JP2005325227A - Catalyst composition for producing polyurethane resin, and method for producing polyurethane resin therewith - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an amine catalyst composition for producing a flexible polyurethane foam, with which the foam is obtained in good productivity and moldability, while improving a working environment on the production of the flexible polyurethane foam and improving the amine odor of the final foam product, and to provide a production method using the same. <P>SOLUTION: This method for producing the flexible polyurethane resin from a polyol and a polyisocyanate is characterized by using a polyurethane resin production catalyst composition comprising a salt of 3-dimethylaminopropionitrile and the salt of a bicyclic tertiary amine represented by the general formula (1) [(n) is an integer of 1 to 3] with an organic acid. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a catalyst composition for producing a polyurethane resin such as soft or semi-rigid, and a method for producing a polyurethane resin using the same. More specifically, the present invention relates to a catalyst composition for improving productivity with less amine odor when producing a polyurethane resin, and a method for producing the same.

  The polyurethane resin is produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, auxiliary agents such as a foaming agent, a surfactant, and a crosslinking agent. In the production of polyurethane resins, it is known to use a large number of metal compounds and tertiary amine compounds as catalysts, and these catalysts are widely used industrially when used alone or in combination.

  Among these catalysts, especially tertiary amine compounds are widely used as catalysts in the production of polyurethane foams using water as a blowing agent and / or low-boiling organic compounds because of their excellent moldability and productivity. Examples of such tertiary amine compounds include conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N , N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylbenzylamine, N, N-dimethylethanolamine and the like (for example, Non-patent document 1). Of these, N-methylmorpholine, N-ethylmorpholine, and the like are used as catalysts for improving moldability and productivity without increasing reactivity (see, for example, Non-Patent Document 2).

  On the other hand, since the metal-based catalyst deteriorates in productivity and moldability, it is often used in combination with a tertiary amine catalyst in most cases and is rarely used alone.

U.S. Pat. No. 4,038,210

Japanese Patent Laid-Open No. 47-028098 Keiji Iwata "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. 118 Keiji Iwata "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. 159

  Morpholine compounds such as N-methylmorpholine and N-ethylmorpholine have a strong odor and the working environment is significantly deteriorated. As a method of solving this problem, a method of using a beta amino nitrile compound instead of the morpholine compound has been proposed (see, for example, Patent Document 1). However, since these amine catalysts promote the water-isocyanate reaction, the initial reactivity (cream time) is accelerated. As a result, the flow time into the mold is insufficient and the moldability deteriorates. In addition, since the catalyst activity is extremely low and the catalyst is used in a large amount, problems such as worsening of amine odor during operation occur.

  In addition, a method using a high molecular weight morpholine compound such as 4- (2-dimethylaminoethyl) morpholine has been proposed (see, for example, Patent Document 2), but these compounds are generally expensive and polyurethane foam. It is said that the manufacturing cost will increase. In addition, when foaming is performed by delaying the initial reactivity, there is a problem that productivity deteriorates.

  The present invention has been made in view of the above problems, and an object thereof is to provide a catalyst for obtaining a polyurethane resin with good productivity and moldability, and a method for producing a polyurethane resin using the catalyst. .

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, it has been found that when a specific amine catalyst is used in the production of a polyurethane resin, the amine odor during the production of the resin is reduced, and the polyurethane resin can be obtained with good moldability and productivity without accelerating the initial reactivity. The invention has been completed.

  That is, this invention is a catalyst composition for polyurethane resin manufacture as shown below, and the manufacturing method of a polyurethane resin using the same.

  [1] 3-Dimethylaminopropionitrile (hereinafter sometimes referred to as compound (1)) and the following general formula (1)

（式中、ｎは１〜３の整数を表す。）
で示される二環式第３級アミンと有機酸との塩（以下、化合物（２）と称する場合がある。）を含有してなるポリウレタン樹脂製造用の触媒組成物。

(In the formula, n represents an integer of 1 to 3.)
A catalyst composition for producing a polyurethane resin, comprising a salt of a bicyclic tertiary amine and an organic acid represented by the formula (hereinafter sometimes referred to as compound (2)).

