CA1276614C - Catalyst for producing polyurethane foams coated with skin - Google Patents
Catalyst for producing polyurethane foams coated with skinInfo
- Publication number
- CA1276614C CA1276614C CA000511825A CA511825A CA1276614C CA 1276614 C CA1276614 C CA 1276614C CA 000511825 A CA000511825 A CA 000511825A CA 511825 A CA511825 A CA 511825A CA 1276614 C CA1276614 C CA 1276614C
- Authority
- CA
- Canada
- Prior art keywords
- process according
- skin
- catalyst
- piperazine
- hydroxyalkyl
- 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 - Lifetime
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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/34—Chemical features in the manufacture of articles consisting of a foamed macromolecular core and a macromolecular surface layer having a higher density than the core
-
- 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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/16—Catalysts
- C08G18/18—Catalysts containing secondary or tertiary amines or salts thereof
- C08G18/20—Heterocyclic amines; Salts thereof
- C08G18/2009—Heterocyclic amines; Salts thereof containing one heterocyclic ring
- C08G18/2027—Heterocyclic amines; Salts thereof containing one heterocyclic ring having two nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
Abstract
Abstract Amine catalysts useful for producing polyurethane foams coated with skin by reaction of an organic polyisocyanate with a polyol. The catalysts comprise 4-methyl-1-(2-hydroxyalkyl)-piperazine, and emit no bad odor, give excellent moldability and are free from deterioration of skin and discoloration of covering materials.
Description
1;2766~L
S P E C I F I C A T I O N
Title of the Invention:
CATALYST FOR PRODUCING POLYURETHANE FOAMS
COATED WITH SKIN
Background of the Invention:
Field of the Invention:
The present inYentiOn relates to the amine catalysts useful for producing polyurethane foams coated with skin.
More particularly, the invention relates to the amine catalysts useful for produci~ polyurethane foams coated with skin, which emit no bad odor, give e~cellent moldability,-and are free from deterioration o~ skin an~ dis-coloration of co~ering materials.
Description of Related Arts:
Polyurethane foams are usually prepared by the reaction of solution A wi~h solution B under high speed mixing agitation, solution A containing polyol, blowing agents, s.urfactant~ catalyst and other promotor a~d solution B con-taining polyisocyanate.
Polyurethane foams coated with skin ~ave a wide range of applications. Among them the.most .common usage is for interior materials of automobile such as for cushion, arm rest, head rest, instrument panel and dash board. These products are usually coated with urethane elastomer, vinyI
chloride resin or a complex of ABS and vinyl chloride resins, and frequently they are prepared in a united product.
A ~r ~L~'7~
On the other hand, tertiary amine catalysts, employed in the production of polyurethane foams, are partly lost by evaporation and the rest remains in the product foams. Amine compounds usually have a peculiar amine odor which emits a bad smell and imp ~ s bad influences to the w~king condition or further to the environmental problem. Amine compounds, if left in the foam, may breed toward th~ outside of the foam and react with vinyl chloride in the skin to accelerate dehydrochlorination and to discolor the skin.
In other instance, halogen compounds such as fire retardant in the foam composition, react with the remaining amine compounds to produce halides ~hich often discolor the skin.
So far, the disco~ration of the skin has been avoided by increasing the thickness of the skin to lessen the breed of the amune catalyst, but it brings about a large cost disadvantage On the other, hand, a variety of amine catalysts have been proposed. ~or example, they include a catalyst which is reactive with raw material isocyanate (Japanese Laid-Open Patent Application No. Sho 58-17115) and a catalyst having a high molecular weig~t to reduce the breeding speed (Japanese Laid-Open Patent Application No. Sho 54-20099). However, there still remained a problem that amine catalysts which deteriorated and discolored the skin to a lesser de~ree did not always provide better physical properties of the foam.
Thus, most eagerly desired was an amine catalyst which eliminates these problems.
4-Methyl-1-(2-hydroxyalkyl)piperazine has been disclosed by some of the present inventors and is one of the known tertiary amine catalysts. However, there has not been described that the 4-methyl-1-(2-hydroxyalkyl)piperazine A` - 2 -lZ'7~ 4 is a catalyst useful to pxevent deterioration and dis-coloration of polyurethane products coated with skin, and further there is not found an example in which the compound has been utilized in this field.
Summary of the Invention:
Considering the above-mentioned circumstances, the present invention intends to provide an amine catalyst which, when employed for the production of urethane foams coated with skin, brings about a minimal degree of deterio-ration and discoloration of the skin, carries no bad odor of itself and is excellent in its physicaI properties for foaming and in preparing ~ood moldability.
The present inventors have long devo~ed themselves to the investigation on the caialytic action of tertiary amines. In the production of urethane-foa~s,. a tertiary amine is necessarily used to make the foams with open cell structure. To Qvercome the serious pro~lem of discoloratio~
of urethane products, they formed four t.ypes of amine catalysts which could be used;
(1) an ami~e catalyst of a very low hoilin~ point;
S P E C I F I C A T I O N
Title of the Invention:
CATALYST FOR PRODUCING POLYURETHANE FOAMS
COATED WITH SKIN
Background of the Invention:
Field of the Invention:
The present inYentiOn relates to the amine catalysts useful for producing polyurethane foams coated with skin.
More particularly, the invention relates to the amine catalysts useful for produci~ polyurethane foams coated with skin, which emit no bad odor, give e~cellent moldability,-and are free from deterioration o~ skin an~ dis-coloration of co~ering materials.
Description of Related Arts:
Polyurethane foams are usually prepared by the reaction of solution A wi~h solution B under high speed mixing agitation, solution A containing polyol, blowing agents, s.urfactant~ catalyst and other promotor a~d solution B con-taining polyisocyanate.
Polyurethane foams coated with skin ~ave a wide range of applications. Among them the.most .common usage is for interior materials of automobile such as for cushion, arm rest, head rest, instrument panel and dash board. These products are usually coated with urethane elastomer, vinyI
chloride resin or a complex of ABS and vinyl chloride resins, and frequently they are prepared in a united product.
A ~r ~L~'7~
On the other hand, tertiary amine catalysts, employed in the production of polyurethane foams, are partly lost by evaporation and the rest remains in the product foams. Amine compounds usually have a peculiar amine odor which emits a bad smell and imp ~ s bad influences to the w~king condition or further to the environmental problem. Amine compounds, if left in the foam, may breed toward th~ outside of the foam and react with vinyl chloride in the skin to accelerate dehydrochlorination and to discolor the skin.
