CA1037634A - Polyester block copolymer film - Google Patents
Polyester block copolymer filmInfo
- Publication number
- CA1037634A CA1037634A CA203,758A CA203758A CA1037634A CA 1037634 A CA1037634 A CA 1037634A CA 203758 A CA203758 A CA 203758A CA 1037634 A CA1037634 A CA 1037634A
- Authority
- CA
- Canada
- Prior art keywords
- film
- block copolymer
- polyester block
- polyester
- segments
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/60—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from the reaction of a mixture of hydroxy carboxylic acids, polycarboxylic acids and polyhydroxy compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
- B29C48/08—Flat, e.g. panels flexible, e.g. films
Abstract
Abstract of the Disclosure A polyester block copolymer film having good slip characteristics and blocking resistance is disclosed. The film is prepared by melt extruding a polyester block copolymer to form a film and cooling the film in a melt state at a temperature of about 40 to 120°C to solidify it. The polyester block copolymer comprises crystalline polyester segments and non-crystalline polymer segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight of about 10,000 to 100,000, the melting point of a self-supporting high polymer substantially constituted with the monomer components of the said crystalline polyester segments along being not lower than about 200°C and the melting point or softening point of a polymer substantially constituted with the said non-crystalline polymer segments themselves being not higher than about 80°C. The resulting film can be used for the same purposes as conventional polyester block copolymer film, but it does not require lubricants in order to make the film easy to handle.
Description
~03763~L
- The present invention relates to a film having good slip characteristics and to a method of production of such a film. More particularly, the invention relates to a polyester block copolymer film, which has improved slip characteristics.
It is well known that polyester block copolymer films have various desirable physical and mechanical properties, such as good thermal adhesion, softness, impact strength, heat resistance, transparency and cold resistance. Ho~ever, the friction co-efficient between such films is exceedingly large, and the co-efficient between the film and a metal surface is also not good, which gives rise to various technical problems during the molding of the film and the processing thereof, such r as coating, lamination and bag formation. Further, these films disadvantageously have a large blocking property.
In order to improve these drawbacks, it is usual to apply a lubricant to the surface of the film, but a film treated in such a way has poor adhesion propertiés with a different film or a ~Rtal foil during lamination, and the heat seal properties of the film itself are also adversely affected.
20 Moreover, when such a film is used for packaging, the lubricant applied to the surface of the film sticks to the packaged materials. Thus, such a treated film is unsuitable, especially for the packaging of foods.
As a result of an attempt to overcome the said dis-advantages, it has now been found that, when a polyester block copolymer film which has been melt extruded and is in a molten state is cooled to cause solidification in a certain range of temperature, the resulting film is improved in slip character-istics as well as blocking resistance without any material 30 deterioration of the other physical and mechanical properties inherent thereto.
- The present invention relates to a film having good slip characteristics and to a method of production of such a film. More particularly, the invention relates to a polyester block copolymer film, which has improved slip characteristics.
It is well known that polyester block copolymer films have various desirable physical and mechanical properties, such as good thermal adhesion, softness, impact strength, heat resistance, transparency and cold resistance. Ho~ever, the friction co-efficient between such films is exceedingly large, and the co-efficient between the film and a metal surface is also not good, which gives rise to various technical problems during the molding of the film and the processing thereof, such r as coating, lamination and bag formation. Further, these films disadvantageously have a large blocking property.
In order to improve these drawbacks, it is usual to apply a lubricant to the surface of the film, but a film treated in such a way has poor adhesion propertiés with a different film or a ~Rtal foil during lamination, and the heat seal properties of the film itself are also adversely affected.
20 Moreover, when such a film is used for packaging, the lubricant applied to the surface of the film sticks to the packaged materials. Thus, such a treated film is unsuitable, especially for the packaging of foods.
As a result of an attempt to overcome the said dis-advantages, it has now been found that, when a polyester block copolymer film which has been melt extruded and is in a molten state is cooled to cause solidification in a certain range of temperature, the resulting film is improved in slip character-istics as well as blocking resistance without any material 30 deterioration of the other physical and mechanical properties inherent thereto.
- 2 ~37~;3~
According to one aspect of the invention there is provided a film of a polyester block copolymer, which has the following physical constants:
(1) Specific gravity 1.003~ 00 (2) Young's modulus (kg/cm2) not more than 1,500 (at 20C) (~) Brealcing strength (kg/cm2) 150-800 (at 20C) (4) ~reaking elongation (~o) not less than 300 (at 20C) (5) Impact strengkh (kg cm/25 u) not less than 8 (at 20C) (6) Thermal adhesion (kgr/cm) not less than 0.5 (at 20C) (7) Oxygen permeability constant 0.5 x 10 10 _ 100 (cc cm/crn2-sec.c~Hg) x 10-1 (at 30C) (8) Clarity (~) not less than 80 (9) ~aæe (~o) nok more than 2, the polyester block copolymer comprising crystalline polyester segments and non-crystalline poly~er segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight of about 10,000 to 100,000, the melting point of a high self-suppor~ing polymer substantially constituted with the monomer components of the said crystalline polyester segments alone being not lower than about 200C and the melting point or softening point of a polymer substantially constituked with the said non-crystalline polymer segments themselves being not higher than about 80C.
According to another aspect of the invention thexe is pxovided a process for preparing a polyester block copolymer film having good slip characteristics and blocking resistance, which comprises melt extruding a polyester block copolymer to ` ~Q~37~34 form a film and cooling the film in a melt state at a tem-perature of about 40 to 120C to solidify it, the polyester block copolymer comprising crystalline polyester segments and non-crystalline polymer segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight o~
about 10,000 to 100,000, the melting point of a high self- -supporting polymer substantially constituted with the monomer components of the said crystalline polyester seg~ents alone being not lower than about 200C and the melting point or softening point of a polymer substantially constituted with the said non-crystalline polymer segments themselves being not higher than about 80C.
Preferably the weight ratio of the crystalline and non-crystalline segments o~ 90 : 10 to 20 : 80 and the number average molecular weight of the block copolymer is about 30,000 to 70,000 when determined by a terminal group measuring procedure.
The crystalline polyester semgnets of the polyest~r block copolymer preferably have a number.average molecular weight of about 600 to 10,000. Examples of such are polyesters essen-tially consisting of aromatic dicarboxylic acid units (e.g.
terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid) and aliphatic, aromatic and/or alicyclic diol units (e.g. ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, decamethy-lene glycol, p-xylylene glycol, cyclohexanedimethanol), such polyesters as above but consisting further of hydroxycarboxylic acid units ~e.g. p-~-hydroxyethoxy)benzoic acid, p-hydroxy-benzoic acid), polyesters essentially consisting of aromatic ether dicarboxylic acid units (e.g. 1,2-bis(4,4'-dicarboxy-methylphenoxy)ethane, di(4-car~oxyphenoxy)ethane) and such diol units as mentioned above, polyesters essentially consist-ing of aromatic amidodicarboxylic acid units (e.g. bis(~-p-carboethoxyphenyl)terephthalimide) and such diol units as men-tioned above, etc.
The non-crystalline polymer segments of the polyester block copolymer preferably have a nu~ber avexage molecular weight of not less than about 400. Thus, they usually have a number average molecular weight of about 400 to 8,000, and more preferably of about 700 to 5,000. Examples of such are poly-ethers (e.g. polyethylene glycol, polypropylene glycol, poly-tetramethylene glycol, ethylene oxide-propylene oxide copolymer, ethylene oxide-tetrahydrofuran copolymer), aliphatic polyesters (e.g. polyneopentyl azelate, polyneopentyl adipate, polyneopentyl sebacate), polylactones (e.g. poly-~-caprolactone, polypivalo-lactone), etc.
The polyester block copolymer can be prepared by a conventional procedure for polycondensation. Pre~
ferred examples of such procedure are as follows:
(1) Heating a mixture of a dimethyl ester of an aromatic acid, a diol capable of forming the non-crystalline polymer se~ments and a diol of low molecular weight at a temperature of about 150 to 240C in the presence of a cata-iyst for ester e~change polycondensation, removing the methanol produced by the ester exchange and subjecting the resulting prepolymer to vacuum distillation so as to eliminate excess diol of low molecular weight to produce the polyester klock copolymer;
(2) Heating a mixture of a polymer capable of forming the crystalline polyester segments and a polymer capable of forming the non-crystalline polymer segments in the presence of a chain extender reactive with the terminal groups of the said - 5 ~
~Q3763~
polymers, and removing volatile components under a highly reduced pressure to produce the polyester block copolymer; and
According to one aspect of the invention there is provided a film of a polyester block copolymer, which has the following physical constants:
(1) Specific gravity 1.003~ 00 (2) Young's modulus (kg/cm2) not more than 1,500 (at 20C) (~) Brealcing strength (kg/cm2) 150-800 (at 20C) (4) ~reaking elongation (~o) not less than 300 (at 20C) (5) Impact strengkh (kg cm/25 u) not less than 8 (at 20C) (6) Thermal adhesion (kgr/cm) not less than 0.5 (at 20C) (7) Oxygen permeability constant 0.5 x 10 10 _ 100 (cc cm/crn2-sec.c~Hg) x 10-1 (at 30C) (8) Clarity (~) not less than 80 (9) ~aæe (~o) nok more than 2, the polyester block copolymer comprising crystalline polyester segments and non-crystalline poly~er segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight of about 10,000 to 100,000, the melting point of a high self-suppor~ing polymer substantially constituted with the monomer components of the said crystalline polyester segments alone being not lower than about 200C and the melting point or softening point of a polymer substantially constituked with the said non-crystalline polymer segments themselves being not higher than about 80C.