  [2] The mixing ratio of compound (1) and compound (2) is in the range of compound (1) / compound (2) = 20 to 95/80 to 5 (weight ratio). 1]. The catalyst composition according to 1].

  [3] The above [1] or [2], wherein the bicyclic tertiary amine represented by the general formula (1) is 1,8-diaza-bicyclo [5.4.0] undecene-7 ] The catalyst composition for polyurethane foam manufacture of description.

  [4] The above [1] to [3] comprising 3-dimethylaminopropionitrile, a salt of a bicyclic tertiary amine represented by the general formula (1) and an organic acid, and a tertiary amine. ] The catalyst composition in any one of.

  [5] A method for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition according to any one of [1] to [4].

  [6] A method for producing a polyurethane resin, comprising reacting a polyol and a polyisocyanate in the presence of the catalyst composition according to the above [1] to [4] and a foaming agent.

  [7] The method for producing a polyurethane resin according to the above [6], wherein the foaming agent is water and / or a low boiling point organic compound.

  Hereinafter, the present invention will be described in detail.

  The catalyst composition for producing a polyurethane resin of the present invention is a polyurethane resin comprising 3-dimethylaminopropionitrile, a salt of a bicyclic tertiary amine represented by the above general formula (1) and an organic acid. A catalyst composition for production.

  In the present invention, as the bicyclic tertiary amine represented by the general formula (1), specifically, 1,5-diaza-bicyclo [4.3.0] nonene-5 (hereinafter referred to as DBN) 1,5-diaza-bicyclo [4.4.0] decene-5 (hereinafter abbreviated as DBD) 1,8-diaza-bicyclo [5.4.0] undecene-7 (hereinafter DBU) Among them, DBU and DBN are preferable, and DBU is particularly preferable. The above bicyclic tertiary amines can be used alone or in combination of two or more.

  In the present invention, the organic acid that forms a salt with the bicyclic tertiary amine represented by the general formula (1) is not particularly limited, and examples thereof include aliphatic carboxylic acids and aliphatic unsaturated carboxylic acids. , Aromatic carboxylic acids, aromatic compounds having a phenolic hydroxyl group, triazole compounds, pyrazole compounds, thiazole compounds, and the like.

  The aliphatic carboxylic acid is not particularly limited, and examples thereof include formic acid, methanoic acid, ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, and undecaic acid. Acid, dodecanoic acid, 2-ethylhexanoic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecadioic acid, decanedicarboxylic acid, 1,11-undecadicarboxylic Examples include acid, 1,12-dodecanedicarboxylic acid, hexadecandioic acid, oxalic acid, and malonic acid.

  Examples of the aliphatic unsaturated carboxylic acid include, but are not limited to, acrylic acid, crotonic acid, vinyl acetic acid, methacrylic acid, tiglic acid, isocrotonic acid, propiolic acid, angelic acid, isanic acid, undecylenic acid, and elaidin. Acid, erucic acid, behenolic acid, brassic acid, propiolic acid, behenolic acid, petrothelic acid, oleic acid, ricineramic acid, ricinoleic acid, 2-chloroacrylic acid, 3-chloroacrylic acid, 2-amino-3-butenoic acid, Examples include 2-amino-3-hydroxy-4-hexynoic acid (acetoacetic acid).

  The aromatic carboxylic acid is not particularly limited. For example, benzoic acid, trimellitic acid, pyromellitic acid, 2-hydroxyisophthalic acid, 4-hydroxyisophthalic acid, 5-hydroxyisophthalic acid, 2,3- Examples include dihydroxybenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, 3,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, and the like.

  The aromatic compound having a phenolic hydroxyl group is not particularly limited, and examples thereof include phenol, trimethylphenol, o-aminophenol, p-octylphenol, o-cresol, m-cresol, and p-cresol. .