In other instance, halogen compounds such as fire retardant in the foam composition, react with the remaining amine compounds to produce halides ~hich often discolor the skin.
So far, the disco~ration of the skin has been avoided by increasing the thickness of the skin to lessen the breed of the amune catalyst, but it brings about a large cost disadvantage On the other, hand, a variety of amine catalysts have been proposed. ~or example, they include a catalyst which is reactive with raw material isocyanate (Japanese Laid-Open Patent Application No. Sho 58-17115) and a catalyst having a high molecular weig~t to reduce the breeding speed (Japanese Laid-Open Patent Application No. Sho 54-20099). However, there still remained a problem that amine catalysts which deteriorated and discolored the skin to a lesser de~ree did not always provide better physical properties of the foam.
Thus, most eagerly desired was an amine catalyst which eliminates these problems.
4-Methyl-1-(2-hydroxyalkyl)piperazine has been disclosed by some of the present inventors and is one of the known tertiary amine catalysts. However, there has not been described that the 4-methyl-1-(2-hydroxyalkyl)piperazine A` - 2 -lZ'7~ 4 is a catalyst useful to pxevent deterioration and dis-coloration of polyurethane products coated with skin, and further there is not found an example in which the compound has been utilized in this field.
Summary of the Invention:
Considering the above-mentioned circumstances, the present invention intends to provide an amine catalyst which, when employed for the production of urethane foams coated with skin, brings about a minimal degree of deterio-ration and discoloration of the skin, carries no bad odor of itself and is excellent in its physicaI properties for foaming and in preparing ~ood moldability.
The present inventors have long devo~ed themselves to the investigation on the caialytic action of tertiary amines. In the production of urethane-foa~s,. a tertiary amine is necessarily used to make the foams with open cell structure. To Qvercome the serious pro~lem of discoloratio~
of urethane products, they formed four t.ypes of amine catalysts which could be used;
(1) an ami~e catalyst of a very low hoilin~ point;
(2) an amine cataIyst having a reactive group;
(3) an amine catalyst of a high moIecular weight; and t4) an amine catalyst of a high boiling pOillt.
In (1), a very low boiling point amine cataly~t is mostly evapor~ted in the course of production of urethane foams leaving no remainder of amine catalyst. However, as mentioned above, this kind of amine compound has intolerable bad odor, deteriorates tbe working condition, and in an extreme 6~4 case it may bring about an environmental problem. Further, a low boiling compound such as this amine catalyst may evaporate while it is kept in a pre-mixed composi-tion solution and the reaction may not proceed at the expected reaction rate. Therefore, (1) does not provide an effective means.
The remedy (3) seems a useful one, because an amine catalyst having a large molecular weight hardly breeds and also hardly evaporates. Emitting of bad odor of the amine is no longer feared. However, for an amine catalyst of a large molecular weight, the catalytic ac-tivity per unit weight is reduced and a larger amo-~t is needed. In addition, the amine is more immiscible and some amines are solid at room temperature. Thus, (3) does not always provide a useful means.
The present inventors noted tertiary amine-compounds which hola reactivity with i ocyanate and the reactive functi-onal group of which forms an amine catalyst of a higher boiling point due to formation of hydrogen bonds.
In other words, they expected to solve the problem of deterio-ration of discoloration of the-skin by the remedies (2) and (a), and their investigations were solely on the tertiary amine c~talysts having these reactive groups. As a result, they found that, when 4-methyl~ 2-hydroxyalkyl)piperazine (hereinafter designated as MHAP) or a mixture of MHAP and a specifi-ed amount of another tertiary amine compound was used as catalyst, skin of the product polyurethane showed very little deterioration and discoloration and physical properties as well as moldability of foams were excellent, and they succeeded in completion of this invention.
.~' ~ - 4 -lZ76~L4 The present invention provides catalysts for producing polyruethane foams coated with skin which are excellent in their physical properties and moldability of foams and the skin of which is least deteriorated and discolored by the reaction of an organic polyisocyanate with a polyol in the presence of a blowing agent and other auxiliary agent, comprising using as catalyst MHAP or a mixture of MHAP with a specified amount of another tertiary amine compound.
The present invention also provides, in another aspect thereof, a process for producing a polyurethane foam coated with a skin, comprising forming an unfoamed skin of a polyurethane elastomer or of a vinyl chloride resin in a mold, reacting an organic polysocyanate with a polyol and foaming with a blowing agent in the presence of a 4-methyl-1-(2-hydroxyalkyl) -piperazine in the mold.
Since the catalyst of this invention contains a hydroxyl group which reacts with isocyanate, the catalyst reacts with isocyanat~ and i5 fixed in the urethane foam in the process of forming the foam and therefore the catalyst does not breed. Further, the catalyst of this invention having a high boiling point does not emit bad odor and hardly breeds from foams. Thus, when MHAP is 6~4 used as polymerizing catalyst for polyurethane products coated with skin, deterioration and discoloration of skin can be reduced to a lesser degree~ Furthermore, the catalyst of this inventlon makes a well-balanced pro~ress between the blowing and the gelling reactions which compete in the urethane forming reactions. As a result, when solution A containing polyol and the other sub-raw materials is mixed with solution B of isocyanate, the resulting mixture is sufficiently fluidic to flow and fill every corner of a mold, even if it is of a complex shape, showing good moldability.
The polyurethane products obtained do not show any difference in their physical properties from those of previous products. Therefore, the catalyst of the present invention can be applied without making any change to the formulation.
- 5a ~
A
~ '76614 Detailed Description of the Invention:
The present invention will be described in more detail.
The MHAP which is used in this invention may be prepared in a known process, for example, such a~ by the reaction disclosed in Japanese Laid-Open Patent Application No. Sho 58-162625.
The al~yl group of hydroxyalkyl of ~H~P is selected from the group consisting of ethyl, n-propyl, n-butyl and iso-butyl, but preferably from ethyl and n-propyl groups.