According to another aspect of the invention thexe is pxovided a process for preparing a polyester block copolymer film having good slip characteristics and blocking resistance, which comprises melt extruding a polyester block copolymer to ` ~Q~37~34 form a film and cooling the film in a melt state at a tem-perature of about 40 to 120C to solidify it, the polyester block copolymer comprising crystalline polyester segments and non-crystalline polymer segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight o~
about 10,000 to 100,000, the melting point of a high self- -supporting polymer substantially constituted with the monomer components of the said crystalline polyester seg~ents alone being not lower than about 200C and the melting point or softening point of a polymer substantially constituted with the said non-crystalline polymer segments themselves being not higher than about 80C.
Preferably the weight ratio of the crystalline and non-crystalline segments o~ 90 : 10 to 20 : 80 and the number average molecular weight of the block copolymer is about 30,000 to 70,000 when determined by a terminal group measuring procedure.
The crystalline polyester semgnets of the polyest~r block copolymer preferably have a number.average molecular weight of about 600 to 10,000. Examples of such are polyesters essen-tially consisting of aromatic dicarboxylic acid units (e.g.
terephthalic acid, isophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid) and aliphatic, aromatic and/or alicyclic diol units (e.g. ethylene glycol, propylene glycol, tetramethylene glycol, pentamethylene glycol, 2,2-dimethyl-trimethylene glycol, hexamethylene glycol, decamethy-lene glycol, p-xylylene glycol, cyclohexanedimethanol), such polyesters as above but consisting further of hydroxycarboxylic acid units ~e.g. p-~-hydroxyethoxy)benzoic acid, p-hydroxy-benzoic acid), polyesters essentially consisting of aromatic ether dicarboxylic acid units (e.g. 1,2-bis(4,4'-dicarboxy-methylphenoxy)ethane, di(4-car~oxyphenoxy)ethane) and such diol units as mentioned above, polyesters essentially consist-ing of aromatic amidodicarboxylic acid units (e.g. bis(~-p-carboethoxyphenyl)terephthalimide) and such diol units as men-tioned above, etc.
The non-crystalline polymer segments of the polyester block copolymer preferably have a nu~ber avexage molecular weight of not less than about 400. Thus, they usually have a number average molecular weight of about 400 to 8,000, and more preferably of about 700 to 5,000. Examples of such are poly-ethers (e.g. polyethylene glycol, polypropylene glycol, poly-tetramethylene glycol, ethylene oxide-propylene oxide copolymer, ethylene oxide-tetrahydrofuran copolymer), aliphatic polyesters (e.g. polyneopentyl azelate, polyneopentyl adipate, polyneopentyl sebacate), polylactones (e.g. poly-~-caprolactone, polypivalo-lactone), etc.
The polyester block copolymer can be prepared by a conventional procedure for polycondensation. Pre~
ferred examples of such procedure are as follows:
(1) Heating a mixture of a dimethyl ester of an aromatic acid, a diol capable of forming the non-crystalline polymer se~ments and a diol of low molecular weight at a temperature of about 150 to 240C in the presence of a cata-iyst for ester e~change polycondensation, removing the methanol produced by the ester exchange and subjecting the resulting prepolymer to vacuum distillation so as to eliminate excess diol of low molecular weight to produce the polyester klock copolymer;
(2) Heating a mixture of a polymer capable of forming the crystalline polyester segments and a polymer capable of forming the non-crystalline polymer segments in the presence of a chain extender reactive with the terminal groups of the said - 5 ~
~Q3763~
polymers, and removing volatile components under a highly reduced pressure to produce the polyester block copolymer; and
(3) ~leating a mixture of a polymer capable of forming the crystalline polyester segments and a lactone so as to effect a rlng opening polyMerization of the lactone and an ester ex-change at the same time to produce the polyester block copolymer, etc.
Examples of the polyester block copolymer include polyethylene terephthalate-polyethylene oxide block copolymer, polytetramethylene terephthalate-polyethylene oxide block copolymer, polyethylene terephthalate-polytetramethylene oxide block copolymer, polytetramethylene terephthalate-polytetra-methylene oxide block copolymer, polyethylene terephthalate-polyethylene oxide propylene oxide block copolymer, polyethylene terephthalate-poly-E-caprolactone block copolymer, polytetra-methylene terephthalate-poly-E-caprolactone block copolymer, polyethylene terephthalate-polypivalolactone block copolymer, polyethylene terephthalate-polyethylene adipate block copolymer, polyethylene terephthalate-polyneopentyl sebacate block copolymer, polytetramethylene terephthalate-polyethylene dodecanate block copolymer, polytetramethylene terephthalate-polyneopentyl dode-canate block copolymer, a block copolymer consistlng of a poly-ester of di(4-carboxy-phenoxy~ethane with ethylene glycol and polyethylene glycol, a block copolymer consisting of a polyester of bis(N-p-carbethoxyphenyl)adipamide with ethylene glycol and polyethylene glycol, etc. Polytetramethylene terephthalate-polytetramethylene oxide (90 : 10 - 40 : 60 by weight) block copolymer is most advantageously employed for the preparation of a packaging film.
3a In order to prepare a film, the polyester block copolymer is melt extruded by means of a conventional extruder, ~3~7tii34 for instance, through a T die. Prior to such melt extruding, the polyester block copolymer should preferably have a water content 0.2 ~ by weight or less. Otherwise, the polyester block copolymer will be hydrolyzed and thus the surface of the resulting film will be uneven, colored and foamy. The temperature employed for melting the copolymer is usually from about 160 to 280C.
The extruded film in a molten state is then cooled at a temperature from about 40 to 120C to cause solidification.
When the cooling is carried out at a temperature of about 0 to 40C, the slip characteristics of the resulting film are inferior so that wrinkles are formed on taking up the fllm and blocking is often produced. In order to effect cooling in the desired range of temperature, any cooling means (e.g. cooling roll, cooling bath) may be used. When a cooling roll is used, the type of surface is not partic~llarl~ important and may be a planished or roughened surface. In order to enhance the slip characteristics, however, the use of a cooling roll having a roughened surface is favorable. The film distance between the die of the extruder and the position at which the cooling under the said condition starts is preferably as short as possible to avoid the production of neck-in in the extruded film, and it is normally from about 10 to 100 mm. The thickness of the film may be appropriately selected according to the intended use and, from a practical viewpoint, is usually from about 30 to 500 ~, more preferably from about 30 to 100 ~. The cooled and solidified film is then taken up in a conventional manner without producing any wrinkles.
The thus obtained film has very good slip character-istics. This is probably due to the crystallization which occurs partially at the surface by the specific cooling method. h~hile the heat seal property of the conventional thermoplastic films is , 37~34 lowered when any crystallization occurs, the film of this invention ~aintains a sufficiently good heat seal property.
In order to further improve the slip characteristics of the film, any inorganic material in the form of fine particles may be incorporated into the polyester block copolymer. Examples of such inorganic materials are oxides and salts of the metals belonging to Groups II, III and IV of the periodic table (short period). More speci~ically, suitable ~aterials include MgO, MgC03, MgS04, CaCo3, CaSo4, BaS04, A1203, SiO2, Ti~2, talc, clay, etc. The average particle size of the inorganic material is preferably from about 0.1 to 10 ~. When the particle size is smaller, the material may not be suf~iciently effective in enhancing the slip characteristics. When larger, the trans-parency and haze of the film may be adversely a~fected and a glittering effect may be produced. Thus, the resulting appear-ance may be un~avorable. The amount of the inorganic material to be incorporated is preferably in a range of about 0.01 to 5 by weight based on the weight of the polyester block copolymer.
A smaller amount may not be effective in enhancing the slip characteristics, while a larger amount may reduce the transparency, thermal adhesion and adhesion to other films.
~ he incorporation o~ the inorganic material may be ef~ected, for instance, by adding the same to any of the starting materials prior to the polymerization~ adding the same to a mixture o~ the starting materials on the polymeri-zation, admixing the same into the polyester block copolymer prior to the melt extrusion, or the like.
Furthermore, any other addi~cives such as stabilizers, ultraviolet ray absorbers, antistatic agents, pigments and thermoplastic resins may be also incorporated into the poly-ester block copolymer, when desired.
;~ ~ 8 -~.
1~3763~ `
The ~ilm of this invention po~sesses the following physical constants:
Specific gravity 1.003-1.300 Young's modulus (kg/cm2) 1,500 or less (preferably 300 to 1000) (at 20~) Breaking strength (kg/cm2) 150-800 (at 20C) Breaking elongation (~0) 300 or more (preferabl~ 300 to 1200) (at 20C) Impact strength (kg.cm/25 ~) 8 or more (preferably 8 to 15) (at 20C) Thermal adhesion (kg/cm) 0.5 or more (pre~erably 0.5 to 3.0) (at 200a) Oxygen permeability 0 5 10-1 constan~ - 100 x 10-(cc.cm/cm2.sec.cmHg~ (at ~0a) Clarity (~O) 80 or more Haze (%) 2 or less Further, the blocking strength of the film should not be more than 1.3 g/cm, usually from about 0.8 to 1.3 g/cm, when no inorganic material i5 incorporated into the film material, and should not be more than 0.5 g/cm, when an inorganic material is present within the preferred range. When an inorganic material is present, the film shows a static friction coefficient o~
about 0.4 to 1.0 and a kinetic friction coefficient of about 0.5 to 2Ø
The film of this invention is exceedingly soft and has goo~ impact strength, cold resistance, heat resistance and thermal adhesion. Its slip characteristics are particularly notable. Due to such advantageous properties, the film may be employed for various uses either alone or as a laminated product.
When the film is laminated with a different polymer film or a , ~ ~ g _ 1C~3763~
metal foil, good adhesion between the laminated layers is obtained because of the absence of any lubricant. In addition, the film exhibits an excellent heat seal property when heat sealed with another film of the same or different material.
Moreover, the film is quite suitable for pachaging foods since no lubricant is applied to the surface thereof.