  The triazole compound is not particularly limited. For example, 1,2,4-triazole, 1,2,3-triazole, benzotriazole, 4-methyl-benzotriazole, 5-methyl-benztriazole, 3- Amino-1,2,4-triazole, 3-methyl-1,2,4-triazole, 1-methyl-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, 3, 5-dibromo-1,2,4-triazole, 3,5-dichloro-1,2,4-triazole, 4-phenyl-1,2,4-triazole, 5-phenyl-1,2,4-triazole, 3-amino-5-phenyl-1,2,4-triazole, 3- (2-aminoethyl) -1,2,4-triazole, 3-amino-5- (4-pyridyl) -1 2,4-triazole, 3-amino-5- (4-pyridyl) -1,2,4-triazole, 3-amino-5- (2-aminoethyl) -1,2,4-triazole and the like can be mentioned. .

  Although it does not specifically limit as a pyrazole compound, For example, pyrazole, 4-bromo pyrazole, 4-amino pyrazole, 3-butyl pyrazole, 4-nitro pyrazole, 4-chloro pyrazole, 3-methyl pyrazole, 4-methyl Pyrazole, 5-methylpyrazole, 3-pentylpyrazole, 3-phenylpyrazole, 3-propylpyrazole, 3-amino-4-phenylpyrazole, 3-amino-5-phenylpyrazole, 4-amino-5-phenylpyrazole, 3 , 5-dimethylpyrazole, 3-methyl-4-chloropyrazole, 3-chloro-4-methylpyrazole, 4-amino-3,5-dimethylpyrazole, 4-bromo-3,5-dimethylpyrazole, 3-methyl- 4-amino-pyrazole and the like can be mentioned.

  The thiazole compound is not particularly limited. For example, thiazole, 2-aminothiazole, 2-nitrothiazole, 2-methylthiazole, 4-aminothiazole, 4-aminothiazole, 4-methylthiazole, 2,4 -Dimethylthiazole, 4,5-dimethylthiazole, 2-amino-5-nitrothiazole, 2-bromo-5-nitrothiazole, 2-amino-5-chlorothiazole, 2-amino-4-phenylthiazole, 4-methyl -5-vinylthiazole and the like.

  Among the catalyst compositions of the present invention, when the compound (1) and the compound (2) are each used alone for the production of a polyurethane resin, the moldability and the odor during operation deteriorate. Since the compound (1) promotes the water-isocyanate reaction, the initial reactivity is remarkably accelerated, the flow time into the mold is insufficient, and the moldability is deteriorated. When the compound (2) is used alone or in a large amount for the production of polyurethane foam, the moldability and foam surface curability are remarkably deteriorated.

  However, surprisingly, when the compound (1) and the compound (2) are mixed and used at a predetermined ratio, not only the initial reactivity is accelerated, but the foam is rapidly cured and the molding does not shrink or deform. Good product can be obtained with good productivity. Further, the initial reaction time can be maintained even when used in a large amount in order to increase curability.

  The mixing ratio in the catalyst composition of the present invention is not particularly limited, but the weight ratio of the compound (1) and the compound (2) is such that the compound (1) / compound (2) = 70/30 to 99 / The range of 1 is preferable, and the range of 80/10 to 99/1 is more preferable. If the ratio of the compound (2) exceeds 30% by weight, the moldability deteriorates, and if it is less than 1% by weight, the effects of the present invention may not be exhibited.

  The catalyst composition of the present invention can contain a catalyst other than the compound (1) and the compound (2) without departing from the spirit of the present invention. Examples of such a catalyst include conventionally known organometallic catalysts and tertiary amines.

  Examples of the organometallic catalyst include stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, and lead octoate. , Lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.

  The tertiary amines are not particularly limited as long as they are conventionally known. For example, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N ", N" -pentamethyldiethylenetriamine, 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, N, N'-dimethylpiperazine, dimethylcyclohexylamine, bis (2-di Tilaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylethanolamine, N, N-dimethylisopropanolamine, N, N-dimethylhexanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethyl-N ′-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propane Examples include diamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, and 3-quinuclidinol. Of these, triethylenediamine and N, N, N ′, N′-tetramethylhexamethylenediamine are particularly preferred from the viewpoint of catalytic activity.

  When the catalyst composition of the present invention is used for the production of polyurethane foam, the amount used is usually 0.01 to 10 parts by weight when the polyol used is 100 parts by weight, but the working environment is improved. Therefore, it is desirable that the amount of catalyst used is small.

