JP2005146109A - Amine catalyst composition for production of polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amine catalyst composition used in the production of a polyurethane resin to reduce aldehydes in polyurethane resin articles such as furniture, cushioning materials (e.g. automotive seat), and insulating materials for houses, to provide a method for producing the same, and to provide a method for producing a polyurethane resin by using the same. <P>SOLUTION: A polyol is reacted with a polyisocyanate in the presence of the catalyst composition used in the production of a polyurethane resin and containing a tertiary amine compound, a complex metal hydride, and a solvent. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a catalyst composition for producing polyurethane resins such as soft, hard, semi-rigid and elastomer. More specifically, the present invention relates to an amine catalyst composition for producing a polyurethane resin having a reduced content of aldehydes in a volatile organic compound (VOC), a method for producing the same, and a method for producing a polyurethane resin using the same. .

  The polyurethane resin is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a crosslinking agent and the like. In particular, polyurethane products produced using a foaming agent are frequently used for furniture, interior parts such as automobile seats, electric refrigerators, and heat insulating materials for houses. Conventionally, it is known that many metal compounds and tertiary amine compounds are used as a catalyst for the production of this polyurethane resin (see, for example, Non-Patent Document 1 for the production and catalyst of polyurethane). These catalysts are often used industrially when used alone or in combination.

  Among these catalysts, particularly tertiary amine compounds are widely used as amine-based catalysts for producing polyurethane resins because of their excellent productivity and moldability. For example, conventionally known triethylenediamine, N, N, N ′, N′-tetramethylhexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, Compounds such as N, N-dimethylcyclohexylamine, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N-dimethylethanolamine, 1,8-diazabicyclo [5.4.0] undecene-7 . In most cases, the metal catalyst is often used in combination with an amine catalyst and is rarely used alone.

  In recent years, health problems such as so-called sick house syndrome and chemical hypersensitivity caused by contamination of indoor air by volatile organic compounds (VOC) have begun to be pointed out. In response to this, the Ministry of Health, Labor and Welfare has set an allowable concentration for 13 substances that may cause sick house syndrome and has begun regulations.

  Among these 13 substances, aldehydes represented by formaldehyde have been subject to VOC regulations strengthening from early on. Regarding the problem that formaldehyde is emitted from residential building materials, etc., the regulation of formaldehyde has been strengthened by the revised Building Standard Law from July 1, 2003. In automobiles, there is a strong demand for reducing VOCs from the interior space of vehicles, and there is an urgent need to reduce VOCs from interior parts such as automobile seats. Conventionally, since polyurethane foam products used for automobile interior parts are manufactured using polyols, polyisocyanates, amine catalysts, and the like, naturally there has been a strong demand for reduction of VOC regulated substances in these raw materials. ing.

  The tertiary amine compound conventionally used as an amine catalyst contains at least formaldehyde and acetaldehyde. In particular, in a method for producing a tertiary amine compound using alcohols or formaldehyde as a raw material, there is a concern that an oxide of alcohol or an excessive amount of formaldehyde may be mixed in the product (production of a tertiary amine compound). (For example, refer to Patent Document 1). In such a production method, after the reaction, a method of reducing the remaining formaldehyde by performing sodium hydroxide treatment has been proposed, but the purpose has not yet been achieved (for the production method of a tertiary amine compound, for example, Patent Document 2).

  In addition, a method using a secondary amine (for example, ethylenediamine, dimethylamine, piperazine, etc.) and a hydrazide (for example, adipic acid dihydrazide, etc.) as a compound for capturing formaldehyde has been proposed (capturing formaldehyde). (For example, refer to Patent Document 3 and Patent Document 4). However, even if these compounds capable of capturing formaldehyde are used, the effect of reducing aldehydes is not sufficient, and further reduction of aldehydes is required.

JP-A-60-130551

JP 59-199655 A JP 2000-169757 A JP 2001-187402 A Edited by Keiji Iwata, "Polyurethane resin handbook", published by Nikkan Kogyo Shimbun, 1987

  The present invention has been made in view of the above problems, and its purpose is to reduce aldehydes such as polyurethane resin products such as furniture and automobile seats, cushioning materials such as automobile seats, and heat insulating materials for houses. It is an object to provide an amine catalyst composition used for producing a target polyurethane resin, a production method thereof and a production method of a polyurethane resin using the same.

