Formula 35) is particularly preferable. [Formula 35]

((In the formula (Ich 35), R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. R ³ represents hydrogen, a hydrocarbon group having from 50 to 50 carbon atoms, Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydroxyl group or an alkoxyl group, and n represents an integer of 1 or more.The hydrocarbon group is an alicyclic structure such as a cis or hexinole or a branched structure such as a phenyl ゃ naphthyl. It may contain an aromatic ring structure.)

Among these, at least one selected from the compounds represented by the following general formula (Ich 36) is preferable.

[Formula 36]

(In the formula (Ich 36), R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group including a hydroxyl group or an alkoxyl group: a hydrocarbon group having 50 to 50 carbon atoms. It may contain an alicyclic structure or branched structure such as xyl, or an aromatic ring structure such as phenyl-naphthyl.)

Examples of the above-mentioned R ³ may be hydrogen, methyl, Echinore group, a propyl group, isopropoxy port propyl group, n- Buchinore group, s _e c- heptyl group, ter I- Buchinore group, a long chain fatty Group, phenyl group, naphthyl group, substituted phenyl group ゃ naphthyl group, group represented by one CH ₂ CH ₂ 〇H, and the like.

Specific phosphorus compounds having at least one P-OH bond of the present invention include ethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate and 3,5-di-tert-butyl-4-hydroxybenzylphosphonate. Methyl, 3,5-di-tert-butyl-isopropyl-4-hydroxybenzylphosphonate Isopropyl, 3,5-di-tert-butyltin 4-hydroxybenzylphosphonate pheninole, 3,5-zy-tert-butynole 4 Octadecyl-hydroxybenzylphosphonate, 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid, and the like. Among these, methyl 3,5-di-tert-butyl-4-hydroxybenzinolephosphonate and methyl 3,5-di-tert-butyl-ru-4-hydroxybenzinolephosphonate are particularly preferred.

Among the phosphorus compounds having the phenol moiety of the present invention in the same molecule, the following general formula

At least one phosphorus compound selected from the specific phosphorus compounds represented by (Chem. 37) is preferable.

[Formula 3 7]

(In the formula (I-Dai 37), R ¹ and R ² each independently represent hydrogen and a hydrocarbon group having 1 to 30 carbon atoms. R ³ and R ⁴ each independently represent hydrogen and 1 carbon atoms. Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group, a hydroxyl group or an alkoxyl group of from 50 to 50. n represents an integer of 1 or more. The hydrocarbon group is an alicyclic structure such as cyclohexyl or the like. It may contain a branched structure or an aromatic ring structure such as phenyl-naphthyl.)

Among at least one of the above-mentioned general formulas (I-Sha 37), the use of at least one kind selected from the following formulas (I-Sha 38) can improve the physical properties and the tactility of the polyester. High and preferred. [Formula 3 8]

(In the above formula (I-Sha 38), R ³ and R ⁴ each independently represent hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group. The hydrocarbon group may contain an alicyclic structure or branched structure such as cyclohexyl or an aromatic ring structure such as phenyl-naphthyl.

Examples of R ³ and R ⁴ include a short-chain aliphatic group such as hydrogen, a methyl group and a butyl group, a long-chain aliphatic group such as octadecyl, a phenyl group, a naphthyl group, and a substituted phenyl group. An aromatic group such as a naphthyl group; a group represented by —CH ₂ CH ₂ OH;

Specific phosphorus compounds of the present invention include diisopropyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 3,5-di-tert-butynole_4 -hydroxybenzinolephosphonate di-n-butyl ^ /, 3 , 5-Di-tert-butynole 4-dihydroxydecinolephosphonate, 3,5-di-tert-butyl-4, hydroxybenzylphosphonate diphenyl, and the like. Among these, 3,5-di-tert-butynole 4-hydroxybenzylphosphonic acid dioctadecinole and 3,5-di-tert-butynole-1 4-hydroxybenzylphosphonic acid diphenyl are particularly preferred. Among the phosphorus compounds having the above, a particularly desirable compound in the present invention is at least one phosphorus compound selected from the compounds represented by the chemical formulas (Ihi 39) and (Ihi 40). [Formula 39]

[Formula 40]

Irganoxl 222 (manufactured by Ciba Specialty Chemicals) as a compound represented by the above chemical formula (I-Dani 39) is commercially available, and is also represented by the chemical formula (I-Dani 40). Irgano X 1425 (Ciba-specialty-chemicals ring) is commercially available and usable.

As the phosphorus conjugate of the present invention, it is preferable to use at least one selected from aluminum salts of phosphorus compounds. The aluminum compound and the phosphorus compound contained in the polyester of the present invention are preferably composed of at least one selected from aluminum salts of phosphorus conjugates. Including the aluminum salt of a phosphorus compound not only enhances the effect of improving the physical properties of the polyester, which is the subject of the present invention, but also increases the tactility by using the aluminum salt of a phosphorus compound during the polymerization of the polyester. Therefore, the productivity of polyester is excellent. It is also possible to coexist another aluminum compound or a phosphorus compound / phenol compound in the aluminum salt of the phosphorus compound. When an aluminum salt of a phosphorus compound is used, the content of the aluminum and phosphorus atoms in the polyester is a feature of the present invention. It needs to be within the scope of the claims.

The aluminum salt of the phosphorus compound is not particularly limited as long as it is a phosphorus compound having an aluminum portion. However, it is preferable to use an aluminum salt of a phosphonic acid compound because the effect of improving the physical properties of the polyester and the catalytic activity are high. The aluminum salt of a phosphorus compound includes a monoanoreminium salt, a dianoreminium salt, a trianoreminium salt, and the like.

Among the above-mentioned aluminum salts of phosphorus compounds, the use of a compound having an aromatic ring structure is preferable because the effect of improving the physical properties of the polyester and the corrosiveness are high.

As the aluminum salt of the phosphorus compound of the present invention, it is preferable to use at least one selected from the compounds represented by the following general formula (I-Dai 41) because the effect of improving the physical properties of the polyester is high and the contact property is high.

[Formula 4 1]

Al ³⁺ (R ^J CT)

(In the formula, R ¹ is hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, a halogen group, an alkoxyl group, or an amino group. R ² represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group or a hydrocarbon group having 50 or more carbon atoms including an alkoxy group, and R ³ represents hydrogen or carbon atoms. Represents a hydrocarbon group having 1 to 50 carbon atoms including a hydrocarbon group of 1 to 50, a hydroxyl group, an alkoxyl group or a carbonyl, 1 represents an integer of 1 or more, m represents 0 or an integer of 1 or more, and 1+ m is 3. n represents an integer of 1 or more.The hydrocarbon group may include an alicyclic structure such as cyclohexanol, a branched structure, or an aromatic ring structure such as phenylnaphthyl.)

Examples of the above R ¹ include phenyl, 1-naphthinole, 2-naphthinole, 9-1 anthryl, 4-bipheninole, 2-bipheninole and the like. As the above R ² , for example, hydrogen, methyl group, ethynole group, propyl group, isopropyl group, n- Butyl group, sec-butyl group, tert-butyl group, long-chain aliphatic group, phenyl group, naphthyl group, substituted phenyl group naphthyl group, group represented by CH ₂ CH ₂ OH, etc. Is mentioned. Examples of R ³ O— include a hydroxide ion, an anocholate ion, an ethylene glycolate ion, an acetate ion and an acetylacetone ion.

Examples of the aluminum salt of the phosphorus compound of the present invention include an aluminum salt of (1-naphthyl) methylphosphonate, an aluminum salt of mononaphthyl) methylphosphonic acid, an anolemminium salt of (.2-naphthinole) methylethylphosphonate, and benzoinolenate. Anoreminium salt of ethyl phosphonate, aluminum salt of benzylphosphonic acid: (91-anthryl) aluminum salt of methylethyl phosphonate, aluminum salt of ethyl 4-hydroxybenzylphosphonate, aluminum salt of ethyl 2-methylbenzylphosphonate, 4 -Aluminum salts of phenyl benzylphosphonate, aluminum salts of methyl 4-aminobenzylphosphonate, aluminum salts of ethyl 4-methoxybenzylphosphonate, aluminum salts of ethyl ethyl phenylphosphonate, etc. It is below. Of these, the aluminum salt of (1-naphthyl) methylphosphonate and the aluminum salt of benzylphosphonate are particularly preferred.

The aluminum salt of the phosphorus compound of the present invention is preferably composed of at least one selected from aluminum salts of phosphorus conjugates having a phenol structure. Further, the aluminum compound, the phosphorus compound and the phenol-based conjugate contained in the polyester of the present invention are composed of at least one selected from aluminum salts of a phosphorus-based conjugate having a phenol structure. Preferably, there is. By containing an aluminum salt of a phosphorus compound having a phenol structure, the effect of improving the physical properties of the polyester, which is an object of the present invention, is enhanced. When used, it has high tactility and therefore has excellent polyester productivity. The phenol structure is preferably a hindered phenol structure. It is also possible to coexist another aluminum compound, a phosphorus compound or a phenolic compound with the aluminum salt of a phosphorus compound having a phenol structure. Aluminum of phosphorus compound having phenol structure When a salt is used, it is necessary that the content thereof be such that the content of aluminum atoms and phosphorus atoms in the polyester falls within the scope of the claims of the present invention. The phosphorus compound having a phenol structure of the present invention Among the aluminum salts,

—At least one selected from aluminum salts of specific phosphorus compounds represented by the general formula (Formula 42) is particularly preferred.

[Formula 4 2]

((In the formula, R ¹ and R ² each independently represent hydrogen or a hydrocarbon group having 1 to 30 carbon atoms. ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms.) Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydroxyl group or an alkoxyl group, and R ⁴ represents a hydrocarbon group having 1 to 50 carbon atoms, including hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydroxyl group, an alkoxyl group, or a carbonyl group. Represents a hydrocarbon block of 50. 1 represents an integer of 1 or more, m represents 0 'or an integer of 1 or more, and 1 + m is 3. n represents an integer of 1 or more. It may contain an alicyclic structure or a branched structure such as hexinole, or an aromatic ring structure such as phenyl-naphthyl.)

Among them, at least one kind selected from the iris products represented by the following general formula (I dan 43) is preferable. [Formula 4 3]

Al ³⁺ (R ⁴ 0 ") _m

(In the formula, R ³ represents hydrogen, a hydrocarbon group having 1 to 50 carbon atoms, a hydrocarbon group having 1 to 50 carbon atoms including a hydroxyl group or an alkoxyl group, and R ⁴ represents hydrogen. Represents a hydrocarbon group having 1 to 50 carbon atoms, including a hydrocarbon group having 1 to 50 carbon atoms, a 7k acid group or an alkoxyl group or a hydrocarbon group having 1 to 50 carbon atoms, where 1 is an integer of 1 or more, and m is 0 or 1 or more. Represents an integer, and 1 + m is 3. The hydrocarbon group may include an alicyclic structure such as cyclohexyl, a branched structure, or an aromatic ring structure such as phenyl-naphthyl.

Examples of R ³ include hydrogen, methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, long-chain aliphatic, and phenylene groups. A naphthyl group; a substituted phenyl group; a naphthyl group; a group represented by —CH ₂ CH ₂ OH; Examples of the above R ⁴ O— include a hydroxide ion, an alcoholate ion, an ethylene glycolate ion, an acetate ion and a acetylethyl acetate ion.

The aluminum salt of the specific phosphorus compound of the present invention includes aluminum salt of 3,5-di-tert-butyl 4-ethyl benzylphosphonate, 3,5-di-tert-butyl-ethyl ester. Aminolemic acid salt of methinole hydroxybenzinolephosphonic acid, aluminum salt of 3,5-di-tert-butyl-4-hydroxybenzyl.phospho ^ / isopropyl oxyacid, 3,5-di-tert-butyl-1-hydroxybenzylphosphonate Examples include phenolic aluminum salts, and aluminum salts of 3,5-di-tert-butyl-4-hydroxyhydroxyphosphonate. Among these, aluminum salts of ethyl 3,5-di-tert-butyl-4-hydroxybenzinolephosphonate and aluminum salts of methyl 3,5-di-tert-butyl-1-hydroxybenzinolephosphonate are particularly preferred. Preferred.

When an alkali metal, an alkaline earth metal, or an aluminum salt is used in the above phosphorus compound, the amount of the metal atom in the finally obtained polyester is determined as the amount of phosphorus added. It is necessary that the atomic content be within the scope of the claims of the present invention. By this method, the generation of foreign matters insoluble in polyester is effectively suppressed, and problems such as yarn breakage during spinning and filter clogging during molding are improved.