Other tertiary amine compounds compatible with MHAP of this invention include ~nown tertiary amines such as triethylamine, N,N-dimethylcyClohexylamine, N,N,N',N'-tetramethylethylenediamine, N,-N,N',N'-tetLamethylpropylene-dizmine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N",Nn--pentamethyldiethyle~etriamine,N,N,N',Nn,Nn--pentamethyl-(3-aminopropyl)ethylenediamine, ~,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethyl-guaniaine, triethylenediamine, N,N'-dimethylpiperazine, N-methylmor~Soline, N-ethylmorpholine, N-(N',N'-dimethyl-aminoethyl)morpholine, 1,2-dimethylimidazole, 3-(dimethyl-amino)propylimidazole, N,N-dimethylethanolamine, dimethyl-amin~ethoxyethanol, N,N,N'~trimethylaminoethylethanolamine, 1,3-bis(N,N-dimethylamino)-2-propanol, N methyl-N'-(.2-dimethylaminoethyl)piperazin.e, bis(2-dimethylaminoethyl)-ether. However, triethylenediamine and/or.bis(2-dimethyl-aminoethyl)ether are preferable.
~Z76~
When a tertiary amine compound is used in a mixture with MHAP, concentration of the tertiary amine is 0 to 70%, preferably 0 to 60% by weight. When triethylenediamine is used, its concentration should be 2 to 20~, preferably 4 to 15% by weight. When the tertiary amine compound is bis(2-dimethylaminoethyl)ether, 1 to 50%, preferably 2 to 40~ by weight is preferred. Further, when the tertiary amine compounds are triethylenediamine and bis(2-dimethylamino-ethyl)ether, concentrations preferred are 1 to 8% and 1 to 25%-, respectively, by weight.
If the amount of tertiary amine compound exceeds the above-mentioned value, the amine remaining in the poly-urethane product will breed and bring about deterioration and discoloration of skin. Further, the tertiary amine, though depending on its kind, emits bad odor and causes serious problems for the personnel The catalyst ~f this inventi-on may be aPplie~, if necessary, in the form.of a solution i~ water or an organic solvent. Solvents to be used include water, polyols having 2 to 4 hydroxyl groups such as ethyleneglycoI, diethylene-glycol, propyleneglycol, dipropyleneglycol, butanediols, 1,6-hexanediol, and glycerine. Among them, preferable.are water,-ethyleneglycoL,.dipropyleneglycol and 1,4-butanediol.
Water is a favorable solvent because it acts to lower the freezing .point of the catalyst of this invention.. In case wa*er is applied, the mixing rate should be not more than 20~, preferably not more than 15.%. When water is present in an amount.-exceeding 20%, the.melting point of the catalyst of this invention is not lowered and, on the contrary, a formulation which is almost free from water does not work A
66~
properly. On the other hand, the amount of organic solvents to be applied is not particularly restricted, but usually in the range from 5 to 70% by weight. A larger amount of an organic solvent makes too low a concentration of amine in the catalyst or influences unignorably the physical properties of the product.
The catalyst of the present invention, that is MHAP
or a mixture of MHAP with a tertiary amine compound as promotor, is usually employed in the form of a mixture with a solvent which is selected depending on purpose. But, i~ the production of urethane foams, MHAP and tertiary amine may be added separately to the pre-mixed polyol solution.
For example, MHAP and an organic solvent which is added on purpose ~s mixed under a nitroqen atmosphere, and a tertiary amine compound as promotor i~ then added to the mixture.
The catalyst of thi5 invention thus prepared can be used Ln the productio~ of polyurethane foams. In usual cases, the amount of catalyst of this invention is used in an amount of Q.01 to 10 parts, preferably 0~05 to 5 parts, to 100 parts of polyol. Less than O.Ol part of the catalyst gives still low catalytic activity and requires a long time before completion of reaction. On the other hand, an amount more than 10 parts gives unfavorable effects to the physical properties of urethane foams, especially decxeases the compression strength (ILD).
Polyisocyanates from which polyurethane foams can be produced with the catalyst of this invention may be known polyisocyanates including, for example, toluene diisocyanate, lZ'7~
diphenyl methane-4,4'-diisocyanate, polymerized isocyanate~
aliphatic polyisocyanate and those prepolymers containing free isocyanate which are produced by the reaction of the :
mentioned compounds with polyols.
Polyols to be used in this invention include known polyesterpolyols, polyetherpolyols, polymer polyols and the mixture thereof. Known polyesterpolyols usually include those compounds whIch are derived usually from dibasic acid and polyhydric alcohol. Kn~wn polyols concerned are poly-ether poIyols and amine polyols. Polyether polyols are obtained from polyhydric alcohols such as glycol, glycerine, pentaerythritol, trimethylolpropane and saccharose by the addition reaction with ethylene oxide or pr~pylene oxide.
Amine polyols are produced by the addition reaction of amine compound such as ammonia, allphatic and aromatic Emine compounds with ethylene oxide or propylene oxide.
Known polymer pol~ols includ~ thosP which -a-re produced from corresponding polyether polyol reacting with ethylenic unsat~rated monomers such as butadiene, acrylonitrile, and styrene i~ the presence of a radical polymerization catalyst.
In this invention, a cross-linking agent or a chain-extending agent may be added if necessary. The cross linking agent and the chain-extending agent mentioned include polyhydric alcohoLs of a low molecular weight such as ethyleneglycol, 1,4-butanediol, glycerine and polyamine polyols of a low molecular weight such as diethanol amine, triethanol amine and polyamines such as ethylenediamine, xylylenediamine and methylene-bis-ortho-chloroaniline.
_ 9 _ ~Z~614 If necessary in this invention, a blowing agent may be used which is selected from the group consisting of halogenated methanes such as FREON 11, FREON 12 ~ methyl-ene chloride and water.
Further, surfactants such as organic silicon compounds coloring agent, flame retardant and other known additives may be added if necessary. The kind and amount of the additives should be in accordance with ordinary usages without going far beyond known procedure.
The method of producing polyurethane in which the catalyst of this invention is applied is a previously and known one. It is applicable to the one shot method and also to the prepolymer method. The process for producing polyur~thane foams of this invention is particularly useful with molded polyurethane coated with skin, hut it is also applied with success to producing foams by the hot mold, semi-hot mold, HR mold and the RI~ method.
When skin is made from vinyl chloride, poly-urethane foams with skin is produced by so-called vacuum mold and slush mold processes, and this inventi-on is applied to either of the pro-cesses. For t~e skin being made from polyurethane elastomer, the integral skin urethane foam process is the best known one and the molding of the foam has recently been carried out almost solely by the RIM mold process, to which the present invention is also applied with success.
Polyurethane foams coated with skin have been used for a variety of industrial products. These products were mostly black colored and therefore discolora~ion of the foams has not been a serious problem. However, it is a * Trade mark 127f~614 recent trend to color industrial products and many of them are colored brightly.