Practical and presently preferred embodiments of the invention are illustratively shown in the following Examples wherein parts are by weight. The determination of the properties was effected according to the following procedures:-(1) Melting point; The specimen was heated in amicro-melting point-measuring apparatus (manufactured by Yanagimoto Seisakusho K.K.~ while elevating the temperature at a rate of 1C/min. The observation was made by a polarizing micro-scope, and the temperature at which the field of view became dark was taken as the melting point.
(2) Softening point: The specimen was heated in the apparatus as above while elevating the temperature at a rate of 1C/min. The observation was made by a microscope, and the temperature at which softening and deforming started was noted.
(3) F~educed viscosity: A determination was made at 30C on a 0.2 % phenol-tetrachloroethane (6 : 4) solution.
Examples of the polyester block copolymer include polyethylene terephthalate-polyethylene oxide block copolymer, polytetramethylene terephthalate-polyethylene oxide block copolymer, polyethylene terephthalate-polytetramethylene oxide block copolymer, polytetramethylene terephthalate-polytetra-methylene oxide block copolymer, polyethylene terephthalate-polyethylene oxide propylene oxide block copolymer, polyethylene terephthalate-poly-E-caprolactone block copolymer, polytetra-methylene terephthalate-poly-E-caprolactone block copolymer, polyethylene terephthalate-polypivalolactone block copolymer, polyethylene terephthalate-polyethylene adipate block copolymer, polyethylene terephthalate-polyneopentyl sebacate block copolymer, polytetramethylene terephthalate-polyethylene dodecanate block copolymer, polytetramethylene terephthalate-polyneopentyl dode-canate block copolymer, a block copolymer consistlng of a poly-ester of di(4-carboxy-phenoxy~ethane with ethylene glycol and polyethylene glycol, a block copolymer consisting of a polyester of bis(N-p-carbethoxyphenyl)adipamide with ethylene glycol and polyethylene glycol, etc. Polytetramethylene terephthalate-polytetramethylene oxide (90 : 10 - 40 : 60 by weight) block copolymer is most advantageously employed for the preparation of a packaging film.
3a In order to prepare a film, the polyester block copolymer is melt extruded by means of a conventional extruder, ~3~7tii34 for instance, through a T die. Prior to such melt extruding, the polyester block copolymer should preferably have a water content 0.2 ~ by weight or less. Otherwise, the polyester block copolymer will be hydrolyzed and thus the surface of the resulting film will be uneven, colored and foamy. The temperature employed for melting the copolymer is usually from about 160 to 280C.
The extruded film in a molten state is then cooled at a temperature from about 40 to 120C to cause solidification.
When the cooling is carried out at a temperature of about 0 to 40C, the slip characteristics of the resulting film are inferior so that wrinkles are formed on taking up the fllm and blocking is often produced. In order to effect cooling in the desired range of temperature, any cooling means (e.g. cooling roll, cooling bath) may be used. When a cooling roll is used, the type of surface is not partic~llarl~ important and may be a planished or roughened surface. In order to enhance the slip characteristics, however, the use of a cooling roll having a roughened surface is favorable. The film distance between the die of the extruder and the position at which the cooling under the said condition starts is preferably as short as possible to avoid the production of neck-in in the extruded film, and it is normally from about 10 to 100 mm. The thickness of the film may be appropriately selected according to the intended use and, from a practical viewpoint, is usually from about 30 to 500 ~, more preferably from about 30 to 100 ~. The cooled and solidified film is then taken up in a conventional manner without producing any wrinkles.
The thus obtained film has very good slip character-istics. This is probably due to the crystallization which occurs partially at the surface by the specific cooling method. h~hile the heat seal property of the conventional thermoplastic films is , 37~34 lowered when any crystallization occurs, the film of this invention ~aintains a sufficiently good heat seal property.
In order to further improve the slip characteristics of the film, any inorganic material in the form of fine particles may be incorporated into the polyester block copolymer. Examples of such inorganic materials are oxides and salts of the metals belonging to Groups II, III and IV of the periodic table (short period). More speci~ically, suitable ~aterials include MgO, MgC03, MgS04, CaCo3, CaSo4, BaS04, A1203, SiO2, Ti~2, talc, clay, etc. The average particle size of the inorganic material is preferably from about 0.1 to 10 ~. When the particle size is smaller, the material may not be suf~iciently effective in enhancing the slip characteristics. When larger, the trans-parency and haze of the film may be adversely a~fected and a glittering effect may be produced. Thus, the resulting appear-ance may be un~avorable. The amount of the inorganic material to be incorporated is preferably in a range of about 0.01 to 5 by weight based on the weight of the polyester block copolymer.
A smaller amount may not be effective in enhancing the slip characteristics, while a larger amount may reduce the transparency, thermal adhesion and adhesion to other films.
~ he incorporation o~ the inorganic material may be ef~ected, for instance, by adding the same to any of the starting materials prior to the polymerization~ adding the same to a mixture o~ the starting materials on the polymeri-zation, admixing the same into the polyester block copolymer prior to the melt extrusion, or the like.
Furthermore, any other addi~cives such as stabilizers, ultraviolet ray absorbers, antistatic agents, pigments and thermoplastic resins may be also incorporated into the poly-ester block copolymer, when desired.
;~ ~ 8 -~.
1~3763~ `
The ~ilm of this invention po~sesses the following physical constants:
Specific gravity 1.003-1.300 Young's modulus (kg/cm2) 1,500 or less (preferably 300 to 1000) (at 20~) Breaking strength (kg/cm2) 150-800 (at 20C) Breaking elongation (~0) 300 or more (preferabl~ 300 to 1200) (at 20C) Impact strength (kg.cm/25 ~) 8 or more (preferably 8 to 15) (at 20C) Thermal adhesion (kg/cm) 0.5 or more (pre~erably 0.5 to 3.0) (at 200a) Oxygen permeability 0 5 10-1 constan~ - 100 x 10-(cc.cm/cm2.sec.cmHg~ (at ~0a) Clarity (~O) 80 or more Haze (%) 2 or less Further, the blocking strength of the film should not be more than 1.3 g/cm, usually from about 0.8 to 1.3 g/cm, when no inorganic material i5 incorporated into the film material, and should not be more than 0.5 g/cm, when an inorganic material is present within the preferred range. When an inorganic material is present, the film shows a static friction coefficient o~
about 0.4 to 1.0 and a kinetic friction coefficient of about 0.5 to 2Ø
The film of this invention is exceedingly soft and has goo~ impact strength, cold resistance, heat resistance and thermal adhesion. Its slip characteristics are particularly notable. Due to such advantageous properties, the film may be employed for various uses either alone or as a laminated product.
When the film is laminated with a different polymer film or a , ~ ~ g _ 1C~3763~
metal foil, good adhesion between the laminated layers is obtained because of the absence of any lubricant. In addition, the film exhibits an excellent heat seal property when heat sealed with another film of the same or different material.
Moreover, the film is quite suitable for pachaging foods since no lubricant is applied to the surface thereof.
Practical and presently preferred embodiments of the invention are illustratively shown in the following Examples wherein parts are by weight. The determination of the properties was effected according to the following procedures:-(1) Melting point; The specimen was heated in amicro-melting point-measuring apparatus (manufactured by Yanagimoto Seisakusho K.K.~ while elevating the temperature at a rate of 1C/min. The observation was made by a polarizing micro-scope, and the temperature at which the field of view became dark was taken as the melting point.
(2) Softening point: The specimen was heated in the apparatus as above while elevating the temperature at a rate of 1C/min. The observation was made by a microscope, and the temperature at which softening and deforming started was noted.
(3) F~educed viscosity: A determination was made at 30C on a 0.2 % phenol-tetrachloroethane (6 : 4) solution.
(4) Breaking strength and breaking elongation: A
determination was carried out at a temperature of 20C at a relative humidity of 65 % by a tensile testing machine ("Tensilon ~TM-lll" - Trade Mark - manufactured by Toyo Sei};i K.K.) at a crosshead speed of 500 mrl/min.
determination was carried out at a temperature of 20C at a relative humidity of 65 % by a tensile testing machine ("Tensilon ~TM-lll" - Trade Mark - manufactured by Toyo Sei};i K.K.) at a crosshead speed of 500 mrl/min.
(5) Impact strength: A determination was made at a temperature of 20C at a relative humidity of 65 ~ by a film impact tester (manufactured by Toyo Seiki K.K.).
(6) Clarity and haze: Using a ligh-t transmission ~t ~ -- 1 0 -~37~:i39~
measuring apparatus or the intesrating sphere type, the amount of incident light ~Tll, the total amount of transmitted light (T2], the amount of light scattered by the apparatus (T3~ and the amount of light scattered by the apparatus and the specimen (T4) were determined, and on the basis of these values, a calculation is effected according to the following equations:
Clarity (Tt~ = T ~ 100 (g~
Transmission of = T4 - T3 (T2/Tl) scattering rays (T~ rl x 100 (%) Ha~e = Td x 100 (%)
measuring apparatus or the intesrating sphere type, the amount of incident light ~Tll, the total amount of transmitted light (T2], the amount of light scattered by the apparatus (T3~ and the amount of light scattered by the apparatus and the specimen (T4) were determined, and on the basis of these values, a calculation is effected according to the following equations:
Clarity (Tt~ = T ~ 100 (g~
Transmission of = T4 - T3 (T2/Tl) scattering rays (T~ rl x 100 (%) Ha~e = Td x 100 (%)
(7) Gas transmission: A determination was made at 30C by a duplex gas transmission measuring apparatus (manu-factured by Rika Seiki Kogyo K.K.~ according to ASTM ~American Society for Tes-ting and Ma-terials) D-1434-5~.
(8) Specific gravity: A determination was made according to JIS (Japanese Industrial Standar~) K-6911.
(9) Thermal adhesion: The specimen was subjected to thermal adhesion at 250C for 1 second under a pressure of 2.0 kg/cm by a heat sealer and, a~ter allowing the specimen to stand for 24 hours, the heat seal strength was determined by a 20 "Tensilon".