  The present inventors have made extensive studies to solve the above problems. As a result, it was found that when a tertiary amine compound, a complex metal hydride and a solvent used in the production of a polyurethane resin were mixed to form a solution, a catalyst composition with a reduced amount of aldehydes was obtained. It came to be completed.

That is, the present invention
1. A catalyst composition for producing a polyurethane resin comprising a tertiary amine compound, a complex metal hydride and a solvent;
2. A catalyst composition for producing a polyurethane resin obtained by dissolving a tertiary amine compound and a complex metal hydride in a solvent;
3. A method for producing a catalyst composition for producing the polyurethane resin, wherein a tertiary amine compound and a complex metal hydride are dissolved in a solvent;
4). A method for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition,
5). The polyol and the polyisocyanate are reacted with one or more selected from the group consisting of water, liquefied carbon dioxide and low-boiling organic compounds as a blowing agent in the presence of the catalyst composition. 5. a featured polyurethane foam manufacturing method, and A process for producing a polyurethane resin, comprising reacting a polyol premix obtained by adding a tertiary amine compound and a complex metal hydroxide to a polyol and dissolving the polyol, and a polyisocyanate.

  Hereinafter, the present invention will be described in more detail.

  The catalyst composition for producing the polyurethane resin of the present invention is a catalyst composition containing a tertiary amine compound, a complex metal hydride and a solvent, and the tertiary amine compound and the complex metal hydride are dissolved in the solvent. A catalyst composition.

  In the present invention, the tertiary amine compound may be selected from those having a structure having at least one tertiary amino group in the molecule, and is not particularly limited. Amine catalysts such as triethylenediamine, N, N′-dimethylpiperazine, N, N-dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, trimethylamine, triethylamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylhexanediamine, 1- (2′- Dimethylaminoethyl) -4-methylpiperazine, N, N, N ′, N ″, N ″ -pentamethyldie Rentriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N ″ -pentamethyldipropylenetriamine, N, N, N ', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [5.4.0] undecene-7, 1-methyl Imidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, 1- (2′-hydroxypropyl) -2-methylimidazole, N-methyldicyclohexylamine, N, N- Dimethylbenzylamine, N, N-dimethyloctylamine, N, N-dimethyldecylamine, N, N- Methyldodecylamine, N, N-dimethylethanolamine, N, N-dimethylisopropanolamine, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethyl-N ′-( 2-hydroxyethyl) ethylenediamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) propanediamine, N- (2-hydroxypropyl) -N, N ′, N ″, N ″ -tetramethyl Diethylenetriamine, N, N-dimethylaminopropylamine, bis (dimethylaminopropyl) amine, N, N-dimethyl-N ′, N′-bis (isopropanol) propanediamine, bis (dimethylaminopropyl) isopropanolamine, N, N , N′-Trimethyl-N ′-(2-hydroxyethyl ) Bis (2-aminoethyl) ether, 3-quinuclidinol and the like are preferred, and among these, tertiary amine compounds produced using alcohols and formaldehyde as raw materials are more preferred.

In the present invention, the complex metal hydride is not particularly limited. For example, sodium borohydride (NaBH ₄ ), potassium borohydride (KBH ₄ ), lithium borohydride (LiBH ₄ ), zinc borohydride (Zn ( BH ₄ ) ₂ ), sodium cyanide borohydride (NaBH ₃ CN), sodium borohydride trimethoxide (NaBH (OCH ₃ ) ₃ ), lithium aluminum hydride (LiAlH ₄ ) and the like, and further lithium aluminum hydride Examples thereof include tris-butyl, trimethoxide, and tri-t-butoxide substituted with part of hydrogen atoms. Among these, sodium borohydride, potassium borohydride, lithium borohydride, and Chi um aluminum hydride is preferably used, more preferably sodium borohydride which can be used for general purposes.