  In the method for producing a polyurethane resin using the catalyst composition of the present invention, a polyol and a polyisocyanate are reacted in the presence of an auxiliary agent such as a foaming agent, a surfactant, and a crosslinking agent. A method for obtaining a polyurethane foam product. Examples of products include flexible polyurethane foam and semi-rigid polyurethane foam.

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

  Examples of the polyether polyol include at least two or more polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentaerythritol, amines such as ethylenediamine, and alkanolamines such as ethanolamine and diethanolamine. For example, Gunter Oeltel "Polyurethane Handbook" (1985 edition) Hanser Publishers (Germany), 42nd to 42nd, by an addition reaction of an alkylene oxide represented by ethylene oxide or propylene oxide with a compound having an active hydrogen group of It can be produced by the method described on page 53.

  Examples of the polyester polyol include those obtained from the reaction of dibasic acid and glycol, such as Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, Ltd. Examples include trimethylolpropane, pentaerythritol waste, phthalic polyester waste, polyester polyol derived by treating waste.

  Examples of the polymer polyol include a polymer polyol obtained by reacting the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.) 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.

  The average molecular weight (Mw) of these polyols is usually 62 to 15000. As the flexible polyurethane foam, those having an average molecular weight (Mw) of 1000 to 15000 are used, and polyether polyols and polymer polyols having an average molecular weight (Mw) of 3000 to 15000 are preferred. More preferred is a flexible polyurethane foam using a polyether polyol and a polymer polyol in combination.

  The polyisocyanate used in the present invention is not particularly limited as long as it is a known one. For example, aromatics such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, and xylylene diisocyanate are used. Aliphatic polyisocyanates such as aliphatic polyisocyanates and hexamethylene diisocyanates, alicyclic 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.

  In the present invention, the use ratio of the polyisocyanate and the polyol is not particularly limited, but is generally represented by an isocyanate index (isocyanate group / active hydrogen group capable of reacting with an isocyanate group) of a flexible foam or a semi-rigid foam. In production, it is in the range of 60-130.

  As a foaming agent used for the manufacturing method of the polyurethane resin of this invention, water, a low boiling-point organic compound, etc. are mentioned, for example. Examples of the low boiling point organic compound include hydrocarbons and halogenated hydrocarbons. As the hydrocarbon, for example, known methane, ethane, propane, butane, pentane, hexane and the like can be used. As the halogenated hydrocarbon, for example, known halogenated methane, halogenated ethanes, fluorinated hydrocarbons, specifically, methylene chloride, HCFC-141b, HFC-245fa, HFC-356mfc and the like 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. 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 parts by weight, based on 100 parts by weight of polyol.

  In the present invention, if necessary, a surfactant, a crosslinking agent, or a chain extender can be used as an auxiliary agent.

  The surfactant used in the present invention may be a conventionally known organosilicone surfactant and is not particularly limited. The usage-amount is 0.1-10 weight part normally with respect to 100 weight part of polyols.

  Examples of the crosslinking agent or chain extender used in the present invention include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol, and glycerin, ethylenediamine, xylylenediamine, and methylenebisorthochloroaniline. Mention may be made of low molecular weight amine polyols such as diethanolamine, triethanolamine etc. or polyamines. Of these, diethanolamine and triethanolamine are preferred.

  In the present invention, a colorant, a flame retardant, an anti-aging agent, a communicating agent, and other known additives can be used as an auxiliary agent 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.

  The product produced by the method for producing a polyurethane resin of the present invention can be used for various applications. In particular, it is suitable for foamed products produced using a foaming agent. Specific applications include, for example, a bed as a cushion, a car seat, and a mattress for a flexible foam, and examples include an automobile-related instrument panel, a headrest, and a handle for a semi-rigid foam.

  When the catalyst composition of the present invention is used, the amine odor at the time of foam production is reduced, and polyurethane foam can be obtained with good moldability and productivity without increasing the initial reactivity.

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

Examples 1 to 4 and Comparative Examples 1 to 9
The example which manufactured the flexible polyurethane foam using the catalyst of this invention and the catalyst of a comparative example is shown below.