In this connection, there has not been any solution to amine catalysts. Now, the problem is solved for the coloration of polyurethane foams coated with skin. At the same time, the amine catalyst which has been used against the worker's will because of its bad odor could be replaced to improve labor conditions. In addition, it is now possible to reduce the thickness of the skin which has been made necessarily thick to minimize the trouble of discoloration.
~his is also effective to reduce the cost of manufacturing.
Description of the Preferred Emhodiment:
The present invention will be better understood from the ~ollowing description made with reference to Examples and Comparison Examples. However, it should be understood that the present invention is not res-tricted to these Examples.
[~reparation of catalyst]
Catalysts used in the following Examples, each named by a letter of the alphabet, were prepared from tertiary amine(s) and solventts), as specified in Table 1, in a 500 ml 4-necked flask provided with a stirrer in a nitrogen atmQsphere..
A!
127~i614 Table 1 (in wt.%) Symbol of Catalyst O P Q R S T
MHEP (1) go.0 86.4 56.760.0 65.0 BDMEE (2~ 3.6 25.9 15.0 TEDA (3) 11.1 7.0 DPG ( ) 10.0 10.0 17.428.9 25.0 M~PP (S) ' 100 (i) 4-Methy}-1-(2-hydroxyethyl)piperazine (2) Bis-(2-dimethylaminoethyl)ether ~3) Triethylenediamine (4) Dipropyleneglycol t5) 4-Methyl-l-(Z-hydroxypropyl)piperazine tExamples of foaming tests]
~xamples 1, 2, 3 and 4:
~sing ~he catalysts O, P, Q and T specified in Table 1, foaming test was carried out with the following formulation. ResuLts are shown in Table ~.
1) Formulation pbw Polyol I 100 Polyol II 5.0 Water 2.0 ~Triethanolamine 5.0 Catalyst varied Isocyanate I 57.5 (Index 105) ~27~61~
R~marks:
Polyol ~;
Product from Sumitomo-Bayer Urethane Co.
Trade name, Sumiphen 3063 OH value, 2~ mg KOH/g Polyol II;
Product from Sumitomo-Bayer Urethane Co.
Trade name, S.B.U. Polyol 0480 O~ value, 550 mg KOH/g IsQcy~nate I;
Product from Sumitomo-Bayer Urethane Co.
Trade name, Sumidure 44v20 NCO group content 31% with crude MDI
(2) Foaming test conditions T~mperature of raw materia~ solution-, 20 + 1C
Speed of agitation, 5Q00 rpm. (for 5 m~n.1 Temperature of mold, 35 - 38C
~3) Items of measurement 1) Density of foam A predetermined amount of solution was po~red in a 2 :~ter beaker, and the foaming reaction was completed. A 7 cm x 7 cm x 6 cm portion was cut at the center of the foam and submitted to the measurement.
2) Hardness of foam Us~ng the above-mentioned foam sample, compressive strength of the foam was measured when the foam was compressed by 40%.
3) Flow property A certain amount of a mixed solution was in~ected fr~m the bottom of an aluminum mold of 50 cm length, 12 cm width and 0.5 cm thickness which was placed on a 25 31ant, the foaming reaction was completed. The distance of flow of the produced foam was measured.
1~66~l~
4) Discoloration test A test piece for the discoloration test was prepared by pouring raw material of polyurethane onto a vinyl chloride resin (GR-20 from Plastech Co.) which was then foamed. The piece obtained was heated in an oven at 80C and the discolora-tion in 400 hr. estimated with a color meter was expressed by the color difference (~E).
In (1), a very low boiling point amine cataly~t is mostly evapor~ted in the course of production of urethane foams leaving no remainder of amine catalyst. However, as mentioned above, this kind of amine compound has intolerable bad odor, deteriorates tbe working condition, and in an extreme 6~4 case it may bring about an environmental problem. Further, a low boiling compound such as this amine catalyst may evaporate while it is kept in a pre-mixed composi-tion solution and the reaction may not proceed at the expected reaction rate. Therefore, (1) does not provide an effective means.
The remedy (3) seems a useful one, because an amine catalyst having a large molecular weight hardly breeds and also hardly evaporates. Emitting of bad odor of the amine is no longer feared. However, for an amine catalyst of a large molecular weight, the catalytic ac-tivity per unit weight is reduced and a larger amo-~t is needed. In addition, the amine is more immiscible and some amines are solid at room temperature. Thus, (3) does not always provide a useful means.
The present inventors noted tertiary amine-compounds which hola reactivity with i ocyanate and the reactive functi-onal group of which forms an amine catalyst of a higher boiling point due to formation of hydrogen bonds.
In other words, they expected to solve the problem of deterio-ration of discoloration of the-skin by the remedies (2) and (a), and their investigations were solely on the tertiary amine c~talysts having these reactive groups. As a result, they found that, when 4-methyl~ 2-hydroxyalkyl)piperazine (hereinafter designated as MHAP) or a mixture of MHAP and a specifi-ed amount of another tertiary amine compound was used as catalyst, skin of the product polyurethane showed very little deterioration and discoloration and physical properties as well as moldability of foams were excellent, and they succeeded in completion of this invention.
.~' ~ - 4 -lZ76~L4 The present invention provides catalysts for producing polyruethane foams coated with skin which are excellent in their physical properties and moldability of foams and the skin of which is least deteriorated and discolored by the reaction of an organic polyisocyanate with a polyol in the presence of a blowing agent and other auxiliary agent, comprising using as catalyst MHAP or a mixture of MHAP with a specified amount of another tertiary amine compound.
The present invention also provides, in another aspect thereof, a process for producing a polyurethane foam coated with a skin, comprising forming an unfoamed skin of a polyurethane elastomer or of a vinyl chloride resin in a mold, reacting an organic polysocyanate with a polyol and foaming with a blowing agent in the presence of a 4-methyl-1-(2-hydroxyalkyl) -piperazine in the mold.