  In the present invention, the solvent is not particularly limited as long as it is a solvent capable of dissolving the complex metal hydride and the tertiary amine compound. However, since it is used for producing a polyurethane resin, alcohols or water is preferable. . As the alcohols, polyfunctional alcohols higher than glycol are preferable for maintaining resin properties, such as ethylene glycol, diethylene glycol and polyethylene glycol, propylene glycol, dipropylene glycol and polypropylene glycol, 1,4-butanediol, 1 , 6-hexanediol, and polyether polyols used for the production of polyurethane resins are selected. Examples of polyether polyols include polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, sucrose, sorbitol, and mannitol, amines such as ethylenediamine, diethylenetriamine, and aminoethylpiperazine, ethanolamine, diethanolamine, and methyldiethanolamine. A molecular weight obtained by addition polymerization reaction of alkylene oxide represented by ethylene oxide or propylene oxide, starting from a compound having at least two active hydrogen groups such as alkanolamines such as triethanolamine Is selected. Of these, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol and water are more preferably used.

  In the catalyst composition of the present invention, the amount of complex metal hydride is preferably in the range of 0.01 to 100 parts by weight with respect to 100 parts by weight of the tertiary amine compound, and 0.01 to 50 parts by weight in terms of cost. The range of is more preferable. The amount of the solvent is usually in the range of 1 to 200 parts by weight, more preferably in the range of 1 to 100 parts by weight with respect to 100 parts by weight of the tertiary amine compound. If the amount is less than 1 part by weight, the complex metal hydride may precipitate without dissolving. In this case, the hydrogenation reaction of aldehydes present in the solution will not proceed sufficiently, resulting in a residual amount of aldehyde. May increase. In addition, when the amount is 200 parts by weight or more, the concentration of the tertiary amine compound in the catalyst composition is low, so that the amount used is increased during the production of the polyurethane resin, and as a result, the physical properties of the resin may be lowered. .

  The method for producing a polyurethane resin using the catalyst composition of the present invention comprises reacting a polyol and a polyisocyanate in the presence of the catalyst composition and, if necessary, a foaming agent, a surfactant, a crosslinking agent, etc. Is the way to get. Examples of products include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam, and elastomer. Among these, the catalyst composition of the present invention is particularly preferably applied to flexible and semi-rigid polyurethane foams and rigid polyurethane foams.

  As the polyol used in the method for producing the polyurethane resin of the present invention, conventionally known polyether polyols, polyester polyols, polymer polyols, and flame retardant polyols such as phosphorus-containing polyols and halogen-containing polyols can be used. These polyols can be used alone or in combination as appropriate.

  In the present invention, examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sucrose, sorbitol, and mannitol, and amines such as ethylenediamine, diethylenetriamine, and aminoethylpiperazine. Reaction of alkylene oxides typified by ethylene oxide and propylene oxide starting from compounds having at least two active hydrogen groups such as alkanolamines such as ethanolamine, ethanolamine, diethanolamine, methyldiethanolamine and triethanolamine For example, Gunter Oertel, "Polyurethane Handbook", (Germany), 1985 Plate, Hanser Publishers, pages 42-53.

  Examples of polyester polyols are those obtained from the reaction of dibasic acids and glycols, as well as by Keiji Iwata, "Polyurethane Resin Handbook", 1987 First Edition, Nikkan Kogyo Shimbun, page 117 Examples include wastes, trimethylolpropane, pentaerythritol wastes, phthalic polyester wastes, polyester polyols obtained by treating waste products, and the like.

  Examples of the polymer polyol include a polymer polyol obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, or styrene in the presence of a radical polymerization catalyst.

  Examples of the flame retardant polyol include phosphorus-containing polyols obtained by adding alkylene oxide to a phosphoric acid compound, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin and trichlorobutylene oxide, and phenol polyols.

  Those having a molecular weight (Mw) of 62 to 15000 can be used. As the flexible and semi-rigid polyurethane foam, those having a molecular weight (Mw) of 1000 to 15000 are used, and polyester polyols, polyether polyols and polymer polyols having a molecular weight (Mw) of 2000 to 15000 are preferred. A rigid polyurethane foam having a molecular weight (Mw) of 62 to 3000 is used, and a polyester polyol, a polyether polyol and a polymer polyol having a molecular weight (Mw) of 100 to 1000 are preferred.

  The polyisocyanate used in the present invention may be any known one, and examples thereof include aromatic polyisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, and xylylene diisocyanate, hexamethylene diisocyanate. Alicyclic polyisocyanates such as aliphatic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof. Examples of TDI and derivatives thereof include a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate or a terminal isocyanate prepolymer derivative of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenyl-polymethylene diisocyanate and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group. Of these organic polyisocyanates, TDI and MDI are preferably used.