  Polyol A, water, triethanolamine and the like were mixed at the raw material mixing ratio shown in Table 1 to prepare Premix A.

プレミックスＡ １００．４ｇを３００ｍｌポリエチレンカップに取り、表２に示す本発明の触媒及び比較例の触媒を添加し、２０℃に温度調整した。

100.4 g of Premix A was taken in a 300 ml polyethylene cup, the catalyst of the present invention shown in Table 2 and the catalyst of Comparative Example were added, and the temperature was adjusted to 20 ° C.

別容器で２０℃に温度調整したイソシアネート液をイソシアネートインデックス｛イソシアネート基／ＯＨ基（モル比）×１００）｝が１００となる５６．２ｇをプレミックスＡのカップの中に入れ、素早く攪拌機にて６０００ｒｐｍで５秒間攪拌した。混合攪拌した混合液を４０℃に温度調節した２リットルポリエチレンカップに移し発泡中の反応性を測定した。次に同じ操作及びスケールにて３０℃に温度調節したモールド（内寸法、２９５×３０５×２０ｍｍのアルミ製）内の端部より混合液を入れ蓋をして発泡成形を行った。混合液を入れた時点から２分後にフォームを脱型した。フォームの脱型時にモールドにスキンが付着している割合を測定し比較した。結果を表３にあわせて示す。

In a separate container, 56.2 g of an isocyanate liquid whose temperature is adjusted to 20 ° C. with an isocyanate index {isocyanate group / OH group (molar ratio) × 100)} of 100 is placed in a premix A cup and quickly stirred. Stir at 6000 rpm for 5 seconds. The mixed and stirred liquid mixture was transferred to a 2 liter polyethylene cup whose temperature was adjusted to 40 ° C., and the reactivity during foaming was measured. Next, the liquid mixture was put in from the end of the mold (inner dimensions, made of aluminum of 295 × 305 × 20 mm) whose temperature was adjusted to 30 ° C. by the same operation and scale, and then foam molding was performed. The foam was demolded 2 minutes after the mixed solution was added. The ratio of the skin adhering to the mold when the foam was removed was measured and compared. The results are shown in Table 3.

なお、各測定項目の測定方法は以下のとおりである。
（１）反応性の測定項目
クリームタイム：発泡開始時間、フォームが上昇開始する時間を目視にて測定
ゲルタイム：反応が進行し液状物質より、樹脂状物質に変わる時間を測定
ライズタイム：フォームの上昇が停止する時間を目視にて測定
（２）モールド作業性
モールド発泡作業を５名のモニターに実施してもらい、蓋閉め作業のし易さをモールド作業性として次のように評価した。
○：発泡後の蓋閉め時間が十分にあり、作業し易い
△：発泡後の蓋閉め時間が不不足であり、作業し難い
×：発泡後の蓋閉め時間が足りず、作業が困難である
（３）フォームの硬化性
フォームの脱型時にモールドフォームのスキン部が付着している割合を測定し比較した。スキン部の付着が少ない程、フォームの硬化性が良く生産性向上につながると判断できる。
○：モールドへのフォームスキン部付着がない
△：モールドへのフォームスキン部付着が一部ある
×：モールドへのフォームスキン部付着が全面にある
（４）フォームの成形性
フォームを脱型後、表面部分のセルの乱れや空隙部及びフォームの寸法安定性を観察して、次のように評価した。
○：セルの乱れ、空隙部及びフォームの収縮がほとんどない
△：一部にセルの乱れや空隙部がある、あるいはフォームの収縮がある
×：全面にセルの乱れや空隙部がある、あるいはフォームの収縮が大きい
（５）作業時の臭気
反応液の調合作業を行っている作業者の１ｍ後方に３名のモニターを立たせ、臭気を観測し、作業時の臭気として次のように評価した。
○：不快な臭気小
△：僅かに不快な臭気あり
×：非常に不快な臭気あり。