(10) Blocking streng-th: A determination was made according to ASTI~; D-1893 in the following manner. Two film specimens (8 cm x 12 cm~ were placed one on top of the other and placed between two glass plates, and a load of 2.0 kg is applied thereto. After 24 hours at a temperature of 40C and at a relative humidity of 65 %, the films were separated from each other by a rod of 6.3 mm in diameter at a rate of 100 nun/min, and the strength required for complete separation was determined by "Tensilon". The measurement was repeated three times, and 30 the average value of the strength per unit width was taken as
- 11 -~ ;
~ ~37634 the blocking strength.
(11) Friction coefficient: A determination was made according to AST~l D-1894-63 but, since the film specimen was soft, the weight of the thread was 38 g/6.3 cm x 6.3 cm. The friction coefficient between the chill faces of the two films was measured at a rate of 20 cm/min.
Example 1 Dimethyl terephthalate (10,000 parts), 1,4-butanediol (5,800 parts~ and titanium tetrabutoxide (6 parts) were charged 10 to a stainless steel reaction vessel,and the contents were heated at 140 to 230C in a nitrogen atmosphere to complete an ester exchange reaction. The reaction mixture was added to a r mixture of polytetramethylene oxide (molecular weight, 1,000;
3!800 parts) and an antioxidant ("Irganox 1010" manufactured by Geigy)(30 parts) previously heated to 230C. The resultin~
mixture was stirred while elevating the temperature up to 245C
and gradually reducing the pressure to about 0.1 mmHg, and a polycondensation was effected for 2 hours under these conditions.
The polymer thus produced was cooled with water, pelletized into 20 a cylindrical form of 3 mm in diameter and 3 mm in length and dried at 80C under a pressure of about 0.1 mn~lg for 5 hours to give polytetramethylene terephthalate-polytetramethylene oxide block copolymer (hereinafter referred to as "polyester block copolymer (I)"). Reduced viscosity, 1.74 dl/g. ~elting point, 215C.
The polyester block copolymer (I) was,after being dried well under reduced pressure so as to obtain a water content of 0.005 % by weight, formed into a film by an extruder in which the diameter of the screw was 40 mm 0, the width of the T die was 500 mm and the lip was 0.7 mm under the following conditions:
temperature of barrel, 240C; temperature of adapter, 245C;
~ ~37634 the blocking strength.
(11) Friction coefficient: A determination was made according to AST~l D-1894-63 but, since the film specimen was soft, the weight of the thread was 38 g/6.3 cm x 6.3 cm. The friction coefficient between the chill faces of the two films was measured at a rate of 20 cm/min.
Example 1 Dimethyl terephthalate (10,000 parts), 1,4-butanediol (5,800 parts~ and titanium tetrabutoxide (6 parts) were charged 10 to a stainless steel reaction vessel,and the contents were heated at 140 to 230C in a nitrogen atmosphere to complete an ester exchange reaction. The reaction mixture was added to a r mixture of polytetramethylene oxide (molecular weight, 1,000;
3!800 parts) and an antioxidant ("Irganox 1010" manufactured by Geigy)(30 parts) previously heated to 230C. The resultin~
mixture was stirred while elevating the temperature up to 245C
and gradually reducing the pressure to about 0.1 mmHg, and a polycondensation was effected for 2 hours under these conditions.
The polymer thus produced was cooled with water, pelletized into 20 a cylindrical form of 3 mm in diameter and 3 mm in length and dried at 80C under a pressure of about 0.1 mn~lg for 5 hours to give polytetramethylene terephthalate-polytetramethylene oxide block copolymer (hereinafter referred to as "polyester block copolymer (I)"). Reduced viscosity, 1.74 dl/g. ~elting point, 215C.
The polyester block copolymer (I) was,after being dried well under reduced pressure so as to obtain a water content of 0.005 % by weight, formed into a film by an extruder in which the diameter of the screw was 40 mm 0, the width of the T die was 500 mm and the lip was 0.7 mm under the following conditions:
temperature of barrel, 240C; temperature of adapter, 245C;
- 12 -", . .~
~3~7~3~L
temperature of T die, 250C; rotation of screw, 42 rpm; film distance between T die and cooling roll, 40 mm; temperature of cooling roll, 70C; take-up rate, 1.9 m/min. A cooling roll having a surface plated with chromium was used. For effecting the cooling of the film uniformly, an air-knife was used on the cooling roll. The take-up of the film was satisfactorily effected without the formation of wrinkles. The properties of r~
the film are shown in Table 1.
Example 2 Using the polyester block copolymer ~I), the production of a film was carried out in the same manner as in Example 1 but changing the temperature of the cooling roll to 40C. The take-up of the film was effected satisfactoril~. The properties of the film are shown in Table 1.
Reference Example l ~ sing -the polyester block copolymer (I), the produc-tion of a film was carried out in the same manner as in Example 1 but changing the temperature of the cooling roll to 19.5C.
The obtained film was excellent in clarity, but the amount of slip between the film and a metal roll and the amount of slip between two layers of the films were insufficient so that wrinkles were formed on taking up the film and a uniform take-up was thus difficult. The properties of the film are shown in Table 1. As shown, the slip characteristics and the blocking resistance are inferior, although the other properties are excellent.
~ - 13 -~3763~
Table 1 Example Example Reference 1 2 Example T~ickness (~) 54.7 55.9 60.3 Clarity (~o) 81.7 86.4 90.5 characterlstics ~ood Good Bad strength (g/cm~ 0.86 1.02 2.54 Specific gravity 1.229 1.228 1.228 Breaking 2 620 590 580 elongation (~) 470 500 520 strength (kg.cm/25 ~) 16.6 17.1 16.
Oxygen permeability constant l.OxlO 10 l.OxlO 10 l.lxlO 10 (cc.cm/cm2.sec.cmHg) Water vapor trans-mission (g/m2.24 hr) 340 355 368 ~calculated as 25 ~) _ 14 -1~1!3'7~i3~
E~ample 3 Dimethyl terephthalate l6200 partsl, 1,4-butanediol (4000 parts) and titanium tetrabutoxide ~5.5 parts~ were charged to a stainless steel reaction vesse:L, and the contents were heated at 140 to 230C in a nitrog-en atmosphere to complete an ester exchange reaction.. The reaction mixture was added to a mixture of polytetramethylene oxide (molecular weight, r 1000; 5000 parts) and an antioxidant ("Sumilizer ~HT" - Trade Mark - manufactured by Sumitomo Chemical Company, Limited) (23 parts~ previously heated to 230C. The resulting mixture was stirred while elevating the temperature to 245C and gradually reducing the pressure to about 0.1 n~Hs, and a polycondensation was effected for 2 hours under these conditions. The produced polymer was drie~ at ~0C under a pressure of about 0.1 mmHg for 5 hours to give polytetramethylene terephthalate-polytetra-methylene oxide block copolymer (hereinafter referred to as "polyester block copolymer (II~"~. Reduced viscosity, 1.99 dl/g.
Melting point, 205C.
The polyester block copolymer (II) was,after being dried well under a reduced pressure to obtain a water content of 0.005 ~ by weight, formed into a film by the use of the same extruder as in Example 1 under the following conditions:
temperature of barrel, 240C; temperature of adapter, 245C;
temperature of T die, 250C; rotation of screw, 42 rpm; fi~m distance between T die and cooling roll, ao mm; temperature of cooling roll, 80C; take-up rate, 1.9 m/min. The amount of slip between the film and a metal roll and the amount of slip between different layers of the film were good, and the take-up of the film was effected satisfactorily. The properties of the film are shown in Table 2.
~ - 15 -~37~3~
Reference Example 2 ~ sing the polyester bloek copolymer (II~, the pro-duction of a film was effected in the same manner as in Example 3 but changing the temperature of the cooling roll to 19.5C.
The obtained film was exeellent in elarity but the slip characteristics were inferior so that wrinkles were formed on taking up the film and a uniform take-up was difficult. The properties of the film are shown in Table 2. ~.s shown, the slip eharaeteristies and the bloeking resistance are inferior, although the other properties are excellent.
Table 2 .
Example Referenee . 3 Exarnple Thickness ( ~1) 54.3 59.5 Clarity ('~/o) 81.2 90.1 Take-up Good Bad eharaeteristies Bloeking 1.26 4.50 strength (g/em) Speeifie 1.176 1.174 gravity Breaking 5 5 5 3 strcngth (kg/em ) Breaking 590 1 630 elongation (~0) l Impaet NB ~B
strength (kg.em/25 ~) Oxygen permeability 10 -10 eonstant 14.4xlO- 4.7xlO
(ec.em/em2.see.cmHg) Water vapor tr~ns- I
mission (g/m2.24 hr) ~ 665 680 (ealeulated as 25 ~
~763~L
Example 4 A solution of 15 % by weight (as the solid content) of a 95 : 5 by weight ~as the solid content~ mixture of a polyester copolymer adhesive ("Vylon 300" - ~rade Mark - manu-factured by Toyo Boseki K.K.) and an isocyanate adhesive ("Collonate L" - Trade Mark - manufactured by Nippon Polyurethane K.K.) in ethyl acetate was applied onto a biaxially stretched film of polyethylene terephthalate (thickness, 19 ~), by a gravure roll (100 mesh x 40 ~, and the film was passed through a drier of 4 m in length at a rate of 30 m/min. The unstretched polyester block copolymer film as obtained in Example 1 or 3 was laminated on the dried film under dry conditions at a nip temperature of 90 to 95C under a nip pressure of 5 kg/cm2.
The surEace of the unstretched polyester block copolymer film layer of the thus obtained film was heat sealed with that of the other thus obtained film. The heat seal strength is shown in Table 3.
Table 3 _ , Heat seal strength (g/cm) Composition o~ ~ilm __ A_ _ _ . _ . .. _ Polyethyleneterephthalate(l9~l)/ 4000 polyester bloclc copolymer (I)(54.7~): _ 500 _......... _ __ Polyethyleneterephthalate(l9~)/ 000 00 polyester block copolymer (II)(54.3~) . 3 5 I .