  The ratio of use of these polyisocyanates and polyols is not particularly limited, but when expressed in terms of isocyanate index (isocyanate groups / active hydrogen groups capable of reacting with isocyanate groups), generally in the production of flexible foams and semi-rigid foams. It is generally in the range of 60 to 130 in the production of rigid foams and urethane elastomers.

  The catalyst used in the method for producing polyurethane according to the present invention is the catalyst composition according to the present invention, but in addition to this, other catalysts with reduced aldehydes as in the present invention may be used in combination. it can. Examples of other catalysts include conventionally known organometallic catalysts and quaternary ammonium salts.

  The organometallic catalyst is not particularly limited, but, for example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride , Dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.

  Although it does not specifically limit as quaternary ammonium salt, For example, conventionally well-known tetramethylammonium organic acid salt, tetraalkylammonium hydroxide, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethyl Examples include ammonium 2-ethylhexanoate.

  The foaming agent used in the method for producing the polyurethane resin of the present invention is water, liquefied carbon dioxide, or a low-boiling organic compound. Examples of the low boiling point organic compound include hydrocarbon and halogenated hydrocarbon compounds. As the hydrocarbon, conventionally known methane, ethane, propane, butane, pentane, cyclopentane, hexane and the like can be used. As the halogenated hydrocarbon, conventionally known halogenated methane, halogenated ethanes, fluorinated hydrocarbons such as methylene chloride, HCFC-141b, HFC-245fa, HFC-356mfc, etc. can be used. In using these foaming agents, water and a low-boiling organic compound may be used alone or in combination. A particularly preferred blowing agent is water or liquefied carbon dioxide. The amount used may vary depending on the density of the target product, but is usually 0.1 parts by weight or more, preferably 0.5 to 10.0 parts by weight, based on 100 parts by weight of polyol.

  In the method for producing a polyurethane resin of the present invention, a surfactant can be used if necessary. Examples of the surfactant used in the present invention include conventionally known organosilicone surfactants, and the amount used is 0.1 to 10 parts by weight with respect to 100 parts by weight of polyol.

  In the method for producing a polyurethane resin of the present invention, a crosslinking agent or a chain extender can be added if necessary. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols (for example, ethylene glycol, 1,4-butanediol, glycerin, etc.), low molecular weight amine polyols (for example, diethanolamine, triethanolamine, etc.) or polyamines ( For example, ethylenediamine, xylylenediamine, methylenebisorthochloroaniline, etc.) can be exemplified. Of these, diethanolamine and triethanolamine are preferred.

  In addition to these, in the method for producing a polyurethane resin of the present invention, a colorant, a flame retardant, an anti-aging agent, a communicating agent, and other known additives can be used as necessary. The types and amounts of these additives can be used within the range normally used without departing from the known formats and procedures.

  As the method for producing the polyurethane of the present invention, a tertiary amine compound and a complex metal hydroxide used in the catalyst composition of the present invention, and, if necessary, a foaming agent, a surfactant, a crosslinking agent, etc. are added to the polyol. The manufacturing form which reacts the polyol premix melt | dissolved then and polyisocyanate is included. In the present invention, the polyol premix is usually produced by mixing and dissolving the raw materials at room temperature, and does not need to be heated. Moreover, the usage-amount of a tertiary amine compound and a complex metal hydroxide has the preferable range of 0.01-1 weight part, respectively with respect to 100 weight part of polyols. If it is less than 0.01 parts by weight, the residual amount of aldehydes may increase. Moreover, when it exceeds 1 weight part, there exists a possibility that the physical property fall of resin obtained may become large.

  The product produced by the method for producing a polyurethane resin of the present invention can be used for various applications. Specific applications include flexible foam, for example, a bed as a cushion, an automobile seat, a mattress, etc., semi-rigid foam, for example, an automobile-related instrument panel, headrest, handle, etc. A freezer, a refrigerator, a heat insulating building material, etc. are mentioned.

  Since the catalyst composition of the present invention has very few aldehydes in the catalyst solution, the aldehydes in the polyurethane product can be reduced when used as a catalyst for producing a polyurethane resin. For this reason, it becomes effective for VOC reduction of a polyurethane product. Moreover, since the catalyst composition of the present invention is in a transparent liquid state and has no insoluble solid matter, it does not cause a problem for production facilities when producing a polyurethane resin.