The measurement method for each measurement item is as follows.
(1) Reactive measurement items Cream time: Measure foaming start time, foam start time visually. Gel time: Measure time when reaction progresses and change from liquid to resinous material. Rise time: Foam rise (2) Mold workability The mold foaming work was carried out by five monitors, and the ease of lid closing work was evaluated as follows as mold workability.
○: The lid closing time after foaming is sufficient and easy to work. △: The lid closing time after foaming is insufficient and difficult to work. ×: The lid closing time after foaming is insufficient and the work is difficult. (3) Curability of foam The ratio of the skin part of the mold foam adhering at the time of demolding the foam was measured and compared. It can be judged that the less the skin part adheres, the better the curability of the foam and the higher the productivity.
○: Foam skin part does not adhere to the mold △: Foam skin part adheres to the mold partially ×: Foam skin part adheres to the entire surface (4) Formability of the foam After demolding the foam, The turbulence of the cells in the surface portion, the voids and the dimensional stability of the foam were observed and evaluated as follows.
○: Cell disturbance, void and foam shrinkage △: Cell disturbance and void part in part, or foam shrinkage ×: Cell disorder and void part in the entire surface, or foam (5) Odor during work Three monitors were placed 1 m behind the workers who were preparing the reaction solution, and the odor was observed and evaluated as the odor during work as follows.
○: Unpleasant odor small △: Slightly unpleasant odor ×: Very unpleasant odor

  As is clear from the examples, since the polyurethane foam using the catalyst of the present invention has good curability and moldability, it is possible to take out the foam product from the mold in a short time, and the defect rate of the product is low. Contributes to foam productivity. Furthermore, the odor at the time of work can be reduced and the work environment can be improved.

On the other hand, Comparative Example 1 and Comparative Example 2 are examples in which a general-purpose tertiary amine catalyst is used alone, but both curability and moldability are insufficient. Comparative Example 3 and Comparative Example 4 are examples in which a general-purpose tertiary amine catalyst and DMAPN are combined, but the initial reactivity (cream time) is increased, so that it is not possible to secure work time such as closing the mold lid. Comparative Example 5 is an example in which a general-purpose tertiary amine catalyst and DMAEM are combined. However, since the initial reactivity (cream time) is increased, it is not possible to secure the working time for closing the mold lid or the like. Further, the moldability is insufficient. Comparative Example 6 is an example in which DMAPN is used alone. However, since the catalytic activity is weak, the amount used is extremely large, and the odor during work is deteriorated. Comparative Example 7 is an example in which DBUP is used alone, but the curability and moldability are significantly deteriorated. Comparative Example 8 is an example in which triethylenediamine and N-methylmorpholine are used in combination, but the odor during operation is remarkably deteriorated. Comparative Example 9 is an example in which triethylenediamine, DMAPN, DMEA, ET, and DBTDL are used in combination. However, since the curability is poor and the moldability is insufficient, the foam productivity is deteriorated. Moreover, since initial reactivity (cream time) becomes early, working time, such as closing a mold lid, cannot be secured.

Claims (7)

3-dimethylaminopropionitrile and the following general formula (1)

(In the formula, n represents an integer of 1 to 3.)
A catalyst composition for producing a polyurethane resin, comprising a salt of a bicyclic tertiary amine and an organic acid represented by the formula: The mixing ratio of 3-dimethylaminopropionitrile (1) to the salt (2) of the bicyclic tertiary amine represented by the general formula (1) and the organic acid (1) / (2) = The catalyst composition according to claim 1, wherein the catalyst composition is in the range of 20 to 95/80 to 5 (weight ratio). The bicyclic tertiary amine represented by the general formula (1) is 1,8-diaza-bicyclo [5.4.0] undecene-7. Catalyst composition. Any one of claims 1 to 3, comprising 3-dimethylaminopropionitrile, a salt of a bicyclic tertiary amine represented by the general formula (1) and an organic acid, and a tertiary amine. The catalyst composition as described in 1. 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. A process for producing a polyurethane resin comprising reacting a polyol and a polyisocyanate in the presence of a catalyst composition according to claim 1 and a foaming agent. The method for producing a polyurethane resin according to claim 6, wherein the foaming agent is water and / or a low-boiling organic compound.