When these la~.inated films were treated with boiling water at 130C for 30 minutes in an autoclave, no separation of the laminated layers was observed.
Example 5 ._ An ester exchange reaction and a polycondensation were effected in the same manner as in Example 1 but :Eine particles of silica ("Syloid 226" ~ Trade Mark - manufac-tured . ~ !.
.~,.. .
1~37~;~4 by Fuji Devison Co., ~td.; average particle size, 1.5 ~) (75 parts) were incorporated into the starting materials to obtain a polytetramethylene terephthalate-polytetramethylene oxide block copolymer containing 0.5 % by weight of fine particles of silica (hereinafter referred to as "polyester block copolymer (III)").
The polyester block copolymer (III) was admixed with the polyester block copolymer (I) so as to obtain a predetermined silica content. The resultant mixture was, after being dried well under reduced pressure to obtain a water content of 0.005 %
by weight, formed into a film by an extruder in which the dia-meter of screw was 20 mm 0, the width of T die was 120 mm and the lip was 0.5 mm under the following conditions: temperature of barrel, 250C; temperature of adapter, 250C; temperature of T die, 250C; rotation of screw, 36 rpm; film distance between T die and cooling roll, 40 mm; temperature o~ coolinc3 roll, 60C;
take-up rate, 1.7 m/min. The thickness, clarity, haze and friction coefficient of the film are shown in Table 4. As shown, the incorporation of fine particles of silica can afford a film excellent in slip characteristics while maintaining a good transparency.
Reference Example 3 The polyester block copolymers (I) and (III) were mixed together to obtain a mixture having a silica content of 0.02 ~ by weight or 0.05~ by weight. After drying, the mixture was formed into a film under the same conditions as in Example 5 but changing the temperature of the cooling roll to 19.2C. The properties of the film are shown in Table 4. As shown, the film was excellent in clarity but inferior in slip characteristics, compared with the corresponding film obtained in Example 5.
~3~634 Table 4 Exam- Silioa Thick- Clarity Haze Static ~inetic Blooklng ple content ness (~) (c/O) fric- fric- strength ~o. (% by (~) tion tion (g/cm~
weight) coef-. coef-_ _ _ ~ ~ ficient ficient _ ~ ~
0.02 55 88.4 2.3 1.73 0.98 0.52 0.05 55 85.4 5.1 1.16 0.58 0.~3 0.10 49 89.0 ~.0 0.49 0.40 0.20 0.25 56 86.0 9.1 0.49 0.44 0.10 0.5 62 87.7 8.2 0.45 0.42 0 Ref-ence 0.02 60 89.9 0.7 Stick Stick 0.90 Exam- . slip sl}p er-ence 0.05 61 90.1 1.6 1.65 0.92 0.82 kxam- . . _ 7~3~
Example 6 An ester exchange reaction and a polycondensation were effected as in Example 3 but fine particles of silica ("Syloid 266" manufactured by Fuji Devison Co., Ltd.; average particle size, 1.5 ~) ~57.5 parts) were incorporated into the starting materials to obtain a polytetramethylene terephthalate-poly-tetramethylene oxide block copolymer containing 0.5 ~ by weight of fine particles of silica (hereinafter referred to as "poly-ester block copolymer (IV~
The polyester block copolymer (IV) was admixed with the polyester block copolymer (II) so as to obtain a predeter-mined silica content. The mixture was, after being dried well under reduced pressure, formed into a film by the use o~ the same extruder as in Example 5 under the following conditions:
temperature of barrel, 250C; temperature of adapter, 250C;
temperature of T die, 250C; rotation of screw, 36 rpm; film distance between T die and cooling roll, 40 mm; temperature of cooling roll, 60C; take~up rate, 1.7 m/min. The properties of the film are shown in Table 5. As shown, the incorporation of fine particles of silica can afford a film excellent in slip characteristics while maintaining a good clarity.
Reference Example A
The polyester block copolymers (II~ and (IV) were mixed together to obtain a mixture having a silica content of 0.02 ~ by weight or 0.05 ~ by weight. A~ter drying, the mixture was subjected to the production of a film under the same con-ditions as in Example 6 but changing the temperature of the cooling roll to 19.2C. The properties of the film are shown in Table 5. It is apparent that the film is excellent in clarity but inferior in slip characteristics, compared with the corresponding film obtained in Example 6.
~. Y
1~37gii3~
Table 5 F.xam- Silica Thick- Clarity Haze ~tatic Kinetic ~locking ple content ness (,o) (~) fric- fric- stren~th No. (% by (~) tion tion ~g/cmJ
weight) coef- coef-_ flclent ficient 6 0~02 59 88~7 1~8 1~95 1~02 0~48 r 6 0~05 54 88~3 2~7 1~03 0~66 0~35 6 0~10 57 88~5 4~9 0~55 0~49 0~22 6 0~25 55 88~0 8~8 0~47 0~45 Ooll 6 0~5 62 87~2 9~3 0~47 0~43 O r Ref- Stick Stick .
ence 0. 02 71 90 ~ 0 O ~ 8 slip sl ip 0 ~ 87 ence 0~05 57 90~3 1~5 1~52 0~97 0~80 r 20 Exam-Exam~le 7 The polyester block copolymer (I) was admixed with fine particles of the inorganic materials shown ln Table 6 with stirring, and the resultant mixture was pelletized, dried and formed into a film under the same conditions as in Example 1 to obtain a film having a thickness of about 55 to 60 ~. The properties of the film are shown in Table 6.
.; - 21 -- 1~3~63~
~1 ~:: o R o E~ V +~ V ~ . ' --- - -I bD~
,!d s~ E ~ O
~ ~ ~ 0 ~ u N r I ~1 ~D h ~I R ~ bO O O O O O O O
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. ___ . . . ____ O I
rl I ~ ~ ,~ O
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c) c~ U~
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~~ _ ~D ~ ~ ~ ~ ~ O
S~ ~ ~
tJ ~ 00 0 00 0 0 0 0 C~ ~
. . . _ _ _ _ ~
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~ ~ U~ O O O O
O rl ~ O O O O O O O
_ ._._ . .. __._ . .. _ .. _ _ h ~4 h ~ R ., ,;
h bD 67 o V r ~ ~
~) r-l h rl ~ ~
::~ ~ O O t~ rl ~~ O rl rl ~
s:~ ~ h R bDX ~ ~D~ r~ ~ h r~ r~ ~
~ ~rl a) O c~ o ~ o ~ O
Z Ci ~ V ~: v ~ V
8#
r¦
# #
O ~ O * # *
Z
h~
~1) u~ tq rl rl ~d rl rl ~d ~D O r-l rl O E-/ O O u~
td ~ h h R, ~ . ~I r-l .Y
h t~ O td ~ h u~ h h E~ ~ ~ V ~
. .
a>_~ l bD O ~ ~D
~-rJ ~1 ~. C10 ~1 ~D h ~ ~ O O ~ Lt~ ~ O E~
~I) h N
a) ~ t~ rl O O O r~ ~ O
ri ¢ P~ u~ r~ It . __ .
o rl r~ ~ ~ ~) rl +~
~ rl ~ ,r~
bD h O rl O rl O O ~ O O C) h a~ rl O ,~ O ,D rl ~ rlrl rl O ~ r~l r-l h r~ h r I bDr~ ~1 ~1 ~ t~ ~ ~ rl rl H E~ U~ V O V O U~ ~ CQU~ U2 , ~' ~r ~3'7~34 It is apparent that the incorporation of fine par-ticles having an average particle size smaller than 0.1 ~
does not afford any appreciable improving effect on the slip characteristics even with an amount of 0.5 ~ by weight. It is also apparent that the incorporation of fine particles having an average particle size laryer than 10 ~ can afford an excellent improving effect on slip characteristics, but greatly lowers the clarity.
Example_8 A 15 % by weight ~as the solid content) solution of a 95 : 5 by weight (as the solid content) mixture of a polyester copolymer adhesive ("Vylon 300" manufactured by Toyo ~oseki K.K.) and an isocyanate adhesive ("Collonate L" manufactured by Nippon Polyurethane K.K.) in ethyl acetate was app:Lied onto a biaxially stretched film of polyethylene terephthalate (thickness, 19 ~) by a gravure roll (100 mesh x 40 ~), and the film was passed through a drier of 4 m in length at a rate of 30 m/min. The film obtained in Example 5 or 6 was laminated onto the dried film under dry conditions at a nip temperature of 90 to 95C under a nip pressure of 5 kg/cm2. The peeling off property between the laminated layers of the thus obtained film and the heat seal strength between the surfaces of the polyester block copolymer ~ilm layers are shown in Table 7.
.~ ~ 23 ~able 7 ~037~34 . ~
, . . . _ __ Silica Heat seal Composition of film content strength (~ by weight) (kg/cm Polyethyleneterephthalate (19~)/ .
polyester block copolymer in 0.02 3-9 Example 5 (55~) . _ . . .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.05 4.0 Example 5 (55~) . .
Polyethyleneterephthalate (19~)/ .
polyester block copolymer in 0.10 3.8 Example 5 (49~) _ .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.25 3.8 Example 5 (56~) . ~ ............................. ...... _ _ , Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.50 3.6 ~xample 5 (62~) .
Polyethyle.neterephthalate (19~)/
polyester block copolymer in 0.02 ~.0 Example 6 (59~) .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.05 3.0 Example 6 (54~) .
.
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.10 2.9 Example 6 (57~) Polyethyleneterephthalate (lg~)/
polyester block copolymer in 0.25 2.8 Example 6 (55~) . .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.50 2.7 Example 6 (62~) What iæ cl~imed is
~3~7~3~L
temperature of T die, 250C; rotation of screw, 42 rpm; film distance between T die and cooling roll, 40 mm; temperature of cooling roll, 70C; take-up rate, 1.9 m/min. A cooling roll having a surface plated with chromium was used. For effecting the cooling of the film uniformly, an air-knife was used on the cooling roll. The take-up of the film was satisfactorily effected without the formation of wrinkles. The properties of r~
the film are shown in Table 1.