Examples of the antimony compound that can be added as a polymerization catalyst in the present invention include antimony trioxide, antimony pentoxide, antimony acetate, and antimony glycooxide as suitable conjugates, and the use of antimony trioxide is particularly preferable. Examples of the genolemanium compound include germanium dioxide, germanium tetrachloride, etc., and particularly preferred is diggermanium dioxide. Both crystalline and amorphous germanium dioxide can be used.

Other heavy media such as titanium compounds and tin compounds include: titanium compounds such as tetra-n-propyl titanate, tetraisopropyl titanate, tetra-n-butyl titanate, tetraisobutyl titanate, and tetra-tert-butyl titanate. , Tetracyclohexinoretitanate, tetrafinoretitanate, tetrabenzi ^^ titanate, lithium titanate, potassium oxalate, ammonium oxalate, ammonium titanate, titanium oxide, titanium and silicon, zirconium and alkali metal Oxide or condensed orthoester of titanium, reaction product of orthoester or condensed orthoester of titanium and hydroxycarboxylic acid, orthoester of titanium, orthoester of titanium Or condensation Reaction product consisting of toester, hydroxycarboxylic acid and phosphorus compound, polyhydric alcohol having at least two hydroxy groups with orthoester or condensed orthoester of titanium, reaction product consisting of 2-hydroxycarboxylic acid and base, etc. Of these, a composite oxide of titanium and silicon, a composite oxide of titanium and magnesium, and a reaction product of an orthoester or condensed orthoester of titanium, a hydroxycarboxylic acid, and a phosphorus compound are preferable. Examples of the Suzui conjugate include dibutinoresuzuoxide, methinolefeninolesuzuoxide, Laetinores, hexetinoresin tin oxide, triethinoresulse hydroxide, monobutylhydroxytin oxide, triisobutyltin acetate, diphenyltin dilaurate, monobutyl / resuzutrichloride, dibutyltin sulfide And dibutyltin hydroxytin oxide, methylstannoic acid, ethyl stannoic acid, and the like. Particularly, use of monobutylhydroxytin oxide is preferable.

The cobalt compound that can be added in the present invention is not particularly limited, but specific examples thereof include cobalt acetate, cobalt nitrate, cobalt chloride, cobalt acetylacetonate, cobalt naphthenate, and hydrates thereof. . Among them, cobalt acetate tetrahydrate is particularly preferred.

It is preferable to add a phenolic compound when producing the polyester according to the method of the present invention, because the thermal stability of the polyester is effectively improved. In addition, by adding a phenolic compound, an effect of improving the tactility can be seen.

The phenolic compound of the present invention is not particularly limited as long as it is a compound having a phenol structure. For example, 2,6-di-tert-butyl-4-monomethylphenol, 2,6-di-tert-butynole- 4-Ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4, ethylphenol, 2,6-ditert-amyl-4-methylphenol, 2,6-diphenol -tert-otatyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-otatinolephenole, 2-isopropinole-4-methinole-6-tert-butynolephenole, 2-tert-butynole-2-ethynole-6-tert-octyl / refenole, 2-isoptinole-4-ethynole-6-tert-hexynolephenole, 2-cyclohexyl-4-n-butyl- 6-Isopropylphenol, 1,1, Tritris (4-H Droxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethyleneglycol-l-bis [3- (3-tert-butyl-5-methynole- 4-Hydroxyphenyl) propionate], 1,6-Hexanediol-bis [3- (3,5-di-tert-butyl-4--4-hydroxyphenyl) propionate], 2,2-thiomethylene Bis [3- (3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], Ν, Ν'-hexamethylenebis (3,5-di-tert-butynole-4-1-hydroxy) Hydrocinamide), 1,3,5-tris (2,6-dimethinole-3-hydroxy-4-tert-butynolebenzinole) Nurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzinole) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4 monohydroxy) Phenyl) p-pionyloxicetyl] isocyanurate, tris (4-tert-butylinole-1,6-dimethyl / le-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6 — (4-hydroxy-3,5-di-tert-butylylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-di-tert-butyl-4-monohydroxy) hydrocinnamate] methane, bis [ (3,3-bis (3-tert-butynole-4-hydroxyphenyl ^ /) petitic acid) Glyconoreestenole, Ν, Ν'-bis [3- (3,5-di-tert-butyl-4) —Hydroxyphenyl) propio-nore] Hydrazine, 2, 2'-Ogizamide Bis [ethino 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2- "tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl- 2-Hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethinole-2,4,6-tris (3,5-di-tert-ptynole-4-hydroxybenzinole) benzene, 3,9-bis [1 , Tridimethyl 2-

{β- (3-tert-Ptinole-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] pentane, 2,2-bis [Four -

(2- (3,5-di-tert-butyl-4-hydroxycinnamoinoleoxy)) ethoxypheninole] propane, β- (3,5-di-tert-butynole-4-hydroxypheninole) propio Acid alkyl ester, tetrakis- [methyl-3- (3 ', 5'-di-tert-butino 4_hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl — 4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, thioethylene-bis [3- (3,5-di-ter) 1: -Butyl-4-hydroxyphenyl) propionate] Ethylenebis (oxethylene) bis [3- (5-tert-butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3 , 5-di-tert-butynole-4-hydroxypheno-propione) G, triethylene glycolone bis-[-3- (3'-tert-butyl / le-4-hydroxy-5-methinolepheninole)] propionate, 1,1,3-tris [2-methinole 4— [ 3- (3,5-ditert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butynolepheninole] butane. These can be used in combination of two or more at the same time. Of these, 1,3,5-trimethinole 2,4,6-tris (3,5-Gee tert- Butynole-4-hydroxybenzyl) benzene, tetrakis- [methyl-3- (3,5, -di-ert-butynole-4-hydroxyphenyl) propionate] methane, thiomethylene-bis [3-(3,5 -Di-tert-butyl-4-hydroxyhydroxypropionate] is preferred.

The phenolic compound of the present invention preferably has a hindered phenol structure.

The phenolic compound of the present invention is used in an amount of 5 × 10 to ⁵ mol per mol of all constituent units of carboxylic acid components such as dicarboxylic acid and polycarboxylic acid of the polyester obtained by polymerization. is preferably in the range from ^_0/0 1 mol% is that more preferably in the range of 1 X 1 0 _ ⁴ mole ^_0/0 0.5 5 mole%.

The production of the polyester according to the present invention can be carried out by a conventionally known method. For example, when manufacturing PET, a method of esterifying terephthalic acid and ethylene glycol followed by polycondensation, or a transesterification reaction of an alkynoleester of terephthalic acid such as dimethyl terephthalate with ethylene glycol is performed. Then, any of the methods of polycondensation can be carried out. Further, the polymerization apparatus may be a batch type or a continuous type.

The catalyst used in polymerizing the polyester according to the method of the present invention has catalytic activity not only in polycondensation reaction but also in esterification reaction and transesterification reaction. The transesterification of an alkyl ester of dicarponic acid such as dimethinole terephthalate with a glycol such as ethylene glycol is usually carried out in the presence of a transesterification catalyst such as zinc. The catalyst of the present invention can also be used in the presence of the catalyst. Further, the catalyst used when polymerizing the polyester according to the method of the present invention has a catalytic property not only in melt polymerization but also in solid phase polymerization and solution polymerization, and the polyester can be produced by any method. It can be manufactured. The catalyst used in polymerizing the polyester according to the method of the present invention can be added to the reaction system at any stage of the polymerization reaction. For example, it can be added to the reaction system before or during the esterification reaction or transesterification reaction and at any stage during the reaction, or immediately before or during the reaction of the polycondensation reaction. In particular, Anoremini It is preferable to add the polymer or its compound immediately before the start of the polycondensation reaction. The method of adding the catalyst or other compound used when polymerizing the polyester according to the method of the present invention may be a powder or neat, or a slurry or a solution of a solvent such as ethylene glycol. There is no particular limitation. Further, a component obtained by previously mixing the components of the catalyst and the other compounds may be added, or they may be added separately. Further, the catalyst solution of the aluminum compound of the present invention and other compounds may be added as a premixed mixture, or they may be added separately. Further, the components of the catalyst and the other compounds may be added to the polymerization system at the same time, or each component may be added at a different time. Further, the whole amount of the catalyst and other compounds may be added at once, or may be added several times.

The polyester referred to in the present invention refers to one or more selected from polyvalent ruponic acids including dicarponic acid and ester-forming derivatives thereof and one or more selected from polyhydric alcohols including daricol. Or a compound comprising a hydroxoxycarponic acid or an ester-forming derivative thereof, or a compound comprising a cyclic ester.

Examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutanoleic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecandicarboxylic acid, and 1 1,3-cyclobutanedicanoleponic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicanoreponic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 2 Aliphatic dicarbonic acids exemplified by 2,5-norpornanedicarboxylic acid, dimeric acid and the like and ester-forming derivatives thereof, unsaturated aliphatic dicarbones exemplified by fumaric acid, maleic acid, itaconic acid, etc. Acid or their ester-forming derivatives, orthophthalic acid, isophthalic acid, Talic acid, 5— (alkali metal) Sulfoisophthalic acid, Difuyunic acid, 1,3-Naphthalenedicarboxylic acid, 1,4-Naphthalenedicanoleponic acid, 1,5-Naphthalenedicarboxylic acid, 2, 6— Naphthalenedicarboxylic acid, 2,7-naphthalene dicanoleponic acid, 4,4, -biphenyldicarboxylic acid, 4,4,1-biphenylsulfur Aromatic dicarbones, such as hondicarboxylic acid, 4,4, -biphenyletherdicarboxylic acid, 1,2-bis (phenoxy) ethane-p, p, zika ^ / bonic acid, pamoic acid, anthracenedi Examples thereof include acids and their esterol-forming derivatives. Of these dicarboxylic acids, terephthalic acid and naphthalene dicarboxylic acid, particularly 2,6-naphthalenedicarboxylic acid, are preferred.

Polycarboxylic acids other than these dicarboxylic acids include ethanetricarboxylic acid, propanetricarboxylic acid, butanetetracarponic acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ', 4'-bif Enyltetracarboxylic acid, and ester-forming derivatives thereof, and the like.

Examples of glycols include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycolone, diethylene glycolone, triethylene glycolone, 1,2-butylene glycol, 1,3-butylene glycol, and 2,3-butylene glycol. Cornole, 1,4-butylene glycolonele, 1,5-pentanedionole, neopentinole glycol, 1,6-hexanediol, 1,2-cyclohexanedione, 1,3-cyclohexanediole , 1, 4 Shiku port to Kisanjio one Honoré, 1, Cyclohexanedicarboxylic meth no Honoré to 2 sik port 1, Cyclohexanedicarboxylic methanol to 3 consequent opening, 1, ⁴ - Cyclohexanedicarboxylic methanol to consequent opening, 1, 4 Shiku port Hexanediethanol, 1,10-decamethyleneglycone, 1,12-dodecanediol, polyethylene glycol, Aliphatic glycols exemplified by polytrimethylene glycol, polytetramethylene glycol, hydroquinone, 4,4'-dihydroxybisphenol, 1,4-bis-hydroxyethoxy) benzene, 1,4-bis (β-hi (Droxyethoxyphenole) Snorehon, Bis (ρ-hydroxyphene), Bis (J) -Hdroxyphen-nore) Snorehon, Bis (ρ-Hydroxyphen) Methane, 1,2-bis ( ρ-Hydroxyphenol) ethane, bisphenol Α, bisphenol C, 2,5-naphthalenediphenol, and aromatic glycol daricols exemplified by ethylene glycol added to these glycolones. Of these glycols, ethylene glycol and 1,4-butylene glycol Are preferred.

As polyhydric alcohols other than these glycols, trimethylol methane, tri Methylonoleethane, trimethylolpropane, pentaerythritol, glycerol, hexanetriol and the like.

Examples of hydroxycarponic acids include lactic acid, citric acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid,-(2-hydroxyethoxy) benzoic acid, and 4-hydroxycyclohexane Acid or their ester-forming derivatives.

Examples of the cyclic ester include _ε -force prolacton, monopropiolatatone, β-methyl-13-propiolatatone, δ-valerolatatatone, glycolide, and lactide.