  Hereinafter, although demonstrated based on an Example and a comparative example, this invention is not limited only to these Examples.

Synthesis example 1
In a 10 L autoclave with a stirrer, 1200 g (11.6 mol) of diethylenetriamine (DETA manufactured by Tosoh Corporation), 1200 g of water and 60 g of catalyst R-Ni (manufactured by Kawaken Fine Chemical Co., Ltd.) were charged. The autoclave was sealed and replaced with hydrogen, and then heated to 90 ° C. with stirring. Subsequently, 4800 g (59.2 mol) of 37% formalin aqueous solution was supplied by a pump over 6 hours while introducing hydrogen into the autoclave at a pressure of 3 MPa. After aging reaction for 1 hour, the reaction solution was taken out by cooling. Subsequently, the catalyst R-Ni was separated and filtered to obtain 7260 g of a reaction solution.

  After adding 165 g of 48% NaOH aqueous solution to a part of about 6000 g of this reaction liquid, water was distilled off under atmospheric pressure using a distillation apparatus, and the product N, N, N ′, N was reduced under reduced pressure. “, N” -pentamethyldiethylenetriamine was distilled to obtain 1250 g. This tertiary amine compound was used as Catalyst A.

Synthesis example 2
About 1200 g of the remaining reaction solution of Synthesis Example 1 was distilled off using an distillation apparatus as it was under atmospheric pressure, and then the product N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine was used under reduced pressure. Was distilled to obtain 235 g. This tertiary amine compound was used as catalyst B.

Synthesis example 3
A 10 L autoclave equipped with a stirrer was charged with 1200 g (10.3 mol) of hexamethylenediamine (reagent), 1200 g of water and 36 g of catalyst R-Ni (manufactured by Kawaken Fine Chemical Co., Ltd.). The autoclave was sealed and replaced with hydrogen, and then heated to 70 ° C. with stirring. Subsequently, 3357 g (41.4 mol) of 37% formalin aqueous solution was supplied by a pump over 6 hours while introducing hydrogen into the autoclave at a pressure of 3 MPa. After aging reaction for 1 hour, the reaction solution was taken out by cooling. Subsequently, the catalyst R-Ni was separated and filtered to obtain 5770 g of a reaction solution.

  After adding 27 g of 48% NaOH aqueous solution to about 1200 g of this reaction solution, water was distilled off under atmospheric pressure using a distillation apparatus, and the product N, N, N ′, N was reduced under reduced pressure. '-Tetramethylhexanediamine was distilled off to obtain 220 g. This tertiary amine compound was used as catalyst C.

Examples 1 to 11 and Comparative Examples 1 to 10
As a tertiary amine compound, 90 g of the catalyst A obtained in Synthesis Example 1, 0.1 g of sodium borohydride as a complex metal hydride, and 9.9 g of dipropylene glycol as a solvent were weighed into a 200 ml glass sample bottle. When a stirrer was introduced and stirring was continued for about 1 hour, a colorless and transparent liquid was obtained. Using this as the catalyst composition of Example 1, quantitative analysis of formaldehyde and acetaldehyde was carried out.

  Similarly, the catalyst compositions of Examples 2 to 11 and Comparative Examples 1 to 10 were obtained by changing the tertiary amine compound, the complex metal hydride, the solvent, and the aldehyde scavenger. These were similarly subjected to quantitative analysis of formaldehyde and acetaldehyde.

  Quantitative analysis was performed according to JIS K0303 2,4-dinitrophenylhydrazine-gas chromatograph method (DNPH-GC method). However, the aldehydes were not collected with gas, but the aldehydes in the catalyst solution and 2,4-dinitrophenylhydrazine were contacted and reacted with each other. These results are also shown in Table 1.