Since the catalyst of this invention contains a hydroxyl group which reacts with isocyanate, the catalyst reacts with isocyanat~ and i5 fixed in the urethane foam in the process of forming the foam and therefore the catalyst does not breed. Further, the catalyst of this invention having a high boiling point does not emit bad odor and hardly breeds from foams. Thus, when MHAP is 6~4 used as polymerizing catalyst for polyurethane products coated with skin, deterioration and discoloration of skin can be reduced to a lesser degree~ Furthermore, the catalyst of this inventlon makes a well-balanced pro~ress between the blowing and the gelling reactions which compete in the urethane forming reactions. As a result, when solution A containing polyol and the other sub-raw materials is mixed with solution B of isocyanate, the resulting mixture is sufficiently fluidic to flow and fill every corner of a mold, even if it is of a complex shape, showing good moldability.
The polyurethane products obtained do not show any difference in their physical properties from those of previous products. Therefore, the catalyst of the present invention can be applied without making any change to the formulation.
- 5a ~
A
~ '76614 Detailed Description of the Invention:
The present invention will be described in more detail.
The MHAP which is used in this invention may be prepared in a known process, for example, such a~ by the reaction disclosed in Japanese Laid-Open Patent Application No. Sho 58-162625.
The al~yl group of hydroxyalkyl of ~H~P is selected from the group consisting of ethyl, n-propyl, n-butyl and iso-butyl, but preferably from ethyl and n-propyl groups.
Other tertiary amine compounds compatible with MHAP of this invention include ~nown tertiary amines such as triethylamine, N,N-dimethylcyClohexylamine, N,N,N',N'-tetramethylethylenediamine, N,-N,N',N'-tetLamethylpropylene-dizmine, N,N,N',N'-tetramethylhexamethylenediamine, N,N,N',N",Nn--pentamethyldiethyle~etriamine,N,N,N',Nn,Nn--pentamethyl-(3-aminopropyl)ethylenediamine, ~,N,N',N",N"-pentamethyldipropylenetriamine, N,N,N',N'-tetramethyl-guaniaine, triethylenediamine, N,N'-dimethylpiperazine, N-methylmor~Soline, N-ethylmorpholine, N-(N',N'-dimethyl-aminoethyl)morpholine, 1,2-dimethylimidazole, 3-(dimethyl-amino)propylimidazole, N,N-dimethylethanolamine, dimethyl-amin~ethoxyethanol, N,N,N'~trimethylaminoethylethanolamine, 1,3-bis(N,N-dimethylamino)-2-propanol, N methyl-N'-(.2-dimethylaminoethyl)piperazin.e, bis(2-dimethylaminoethyl)-ether. However, triethylenediamine and/or.bis(2-dimethyl-aminoethyl)ether are preferable.
~Z76~
When a tertiary amine compound is used in a mixture with MHAP, concentration of the tertiary amine is 0 to 70%, preferably 0 to 60% by weight. When triethylenediamine is used, its concentration should be 2 to 20~, preferably 4 to 15% by weight. When the tertiary amine compound is bis(2-dimethylaminoethyl)ether, 1 to 50%, preferably 2 to 40~ by weight is preferred. Further, when the tertiary amine compounds are triethylenediamine and bis(2-dimethylamino-ethyl)ether, concentrations preferred are 1 to 8% and 1 to 25%-, respectively, by weight.
If the amount of tertiary amine compound exceeds the above-mentioned value, the amine remaining in the poly-urethane product will breed and bring about deterioration and discoloration of skin. Further, the tertiary amine, though depending on its kind, emits bad odor and causes serious problems for the personnel The catalyst ~f this inventi-on may be aPplie~, if necessary, in the form.of a solution i~ water or an organic solvent. Solvents to be used include water, polyols having 2 to 4 hydroxyl groups such as ethyleneglycoI, diethylene-glycol, propyleneglycol, dipropyleneglycol, butanediols, 1,6-hexanediol, and glycerine. Among them, preferable.are water,-ethyleneglycoL,.dipropyleneglycol and 1,4-butanediol.
Water is a favorable solvent because it acts to lower the freezing .point of the catalyst of this invention.. In case wa*er is applied, the mixing rate should be not more than 20~, preferably not more than 15.%. When water is present in an amount.-exceeding 20%, the.melting point of the catalyst of this invention is not lowered and, on the contrary, a formulation which is almost free from water does not work A
66~
properly. On the other hand, the amount of organic solvents to be applied is not particularly restricted, but usually in the range from 5 to 70% by weight. A larger amount of an organic solvent makes too low a concentration of amine in the catalyst or influences unignorably the physical properties of the product.
The catalyst of the present invention, that is MHAP
or a mixture of MHAP with a tertiary amine compound as promotor, is usually employed in the form of a mixture with a solvent which is selected depending on purpose. But, i~ the production of urethane foams, MHAP and tertiary amine may be added separately to the pre-mixed polyol solution.
For example, MHAP and an organic solvent which is added on purpose ~s mixed under a nitroqen atmosphere, and a tertiary amine compound as promotor i~ then added to the mixture.
The catalyst of thi5 invention thus prepared can be used Ln the productio~ of polyurethane foams. In usual cases, the amount of catalyst of this invention is used in an amount of Q.01 to 10 parts, preferably 0~05 to 5 parts, to 100 parts of polyol. Less than O.Ol part of the catalyst gives still low catalytic activity and requires a long time before completion of reaction. On the other hand, an amount more than 10 parts gives unfavorable effects to the physical properties of urethane foams, especially decxeases the compression strength (ILD).
Polyisocyanates from which polyurethane foams can be produced with the catalyst of this invention may be known polyisocyanates including, for example, toluene diisocyanate, lZ'7~
diphenyl methane-4,4'-diisocyanate, polymerized isocyanate~
aliphatic polyisocyanate and those prepolymers containing free isocyanate which are produced by the reaction of the :
mentioned compounds with polyols.
Polyols to be used in this invention include known polyesterpolyols, polyetherpolyols, polymer polyols and the mixture thereof. Known polyesterpolyols usually include those compounds whIch are derived usually from dibasic acid and polyhydric alcohol. Kn~wn polyols concerned are poly-ether poIyols and amine polyols. Polyether polyols are obtained from polyhydric alcohols such as glycol, glycerine, pentaerythritol, trimethylolpropane and saccharose by the addition reaction with ethylene oxide or pr~pylene oxide.
Amine polyols are produced by the addition reaction of amine compound such as ammonia, allphatic and aromatic Emine compounds with ethylene oxide or propylene oxide.
Known polymer pol~ols includ~ thosP which -a-re produced from corresponding polyether polyol reacting with ethylenic unsat~rated monomers such as butadiene, acrylonitrile, and styrene i~ the presence of a radical polymerization catalyst.