Further, the polyester of the present invention can contain a known phosphorus-based conjugate as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable, and examples thereof include dimethyl phenylphosphonate, diphenyl phenylphosphonate, (2-carboxyethyl) methylphosphinic acid, (2-carboxyethyl) phenylphosphinic acid, and (2-methylphosphonyl). Methoxylenophosphinic acid, Methyl ferrophosphinic acid, (4-Methoxycanolepodinolepheninole) Methinole phenolenophosphinate, [2- (j3-hydroxyethoxycanoleponinole) ethinole] Methynolephosphinic acid Ethylene glycolonoester, (1,2-dicano <repoxyshetyl) dimethylphosphinoxide, 9,10-dihydro-10-oxaxa (2,3-carboxypropinole) -10-phosphaphenanthrene -10- oxide. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester.

Examples of the ester-forming derivatives of polycarboxylic acids or hydroxycarboxylic acids include these alkynole esters, acid chlorides, and acid anhydrides. The polyester used in the present invention is preferably a polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalenedicarboxylic acid or its ester-forming derivative, and whose main glycol component is acetylene glycol. Polyester whose main acid component is terephthalic acid or its ester-forming derivative or naphthalene dicarboxylic acid or its ester / forming derivative is defined as terephthalic acid or its ester-forming derivative and its

'A total of 70 mol% or more of boric acid or its ester-forming derivative Is preferably a polyester containing, more preferably a polyester containing more than 80 mol%, more preferably from polyester containing 90 mole ^_0/0 above. The polyester in which the main dalicol component is alkylenedaricol is preferably a polyester containing 70 mol% or more of anorekylendaricol in total with respect to all glycol components, more preferably 80 mol% or more. a polyester, more preferably Ru polyester der containing 90 mole ^_0/0 above. The alkylene glycol referred to here may contain a substituent or an alicyclic structure in the molecular chain.

Naphthalenedicarboxylic acid or its esterol-forming derivative used in the present invention

Preferred are 1,5-naphthalenedicarponic acid, 2,6-naphthalenedicanoleponic acid, 2,7-naphthalenedicarboxylic acid, and ester-forming derivatives thereof. As the phenolic glycol used in the present invention, ethylene glycol 1,2-propylene glycolone, 1,3-propylene glycolone, 1,2-butylene glycolone, 1,3-butylene glycolone, 2,3 Butylene glycolone, 1,4-butylene glycolone, 1,5-pentanedionole, Nestypentinoglycol, 1,6-hexanediol, 1,2-cyclohexanediol, 1, 1,3-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanedimethanol , 4-six-hexanediethanol, 1,10-decamethylene glycol, 1,12-dodecanediol, and the like. Two or more of these may be used at the same time.

The polyester of the present invention contains oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, and suberic acid as acid components other than terephthalic acid or its ester-forming derivative, naphthalenedicarboxylic acid or its ester-forming derivative. , Azelaic acid, sepasic acid, decane dicarboxylic acid, dodecane diacid Λ ^ bonic acid, tetradecane dicarboxylic acid, hexadecan dicarboxylic acid, 1,3-cyclobutane dicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1 1,2-cyclohexanedicanoleponic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedica Saturated aliphatic dicarboxylic acids exemplified by rubonic acid, 2,5-norbornanedicarboxylic acid, dimer acid and the like, and ester-forming derivatives thereof, and unsaturated aliphatic exemplified by fumaric acid, maleic acid and itaconic acid Dicarboxylic acids or their ester-forming derivatives, orthophthalic acid, isophthalic acid, 5- (alkali metal) sulfoisophthalic acid, dipheninic acid, 4,4, -biphenyldicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid Acids, 4,4, -biphenyletherdicanoleponic acid, 1,2-bis (phenoxy) ethane-p, '-dicarbonic acid, pamoic acid, aromatic dicarboxylic acids exemplified by anthracenedicarboxylic acid, etc. Ester-forming derivatives of ethanetricarboxylic acid, propanetricarboxylic acid, butanetetraca Polycarboxylic acids such as boric acid, pyromellitic acid, trimellitic acid, trimesic acid, 3,4,3 ', 4, biphenyltetracarponic acid, and their ester-forming derivatives It can be included as a copolymer component. Also, lactic acid, cunic acid, malic acid, tartaric acid, hydroxyacetic acid, 3-hydroxybutyric acid, p-hydroxybenzoic acid, P- (2-hydroxyethoxy) benzoic acid, 4-hydroxycyclohexanecarboxylic acid, etc. And a hydroxycarboxylic acid or an ester-forming derivative thereof. It is also possible to include a cyclic ester exemplified by ε-force prolatatatone, β-propiolactone, β-methinolate β-propiolactone, δ-palette ratatone, glycolide, lactide and the like.

In the polyester of the present invention, diethylene glycolone, triethylene glycolone, and polyethylene glycolone are used as glycol components other than anoalkylene glycol.

, Polytrimethylene glycol, polytetramethylene glycol, etc., aliphatic glycols, hydroquinone, 4,4, dihydroxybisphenol, 1,4-bis (β-hydroxyxetoxy) benzene, 1,4-bis ( —Hydroxyxetoxyphenyl) snorefon, bis (ρ-hydroxypheninole) ether, bis (ρ-hydroxypheninole) sunolefon, bis (ρ-hydroxyphene) methane, 1,2-bis ( ρ-Hydroxyphenolene), bisphenolone ス, bisphenolone C, 2,5-naphthalenedienole, aromatic daricols exemplified by dalicol in which ethylene oxide is added to glyco ^^, and trimethylo Methane, trimethylolone, trimethylololepropane, pentaerythritol, glycerol, polyhydric alcohols exemplified by hexanetriol, and the like can be contained as a copolymerization component.

Further, the polyester of the present invention may contain a known phosphorus compound as a copolymer component. As the phosphorus compound, a bifunctional phosphorus compound is preferable. For example,

, Dimethinole pheninolephosphonate, dipheninole pheninolephosphonate, (2-methoxyphenolyl) methylphosphinic acid, (2-carboxynorethyl) phenylphosphinic acid, (2-methoxycarboxynorethyl) phenylphosphine Methyl acid, (4-Methoxycanoleponinolephenine) Methinole phenolenophosphinate, [2- (jS-hydroxyshethoxycanoleboninole) ethynole] Ethylene glycol ester of methylphosphinic acid, (1, 2-dicapoxytinole) dimethyl ^ / phosphine oxide, 9,10-dihydro-10-oxa- (2,3-carboxypropyl) -10-phosphaphenanthrene-10-oxide. By including these phosphorus compounds as copolymer components, it is possible to improve the flame retardancy and the like of the obtained polyester.

Examples of the polyester of the present invention include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly (1,4-cyclohexanedimethylene terephthalate), polyethylene naphthalate, polybutylene naphthalate, polypropylene naphthalate and copolymers thereof. Of these, polyethylene terephthalate and its copolymer are particularly preferred.

As a component of the polyester in the present invention, it is a preferred embodiment to use a polycarboxylic acid having a sulfonic acid metal salt base as a copolymerization component in order to improve the dyeability when polyester is used as a fiber.

The metal sulfonate group-containing compound used as the copolymerization monomer is not particularly limited, but may be 5-sodium sulfoisophthalic acid, 2-sodium sulfoterephthalanoleic acid, 5-lithium sulfoisophthalanoleic acid, Examples thereof include lithium sulfotelephthalenoleic acid, 5-force lithium snorephoisophthalenoleic acid, 2-force lithium snolephoterephthalenoleic acid, and lower alkyl ester derivatives thereof. In the present invention, it is particularly preferable to use 5-sodium sulfoisophthalic acid or an ester-forming derivative thereof. Copolymerization amount of the metal sulfonate group-containing compound for the acid components constituting the polyester, from 0.3 to 10.0 mole ^_0/0, more preferably is 0.80 to 5.0 mole ^_0/0

. If the copolymerization amount is too small, the dyeability of the basic dye is inferior. If the copolymerization amount is too large, not only the fiber-forming properties are poor, but also the fiber does not have sufficient strength due to the thickening phenomenon. Further, a metal sulfonate-containing compound 2.0 mole ⁰ /. By performing the above copolymerization, it is possible to impart normal pressure dyeability to the obtained modified polyester fiber. In addition, it is possible to appropriately reduce the amount of the metal sulfonate group-containing compound by selecting an appropriate easy dye monomer. Examples of the easily dyeable monomer include, but are not particularly limited to, long-chain daricol compounds such as polyethylene daricol and polytetramethylene daricol, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, and azelaic acid. Can be

After the polyester is polymerized according to the method of the present invention, the catalyst can be removed from the polyester or the catalyst can be deactivated by adding a phosphorus compound or the like, thereby further improving the thermal stability of the polyester.

The polyesternole of the present invention can contain antioxidants such as phenolic and aromatic amines. By containing one or more of these, for example, the heat stability of polyesternole can be enhanced. You can do things.

The polyester of the present invention may contain a bluing agent, an organic, inorganic, or organic metal dye, a pigment, a fluorescent whitening agent, and the like.One or more of these may be contained. By doing so, coloring such as yellowing of the polyester can be suppressed.

The polyester of the present invention contains other optional polymers, stabilizers, antioxidants, antistatic agents, antifoaming agents, dyeing improvers, dyes, pigments, anti-glazing agents, and other additives. You can.

These additives can be added during or after the polymerization of the polyester or at any stage during the molding of the polyester.The suitable stage depends on the properties of the compound and the requirements of the polyester molded article. They differ depending on the performance. Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples as well as the present invention.

The evaluation method used in the examples of the present invention will be described below.

(1) Content of metallic phosphorous in polymer

The contents of phosphorus and antimony and germanium were measured by X-ray fluorescence. Measurement Place the sample polyester in a stainless steel ring with a height of 5 mm and a diameter of 4 Omm n placed on a photographic foe type plate, and place in an oven at 300 mm. C, Heat for 10 minutes to melt. This was taken out, and after cooling, a molded sample was taken out of the ring and measured on a smooth surface. Separately, several polyesters whose content was determined by the chemical analysis method were molded by the above method, and the fluorescence: X-ray intensity was measured, and the values obtained by the chemical analysis method and the calibration curve of the fluorescent X-ray intensity were obtained. It was created. The phosphorus, antimony, and germanium contents in each sample were calculated based on the calibration curve from the fluorescent X-ray intensity data of the measurement sample polyester.

The content of other metals was measured by the following method. 1.0 g of polyester is weighed in a platinum crucible, slurried in an electric furnace at 550 ° C, cooled to room temperature, and the ash content is reduced to 6 N hydrochloric acid (hydrofluoric acid / hydrochloric acid in the case of titanium). Mixture), evaporate to dryness, and dissolve in 1.2 N hydrochloric acid. Samples to be subjected to high-frequency plasma emission analysis (ICPS-2000, manufactured by Shimadzu Corporation) and atomic absorption analysis (M-640-12, manufactured by Shimadzu Corporation) did. Separately, using a standard solution for atomic absorption for each metal to be measured, a solution for preparing a calibration curve in the concentration range of 0.01 to 30 mgZl was prepared, and high-frequency plasma emission analysis (Al, Ca, Mg, Co) and ぴAtomic absorption spectroscopy (Na, Li, K) was performed to create a calibration curve, and the metal content in the polyester was calculated from the analytical data of each sample based on the calibration curve.

(2) Intrinsic viscosity of polyester (IV)

Polyestenol O.lg was dissolved in 25 ml of a 6/4 mixed solvent in a weight ratio of phenol 1,1,2,2-tetrachloroethane and measured at 30 ° C. using an Ubbelohde viscometer.

(3) Acid value

The polyester is freeze-ground and vacuum dried at ₃₀ ° C for at least 12 hours. Precisely weigh 0.1 g of the sample in a test tube, add 10 ml of benzyl alcohol, and dissolve. Dissolution Afterwards, it is cooled in a zk bath. 1 Oml of clonal form was added, and titration was performed using a solution of 0.1 N NaOH in methanol / Z benzyl alcohol == 1/9 using phenolphthalein as an indicator to determine an acid value.

(4) Diethylene glycol content (DEG)

After 0.1 g of polyester was thermally decomposed at 250 ° C. in 2 ml of methanol, it was quantified and determined by gas chromatography (using GC-MB manufactured by Shimadzu Corporation). The column used was a column packed with PEG-HT manufactured by Jenore Science.