Example 2 Using the polyester block copolymer ~I), the production of a film was carried out in the same manner as in Example 1 but changing the temperature of the cooling roll to 40C. The take-up of the film was effected satisfactoril~. The properties of the film are shown in Table 1.
Reference Example l ~ sing -the polyester block copolymer (I), the produc-tion of a film was carried out in the same manner as in Example 1 but changing the temperature of the cooling roll to 19.5C.
The obtained film was excellent in clarity, but the amount of slip between the film and a metal roll and the amount of slip between two layers of the films were insufficient so that wrinkles were formed on taking up the film and a uniform take-up was thus difficult. The properties of the film are shown in Table 1. As shown, the slip characteristics and the blocking resistance are inferior, although the other properties are excellent.
~ - 13 -~3763~
Table 1 Example Example Reference 1 2 Example T~ickness (~) 54.7 55.9 60.3 Clarity (~o) 81.7 86.4 90.5 characterlstics ~ood Good Bad strength (g/cm~ 0.86 1.02 2.54 Specific gravity 1.229 1.228 1.228 Breaking 2 620 590 580 elongation (~) 470 500 520 strength (kg.cm/25 ~) 16.6 17.1 16.
Oxygen permeability constant l.OxlO 10 l.OxlO 10 l.lxlO 10 (cc.cm/cm2.sec.cmHg) Water vapor trans-mission (g/m2.24 hr) 340 355 368 ~calculated as 25 ~) _ 14 -1~1!3'7~i3~
E~ample 3 Dimethyl terephthalate l6200 partsl, 1,4-butanediol (4000 parts) and titanium tetrabutoxide ~5.5 parts~ were charged to a stainless steel reaction vesse:L, and the contents were heated at 140 to 230C in a nitrog-en atmosphere to complete an ester exchange reaction.. The reaction mixture was added to a mixture of polytetramethylene oxide (molecular weight, r 1000; 5000 parts) and an antioxidant ("Sumilizer ~HT" - Trade Mark - manufactured by Sumitomo Chemical Company, Limited) (23 parts~ previously heated to 230C. The resulting mixture was stirred while elevating the temperature to 245C and gradually reducing the pressure to about 0.1 n~Hs, and a polycondensation was effected for 2 hours under these conditions. The produced polymer was drie~ at ~0C under a pressure of about 0.1 mmHg for 5 hours to give polytetramethylene terephthalate-polytetra-methylene oxide block copolymer (hereinafter referred to as "polyester block copolymer (II~"~. Reduced viscosity, 1.99 dl/g.
Melting point, 205C.
The polyester block copolymer (II) was,after being dried well under a reduced pressure to obtain a water content of 0.005 ~ by weight, formed into a film by the use of the same extruder as in Example 1 under the following conditions:
temperature of barrel, 240C; temperature of adapter, 245C;
temperature of T die, 250C; rotation of screw, 42 rpm; fi~m distance between T die and cooling roll, ao mm; temperature of cooling roll, 80C; take-up rate, 1.9 m/min. The amount of slip between the film and a metal roll and the amount of slip between different layers of the film were good, and the take-up of the film was effected satisfactorily. The properties of the film are shown in Table 2.
~ - 15 -~37~3~
Reference Example 2 ~ sing the polyester bloek copolymer (II~, the pro-duction of a film was effected in the same manner as in Example 3 but changing the temperature of the cooling roll to 19.5C.
The obtained film was exeellent in elarity but the slip characteristics were inferior so that wrinkles were formed on taking up the film and a uniform take-up was difficult. The properties of the film are shown in Table 2. ~.s shown, the slip eharaeteristies and the bloeking resistance are inferior, although the other properties are excellent.
Table 2 .
Example Referenee . 3 Exarnple Thickness ( ~1) 54.3 59.5 Clarity ('~/o) 81.2 90.1 Take-up Good Bad eharaeteristies Bloeking 1.26 4.50 strength (g/em) Speeifie 1.176 1.174 gravity Breaking 5 5 5 3 strcngth (kg/em ) Breaking 590 1 630 elongation (~0) l Impaet NB ~B
strength (kg.em/25 ~) Oxygen permeability 10 -10 eonstant 14.4xlO- 4.7xlO
(ec.em/em2.see.cmHg) Water vapor tr~ns- I
mission (g/m2.24 hr) ~ 665 680 (ealeulated as 25 ~
~763~L
Example 4 A solution of 15 % by weight (as the solid content) of a 95 : 5 by weight ~as the solid content~ mixture of a polyester copolymer adhesive ("Vylon 300" - ~rade Mark - manu-factured by Toyo Boseki K.K.) and an isocyanate adhesive ("Collonate L" - Trade Mark - manufactured by Nippon Polyurethane K.K.) in ethyl acetate was applied onto a biaxially stretched film of polyethylene terephthalate (thickness, 19 ~), by a gravure roll (100 mesh x 40 ~, and the film was passed through a drier of 4 m in length at a rate of 30 m/min. The unstretched polyester block copolymer film as obtained in Example 1 or 3 was laminated on the dried film under dry conditions at a nip temperature of 90 to 95C under a nip pressure of 5 kg/cm2.
The surEace of the unstretched polyester block copolymer film layer of the thus obtained film was heat sealed with that of the other thus obtained film. The heat seal strength is shown in Table 3.
Table 3 _ , Heat seal strength (g/cm) Composition o~ ~ilm __ A_ _ _ . _ . .. _ Polyethyleneterephthalate(l9~l)/ 4000 polyester bloclc copolymer (I)(54.7~): _ 500 _......... _ __ Polyethyleneterephthalate(l9~)/ 000 00 polyester block copolymer (II)(54.3~) . 3 5 I .
When these la~.inated films were treated with boiling water at 130C for 30 minutes in an autoclave, no separation of the laminated layers was observed.
Example 5 ._ An ester exchange reaction and a polycondensation were effected in the same manner as in Example 1 but :Eine particles of silica ("Syloid 226" ~ Trade Mark - manufac-tured . ~ !.
.~,.. .
1~37~;~4 by Fuji Devison Co., ~td.; average particle size, 1.5 ~) (75 parts) were incorporated into the starting materials to obtain a polytetramethylene terephthalate-polytetramethylene oxide block copolymer containing 0.5 % by weight of fine particles of silica (hereinafter referred to as "polyester block copolymer (III)").
The polyester block copolymer (III) was admixed with the polyester block copolymer (I) so as to obtain a predetermined silica content. The resultant mixture was, after being dried well under reduced pressure to obtain a water content of 0.005 %
by weight, formed into a film by an extruder in which the dia-meter of screw was 20 mm 0, the width of T die was 120 mm and the lip was 0.5 mm under the following conditions: temperature of barrel, 250C; temperature of adapter, 250C; temperature of T die, 250C; rotation of screw, 36 rpm; film distance between T die and cooling roll, 40 mm; temperature o~ coolinc3 roll, 60C;
take-up rate, 1.7 m/min. The thickness, clarity, haze and friction coefficient of the film are shown in Table 4. As shown, the incorporation of fine particles of silica can afford a film excellent in slip characteristics while maintaining a good transparency.
Reference Example 3 The polyester block copolymers (I) and (III) were mixed together to obtain a mixture having a silica content of 0.02 ~ by weight or 0.05~ by weight. After drying, the mixture was formed into a film under the same conditions as in Example 5 but changing the temperature of the cooling roll to 19.2C. The properties of the film are shown in Table 4. As shown, the film was excellent in clarity but inferior in slip characteristics, compared with the corresponding film obtained in Example 5.
~3~634 Table 4 Exam- Silioa Thick- Clarity Haze Static ~inetic Blooklng ple content ness (~) (c/O) fric- fric- strength ~o. (% by (~) tion tion (g/cm~
weight) coef-. coef-_ _ _ ~ ~ ficient ficient _ ~ ~
0.02 55 88.4 2.3 1.73 0.98 0.52 0.05 55 85.4 5.1 1.16 0.58 0.~3 0.10 49 89.0 ~.0 0.49 0.40 0.20 0.25 56 86.0 9.1 0.49 0.44 0.10 0.5 62 87.7 8.2 0.45 0.42 0 Ref-ence 0.02 60 89.9 0.7 Stick Stick 0.90 Exam- . slip sl}p er-ence 0.05 61 90.1 1.6 1.65 0.92 0.82 kxam- . . _ 7~3~
Example 6 An ester exchange reaction and a polycondensation were effected as in Example 3 but fine particles of silica ("Syloid 266" manufactured by Fuji Devison Co., Ltd.; average particle size, 1.5 ~) ~57.5 parts) were incorporated into the starting materials to obtain a polytetramethylene terephthalate-poly-tetramethylene oxide block copolymer containing 0.5 ~ by weight of fine particles of silica (hereinafter referred to as "poly-ester block copolymer (IV~
The polyester block copolymer (IV) was admixed with the polyester block copolymer (II) so as to obtain a predeter-mined silica content. The mixture was, after being dried well under reduced pressure, formed into a film by the use o~ the same extruder as in Example 5 under the following conditions:
temperature of barrel, 250C; temperature of adapter, 250C;
temperature of T die, 250C; rotation of screw, 36 rpm; film distance between T die and cooling roll, 40 mm; temperature of cooling roll, 60C; take~up rate, 1.7 m/min. The properties of the film are shown in Table 5. As shown, the incorporation of fine particles of silica can afford a film excellent in slip characteristics while maintaining a good clarity.