In this invention, a cross-linking agent or a chain-extending agent may be added if necessary. The cross linking agent and the chain-extending agent mentioned include polyhydric alcohoLs of a low molecular weight such as ethyleneglycol, 1,4-butanediol, glycerine and polyamine polyols of a low molecular weight such as diethanol amine, triethanol amine and polyamines such as ethylenediamine, xylylenediamine and methylene-bis-ortho-chloroaniline.
_ 9 _ ~Z~614 If necessary in this invention, a blowing agent may be used which is selected from the group consisting of halogenated methanes such as FREON 11, FREON 12 ~ methyl-ene chloride and water.
Further, surfactants such as organic silicon compounds coloring agent, flame retardant and other known additives may be added if necessary. The kind and amount of the additives should be in accordance with ordinary usages without going far beyond known procedure.
The method of producing polyurethane in which the catalyst of this invention is applied is a previously and known one. It is applicable to the one shot method and also to the prepolymer method. The process for producing polyur~thane foams of this invention is particularly useful with molded polyurethane coated with skin, hut it is also applied with success to producing foams by the hot mold, semi-hot mold, HR mold and the RI~ method.
When skin is made from vinyl chloride, poly-urethane foams with skin is produced by so-called vacuum mold and slush mold processes, and this inventi-on is applied to either of the pro-cesses. For t~e skin being made from polyurethane elastomer, the integral skin urethane foam process is the best known one and the molding of the foam has recently been carried out almost solely by the RIM mold process, to which the present invention is also applied with success.
Polyurethane foams coated with skin have been used for a variety of industrial products. These products were mostly black colored and therefore discolora~ion of the foams has not been a serious problem. However, it is a * Trade mark 127f~614 recent trend to color industrial products and many of them are colored brightly.
In this connection, there has not been any solution to amine catalysts. Now, the problem is solved for the coloration of polyurethane foams coated with skin. At the same time, the amine catalyst which has been used against the worker's will because of its bad odor could be replaced to improve labor conditions. In addition, it is now possible to reduce the thickness of the skin which has been made necessarily thick to minimize the trouble of discoloration.
~his is also effective to reduce the cost of manufacturing.
Description of the Preferred Emhodiment:
The present invention will be better understood from the ~ollowing description made with reference to Examples and Comparison Examples. However, it should be understood that the present invention is not res-tricted to these Examples.
[~reparation of catalyst]
Catalysts used in the following Examples, each named by a letter of the alphabet, were prepared from tertiary amine(s) and solventts), as specified in Table 1, in a 500 ml 4-necked flask provided with a stirrer in a nitrogen atmQsphere..
A!
127~i614 Table 1 (in wt.%) Symbol of Catalyst O P Q R S T
MHEP (1) go.0 86.4 56.760.0 65.0 BDMEE (2~ 3.6 25.9 15.0 TEDA (3) 11.1 7.0 DPG ( ) 10.0 10.0 17.428.9 25.0 M~PP (S) ' 100 (i) 4-Methy}-1-(2-hydroxyethyl)piperazine (2) Bis-(2-dimethylaminoethyl)ether ~3) Triethylenediamine (4) Dipropyleneglycol t5) 4-Methyl-l-(Z-hydroxypropyl)piperazine tExamples of foaming tests]
~xamples 1, 2, 3 and 4:
~sing ~he catalysts O, P, Q and T specified in Table 1, foaming test was carried out with the following formulation. ResuLts are shown in Table ~.
1) Formulation pbw Polyol I 100 Polyol II 5.0 Water 2.0 ~Triethanolamine 5.0 Catalyst varied Isocyanate I 57.5 (Index 105) ~27~61~
R~marks:
Polyol ~;
Product from Sumitomo-Bayer Urethane Co.
Trade name, Sumiphen 3063 OH value, 2~ mg KOH/g Polyol II;
Product from Sumitomo-Bayer Urethane Co.
Trade name, S.B.U. Polyol 0480 O~ value, 550 mg KOH/g IsQcy~nate I;
Product from Sumitomo-Bayer Urethane Co.
Trade name, Sumidure 44v20 NCO group content 31% with crude MDI
(2) Foaming test conditions T~mperature of raw materia~ solution-, 20 + 1C
Speed of agitation, 5Q00 rpm. (for 5 m~n.1 Temperature of mold, 35 - 38C
~3) Items of measurement 1) Density of foam A predetermined amount of solution was po~red in a 2 :~ter beaker, and the foaming reaction was completed. A 7 cm x 7 cm x 6 cm portion was cut at the center of the foam and submitted to the measurement.
2) Hardness of foam Us~ng the above-mentioned foam sample, compressive strength of the foam was measured when the foam was compressed by 40%.
3) Flow property A certain amount of a mixed solution was in~ected fr~m the bottom of an aluminum mold of 50 cm length, 12 cm width and 0.5 cm thickness which was placed on a 25 31ant, the foaming reaction was completed. The distance of flow of the produced foam was measured.
1~66~l~
4) Discoloration test A test piece for the discoloration test was prepared by pouring raw material of polyurethane onto a vinyl chloride resin (GR-20 from Plastech Co.) which was then foamed. The piece obtained was heated in an oven at 80C and the discolora-tion in 400 hr. estimated with a color meter was expressed by the color difference (~E).
5) Odor With the catalysts employed in the foaming tests, odor of the catalysts was e~pressed by the following symbols:
o: Very weak o: Weak x : Strong xx: Very strong Comparison Examples 1 and 2-Foaming tests were conducted in the same m~nner as in Example 1, except that the catalysts used were-TEDA-L33 (a 33.3% solution triethylenediamine i~ dipropylenegl~col, supplied from Toyo Soda Indu-stry Co.,Ltd.) and TEA (triethyl-amine). Results are shown in Table 2.
12~66~4 Table 2 Comparison Example Example _ _ No. of Example 1 2 3 4 1 2 Catalyst (symbol TEDA TEABlank ) and name) O P Q T -L33 test Catalyst t~}~w).-~ 1.30 1.3~ 0.48 1.71 0.410.68 Reaction ra~el~
CT -~sec) 23 19 19 24 26 22 GT (sec) 75 -65 75 75 75 75 RT (sec~ 94 79 92 95 103 96 Physica7 prDpe l-ies Densit~ (kg~m9~ 96.8 86.0 74 96.5132 87.3 Hardness (kg/cm23 O.30 0.23 0.15 0.28 0.77 0.24 ~low ~roparty ~cm3 2~ 32 43 26 16 30 Discoloration ~3 2.6.3 26.7 28.5 26.8 40.525.3 24.6 . ... - ~ ... - . ..... _ Odor ~ ~ O ~ O X X
.~
1) CT : Cream time --GT : Gel time ~T -: ~ise time 2) Blan~ test : Discoloration of uinyl chloride resin without polyurethane foam.