(5) Differential scanning calorimetry (DSC)

The measurement was carried out using TA insulnomentone ± $ | DSC 2920. Put about 10.Omg of polyester in a special aluminum pan for TA instrument sandstone autosampler, seal, heat to 280 ° C at a heating rate of 50 ° C / min, and reach 280 ° C for 1 minute Immediately after holding, they were entangled in liquid nitrogen. After that, the temperature was raised from room temperature to 300 ° C at a rate of 20 ° CZ, and the crystallization temperature Tc1 and melting point Tm at the time of temperature rise were determined. After holding at 300 ° C for 2 minutes, the temperature was lowered at 10 ° C / min, and the crystallization temperature Tc2 at the time of cooling was determined. Te1, Tm, and Tc2 were the temperatures at the local maximums of the respective peaks.

(6) Hue,

Using a color difference meter (Tokyo Denshoku Co., Ltd., ODEL TC-1500MC-88), it was measured as L value, a value, and b value of "Hunter." A chip having a diameter of about 2 mm and a length of about 3 mm obtained by the method described in the Examples was air-dried on a filter paper at room temperature for about one day and night, and then used for force measurement.

(7) Evaluation of rise in filter during spinning and yarn breakage during drawing

After drying the PET resin chip obtained by melt polymerization, it is fed to a melt extruder, and a filter with a pore size of 0.14πηηΦ is used with a filter of 20 μΐη.

The mixture was discharged at 290 ° C. from a spinneret having eight pieces, cooled and oiled according to a conventional method, and then taken out at 172 Om / min. Continue with preheating roller 80 ° C, set temperature 1

It was drawn 2.127 times at 50 ° C. to obtain a polyester drawn yarn of 47 dtex and 108 filaments. Examples 1 to 5 were evaluated using different spinning machine stands. The following evaluation was made according to the degree of increase in the filtration pressure during spinning.

〇: Little increase in filtration pressure is observed

Δ: Increase in filtration pressure is observed

X: Filtration pressure increases significantly

The following evaluation was made based on the frequency of yarn breakage during stretching.

〇: Almost no thread breakage

△: Yarn break occurs

X: Thread breaks occur frequently

(8) Thermal stability parameter (TS)

1 g of PET resin chip with melt-polymerized IV of 0.64-0.66 d1 / g (before melting test; [IV],) is placed in a glass test tube with an inner diameter of about 14 mm, and dried under vacuum at 130 for 12 hours After that, the glass test tube was connected to a vacuum line, and the pressure was reduced and the nitrogen filled was repeated 5 times or more, and then nitrogen was sealed to 10 OTorr and the tube was sealed. After immersing this test tube in a 300 ° C salt bath and maintaining it in a molten state for 2 hours, remove the sample, freeze-pulverize it, dry it in a vacuum, and measure the IV (after the melting test; [IV] _f ) did. TS was calculated using this [IV] _{f power and the following} formula. The formula was quoted from a previous report (Ueyama et al .: The Journal of the Rubber Association of Japan, Vol. 63, No. 8, page 497, 1990).

TS = 0. 245 {[IV] f - 1 · 47 - [IV] 1 - 1 · 47}

(9) Thermal oxidation stable raw parameters (TOS)

Melt polymerized PET resin chips with an IV of 0.64 to 0.66 d1 / g were frozen and extruded by conventional methods into powders of 20 mesh or less. 0.3 g of the powder was vacuum-dried at 130 ° C for 12 hours, placed in a glass test tube with an inner diameter of about 8 mm and a length of about 140 mm, vacuum-dried at 70 ° C for 12 hours, and then dried with silica gel. Was connected to the top of the test tube, immersed in a 230 ° C salt path under dry air, and heated for 15 minutes. From the IV of the PET after the calorific heat test, it was determined using the same formula below as the above TS. Here, [I V] i and [I V] 指す indicate the I V (d 1 / g) before the heating test and after the calorific heat test, respectively.

Freezing and milling were performed using a freezer mill (US Spexne: Model h¾6750). After putting about 2 g of resin chip and dedicated impactor in the dedicated cell, remove the cell The apparatus was set in the apparatus, filled with liquid nitrogen and maintained for about 10 minutes, and then pulverized at RATE 10 (the impactor was moved about 20 times per second) for 5 minutes. TOS = 0. 245 {[IV] fi I "1 · 47 -. [IV], 47}

(10) Thermal stability of Huinolem '14

(i) Film formation

The PET resin chip obtained by melt polymerization in each of Examples and Comparative Examples described below was vacuum-dried at 135 ° C. for 6 hours. Thereafter, the mixture was fed to an extruder, melted and extruded in a sheet form at 280 ° C, and quenched and solidified on a metal jaw maintained at a surface temperature of 20 ° C to obtain a cast finolem having a thickness of 1400 μπι.

Next, this cast film is heated to 100 ° C by a heated jaw group and an infrared heater, and then stretched 3.5 times at a set value in the longitudinal direction with a jaw group having a peripheral speed difference. Thus, a uniaxially oriented PET film was obtained. Subsequently, the film was stretched 4.0 times with a tenter in the width direction at 120 ° C with the set value.The film width was fixed, and the film was heated with an infrared heater at 260 ° C for 0.5 seconds. After a 3% relaxation treatment at 23 ° C for 23 seconds, a biaxially oriented PET film having a thickness of 100 µπι was obtained.

(11) Film formation with recovered pellets

The PET film obtained by the method described in (i) above was cut into strips, dried in a vacuum, put into an extruder, and extruded at a temperature of 280 ° C at a temperature of 280 ° C from a nozzle having a diameter of 5 mm. Thereafter, the pellet was cooled and cut to obtain a recovered pellet.

The PET resin chips obtained by melt polymerization and the above-mentioned recovered pellets were mixed at a weight ratio of 50:50, and vacuum-dried at 135 ° C for 6 hours. Then, it was fed to an extruder, melted and extruded into a sheet at 280 ° C, and rapidly cooled and solidified on a metal roll maintained at a surface temperature of 20 ° C to obtain a cast film having a thickness of 1400 im.

Next, this cast film is heated to 100 ° C by a heated roll group and an infrared heater, and then stretched 3.5 times in a longitudinal direction by a set value in a group of jaws having a difference in peripheral speed to a uniaxial orientation. PET film was obtained. Subsequently, the film was stretched 4.0 times at a set value in the width direction at 120 ° C. with a tenter to obtain a biaxially oriented PET film having a thickness of 100 μm. The obtained film was cut into strips again, and a recovered pellet was obtained in the same manner as described above to form a film. This operation was repeated more than 5 times. (iii) Thermal stability evaluation of film

The obtained film was cut into a test piece having a length of 8 cm and a width of 4 cm, and the obtained film was gradually pulled in the length direction to evaluate the easiness of the cut. Those that were hard to cut were evaluated as good. 〇: good, X: bad.

(1 1) Heat aging resistance of film

(10) The film obtained by the method of (i) is cut into test pieces of 10 cm in length and 5 cm in width, and the test pieces are treated at 200 ° C for 100 hours using a complete gear hot air dryer. The heat resistance of the film was evaluated based on the ease of cutting when the film was gradually pulled in the length direction. Those that were hard to cut were evaluated as good. 〇: Good, X bad.

(1 2) NMR measurement of synthesized phosphorus compounds

The I匕合was dissolved in CDC1 ₃ or d6-DMS0, Varian GEMINI at room temperature - was 200 using a connexion Toru j boss.

(13) Melting point measurement of synthesized phosphorus compounds

The compound was placed on a cover glass, and measured at a heating rate of 1 ° C / min using a Yanaco MICRO MELTING POINT APPARATUS.

(14) Elemental analysis of synthesized phosphorus compounds

Phosphorus was analyzed by molybdenum blue colorimetry after wet decomposition of PET resin chips. Other metals were analyzed by high-frequency plasma emission spectrometry and atomic absorption spectrometry after dissolution of the ashed Z acid.

(Example 11)

(Synthesis example of phosphorus compound)

Synthesis of phosphorus compound (phosphorus compound A) represented by the following formula (Formula 44) [Dani 4 4]

Synthesis of Sodium (0-ethyl 3, 5-di-tert-butyl-4-hydroxybenzylphosphonate)

A mixture of 6.5 g (84 mmol) of a 50% sodium hydroxide aqueous solution and 6.lml of methanol was mixed with diethyl (3,5-di-tert-butyi-4-hydroxybenzyl) phosphonate (Irganoxl222 (teno-specialty chemicals) at midnight. Ring)) 5 g (l½mol) of a methanol solution (6 lm 1) was added, and the mixture was heated and refluxed under a nitrogen atmosphere for 24 hours. After the reaction, 7.33 g (70 mmol) of concentrated hydrochloric acid was added while cooling the reaction mixture, the precipitate was collected by filtration, washed with isopropanol, and the filtrate was distilled off under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was filtered off, the isopropanol was distilled off under reduced pressure, and the residue was washed with hot heptane, dried and dried with X Sodium (0-ethyl. 3, 5-di-tert-butyl). -4-hydroxybenzylphosphonate) ¾ "3.4 g (69%) were obtained.

Shape: white powder

Melting point: 294-302 ° C (^)

—Thigh (d6-DMS0, δ): 1.078 (3Η, t, J = 7Hz), 1.354 (18H, s), 2.711 (2H, d),

3.724 (2H, m, J = 7Hz), 6.626 (1H, s), 6. 9665 (2H, s)

Elemental analysis (theoretical values in Katsuki): Na 6.36% (6.56%), P 9.18% (8.84%)

0-ethyl 3,5-di-tert-butyi-4-] Synthesis of ydroxybenzylphosphonic acid

1.5 g of concentrated hydrochloric acid was added to 20 ml of an aqueous solution of sodium (0-ethyl 3,5-di-tert-butyl-4-hydroxybenzyl-phosphonate) lg (2.8 mmol) under stirring at room temperature, and the mixture was stirred for 1 hour. 150 ml of water was added to the reaction mixture, and the precipitated crystals were collected by filtration, washed and dried to obtain 826 mg (88%) of 0-ethyl13,5-di-tert-butyl-4-hydroxybenzylphosphonic acid. Shape: Plate Crystal ''

Melting point: 126-127 ° C

_{- MR (CDC1 3, δ)} : 1.207 (3Η, t, J = 7Hz), 1.436 (18H, s), 3.013 (2H, d), 3.88 8 (2H, m, J = 7Hz), 7.088 (2H, s), 7.679-8.275 (1H, br)

(Example of polyester polymerization)

Using a 2-liter stainless steel autoclave with a stirrer as a polycondensation catalyst for a mixture of bis (2-hydroxyethyl) terephthalate oligomers produced from high-purity terephthalic acid and ethylene glycol in a conventional manner. Add a 2.5 g / 1 solution of aluminum trisacetyl acetonate in ethylene glycol and a 20/1 / ethylene glycol solution of phosphorus compound A and a 50 g / 1 solution of sodium acetate in ethylene dalicol. Was. These compounds were added so that the content of each metal atom and phosphorus atom in the finally obtained polymer was as shown in Table 1. Since the metal component in the added catalyst rarely volatilizes during polymerization and molding, the numerical value obtained from the analysis result is almost the same as the charged amount.However, the phosphorus component volatilizes during polymerization and molding, so it is analyzed. More than the result was added. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. After the addition of the above solution, the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, over 50 minutes, the pressure of the reaction system was gradually lowered while the temperature was raised to 275 ° C., and the polycondensation reaction was further performed at 275 ° C. and 0.1 Torr as 0.1 l Torr. Table 1 shows the polymerization time required until the IV of polyethylene terephthalate reached 0.65 dl / g. In addition, polyethylene terephthalate having an IV of 0.65 d 1 / g obtained by the above polycondensation was formed into chips according to a conventional method. That is, when a predetermined stirring torque is reached in the melt polymerization, nitrogen is introduced into the autoclave, the pressure is returned to normal pressure, the polycondensation reaction is stopped, and then the molten polymer is continuously reacted under a pressure of about IMPa. The resin was extruded into cold water in a strand form from the lower discharge nozzle and quenched, and a cutter was used to obtain a cylinder-shaped resin tip with a length of about 3ηπη and a diameter of about 2 mm. The holding time in cold water was about 20 seconds. The physical properties of PET were measured using this resin chip. The result is that the IV is 0.65 dl / _g , the acid value is 2 eq / ton, DEG is 2. lmol ° / o, and Tm is 256.6. C and Tel were 166.0 ° C and Tc2 was 188.6 ° C. L value is 66.0, a value is -1.8 The ゎ value was 3.6.