Reference Example A
The polyester block copolymers (II~ and (IV) were mixed together to obtain a mixture having a silica content of 0.02 ~ by weight or 0.05 ~ by weight. A~ter drying, the mixture was subjected to the production of a film under the same con-ditions as in Example 6 but changing the temperature of the cooling roll to 19.2C. The properties of the film are shown in Table 5. It is apparent that the film is excellent in clarity but inferior in slip characteristics, compared with the corresponding film obtained in Example 6.
~. Y
1~37gii3~
Table 5 F.xam- Silica Thick- Clarity Haze ~tatic Kinetic ~locking ple content ness (,o) (~) fric- fric- stren~th No. (% by (~) tion tion ~g/cmJ
weight) coef- coef-_ flclent ficient 6 0~02 59 88~7 1~8 1~95 1~02 0~48 r 6 0~05 54 88~3 2~7 1~03 0~66 0~35 6 0~10 57 88~5 4~9 0~55 0~49 0~22 6 0~25 55 88~0 8~8 0~47 0~45 Ooll 6 0~5 62 87~2 9~3 0~47 0~43 O r Ref- Stick Stick .
ence 0. 02 71 90 ~ 0 O ~ 8 slip sl ip 0 ~ 87 ence 0~05 57 90~3 1~5 1~52 0~97 0~80 r 20 Exam-Exam~le 7 The polyester block copolymer (I) was admixed with fine particles of the inorganic materials shown ln Table 6 with stirring, and the resultant mixture was pelletized, dried and formed into a film under the same conditions as in Example 1 to obtain a film having a thickness of about 55 to 60 ~. The properties of the film are shown in Table 6.
.; - 21 -- 1~3~63~
~1 ~:: o R o E~ V +~ V ~ . ' --- - -I bD~
,!d s~ E ~ O
~ ~ ~ 0 ~ u N r I ~1 ~D h ~I R ~ bO O O O O O O O
p~
. ___ . . . ____ O I
rl I ~ ~ ,~ O
R ~ ~ ~ ~1 P~ .,~ .P~ ~D ~ ~ ';t ~rl h ~rl o ~rl ~ ~1 ~ I O O O O O
c) c~ U~
__ . . ... r .~ I ~ ~ X ~ ~ 0 0~ u~
O S~ C) ~ O P~
~-~1 o a) a) ,1-~ - .
~ h rl o rl ~ ~1 +~ r I O O
rQ ~ C) O ~ U~
~~ _ ~D ~ ~ ~ ~ ~ O
S~ ~ ~
tJ ~ 00 0 00 0 0 0 0 C~ ~
. . . _ _ _ _ ~
~ ~ .
~ ~ U~ O O O O
O rl ~ O O O O O O O
_ ._._ . .. __._ . .. _ .. _ _ h ~4 h ~ R ., ,;
h bD 67 o V r ~ ~
~) r-l h rl ~ ~
::~ ~ O O t~ rl ~~ O rl rl ~
s:~ ~ h R bDX ~ ~D~ r~ ~ h r~ r~ ~
~ ~rl a) O c~ o ~ o ~ O
Z Ci ~ V ~: v ~ V
8#
r¦
# #
O ~ O * # *
Z
h~
~1) u~ tq rl rl ~d rl rl ~d ~D O r-l rl O E-/ O O u~
td ~ h h R, ~ . ~I r-l .Y
h t~ O td ~ h u~ h h E~ ~ ~ V ~
. .
a>_~ l bD O ~ ~D
~-rJ ~1 ~. C10 ~1 ~D h ~ ~ O O ~ Lt~ ~ O E~
~I) h N
a) ~ t~ rl O O O r~ ~ O
ri ¢ P~ u~ r~ It . __ .
o rl r~ ~ ~ ~) rl +~
~ rl ~ ,r~
bD h O rl O rl O O ~ O O C) h a~ rl O ,~ O ,D rl ~ rlrl rl O ~ r~l r-l h r~ h r I bDr~ ~1 ~1 ~ t~ ~ ~ rl rl H E~ U~ V O V O U~ ~ CQU~ U2 , ~' ~r ~3'7~34 It is apparent that the incorporation of fine par-ticles having an average particle size smaller than 0.1 ~
does not afford any appreciable improving effect on the slip characteristics even with an amount of 0.5 ~ by weight. It is also apparent that the incorporation of fine particles having an average particle size laryer than 10 ~ can afford an excellent improving effect on slip characteristics, but greatly lowers the clarity.
Example_8 A 15 % by weight ~as the solid content) solution of a 95 : 5 by weight (as the solid content) mixture of a polyester copolymer adhesive ("Vylon 300" manufactured by Toyo ~oseki K.K.) and an isocyanate adhesive ("Collonate L" manufactured by Nippon Polyurethane K.K.) in ethyl acetate was app:Lied onto a biaxially stretched film of polyethylene terephthalate (thickness, 19 ~) by a gravure roll (100 mesh x 40 ~), and the film was passed through a drier of 4 m in length at a rate of 30 m/min. The film obtained in Example 5 or 6 was laminated onto the dried film under dry conditions at a nip temperature of 90 to 95C under a nip pressure of 5 kg/cm2. The peeling off property between the laminated layers of the thus obtained film and the heat seal strength between the surfaces of the polyester block copolymer ~ilm layers are shown in Table 7.
.~ ~ 23 ~able 7 ~037~34 . ~
, . . . _ __ Silica Heat seal Composition of film content strength (~ by weight) (kg/cm Polyethyleneterephthalate (19~)/ .
polyester block copolymer in 0.02 3-9 Example 5 (55~) . _ . . .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.05 4.0 Example 5 (55~) . .
Polyethyleneterephthalate (19~)/ .
polyester block copolymer in 0.10 3.8 Example 5 (49~) _ .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.25 3.8 Example 5 (56~) . ~ ............................. ...... _ _ , Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.50 3.6 ~xample 5 (62~) .
Polyethyle.neterephthalate (19~)/
polyester block copolymer in 0.02 ~.0 Example 6 (59~) .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.05 3.0 Example 6 (54~) .
.
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.10 2.9 Example 6 (57~) Polyethyleneterephthalate (lg~)/
polyester block copolymer in 0.25 2.8 Example 6 (55~) . .
Polyethyleneterephthalate (19~)/
polyester block copolymer in 0.50 2.7 Example 6 (62~) What iæ cl~imed is
Claims (18)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A film of a polyester block copolymer, which has the following physical constants:
(1) Specific gravity 1.003-1.300 (2) Young's modulus (kg/cm2) not more than 1,500 (at 20°C) (3) Breaking strength (kg/cm2) 150-800 (at 20°C) (4) Breaking elongation (%) not less than 300 (at 20°C) (5) Impact strength (kg?cm/25 µ) not less than 8 (at 20°C) (6) Thermal adhesion (kg/cm) not less than 0.5 (at 20°C) (7) Oxygen permeability constant 0.5 x 10-10 - 100 (cc?cm/cm2?sec?cmHg) x 10-10 (at 30°C) (8) Clarity (%) not less than 80 (9) Haze (%) not more than 2, the polyester block copolymer comprising crystalline polyester segments and non-crystalline polymer segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight of about 10,000 to 100,000, the melting point of a high self-supporting polymer substantially constituted with the monomer components of the said crystalline polyester segments alone being not lower than about 200°C and the melting point or softening point of a polymer substantially constituted with the said non-crystalline polymer segments themselves being not higher than about 80°C.
(1) Specific gravity 1.003-1.300 (2) Young's modulus (kg/cm2) not more than 1,500 (at 20°C) (3) Breaking strength (kg/cm2) 150-800 (at 20°C) (4) Breaking elongation (%) not less than 300 (at 20°C) (5) Impact strength (kg?cm/25 µ) not less than 8 (at 20°C) (6) Thermal adhesion (kg/cm) not less than 0.5 (at 20°C) (7) Oxygen permeability constant 0.5 x 10-10 - 100 (cc?cm/cm2?sec?cmHg) x 10-10 (at 30°C) (8) Clarity (%) not less than 80 (9) Haze (%) not more than 2, the polyester block copolymer comprising crystalline polyester segments and non-crystalline polymer segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average molecular weight of about 10,000 to 100,000, the melting point of a high self-supporting polymer substantially constituted with the monomer components of the said crystalline polyester segments alone being not lower than about 200°C and the melting point or softening point of a polymer substantially constituted with the said non-crystalline polymer segments themselves being not higher than about 80°C.
2. The film according to claim 1, which has a block-ing strength of not more than about 1.3 g/cm.
3. The film according to claim 1, wherein the poly-ester block copolymer is incorporated with at least one inor-ganic material in fine particles in an amount of about 0.01 to 5 % by weight based on the weight of the polyester block copolymer.
4. The film according to claim 3, wherein the inorganic material is in fine particles having a particle size of about 0.1 to 10 µ in average.
5. The film according to claim 4, wherein the inorganic material is a member selected from the group con-sisting of oxides and salts of the metals belonging to Groups II, III and IV of the periodic table.
6. The film according to claim 3, which has a block strength of not more than about 0.5 g/cm.
7. The film according to claim 6, which has a static friction coefficient of about 0.4 to 1.0 and a kinetic friction coefficient of about 0.5 to 2Ø
8. The film according to claim 1, which is prepared by melt extruding a polyester block copolymer to form a film and cooling the film to a temperature of about 40 to 120°C in order to solidify it.
9. A process for preparing a polyester block co-polymer film having good slip characteristics and blocking resistance, which comprises melt extruding a polyester block copolymer to form a film and cooling the film in a melt state at a temperature of about 40 to 120°C to solidify it, the polyester block copolymer comprising crystalline polyester segments and non-crystalline polymer segments in a weight ratio of 99 : 1 to 10 : 90 and having a number average mole-cular weight of about 10,000 to 100,000, the melting point of a high self-supporting polymer substantially constituted with the monomer components of the said crystalline polyester segments alone being not lower than about 200°C and the melt-ing point or softening point of a polymer substantially con-stituted with the said non crystalline polymer segments themselves being not higher than about 80°C.