7~
Examples 5 and 6:
Using catalysts R and S appearing in Tahle 1, the foaming test was conducted with the following formulation. Results obtained are shown in Table 3.
(1) Formulation pbw POLYOL 11 I (trade mark) 60 POLYOL IV ( trade mark) 40 Water 2.7 SILICONE (trade mark) 2.0 Catalyst varied Isocyanate II 34.0 (Index 105) Remarks.
POLYOL III;
Product of San'yo Chemical Co_ Trade mark, FA-703 OH value, 33 mg K~/g POLYOL IV;
Product of San'yo Chemical Co.
Trade mark, FA-728 OH value, 28 mg.ROH/g SILICONE I;
Produc~ of Toray Silicone Co.
Trade name SRX-274C
Silicone surfactant Isocyanate II;
Product of Nippon Polyurethane Co.
Consisting of T-81/MR-200=80/20 (TDI and crude MDI blended) `t 12~6: L~ 2) Foaming test conditions Temperature o~ raw material solution, 20 1 1C
Stirring speed, 6000 rpm (5 sec.) Mold temperature, 50 + 2C
(3) Items of measurement 1) Reaction profiles .Foaming reaction was performed in a 2 liter polyethylene beaker an~ CT, GT and RT were estimated.
2) Discoloxation test Foam prepared in a 2 liter polyethylene beaker by foaming was pasted with a piece of gray vinyl chloride resin, and the chan~e of colQr was o~servea in 400 hours during-which period the object was kept at 80C.
Comparison Examples 3 and 4:
~ he same fo~ming tests as in Example 4, except that the catalysts used were TEnA~L33 and TMEMDA (N,N,N',N'-tetramethylhexamethylenediami-ne), was conducted with the results shown in Table 3-.
~ 2766~4 Table 3 Example Comparison Example No. of Example 4 5 3 4 _ _ ______ _ _ Catalyst (symbol . TEDA TMHMDA
and name) R S -L33 Amount of catalyst (pbw)1.55 1.311.00 0.75 _ Reactio~ rate CT (sec ) 5 4 5 5 GT (sec )80 80 80 ao RT (sec )106 112 lQ7 108 Discoloration Almost no Almost no Dar~ened Darkened test change change .... ._
o: Very weak o: Weak x : Strong xx: Very strong Comparison Examples 1 and 2-Foaming tests were conducted in the same m~nner as in Example 1, except that the catalysts used were-TEDA-L33 (a 33.3% solution triethylenediamine i~ dipropylenegl~col, supplied from Toyo Soda Indu-stry Co.,Ltd.) and TEA (triethyl-amine). Results are shown in Table 2.
12~66~4 Table 2 Comparison Example Example _ _ No. of Example 1 2 3 4 1 2 Catalyst (symbol TEDA TEABlank ) and name) O P Q T -L33 test Catalyst t~}~w).-~ 1.30 1.3~ 0.48 1.71 0.410.68 Reaction ra~el~
CT -~sec) 23 19 19 24 26 22 GT (sec) 75 -65 75 75 75 75 RT (sec~ 94 79 92 95 103 96 Physica7 prDpe l-ies Densit~ (kg~m9~ 96.8 86.0 74 96.5132 87.3 Hardness (kg/cm23 O.30 0.23 0.15 0.28 0.77 0.24 ~low ~roparty ~cm3 2~ 32 43 26 16 30 Discoloration ~3 2.6.3 26.7 28.5 26.8 40.525.3 24.6 . ... - ~ ... - . ..... _ Odor ~ ~ O ~ O X X
.~
1) CT : Cream time --GT : Gel time ~T -: ~ise time 2) Blan~ test : Discoloration of uinyl chloride resin without polyurethane foam.
7~
Examples 5 and 6:
Using catalysts R and S appearing in Tahle 1, the foaming test was conducted with the following formulation. Results obtained are shown in Table 3.
(1) Formulation pbw POLYOL 11 I (trade mark) 60 POLYOL IV ( trade mark) 40 Water 2.7 SILICONE (trade mark) 2.0 Catalyst varied Isocyanate II 34.0 (Index 105) Remarks.
POLYOL III;
Product of San'yo Chemical Co_ Trade mark, FA-703 OH value, 33 mg K~/g POLYOL IV;
Product of San'yo Chemical Co.
Trade mark, FA-728 OH value, 28 mg.ROH/g SILICONE I;
Produc~ of Toray Silicone Co.
Trade name SRX-274C
Silicone surfactant Isocyanate II;
Product of Nippon Polyurethane Co.
Consisting of T-81/MR-200=80/20 (TDI and crude MDI blended) `t 12~6: L~ 2) Foaming test conditions Temperature o~ raw material solution, 20 1 1C
Stirring speed, 6000 rpm (5 sec.) Mold temperature, 50 + 2C
(3) Items of measurement 1) Reaction profiles .Foaming reaction was performed in a 2 liter polyethylene beaker an~ CT, GT and RT were estimated.
2) Discoloxation test Foam prepared in a 2 liter polyethylene beaker by foaming was pasted with a piece of gray vinyl chloride resin, and the chan~e of colQr was o~servea in 400 hours during-which period the object was kept at 80C.
Comparison Examples 3 and 4:
~ he same fo~ming tests as in Example 4, except that the catalysts used were TEnA~L33 and TMEMDA (N,N,N',N'-tetramethylhexamethylenediami-ne), was conducted with the results shown in Table 3-.
~ 2766~4 Table 3 Example Comparison Example No. of Example 4 5 3 4 _ _ ______ _ _ Catalyst (symbol . TEDA TMHMDA
and name) R S -L33 Amount of catalyst (pbw)1.55 1.311.00 0.75 _ Reactio~ rate CT (sec ) 5 4 5 5 GT (sec )80 80 80 ao RT (sec )106 112 lQ7 108 Discoloration Almost no Almost no Dar~ened Darkened test change change .... ._
Claims (14)
1. A process for producing a polyurethane foam coated with a skin, comprising forming an unfoamed skin of a polyurethane elastomer or of a vinyl chloride resin in a mold, reacting an organic polyisocyanate with a polyol and foaming with a blowing agent in the presence of a 4-methyl-1(2-hydroxyalkyl)piperazine in the mold.