Using this PET resin chip, the evaluation of the increase in filtration pressure during spinning and the breakage of yarn during stretching were performed. Table 1 shows the evaluation results.

(Examples 1-2 to 11 and Comparative Examples 1 to 1)

A polyester was polymerized in the same manner as in Example 11 except that the catalyst was changed. Table 1 shows the compounds used as catalysts in each of the examples and comparative examples. These compounds were added so that the content of each metal atom or phosphorus atom in the finally obtained polymer was as shown in Table 1. Table 1 shows the polymerization results of each of the examples and comparative examples, and the evaluation results of the increase in the filtration pressure during spinning and the yarn breakage during stretching. IrganoX14425 was manufactured by Ciba Specialty Chemicals, Inc. Phosphorus compound A was synthesized by the same method as in Example 1-1.

As is clear from the above-mentioned Examples and Comparative Examples, those having a metal content in polyester within the scope of the claims of the present invention are excellent in operability of spinning and drawing, whereas those of the present invention Those outside the scope of the claims cause a remarkable rise in the filtration pressure during spinning, and frequent yarn breakage during drawing, resulting in poor operability.

(Example 2-1)

To a mixture of bis (2-hydroxyethynole) terephthalate oligomer prepared from terephthalenoic acid of high purity and ethylene dalicol according to a conventional method, 2.5 g of aluminum trisacetylacetonate was used as a polycondensation catalyst. Ethylene glycol firewood 1 and lithium acetate dihydrate 50 g Z 1 in ethylene glycol solution were added. These compounds were added so that the content in the finally obtained polymer was as shown in Table 1. However, the content indicates the percentage of monolith as a metal atom with respect to the acid component in the polymer. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. After the addition of the above solution, the mixture was stirred at 240 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, it took 50 minutes to gradually raise the temperature of the reaction system to 275 ° C while gradually reducing the pressure of the reaction system to 0.1 Torr, and further polycondensation at 275 ° C and 0.1 Torr. The reaction was performed. Table 2 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.65 dl / g. In addition, IV obtained by the above polycondensation was obtained by subjecting polyethylene terephthalate of 0.65 dl Z g to chipping according to a conventional method. ∞ w 1

[table 1]

1) Poly; content of the metal atoms per ester 10 ⁶ g.

2) the total content of alkali metal atoms and alkaline earth metal atoms per polyester 10 ⁶ g.

'Was used to evaluate the increase in filtration pressure during spinning and yarn breakage during stretching. Table 2 shows the evaluation results.

(Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-2)

A polyester was polymerized in the same manner as in Example 2-1 except that the catalyst was changed. Table 2 shows the results. In Examples 2-6, in addition to the addition of magnesium acetate and aluminum phosphate as polycondensation catalysts, dimethyl ferrphosphonate was added at a rate of 0.01 mol ° / mol to the acid component in the polymer. Was added.

As is clear from the above-mentioned Examples and Comparative Examples, those having a metal content in polyester within the scope of the claims of the present invention are excellent in operability of spinning and drawing, whereas those of the present invention Those outside the scope of the claims are inferior in operability because the filtration pressure rises remarkably during spinning, and yarn breakage frequently occurs during drawing.

(Example 3-1)

To a mixture of bis (2-hydroxyethyl) terephthalate oligomer prepared from conventional terephthalic acid and ethylene dariconole according to a conventional method, 2.5 g of aluminum trisacetyl acetate was used as a polycondensation catalyst. l of ethylene glycol solution and 10 g / ethylene glycol solution of Irgano xl 425 (manufactured by Ciba Specialty Chemicals) were added. These compounds were added so that the content of metal phosphate in the finally obtained polymer was as shown in Table 3. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. After the addition of the above solution, the mixture was stirred at 245 ° C for 10 minutes under a nitrogen atmosphere at normal pressure. Then, over 50 minutes, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C, and the polycondensation reaction was further performed at 275 ° (0.1 Torr) with 0.1 lTorr. The polymerization time required for the IV to reach 0.65 dlZg is shown in Table 1. In addition, the polyethylene terephthalate having an IV of 0.65 dl / g obtained by the above polycondensation was prepared according to a conventional method. The physical properties of PET were measured using this resin chip, the result was IV of 0.65 dl / g, acid value of 6 eq / ton, DEG of 2. lmol ° /. The temperature was 256.3 ° C. and Tc2 was 186.2 ° C. The L value was 68.9, the a value was −2.56, and the b value was 5.49.

Of filtration pressure increase during spinning and yarn breakage during stretching [Table 2]

CO

1) Ratio of the sum of mole% of alkali metal and alkaline earth metal in polyester (Μ) and mole% of aluminum (A I)

2) Total amount of argari metal and alkaline earth metal in polyester (ppm)

E performed. Table 3 shows the evaluation results.

(Example 3-2 to 3-9, Comparative Example 3-1-3-3)

A polyester was polymerized in the same manner as in Example 3-1 except that the catalyst was changed. Table 3 shows the compounds used as catalysts in each Example and Comparative Example. These compounds were added so that the content of metallic phosphorous in the polymer finally obtained was as shown in Table 3. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. In Examples 3-9, antimony trioxide was used in combination as a catalyst. Antimony trioxide was added so that the content of antimony atoms in the polymer finally obtained was 50 ppm. Table 3 shows the polymerization results of each Example and Comparative Example, and the evaluation results of the increase in filtration pressure during spinning and the breakage of yarn during stretching. The Irganox 1425 used was that of Chino Specialty Chemicals Co., Ltd., and the Linyi Conjugate A used was the one synthesized by the method described above.

As is clear from the above Examples and Comparative Examples, those in which the contents of the metal and phosphorus in the polyester are within the scope of the claims of the present invention are excellent in the operability of spinning and drawing. On the other hand, those outside the scope of the claims of the present invention result in a remarkable increase in filtration pressure during spinning or frequent yarn breakage during drawing, resulting in poor operability.

(Example 4-1)

Using a 2-liter stainless steel autoclave equipped with a stirrer, polycondensation is performed on a mixture of bis (2-hydroxyethyl) terephthalate and oligomer prepared from high-purity terephthalic acid / leic acid and ethylene glycol according to a conventional method. As a catalyst, 13 g / 1 of an ethylene glycol solution of aluminum chloride was added in an amount of 0.014 mol% as an aluminum atom to the acid component of the polyester, and 10 gZ of Irga no 1425 (manufactured by Chipa Specialty Chemicals) was added. 0.022 mol% of an ethylene glycol solution was added as Irganoxl 425 to the acid component constituting the polyester, and the mixture was stirred at 245 at normal pressure under a nitrogen atmosphere for 10 minutes. Then, over 50 minutes, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C, and the polycondensation reaction was further performed at 275 ° C and 0.1 Torr as 0.1 l Torr. By the time the IV of polyethylene terephthalate reaches 0.65 dlZg [Table 3]

00

1) Total content of alkali metal and alkaline earth metal atoms in polyester (ppnt)

2) The ratio of the total content (ppm) of alkali gold atoms and alkaline earth metal atoms in polyester to the content of aluminum atoms (ppm)

3) Polyester Φ ratio of phosphorus atom content と (pm) to aluminum atom content (u in)

4) Polyester containing 5 Oppm as anti-atom

Table 4 shows the required polymerization time. In addition, polyethylene terephthalate having an IV of 0.65 dlZg obtained by the above polycondensation was formed into chips according to a conventional method. Table 4 shows the ratio of aluminum atoms to phosphorus atoms as a result of measuring the amount of aluminum atoms and the amount of phosphorus atoms contained in the resin chip. The amount of calcium atoms contained in the PET resin chip was 45 ppm, and thus the total content of metal atoms was 65 ppm. Using this PET resin chip, the evaluation of thermooxidative stability, the increase in filtration pressure during spinning, and the evaluation of yarn breakage during stretching were performed. Table 4 shows the evaluation results.

(Example 4_2)

(Synthesis example of phosphorus compound)

Synthesis of phosphorus compound (NMPA) represented by the following formula (I-Dai 21)

Under a nitrogen atmosphere, a mixture of 8.31 g (50 mmol ol) of triethyl phosphite and 8.83 g (50 mmol) of 1-chloromethylnaphthalene was added at 200 ° C (outside temperature) until the gas (C2H5C1) generation was completed. Heated for minutes. After cooling to room temperature, 10.38 g (crude yield 75%) of MPA as a colorless oily liquid was obtained.

^ -NMR (CDCls, δ): 1.151 (6Η, t), 3.641 (2H, d), 3.948 (4H, m), 7.381—7.579 (4H, m), 7.749-7.867 (2H, m), 8.088- 8133 (1H, m)

(Example of polyester polymerization)

A polyester was polymerized in the same manner as in Example 4-1 except that the catalyst was changed. In this example, a polycondensation catalyst was prepared by adding a solution of aluminum trisacetyl acetonate in 2.5 g / 1 ethylene glycol at 0.014 mol% as aluminum atoms with respect to the acid component constituting the polyester. 0. the 50 g / 1 of ethylene glycol solution of NMPA as NMPA relative to the acid component constituting the polyester ^{_{02mo l 0/0, I rganoxl}} 330 ( Chiba * Specialty Ke Mikaruzune: fc) finally obtained polyester converted in 0.1 wt ^_0/0, the 50 g / 1 of ethylene da recall solution of acetic acid lithium Umuni hydrate using 0. 01 mo 1% of lithium atom relative to the acid component constituting the polyester.

The polymerization time required for the IV of polyethylene terephthalate to reach 0.65 d1 Zg, the amount of aluminum atoms contained in the obtained PET resin chip and Table 4 shows the results of measuring the amount of phosphorus atoms and the ratio of aluminum atoms to phosphorus atoms. The amount of lithium atoms contained in the PET resin chip was 4 ppm, so the total content of metal atoms was 24 p. Table 4 shows the results of evaluating the stability of thermal oxidation by using PET resin chips, as well as evaluating the increase in filtration pressure during spinning and yarn breakage during stretching.

(Comparative Example 4-1)

A polyester was polymerized in the same manner as in Example 41-11 except that the catalyst was changed. As a polycondensation catalyst, a solution of 13 g Z1 of ethylene chloride in aluminum chloride with aluminum chloride at 0.015 mol% of aluminum acid and a 50 g / 1 solution of lithium acetate dihydrate in ethylene glycol were added to polyester. 0.06 mo 1% was used as a lithium atom with respect to the acid component constituting the metal. Table 4 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.65 d1 / g. Table 4 shows the results of the evaluation of the thermo-oxidative stability, the increase in the filtration pressure during spinning, and the evaluation of the yarn breakage during stretching using a PET resin chip with an IV of 0.65 dlZg.

As is evident from the above Examples and Comparative Examples, it is a polyester polymerized using an aluminum compound, a phosphorus compound and a phenolic compound, and the ratio of phosphorus atoms to aluminum atoms in the polyester is determined by the present invention. What is claimed in the claims is that the polyester has excellent thermal acid stability and excellent spinning and drawing operability. On the other hand, those that do not use a phosphorus compound and a phenolic compound are inferior in thermal oxidative stability, markedly increase in filtration pressure during spinning, and frequently cause yarn breakage during drawing, resulting in poor operability. .

(Example 5-1)

(Polymerization example of polyester)

To a mixture of bis (2-hydroxyethyl) terephthalate and oligomers produced from high-purity terephthalic acid and ethylene dalicol according to a conventional method, 2.5 g / 1 of ethylene trisacetylacetonate was used as a polycondensation catalyst. A glycol solution and the above-mentioned 10 gZ1 ethylene dalicol solution of phosphorus compound A were added. These compounds are the aluminum atoms in the final polymer. [Table 4]

1) Ratio of the amount of phosphorus atoms (ppm) and the amount of aluminum atoms (pptn) contained in polyester

The syrup was added so that the phosphorus atom content was as shown in Table 5. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. After the addition of the above solution, the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, over 50 minutes, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C, and the polycondensation reaction was further performed at 275 ° C and 0.1 Torr as 0.1 ltor. Table 1 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.65 dl / g. In addition, polyethylene terephthalate having an IV of 0.65 d 1 / g obtained by the above polycondensation was subjected to chipping according to a conventional method. Using this PET resin chip, the increase in the filtration pressure during spinning and the evaluation of yarn breakage during stretching were performed. Table 5 shows the evaluation results.