10. The process according to claim 9, wherein the weight ratio of the crystalline polyester segments and the non-crystalline polymer segments is from 90 : 10 to 20 : 80.
11. The process according to claim 9, wherein the non-crystalline polymer segments are those having a molecular weight of about 400 to 8,000 when a polymer is produced with them alone.
12. The process according to claim 9, wherein the crystalline polyester segments are constituted with terephthalic acid or its mixture with isophthalic acid as the dicarboxylic acid component and ethylene glycol or tetramethylene glycol as the glycol component and the non-crystalline polymer segments are constituted with polyethylene glycol or polytetramethylene glycol.
13. The process according to claim 9, wherein the polyester block copolymer is a polytetramethylene phthalate-polytetramethylene oxide (90 : 10 to 40 : 60 by weight) block copolymer.
14. The process according to claim 9, wherein the polyester block copolymer having a water content of not more than 0.2 % by weight is melt extruded at a temperature of about 160 to 280°C by the aid of an extruder.
15. The process according to claim 14, wherein.
the extruded film in a melt state is cooled at a temperature of about 40 to 120°C by the aid of a cooling roll to make solidified.
the extruded film in a melt state is cooled at a temperature of about 40 to 120°C by the aid of a cooling roll to make solidified.
16. The process according to claim 9, wherein the polyester block copolymer is incorporated with at least one inorganic material in fine particles in an amount of about 0.01 to 5 % by weight based on the weight of the polyester block copolymer.
17. The process according to claim 16, wherein the inorganic material is in fine particles having a particle size of about 0.1 to 10 µ in average.
18. The process according to claim 17, wherein the inorganic material is a member selected from the group con-sisting of oxides and salts of the metals belonging to Groups II, III and IV of the periodic table.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7428673A JPS551942B2 (en) | 1973-06-30 | 1973-06-30 | |
| JP7428473A JPS551929B2 (en) | 1973-06-30 | 1973-06-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1037634A true CA1037634A (en) | 1978-08-29 |
Family
ID=26415429
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA203,758A Expired CA1037634A (en) | 1973-06-30 | 1974-07-02 | Polyester block copolymer film |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US3968183A (en) |
| BR (1) | BR7405379D0 (en) |
| CA (1) | CA1037634A (en) |
| DE (1) | DE2431076B2 (en) |
| GB (1) | GB1443109A (en) |
Families Citing this family (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5713469B2 (en) * | 1974-12-19 | 1982-03-17 | ||
| NL7609363A (en) * | 1975-08-27 | 1977-03-01 | Rhone Poulenc Textile | ARYL GROUPS CONTAIN BLOCK COPOLYESTERS AND WIRES BASED ON THESE COPOLYESTERS. |
| US4053538A (en) * | 1976-04-09 | 1977-10-11 | Armstrong Cork Company | Block polymers from isocyanurate-based polyesters and conventional polyester segments |
| DE2710379A1 (en) * | 1977-03-10 | 1978-09-14 | Huels Chemische Werke Ag | PROCESS FOR EVEN MIXING OF ADDITIVES IN THERMOPLASTIC PLASTICS |
| JPS5825331B2 (en) * | 1977-07-13 | 1983-05-26 | 東レ株式会社 | polyester film |
| JPS5819686B2 (en) * | 1977-08-30 | 1983-04-19 | 帝人株式会社 | printing film for packaging |
| JPS57123050A (en) * | 1980-12-01 | 1982-07-31 | Toray Industries | Polyester composite film |
| US4442262A (en) * | 1980-11-22 | 1984-04-10 | Kureha Kagaku Kogyo Kabushiki Kaisha | Composition of polyester-block copolymer |
| CA1226089A (en) * | 1982-12-02 | 1987-08-25 | Cornelius M.F. Vrouenraets | Packaging film permeable to smoke constituents and packaged, smoked foodstuff |
| US4685455A (en) * | 1984-10-16 | 1987-08-11 | Akzo Nv | Watervapor-permeable, pressure sensitive, antiseptic wound covering material |
| US4751132A (en) * | 1985-10-28 | 1988-06-14 | E. I. Du Pont De Nemours And Company | Process for making polyetherester elastomer film |
| US4731407A (en) * | 1985-10-28 | 1988-03-15 | E. I. Du Pont De Nemours And Company | Polyetherester elastomer composition |
| US4990400A (en) * | 1987-02-12 | 1991-02-05 | Diafoil Company, Limited | Polyester films, magnetic recording media and film capacitors produced therefrom |
| NL8702422A (en) * | 1987-10-12 | 1989-05-01 | Akzo Nv | ABSORBING HYGIENIC PRODUCT. |
| GB2234704B (en) * | 1989-07-28 | 1993-04-14 | Toyo Kohan Co Ltd | Method for producing steel sheet laminated with a polyester resin film |
| CA2000356C (en) * | 1989-11-09 | 1995-08-22 | Atsuo Tanaka | Copolyester resin film laminated metal sheet and method for production thereof |
| CA2029943C (en) * | 1989-11-15 | 1999-10-12 | Ryousuke Wake | Resin-coated steel sheet for drawn-and-ironed cans and drawn-and-ironed cans manufactured therefrom |
| US5114998A (en) * | 1990-12-06 | 1992-05-19 | Hoechst Celanese Corp. | Stabilized talc-filled polyester compositions |
| US5114996A (en) * | 1990-12-06 | 1992-05-19 | Hoechst Celanese Corp. | Stabilized talc-filled polyester compositions |
| US5114997A (en) * | 1990-12-06 | 1992-05-19 | Hoechst Celanese Corp. | Stabilized talc-filled polyester compositions |
| US5114995A (en) * | 1990-12-06 | 1992-05-19 | Hoechst Celanese Corp. | Stabilized talc-filled polyester compositions |
| EP0744434A1 (en) * | 1995-05-26 | 1996-11-27 | Du Pont De Nemours International S.A. | Packaging film for respiring materials |
| EP0761715B1 (en) * | 1995-08-17 | 2003-11-05 | Solar Dew | Copolyether amide and water vapour permeable film made therefrom |
| US6677258B2 (en) | 1996-05-29 | 2004-01-13 | E. I. Du Pont De Nemours And Company | Breathable composite sheet structure and absorbent articles utilizing same |
| US7307031B2 (en) | 1997-05-29 | 2007-12-11 | The Procter & Gamble Company | Breathable composite sheet structure and absorbent articles utilizing same |
| US5938648A (en) * | 1997-12-03 | 1999-08-17 | The Procter & Gamble Co. | Absorbent articles exhibiting improved internal environmental conditions |
| US6187696B1 (en) | 1997-12-03 | 2001-02-13 | E. I. Du Pont De Nemours And Company | Breathable composite sheet structure |
| NL1010367C2 (en) | 1998-10-21 | 2000-04-25 | Akzo Nobel Nv | Water vapor permeable thermoplastic polyurethane film. |
| US6500890B2 (en) * | 2000-12-15 | 2002-12-31 | Wellman, Inc. | Polyester bottle resins having reduced frictional properties and methods for making the same |
| US7759449B2 (en) | 2000-12-15 | 2010-07-20 | Wellman, Inc. | Methods for introducing additives into polyethylene terephthalate |
| US20030039783A1 (en) * | 2001-03-30 | 2003-02-27 | Stafford Steven Lee | Polyesters and polyester containers having a reduced coefficient of friction and improved clarity |
| US6764753B2 (en) * | 2001-04-11 | 2004-07-20 | E. I. Du Pont De Nemours And Company | Smokable films comprising a polyamide and a copolyester elastomer |
| ITMI20020864A1 (en) * | 2002-04-22 | 2003-10-22 | Novamont Spa | AMORPHO-CRYSTALLINE BLOCK COPOLYMERS |
| EP2888108A1 (en) | 2012-08-21 | 2015-07-01 | 3M Innovative Properties Company | Articles with binder-deficient slip coating and method for making same |
| WO2020054777A1 (en) * | 2018-09-14 | 2020-03-19 | Ａｇｃ株式会社 | Method for producing pellets, pellets and ion exchange film |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2823421A (en) * | 1952-05-12 | 1958-02-18 | Du Pont | Stretching of polyethylene terephthalate film |
| DE1183667B (en) * | 1957-07-09 | 1964-12-17 | Lonza Ag | Process for the production of smooth hoses, in particular film hoses, made of thermoplastic material, and an injection head on a heated extruder for carrying out the process |
| NL264253A (en) * | 1960-05-03 | 1900-01-01 | ||
| DE1264746B (en) * | 1962-09-11 | 1968-03-28 | Nihonbashi Muromachi | Process for the production of thermoplastic plastic films with a rough surface |
| DE1211386B (en) * | 1964-06-26 | 1966-02-24 | Bayer Ag | Process for the production of films with a high modulus of elasticity from film-forming reaction products obtained by the isocyanate polyaddition process |
| US3446778A (en) * | 1964-08-04 | 1969-05-27 | Goodyear Tire & Rubber | Block copolyester containing crystallizable polymeric units and rubbery polyester units |
| US3627625A (en) * | 1970-05-27 | 1971-12-14 | Ici Ltd | Biaxially oriented sheet |
-
1974
- 1974-06-26 GB GB2835474A patent/GB1443109A/en not_active Expired
- 1974-06-27 US US05/483,707 patent/US3968183A/en not_active Expired - Lifetime
- 1974-06-28 BR BR5379/74A patent/BR7405379D0/en unknown
- 1974-06-28 DE DE2431076A patent/DE2431076B2/en not_active Ceased
- 1974-07-02 CA CA203,758A patent/CA1037634A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2431076A1 (en) | 1975-01-16 |
| DE2431076B2 (en) | 1981-05-14 |
| BR7405379D0 (en) | 1975-01-21 |
| US3968183A (en) | 1976-07-06 |
| GB1443109A (en) | 1976-07-21 |
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