2. A process according to claim 1, wherein the skin is made from a polyurethane elastomer.
3. A process according to claim 1, wherein the skin is made from a vinyl chloride resin.
4. A process according to claim 1, wherein piperazine has 2 to 4 carbon atoms in the hydroxyalkyl group.
5. A process according to claim 4, wherein the hydroxyalkyl group is hydroxyethyl.
6. A process according to claim 4, wherein the hydroxyalkyl group is hydroxypropyl.
7. A process according to claim 1, comprising adding another tertiary amine as a promotor.
8. A process according to claim 7, wherein the promotor is triethylenediamine bis-(2-dimethyl-amino-ethyl) ether or a mixture thereof.
9. A process according to claim 8, wherein the concentrations of 4-methyl-1-(2-hydroxyalkyl) piperazine and bis-(2-dimethylaminoethyl) ether are 98 to 50% and 1 to 50%, respectively, by weight based on the two materials.
10. A process according to claim 8, wherein there are employed 4-methyl-1-(2-hydroxyalkyl) piperazine, triethylenediamine and bis-(2-dimethyl-aminoethyl) ether in an amount of 98 to 67%, 1 to 8%
and 1 to 25%, respectively, by weight based on these three materials.
and 1 to 25%, respectively, by weight based on these three materials.
11. A process according to claim 8, wherein the concentrations of 4-methyl-1-(2-hydroxyalkyl) piperazine, and triethylenediamine are 98 to 85%
and 2 to 20% respectively, by weight based on these two materials.
and 2 to 20% respectively, by weight based on these two materials.
12. A process according to claim 1, comprising including a solvent with the 4-methyl-1-(2-hydroxy-alkyl) piperazine.
13. A process according to claim 12, wherein the solvent is selected from the group consisting of dipropylene glycol, ethylene glycol, 1,4-butanediol and water.
14. A process according to claim 13, wherein water is the solvent and the concentration of the piperazine is not more than 15% by weight.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60139121A JPH0615602B2 (en) | 1985-06-27 | 1985-06-27 | Catalyst for producing polyurethane foam with skin |
| JP60-139121 | 1985-06-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1276614C true CA1276614C (en) | 1990-11-20 |
Family
ID=15237988
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000511825A Expired - Lifetime CA1276614C (en) | 1985-06-27 | 1986-06-18 | Catalyst for producing polyurethane foams coated with skin |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4701473A (en) |
| EP (1) | EP0210440B1 (en) |
| JP (1) | JPH0615602B2 (en) |
| KR (1) | KR930006914B1 (en) |
| CA (1) | CA1276614C (en) |
| DE (1) | DE3682843D1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4994502A (en) * | 1987-07-01 | 1991-02-19 | Basf Corporation | Process for the preparation of integral skin polyurethane steering wheels |
| US4980385A (en) * | 1989-05-22 | 1990-12-25 | Basf Corporation | Polyurethane/polycarbonate compatibility |
| US5086084A (en) * | 1989-08-29 | 1992-02-04 | Lee H. Ambrose | Polyvinyl chloride/polyurethane hybrid foams |
| JP3044261B2 (en) * | 1990-04-11 | 2000-05-22 | 東ソー株式会社 | Method for producing flexible polyurethane foam with excellent air permeability |
| JPH04298519A (en) * | 1990-09-19 | 1992-10-22 | Tokyo Seat Kk | Production of molded urethane foam |
| US5240964A (en) * | 1990-09-19 | 1993-08-31 | Tokyo Seat Co., Ltd. | Process for producing urethane foam with high density skin |
| JP2552947B2 (en) * | 1990-09-19 | 1996-11-13 | 東京シート株式会社 | Method for manufacturing urethane foam molded product |
| JP2552954B2 (en) * | 1990-11-29 | 1996-11-13 | 東京シート株式会社 | Method for manufacturing urethane foam molded product |
| US5265558A (en) * | 1992-05-19 | 1993-11-30 | Schoenrock Thomas | Foam bed for domestic animals having integrally formed, liquid impermeable outer skin |
| US6745770B2 (en) | 2002-01-08 | 2004-06-08 | Resmed Limited | Flow diverter for controlling the pressure and flow rate in a CPAP device |
| JP5055730B2 (en) * | 2005-09-13 | 2012-10-24 | 東ソー株式会社 | Catalyst composition for producing polyurethane resin and method for producing polyurethane resin |
| US7568758B2 (en) | 2007-01-03 | 2009-08-04 | Kolcraft Enterprises | High chairs and methods to use high chairs |
| JP5561261B2 (en) * | 2011-09-20 | 2014-07-30 | 東ソー株式会社 | Catalyst composition for producing polyurethane resin and method for producing polyurethane resin |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3623931A (en) * | 1967-11-13 | 1971-11-30 | Hollis L Van Hosen | Method of making plastic cushion product |
| DE2732292A1 (en) * | 1977-07-16 | 1979-02-01 | Bayer Ag | METHOD FOR MANUFACTURING POLYURETHANE PLASTICS |
| JPS58162625A (en) * | 1982-03-23 | 1983-09-27 | Toyo Soda Mfg Co Ltd | Catalyst for polyurethane production |
-
1985
- 1985-06-27 JP JP60139121A patent/JPH0615602B2/en not_active Expired - Fee Related
-
1986
- 1986-06-18 CA CA000511825A patent/CA1276614C/en not_active Expired - Lifetime
- 1986-06-23 US US06/877,403 patent/US4701473A/en not_active Expired - Lifetime
- 1986-06-23 KR KR1019860005008A patent/KR930006914B1/en not_active IP Right Cessation
- 1986-06-26 DE DE8686108730T patent/DE3682843D1/en not_active Expired - Fee Related
- 1986-06-26 EP EP86108730A patent/EP0210440B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| DE3682843D1 (en) | 1992-01-23 |
| EP0210440A1 (en) | 1987-02-04 |
| EP0210440B1 (en) | 1991-12-11 |
| JPS62514A (en) | 1987-01-06 |
| US4701473A (en) | 1987-10-20 |
| KR930006914B1 (en) | 1993-07-24 |
| JPH0615602B2 (en) | 1994-03-02 |
| KR870000368A (en) | 1987-02-18 |
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