(Example 5 2)

To a mixture of bis (2-hydroxyethyl) terephthalate and oligomer prepared from high-purity terephthalic acid and ethylene glycol according to a conventional method, 2.5 g / 1 of aluminum trisacetyl acetonate was used as a polycondensation catalyst. An ethylene glycol solution and a 10 g / 1 ethylene glycol solution of Irgano xl 425 (manufactured by Chipa Specialty Chemicals) were added. These compounds were added so that the contents of aluminum and phosphorus in the finally obtained polymer were as shown in Table 5. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. After the addition of the above solution, the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Then, over 50 minutes, the temperature of the reaction system was gradually reduced while the temperature was raised to 275 ° C, and the polycondensation reaction was further performed at 275 ° C and 0.1 T rr as 0.1 l Tor. Table 1 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.65 d.1 / g. In addition, polyethylene terephthalate having an IV of 0.65 d1 ng obtained by the above polycondensation was formed into chips according to a conventional method. Using this PET resin chip, an increase in the filtration pressure during spinning and an evaluation of yarn breakage during stretching were performed. Table 5 shows the evaluation results.

(Comparative Example 5-1 to 5-2)

A polyester was polymerized in the same manner as in Example 5-1 except that the catalyst was changed. Table 5 shows compounds used as catalysts in each of Examples and Comparative Examples. These iris conjugates have a high content of aluminum and phosphorus in the final polymer. Was added to the amount shown in Table 5. An appropriate amount was selected according to the characteristics of the reactor used for the polymerization and the polymerization conditions. Table 5 shows the polymerization results and the evaluation results of the increase in filtration pressure during spinning and the breakage of yarn during stretching. The above-mentioned phosphorus compound A was used. As is evident from the above examples and comparative examples, those in which the contents of anoremidine and phosphorus in the polyester are within the scope of the claims of the present invention are those of spinning and elongation. On the other hand, those which are out of the scope of the claims of the present invention result in a remarkable increase in filtration pressure during spinning and frequent breakage of yarn during stretching, resulting in poor operability.

(Example 6-1)

(Polymerization example of polyester)

High purity terephthalic acid and twice the molar amount of ethylene dalicol were charged into a 2-liter stainless steel autoclave equipped with a stirrer, and 0.3 mol% of triethylamine was added to the acid component, and 0.25 MPa was applied. The esterification reaction was performed for 120 minutes while distilling water out of the system at a pressure of 245 ° C to obtain a mixture of bis (2-hydroxyxethyl) terephthalate and oligomer. To this mixture, a polycondensation catalyst of aluminum trisacetinoleacetonate in ethylene glycol at a concentration of 2.5 g / 1 was added in an amount of 0.07 mo 1% as an aluminum atom to the acid component in the polyester. A 10 g / 1 ethylene glycol solution of the phosphorus compound A was added as a phosphorus atom to the acid component in the polyester in an amount of 0.2 mo 1%, and the mixture was stirred at 245 ° C. for 10 minutes under a normal pressure under a nitrogen atmosphere. Then, over 50 minutes, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C, and the polycondensation reaction was further performed at 275 ° C and 0.1 Torr as 0.1 l Tor. Table 6 shows the polymerization time required for the IV of polyethylene terephthalate to reach 0.65 d1 / g.

(Example 6—2 to 6—3, Comparative Example 6—1 to 6—3)

A polyester was polymerized in the same manner as in Example 6-1 except that the catalyst was changed. Table 6 shows the compounds used as catalysts and the amounts added in each Example and Comparative Example. The amount of addition indicates the amount of aluminum atoms or phosphorus atoms with respect to the acid component in the polymer. Table 6 shows the polymerization results. Phosphorus compound A used above, Irganoxl 425 used from Chipa Specialty Chemicals [Table 5]

CO CJl

1) Ratio of phosphorus atom content (ppm) and aluminum atom content (ppm) in polyester

did. In Comparative Example 6-3, polymerization was performed for 120 minutes or more, but did not reach the predetermined viscosity.

(Example 6-4)

A solution was prepared by previously mixing aluminum-dimethyltrisacetylacetonate used as a polycondensation catalyst and Irganox 1425 in ethylene daryl. A polyester was polymerized in the same manner as in Example 6-3 except that the solution was added as a catalyst. The polymerization time required until the IV of the polyethylene terephthalate reached 0.65 dl / g was almost the same as in Example 6-3.

As is evident from the above Examples and Comparative Examples, those in which the addition ratio of the aluminum compound to the phosphorus compound falls within the scope of the claims of the present invention are excellent in catalytic activity and, consequently, excellent in productivity of polyester. On the other hand, what is out of the claims of the present invention results in poor catalytic activity and poor polyester productivity.

(Example 7-1)

(Polymerization example of polyester)

2 liter stainless steel autoclave equipped with a stirrer was charged with high-purity terephthalic acid twice Monore amount of ethylene glycol, and. Against the acid component a Riechiruamin with 0. 3mo l ° / ₀ added 0.2 5 The esterification reaction was carried out for 120 minutes at 245 ° C. under a pressure of MPa while distilling water out of the system to obtain a mixture of bis (2-hydroxyethyl) terephthalate and polyoligomer. To this mixture, 2.5 g / 1 ethylene glycol of aluminum trisacetylacetonate as polycondensation catalyst? At night, 0.014 mol 1% is added as an aluminum atom to the acid component in the polyester, and the above-mentioned 10 gZ1 ethylene glycol solution of the phosphorus compound A is added as 0.1 atom as a phosphorus atom to the acid component in the polyester. 03 mol%, and add ethylene glycol solution of 50 g / l lithium acetate hydrate to the acid component in an amount of 0.01 mol% as lithium atom with respect to the acid component. Stirred for 10 minutes. Then, over 50 minutes, the temperature of the reaction system was gradually lowered while the temperature was raised to 275 ° C, and the polycondensation reaction was further performed at 275 ° C and 0.1 Torr at 0.1 Torr. . Table 7 shows the polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.65 d1 / g. [Table 6]

CD

1) Molar ratio between phosphorus atom and aluminum atom

In addition, polyethylene terephthalate having an IV of 0.65 d 1 / g obtained by the above polycondensation was formed into chips according to a conventional method. Using the PET resin chip, the thermal stability parameter (TS) and the thermo-oxidative stability parameter (TOS) were determined. Table 7 shows the results.

In addition, a film was formed using a PET resin chip, a collected pellet was formed, and a finolem was formed using a collected bellet. Table 7 shows the results of the thermal stability and heat aging resistance of the film.

The catalyst of the present invention has high catalytic properties and was obtained by using this: The film made of PET was excellent in both thermal stability and heat aging resistance.

(Example 7-2)

(Synthesis example of phosphorus compound)

Synthesis of phosphorus compound (phosphorus compound B) represented by the following formula 45

[Dani 45]

Synthesis of 1- (1-naphthyl) methy 丄 phosphonic acid dieth ester

Under a nitrogen atmosphere, a mixture of 8.31 g (50 t ol) of triethynole phosphite and 8.83 g (50 mmol) of trichloromethylnaphthalene at 200 ° C (external temperature) for about 30 minutes until the generation of gas (EtCl) ends. Heated. After cooling to room temperature, 10.38 g (75% crude yield) of a colorless oily liquid (1-naphthyiethyl phosphonic acid diethylester) was obtained.

'H-NMR (CDCI3, δ): 1.151 (6Η, t), 3.641 (2H, d), 3.948 (H, m), 7.381-7.579 (4H, m), 7.749-7.867 (2H, m), 8.088 -8.133 (1H, m)

2. Synthesis of Sodium [0-ethyl (1-napirtyl) raethylphosphonate] To a mixed solution of 6.5 g (8 mol) of a 50% aqueous sodium hydroxide solution and 6.lml of methanol was added 6.lml of a methanol solution of 5 g (18 mmol) of (1-naphthyl) methylphosphonic acid diethylester, and the mixture was refluxed for 24 hours under a nitrogen atmosphere. went. After the reaction, 6.59 g (63 mmol) of concentrated hydrochloric acid was added while cooling the reaction mixture, the precipitate was collected by filtration, washed with isopropanol, and the filtrate was distilled off under reduced pressure. The obtained residue was dissolved in hot isopropanol, the insoluble matter was collected by filtration, and isopropanol was distilled off under reduced pressure. The residue was washed with hot n-heptane, recrystallized from isopropanol, and dried to obtain 3.8 g (78%) of sodium [0-ethyl (l-naphtyl) me thylp osphonate].

Shape: needle crystal

Melting point: ² 77- l ° C (decomposition)

aH-NMR (d6-DMS0, δ): 0.961 (3Η, t, J = 7 Hz), 3.223 (2H, d), 3.589 (2H, m), 7.3 65-7.468 (4H, m, J = 7 Hz), 7.651-8.314 (3H, m)

3.Synthesis of 0-ethyl (1-naphtyl) methylphosphonic acid (phosphorus compound B) Concentrated hydrochloric acid 1.9 _{g in} 10 ml of aqueous solution of sodium [0-ethyl (1-naphtyl) methylphosphonate] lg (3.7 ol) with stirring at room temperature Was added and stirred for 1 hour. The reaction mixture was extracted with toluene, the toluene phase was washed with water, and the toluene was distilled off under reduced pressure to give 497 mg (54%) of 0-ethyl (l-naphtyl) met hylp osphonic acid.

Shape: colorless oily liquid

_{- NMR (CDC1 3, δ)} : 1.085 (3H, t, J = 7Hz), 3.450 (2H, d), 3.719 (2H, m, 7Hz), 7.369-7.532 (4H, m), 7.727-8.043 (3H , m), 10.939 (1H, s)

(Polyester's polymerization example)

A polyester was polymerized in the same manner as in Example 7-1 except that the catalyst was changed. Table 7 shows the compounds used as catalysts and the amounts added. The addition amount of the aluminum compound indicates the addition amount as an aluminum atom to the acid component in the polyester, and the addition amount of the phosphorus compound B indicates the addition amount of phosphorus atoms to the acid component in the polyester. Table 7 shows the polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.65 dlZg.

Further, polyethylene terephthalate having an IV of 0.65 d 1 / g obtained by the above polycondensation was subjected to chipping according to a conventional method. This: heat using PET resin chips The qualitative parameters (TS) and thermo-oxidative stability parameters (TOS) were determined. Table 7 shows the results.

In addition, the above-mentioned: film formation using a PET resin chip, preparation of a recovered pellet, and film formation using the recovered pellet were performed. Table 7 shows the results of evaluating the thermal stability and heat aging resistance of the film.

The catalyst according to the invention has a relatively high tactility and was obtained by using it: The film made of PET was excellent in both heat stability and heat resistance.

(Comparative Example 7-1)

Antimony trioxide as a catalyst, the performing procedure of Example 7-1 the same way except that the amount added was used as a 0.05 molar ^_0/0 as antimony atom relative to the acid component in PET Was. As antimony trioxide, commercially available Antimony (III) oxide (ALDRICH CHEMICAL ne, purity: 99.999%) was used. The antimony trioxide used was a solution of ethylene glycol dissolved in ethylene glycol by stirring at 150 ° C. for about 1 hour so that the concentration became about 10 gZl. Table 7 shows the polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.65 d1 / g.

In addition, polyethylene terephthalate having an IV of 0.65 dlZg obtained by the above polycondensation was formed into chips according to a conventional method. Using this PET resin chip, the thermal stability parameter (TS) and the thermal oxidation stability parameter (TOS) were determined. Table 7 shows the results.

Further, using the PET resin chip, a film was formed, a recovered pellet was formed, and a film was formed using the recovered pellet. Table 7 shows the results of evaluating the thermal stability and heat resistance of the film.

Although the catalyst of the present invention was excellent in catalytic activity, the thermal stability of a film made of PET obtained using the catalyst was inferior to those of Examples.

(Comparative Example 7-2)

Comparative Example 7—except that the above-mentioned phosphorus compound A was added to the catalyst of Comparative Example 7-1 so that the added amount thereof was 0.03 mol% as a phosphorus atom with respect to the acid component in the PET. The same operation as in 1 was performed. As antimony trioxide, commercially available Antimony (III) oxide (ALDRICH CHEMICAL based, purity: 99 · 999%) was used. Triacid The antimony was added to the ethylene glycol to a concentration of about 10 g / 150. (The solution dissolved by stirring for about 1 hour was used. The polymerization time (AP) required until the polyethylene terephthalate IV reached 0.esdiZg is shown in Table 7. Almost no change in the catalytic activity of antimony trioxide due to this was observed.