実施例１〜実施例１１までで明らかなごとく、第３級アミン化合物、錯金属水素化物及び溶媒からなる本発明の触媒組成物はホルムアルデヒド及びアセトアルデヒドの残存量が非常に少ない。比較例１〜比較例５は第３級アミン化合物のみの例であるが、ホルムアルデヒドが１００ｐｐｍ以上存在している。比較例６〜比較例８は従来のアルデヒド補足剤の使用例であるが、殆ど補足効果を示していない。比較例９〜比較例１０は第３級アミン化合物と錯金属水素化物のみの組成液の例であるが、錯金属水素化物が溶解しないためホルムアルデヒドの低下量が大きくなく、また組成液中に固形物が残る。

As is apparent from Examples 1 to 11, the catalyst composition of the present invention comprising a tertiary amine compound, a complex metal hydride and a solvent has very little residual amount of formaldehyde and acetaldehyde. Comparative Examples 1 to 5 are only examples of tertiary amine compounds, but formaldehyde is present at 100 ppm or more. Comparative Examples 6 to 8 are examples of using conventional aldehyde scavengers, but show little supplementary effect. Comparative Examples 9 to 10 are examples of a composition liquid containing only a tertiary amine compound and a complex metal hydride. However, since the complex metal hydride does not dissolve, the amount of decrease in formaldehyde is not large, and the composition liquid is solid. Things remain.

Example 12
The example which manufactured the polyurethane foam using the catalyst composition of this invention is shown.

In Example 8 with 100 g of polyol (manufactured by Sanyo Chemical Co., Ltd., FA-703), 2.8 g of water, 3.0 g of triethanolamine (reagent made by Kanto Chemical), and 0.1 g of the catalyst composition obtained in Example 1. 0.6 g of the obtained catalyst composition was placed in a 300 ml polyethylene cup and stirred for 10 seconds with a stirrer (2000 rpm). The temperature of the polyol premix was adjusted to 25 ° C. In a separate container, 61.5 g of an isocyanate liquid (diphenylmethane diisocyanate: MR200 manufactured by Nippon Polyurethane Co., Ltd.) having an index {isocyanate group / OH group (molar ratio) × 100)} of 105 was added to a polyol premix cup. The mixture was quickly stirred with a stirrer at 6000 rpm for 5 seconds. The mixed and stirred liquid mixture was transferred to a 2 l polyethylene cup whose temperature was adjusted to 40 ° C. and foamed. The reactivity during foam molding was a cream time of 15 seconds, a gel time of 46 seconds, and a rise time of 66 seconds. Further, when the appearance and cell state of the molded foam were observed, it was determined that the foam was normal without any deformation or shrinkage on the appearance and without cell roughness. The molded foam was cut and the core density was measured and found to be 45 kg / m ³ . The reactivity measurement method is as follows.
・ Reactivity measurement items Cream time: Measure foaming start time and foam start time visually. Gel time: Measure time when reaction progresses and change from liquid to resinous material. Rise time: Stop rising of foam. Measurement time

Claims (9)

A catalyst composition for producing a polyurethane resin, comprising a tertiary amine compound, a complex metal hydride and a solvent. A catalyst composition for producing a polyurethane resin obtained by dissolving a tertiary amine compound and a complex metal hydride in a solvent. The mixing ratio of the tertiary amine compound and the complex metal hydride is in the range of 0.01 to 100 parts by weight of the complex metal hydride with respect to 100 parts by weight of the tertiary amine compound. A catalyst composition for producing a polyurethane resin according to claim 2. 4. The complex metal hydride is one or more selected from the group consisting of sodium borohydride, potassium borohydride, lithium borohydride and lithium aluminum hydride. A catalyst composition for producing a polyurethane resin as described in 1. The method for producing a catalyst composition for producing a polyurethane resin according to any one of claims 1 to 4, wherein the tertiary amine compound and the complex metal hydride are dissolved in a solvent. A process for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition according to any one of claims 1 to 4. One kind selected from the group consisting of water, liquefied carbon dioxide and low-boiling organic compounds as a blowing agent in the presence of the catalyst composition according to any one of claims 1 to 4, wherein the polyol and the polyisocyanate are present. Alternatively, a process for producing a polyurethane foam, wherein two or more kinds are reacted. A method for producing a polyurethane resin, comprising reacting a polyol premix obtained by adding a tertiary amine compound and a complex metal hydroxide to a polyol and dissolving the polyol, and a polyisocyanate. 9. The production of a polyurethane resin according to claim 8, wherein the amount of the tertiary amine compound and the complex metal hydroxide is 0.01 to 1 part by weight with respect to 100 parts by weight of the polyol, respectively. Method.