(Comparative Example 7-3)

Germanium dioxide as a catalyst, the addition amount is the same procedure as in Example 7-1, except for using as a 0.03 mol ^_0/0 as gain Rumaniumu atom relative to the acid component in PET. Table 7 shows the polymerization time (AP) required for the IV of polyethylene terephthalate to reach 0.esdiZg.

Further, polyethylene terephthalate having an IV of 0.65 d 1 / g obtained by the above polycondensation was subjected to chipping in a conventional manner. Using this PET resin chip, the thermal stability parameter (TS) and thermal oxidation stability parameter (TOS) were determined. Table 7 shows the results.

Although the catalyst of the present invention has excellent catalytic activity, the thermal stability and heat resistance of a PET film obtained using the same are inferior to those of the examples. Was something.

(Comparative Examples 7-4)

The same operation as in Example 7-1 was carried out except that aluminum acetyl acetonate was used as a catalyst and the amount of aluminum acetyl acetonate was 0.014 mol% as an aluminum atom with respect to an acid component in the PET. I got it. Polymerization was carried out for 150 minutes or more, but the IV of poly (ethylene terephthalate) did not reach 0.65 d1 / g.

(Comparative Example 7-5)

Lithium acetate dihydrate as a catalyst, in the same manner as in Example 7-1 except that the addition amount is used so as to be 0.01 mol ^_0/0 of lithium atom relative to the acid component in PET went. Polymerization was performed for 150 minutes or more. The IV of the plate did not reach 0.65 dlZg.

As is evident from the above Examples and Comparative Examples, those having the thermal stability parameter of the PET resin chip within the scope of the claims of the present invention have excellent thermal stability of the film and excellent film quality. At the same time, the reuse of waste film will also be excellent. On the other hand, those outside the scope of the claims of the present invention are inferior in thermal stability of the film, so that the quality of the film obtained by recycling the waste film is inferior and cannot be obtained.

Further, although the anolemminium compound and the lithium compound are originally inferior in catalytic activity, the catalyst of the present invention coexisting with the phosphorus compound has excellent catalytic activity, and the resulting polyester has excellent thermal stability. On the other hand, even when the phosphorus compound is used together with the antimony conjugate, the catalytic activity of the antimony compound is not affected.

(Example 8-1)

(Example of preparation of aqueous solution of basic aluminum acetate)

Deionized water was added at a ratio of 50 ml to 1 g of basic aluminum acetate (hydroxyaluminum diacetate; manufactured by ALDRICH), and the mixture was stirred at room temperature for about 12 hours. Thereafter, stirring was continued while gradually increasing the liquid temperature. When the liquid temperature reaches about 60 ° C, maintain the temperature and stir for about 2 hours.Continue stirring while increasing the liquid temperature.When the liquid temperature reaches about 75 ° C, stir for 2 hours or more. A clear aqueous solution was obtained.

(Example of polyester polymerization)

As a polycondensation catalyst, water of the above basic aluminum acetate was used as a polycondensation catalyst for a mixture of bis (2-hydroxyxethinole) terephthalate and polyolomer produced from high-purity terephthalic acid and twice the molar amount of ethylene glycol in a conventional manner. 0.035 mol% of aluminum atom with respect to acid component in polyester and l Og / 1 solution of Irgano X 1425 (Chipa 'Specialty Chemicals) in ethylene glycol with acid component in polyester After adding 0.02 mol% as 425, the mixture was stirred at 245 ° C. for 15 minutes under a nitrogen atmosphere at normal pressure. Then, the temperature of the reaction system was gradually decreased while raising the temperature to 275 ° C over 55 minutes to obtain 66.5 Pa (0.5 To rr), and the pressure was further increased at 275 ° C and 66.5 Pa for 90 minutes. A condensation reaction was performed. Table 8 shows the IV and Tm of the obtained PET. 7] Film heat Film resistance /

匕合合 mo mo Zmo l l¾ A n ノ, t o 丁 l n Uoc

Womanbiki ffi ¾i¾1 L! ±.

Example: Tilacetone 0.014

7- 丄 WF linalum hydrate 0.01

I I ン ^ ^ ^ A A A Α Α Α Α A

〇 Example Example 0.014

7-2 Phosphorus compound B 0.03 116 0.14 0.04 〇比較 Comparative example 7-1 Antimony trioxide 0.05 75 0.23 0.01 Under X 比較 Comparative example 7-2 Antimony trioxide 0.05 '

Phosphorus compound A 0.03 77

Comparative Example ⁷ one ³ germanium dioxide 0.03 68 0.20 0.23 XX aluminum tris § Se

Comparative Example. ⁷ one ⁴ ■ Chiruasetone one Bok 0.014 150 or more

Comparative Example ⁷ one ⁵ Lithium acetate dihydrate 0.01 150 or more

(Example 8-2) .. (Example of preparation of basic aluminum acetate solution in ethylene glycol)

Basic aluminum acetate _{_{(CH 3 C00A1 (0H) 2}} · 1 / 3H 3 B0 3; manufactured by ALDRICH) was stirred丄2 hours or more in Echire glycol, to obtain an ethylene glycol solution of about 5 _g / l concentration.

(Example of polyester polymerization)

As a polycondensation medium, the above base '! · Ethylene glycol solution of raw aluminum acetate is 0.035mo 1% as an aluminum atom with respect to the acid component in the polyester and Irganoxl 425 (Chipa succinoleti chemicano) The same operation as in Example 8-1 was carried out except that a solution of 10 gZ1 ethylene dalicol of the (resin; h ^) was added to the acid component as Irganoxl 425 at 0.02 mol%. Table 8 shows the IV and Tm of the obtained PEs.

(Comparative Example 8-1)

As a polycondensation catalyst, about 10 g of a basic aluminum acetate (hydroxylaminodimethyl acetate, manufactured by ALDRICH) / resin slurry of ethylene darico-resin is converted to aluminum atom with respect to the acid component in the polyester. 035mo 1% and Irgan 0x1425 (based on specialty chemicals) 10 gZl Ethylene glycol? Except for adding 0,02mol% of acid component to Irga no xl 425 as Irgano xl 425 Example 8—Operation similar to 1 was performed. Table 8 shows the obtained IV and 111 of PET _!

(Example 8 3)

(Example of preparation of basic aluminum acetate in ethylene glycol solution)

Deionized water was added at a ratio of 10 ml to 1 g of basic aluminum acetate stabilized with about 1 Z 16 mol of folic acid, and the mixture was stirred at room temperature for several hours. Thereafter, the mixture was stirred at about 70 ° C for about 12 hours to obtain a clear aqueous solution. Ethylene glycol was added at a volume ratio of 20 times the volume of the aqueous solution, followed by stirring at room temperature for several hours. Thereafter, water was distilled off from the system while stirring the solution at about 100 ° C. for several hours to obtain an ethylene glycol solution.

(Polyestenol polymerization example) A mixture of bis (2-hydroxyxethyl) terephthalate and polyolomer produced from high-purity terephthalic acid and twice the molar amount of ethylene glycol according to a conventional method is used as a polycondensation catalyst for ethylene glycol of the above basic aluminum acetate. The solution was 0.014 mol 1% aluminum atom with respect to the acid component in the polyester and 101 mg solution of Irga no xl 425 (manufactured by Chipa Specialty Chemicals) in ethylene glycol with respect to the acid component. As 425, 0.0 lmo 1% was added, and the mixture was stirred at 245 ° C for 10 minutes under a nitrogen atmosphere at normal pressure. Then, the temperature of the reaction system was gradually lowered while raising the temperature to 275 ° C over 45 minutes to obtain 66.5 Pa (0.5 To rr), and the pressure was further increased at 275 ° C and 66.5 Pa for 120 minutes. A condensation reaction was performed. PET of 1 was 0.38 d 1 / g. (Example 8-4)

(Preparation example of mixed solution of basic aluminum acetate in water and Z-ethylene glycol) Basic aluminum acetate (hydroxyaluminum diacetate; manufactured by ALDRICH) Deionized water is added at a ratio of 5 Oml to 1 g and stirred at room temperature for 12 hours. did. Thereafter, the mixture was stirred at about 70 ° C. for 6 hours to obtain a clear aqueous solution. To this aqueous solution 1, 3 times (volume ratio) of ethylene glycol was added, and stirred at room temperature for 6 hours to obtain a catalyst solution. ,

(Polymerization example of polyester)

Heat medium circulation type 2-liter stainless steel autoclave equipped with a stirrer is charged with high-purity terephthalic acid and twice the amount of ethylene glycol, and triethylamine is added at 0.3 mol% to the acid component. The esterification reaction was performed for 115 minutes while distilling water out of the system at, and a mixture of bis (2-hydroxyethyl) terephthalate (BHET) and oligomer (hereinafter referred to as BHET mixture) with an esterification rate of 95% or more I got As a polycondensation catalyst, the above BHET mixture was mixed with a mixed solution of the above basic aluminum acetate-water in water and ethylene glycol in an amount of 0.014 mol% as an aluminum atom to the acid component in the polyester and Irganoxl 425 (T). (B Specialty Chemicals Co., Ltd.) in 100 _g Z1 ethylene glycol solution is added to the acid component as Irgano X 1425 at 0.0 lmo 1%, and under nitrogen atmosphere at normal pressure and 250 ° C for 15 minutes Stirred. Then take 60 minutes to reach 275 ° C. The pressure of the reaction system was gradually lowered while the temperature was raised to 66.5 Pa (0.5 Torr), and a polycondensation reaction was further performed at 275 ° C. and 66.5 Pa. The polycondensation time required to obtain a PET with an IV of 0.61 dl / g was 132 minutes, and the catalyst had practical catalytic activity. Obtained: Table 9 shows the physical properties of PET.

(Example 8-5)

(Example of preparation of basic aluminum acetate in ethylene glycol? Night)

The above basic aluminum acetate mixed solution of water and ethylene glycol is mixed with 90 ~ 1.

Water was distilled off from the system while stirring at 10 ° C for several hours. As a result, an ethylene glycol solution having a concentration of about 6.5 g / l was obtained.

(Example of polyester polymerization)

As a polycondensation catalyst, the above-mentioned ethylene dalicol solution of basic aluminum acetate was used in an amount of 0.014mo 1% as an aluminum atom with respect to the acid component in the polyester and 100 g of Irgano x 1425 (manufactured by Ciba Specialty Chemicals). The polyester was polymerized in the same manner as in Example 8-4, except that 1/1 ethylene dalicol ^ ¾ was added to the acid component as Irganox 1425 at 0.01mo 1%. The polymerization time was 133 minutes, and the IV of the obtained PET was 0.6 Odl / g. Table 9 shows other physical properties.

(Example 8-6)

(Preparation example of basic aluminum acetate in ethylene glycol solution)

Basic aluminum acetate _{(CHsCOOAl (0H) 2 · 1} / 3H 3 B0 3; manufactured by ALDRICH) was stirred for 5 hours at about 70 ° C in Echire glycol, to give the ethylene da recall solvent solution of about 5 g / l concentration Was.

(Example of polyester polymerization)

To a mixture of bis (2-hydroxyethyl) terephthalate and an oligomer prepared from high-purity terephthalic acid and ethylene glycol according to a conventional method, a 5 g / l ethylene glycol solution of the above basic aluminum acetate as a polycondensation catalyst in a polyester. 0.104 mol% as an aluminum atom with respect to the acid component and 10 g of Zr-ethylene glycol solution of Irgano X 1425 (manufactured by Ciba Specialty Chemicals) as Irganox 1425 with respect to the acid component 0. 01 mo 1% was added, and the mixture was stirred at 245 ° C. for 10 minutes under a nitrogen atmosphere at normal pressure. Next, it took 50 minutes to gradually raise the temperature of the reaction system to 275 ° C and gradually reduce the pressure of the reaction system to 13.3 Pa (0.IT orr). A condensation reaction was performed. A polycondensation reaction was performed for 90 minutes to obtain PET of IV.65.dl / g. The amount of the obtained 丁 was 2 equivalents, the Tm was 256 ° C, the value was 68.9, the a value was 1.3, and the b value was 4.2.

(Examples 8-7)

(Preparation example of ethylene glycol solution of aluminum lactate)

An aqueous solution of about 67 gZ1 of aluminum lactate was prepared at room temperature. Thereafter, ethylene glycol was added, and water was distilled off by heating at about 100 ° C. to obtain an ethylene glycol solution of about 29 g / l.

(Example of polyester polymerization)

As a polycondensation catalyst, the above ethylene glycol solution of aluminum lactate was used as 0.014 mol 1% as an anolemmin atom with respect to the acid component in the polyester and 100 g / l of Irganox 1425 (manufactured by Chipa Specialty Chemicals). The polyester was polymerized in the same manner as in Example 8-4, except that 0.01 mo 1 ° / ₀ was added as Irganoxl 425 to the acid component of the recall solution. The polymerization time was 124 minutes, and the IV of the obtained PET was 0.60 dl / g. Table 9 shows other physical properties.

(Comparative Example 8-2)

As an insect medium, about 5 g of aluminum lactate / 1 ethylene glycol slurry is 0.014mo 1% as aluminum atom with respect to the acid component in the polyester, and Irga no x 1425 (Ciba Polyester was prepared in the same manner as in Example 8-4, except that a 100 g / 1 ethylene glycol solution of tea chemical / resin ± ¾) was added to the acid component as Irganoxl 425, with 0.01 mo 1% added. Was polymerized. The polymerization time was 168 minutes, and the IV of the obtained PET was 0.61 dl / g, which was inferior to the catalytic activity.

(Evaluation results)

From the examples and comparative examples of the present invention, a solution in which aluminum carboxylate is dissolved Was used as a catalyst: ^ is excellent in polymerization activity and the quality of the obtained polyester is excellent, whereas ^^ used as a catalyst without dissolving results in poor polymerization activity. .. —

δ bacteria.

One

Education i.

s

Condition

0 8- [Industrial applications]

The polyester of the present invention includes, for example, interior fabrics represented by clothing fibers, curtains, carpets, futons, etc., textiles for industrial materials represented by bedding fibers, tire cords, ropes, etc., various fabrics, various knits, Fibers such as short-fiber nonwoven fabric and long-fiber nonwoven fabric, packaging films, industrial films, optical films, magnetic tape films, photographic films, street laminating films, contensor films, heat-shrink finolems, gasparia films , White films, films such as easy cut-finolene, non-metallic heat drawn bottles, heat-resistant drawn bottles, hollow molded articles such as direct blow bottles, gas barrier bottles, pressure-resistant bottles, heat-resistant bottles, etc., sheets such as A-PET and C-PET , Glass fiber reinforced polyester, elastomer Various molded products such as A ring plastics, and paints and adhesives can be applied to such.

Claims

Claim 1 1. It contains at least one selected from the group consisting of alkali metals and their compounds and alkaline earth metals and their compounds, and at least one selected from the group consisting of aluminum and its compounds, and Polyesters characterized by containing them in amounts satisfying the following formulas (1) and (2).

(1) 《Μ》 <0.05

(2) 〈く Μ》 Ζ 《Α 1》 ≤20

(<< Μ >> indicates the mole% of the total of the alkali metal atoms and the alkaline earth metal atoms with respect to the acid component in the polyester, and << Α 1 >> indicates the mole% of the aluminum atoms with respect to the acid component in the polyester. Is shown.)

2. The polyester according to claim 1, wherein the content of aluminum and its compound satisfies the following formula (3).

(3) 0.001≤ << ≤1 >> ≤0.05

(<< Α1 >> indicates mol% of aluminum atom to acid component in polyester

3. The polyester according to claim 1, wherein the polyester contains a total of 25 atomic% or less of an alkaline metal atom and an alkaline earth metal atom.

4. The polyester according to any one of claims 1 to 3, wherein the polyester does not contain an alkaline earth metal.

5. The polyesternole according to any one of claims 1 to 4, comprising a phosphorus compound.

6. At least one selected from the group consisting of alkaline earth metals and their compounds, and at least one selected from the group consisting of aluminum and its compounds; A polyester characterized by containing at least one selected from the group consisting of: and an amount that satisfies the following formulas (4) to (6).

(4) 0.1 ≤ [M] ≤ 150

(5) CM] / [A 1] ≤ 40 (6) [P] / [A 1] ≥0.01

(In the formulas (4) to (6), [M] indicates the total amount (ppm) of the alkali metal atoms and alkaline earth metal atoms contained in the polyester, and [A1] and [P] are the polyesters. The amounts (ppm) of aluminum atoms and phosphorus atoms contained in each are indicated.)

7. The polyester according to claim 6, wherein the content of aluminum and its compound satisfies the following formula (7).

(7) 0.5 ≤ [A 1] ≤ 500

(In the formula (7), [A1] indicates the amount (p pm) of aluminum atoms contained in the polyester.)

8. The polyester according to claim 6, wherein the content of the phosphorus compound satisfies the following formula (8).

(8) 1≤ [P] ≤ 1000

(In the formula (8),. [P] indicates the amount (ppm) of phosphorus atoms contained in the polyester.)

9. At least one selected from the group consisting of lithium, sodium, potassium, beryllium, magnesium, calcium, and their arsenic, and at least one selected from the group consisting of aluminum and its compounds, and phosphorus compounds Containing at least one selected from the group consisting of compounds, and having a total content of lithium, sodium, potassium, beryllium, magnesium, calcium, and their compounds of 7.0 mol or less in terms of metal atoms per 10 ^{βg of} polymer. A polyester, characterized in that:

10. The polyester according to claim 9, wherein the content of aluminum and its conjugate is 0.5 to 500 p in terms of aluminum atom.

11. The polyester according to claim 9, wherein the content of the phosphorus compound is 1 to 1000 ppm in terms of phosphorus atom.

12. A polyester containing at least one selected from the group consisting of aluminum and its conjugates, at least one selected from the group consisting of phosphorus compounds, and at least one selected from the group consisting of phenolic compounds. And a ratio of the amount of phosphorus atoms [P] (p pm) to the amount of aluminum atoms [Al] (p pm) contained in the polyester is in the range of 0.01 to 50. Nore.

13. The polyester according to claim 12, wherein the content of aluminum and its compound is 0.5 to 500 ppm in terms of aluminum atoms.

14. A polyester containing at least one selected from the group consisting of phosphorus compounds and at least one selected from the group consisting of phenolic conjugates, and wherein the total amount of metal atoms contained in the polyester is relative to the polyester Polyesternole characterized by being at most 100 ppm.

15. The polyester according to any one of claims 12 to 14, wherein the content of the phosphorus compound is l 1000 ppm in terms of a phosphorus atom.

16. The polyester according to any one of claims 12 to 15, wherein the phosphorus compound contained in the polyester and the phenol-based conjugate are bonded to each other.

17. A polyester containing at least one member selected from the group consisting of aluminum and its compounds and at least one member selected from the group consisting of phosphorus compounds, wherein the amount of phosphorus atoms contained in the polyester (ppm) is equal to the number of aluminum atoms. The ratio to the amount (ppm) of the polystyrene is in the range of 0.5 to 20.

18. The polyester according to claim 17, wherein the content of aluminum atoms contained in the polyester is in the range of 1 ppm to 100 pm.

19. The polyester according to claim 17 or 18, wherein the content of the phosphorus atom contained in the polyester is in the range of 5 ppm to 200 ppm.

20. The polyester according to claim 1 produced using the metal and Z or compound according to any of claims 1 to 19 as a catalyst.

21. A method for producing a polyester according to claim, wherein the metal and / or compound according to any one of claims 1 to 19 is used as a catalyst.

22. In producing polyester, at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds A method for producing a polyester, wherein one kind is added and a molar ratio of the added phosphorus atom and aluminum atom is in a range of 0.5 to 20.

23. The method for producing a polyester according to claim 22, wherein the addition amount of the aluminum atom is in the range of 0.001 mol% to 0.1 mol% based on the acid component constituting the polyester. .

24. The method according to claim 22 or 23, wherein the amount of the phosphorus atom added is in the range of 0.0005mo1% to 0.2mo1% based on the acid component constituting the polyester. Polyester manufacturing method.

25. Polyester made according to the method of any of claims 22 to 24, V.

26. A polyester polymerization catalyst comprising at least one selected from the group consisting of aluminum and its compounds and at least one selected from the group consisting of phosphorus compounds, wherein the molar ratio of phosphorus atoms to anolemmium atoms is 0. A polyester polymerized hornworm medium, which is in the range of 5 to 20.

27. A polyester produced using the catalyst of claim 26.

28. A method for producing a polyester, comprising using the catalyst according to claim 26 when producing the polyester.

29. A polyester polymerization catalyst comprising a polyester polymerization catalyst, wherein the thermal stability parameter (TS) of polyethylene terephthalate (PET) polymerized using the catalyst satisfies the following equation (9). .

(9) TS <0.20

(In the above formula, TS is a PET having an intrinsic viscosity ([IV] i) of 0.64-0.66 d 1 / g in a glass test tube, and dried under vacuum at 130 ° C for 12 hours. It is a value calculated from the intrinsic viscosity ([IV] _f ) after maintaining the molten state at 300 ° C for 2 hours under a non-flowing nitrogen atmosphere by the following formula.

TS = 0. 245 ([IV] f - 47 -. [IV] 1 47)

30. The polyester solvent according to claim 29, comprising at least one selected from the group consisting of phosphorus compounds as a component of the catalyst.

3 1. Polyester heavy metal consisting of metal or metal compound and phosphorus compound A polyester polymerization catalyst having an activity parameter (AP) satisfying the following expression (10).

(1 0) AP (min) <APX (min)

(In the above formula (10), AP is a polyethylene terephthalate having an intrinsic viscosity of 0.65 d 1 / g at a temperature of 275 ° C and a reduced pressure of 0.1 l Torr using a predetermined amount of catalyst. A PX indicates the time (min) required to polymerize PET under the same conditions as above using only the same amount of metal or metal compound among the above catalysts. ).

32. The polyester polymer according to claim 31, wherein the thermal stability parameter (TS) of polyethylene terephthalate (PET) polymerized using the catalyst satisfies the following expression (9). Insect medium.

(9) TS <0.20

3. The thermal acid stability parameter (TOS) of polyethylene terephthalate (PET) polymerized using the catalyst further satisfies the following formula (11). Polyester heavy vehicle described in any of 2 above.

(1 1) TO S <0.10

(In the above formula (11), TOS is a PET resin chip with a melt-polymerized IV of 0.64-0.66 d 1 / g. 0.3 g was dried in a vacuum for 12 hours, placed in a glass test tube, vacuum-dried at 70 ° C for 12 hours, and then heated under silica gel-dried air at 230 ° C for 15 minutes. From the following formula.

TOS = 0.245 ([IV] ί ¹ · ⁴⁷ _ [IV] ¹ · ⁴⁷ )

[IV] i and [IV] _fl refer to the IV (d \ / g) before and after the heating test, respectively. )

34. The polyester polymerization catalyst according to any one of claims 29 to 33, wherein the activity parameter (AP) satisfies the following formula (12).

(1 2) AP (min) <2T (min)

(In the above formula (1 2) ', AP polymerizes polyethylene terephthalate with an intrinsic viscosity of 0.65 d 1 / g at a temperature of 275 ° C and a pressure of 0.1 l Torr using a predetermined amount of catalyst. Do Is the time (min) required for the reaction, and T is the AP when the antimony atom is added to the acid component in the poly (ethylene terephthalate) by using antimony trioxide as a catalyst so that the antimony atom becomes 0.05 mol%. It is. )

35. The polyester polymerization catalyst according to any one of claims 29 to 34, wherein the catalyst comprises at least one selected from the group consisting of aluminum and a compound thereof as a component of the catalyst.

36. A polyester polymerization catalyst comprising a solution in which at least one selected from the group consisting of aluminum carboxylate is dissolved in water and / or an organic solvent.

37. The polyester polymerization catalyst according to claim 36, wherein the aluminum carboxylate is at least one selected from the group consisting of compounds having the structure of an aluminum salt of acetic acid.

38. The polyester polymerization catalyst according to claim 36, further comprising at least one selected from the group consisting of phosphorus compounds.

39. The catalyst for polymerization of polyesterol polymerization according to any one of claims 36 to 38, wherein a solution in which at least one selected from the group consisting of aluminum carboxylate is dissolved in water is used. Production method.

40. A method for producing a polyester, comprising using the polyester polymerization catalyst according to any one of claims 29 to 38 when producing the polyester.

41. A polyester produced using the polyester polymerization catalyst according to any one of claims 29 to 38.