JP5440127B2 - Amine catalyst composition for producing polyurethane resin and method for producing polyurethane resin using the same - Google Patents

Description

  The present invention relates to an amine catalyst composition for producing a polyurethane resin and a method for producing a polyurethane resin using the same. The catalyst composition of the present invention is extremely useful as a catalyst for producing a polyurethane resin that reduces volatile amine catalysts and has almost no heavy metal catalyst during the production of a polyurethane resin.

  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 flame retardant, a crosslinking agent and the like. It is known that many metal compounds and tertiary amine compounds are used as catalysts for the production of polyurethane resins. These catalysts are often used industrially when used alone or in combination.

  In the production of polyurethane foam using water and / or a low-boiling organic compound as a foaming agent, among these catalysts, tertiary amine compounds are widely used because of their excellent productivity and moldability. 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-dimethylethanolamine and the like. For example, refer nonpatent literature 1).

  In most cases, the metal compound is often used in combination with a tertiary amine catalyst because the productivity and moldability are deteriorated, and the metal compound is rarely used alone.

  The above-mentioned tertiary amine catalyst is gradually discharged from the polyurethane product as a volatile amine, and causes, for example, an odor problem due to the volatile amine and a discoloration problem of other materials such as a skin vinyl chloride in an automobile interior material or the like. Further, the tertiary amine catalyst generally has a strong bad odor, and the working environment during the production of the polyurethane resin is significantly deteriorated. For these volatile tertiary amine catalysts, as a method for solving this problem, an amine catalyst having a hydroxyl group capable of reacting with polyisocyanate or a primary and secondary amino group in the molecule (hereinafter referred to as a reactive catalyst). And a method using a bifunctional cross-linking agent having a tertiary amino group in the molecule has been proposed (see, for example, Patent Document 1 to Patent Document 5).

  The method using the amine catalyst described above is said to be able to avoid the above problem because it is immobilized in the polyurethane resin skeleton in a form reacted with polyisocyanate, and is certainly effective in reducing the odor of the final resin product. These amine catalysts are inferior in the activity of the resinification reaction (reaction of polyol and isocyanate), so that there is a problem that curability is lowered. The method using the above-mentioned crosslinking agent is effective in reducing the odor of the final resin product and improving the working environment when producing the polyurethane resin, but the physical properties such as hardness of the polyurethane resin are insufficient.

  On the other hand, Patent Document 6 describes an example in which 2-hydroxymethyltriethylenediamine, 3-quinuclidinol, and 3-hydroxymethylquinuclidine are used alone, but the catalytic activity is low, and the odor of the final resin product is related. It is not described.

  Patent Documents 7 and 8 describe examples in which an amine compound having a hydroxy group, a primary amino group, and a secondary amino group in the molecule is used as a catalyst for producing a rigid polyurethane foam. It is used for the purpose of improving the fluidity and thermal conductivity, and does not mention odor problems.

  On the other hand, the metal-based catalyst does not cause odor problems such as the above-described amine catalyst or problems of degrading other materials. However, when the metal-based catalyst is used alone, as described above, productivity, physical properties, and moldability are reduced. As the catalyst gets worse, some metal-based catalysts contain heavy metals such as lead, tin, mercury, etc., and toxicity problems and environmental problems caused by heavy metals remaining in the products have been addressed.

JP-A-46-4846 Japanese Patent Publication No. 61-31727 Japanese Patent No. 2971979 Japanese Unexamined Patent Publication No. 63-265909 JP 2008-45113 A JP-A-9-104735 JP 2003-82051 A JP 2003-105051 A Keiji Iwata "Polyurethane Resin Handbook" (1987 first edition) Nikkan Kogyo Shimbun, p. 118

  The present invention has been made in view of the above-mentioned background art, and its purpose is to produce a novel catalyst composition and a polyurethane product using the same without causing odor problems, toxicity, and environmental problems, It is to provide a production method that can be obtained with good moldability.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have used triethylenediamine having a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group in the molecule as a catalyst for producing a polyurethane resin, and triethylenediamine. When used in combination, it was found that polyurethane products can be obtained without causing odor problems, toxicity, and environmental problems, and the present invention has been completed.

  That is, the present invention is a polyurethane resin production catalyst composition as shown below and a polyurethane resin production method using the same.

  [1] The following general formula (1)

［式中、Ｘは、ヒドロキシ基、ヒドロキシメチル基、又はヒドロキシエチル基を表す。］
で示されるアミン化合物と、下記一般式（２）

[Wherein, X represents a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group. ]
An amine compound represented by the following general formula (2)

［式中、Ｒ_１、Ｒ_３、Ｒ_５は、各々独立して水素原子又は炭素原子１〜４の直鎖又は分岐鎖のアルキル基を表し、Ｒ_２、Ｒ_４は、各々独立してヒドロキシ基、ヒドロキシメチル基、ヒドロキシエチル基又は水素原子を表す。］
で示されるアミン化合物とを含むポリウレタン樹脂製造用の触媒組成物。
［２］一般式（１）で示されるアミン化合物が、２−ヒドロキシメチルトリエチレンジアミンであることを特徴とする上記［１］に記載のポリウレタン樹脂製造用の触媒組成物。

[Wherein R ₁ , R ₃ and R ₅ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R ₂ and R ₄ each independently represent a hydroxy group. Represents a group, a hydroxymethyl group, a hydroxyethyl group or a hydrogen atom. ]
The catalyst composition for manufacture of the polyurethane resin containing the amine compound shown by these.
[2] The catalyst composition for producing a polyurethane resin as described in [1] above, wherein the amine compound represented by the general formula (1) is 2-hydroxymethyltriethylenediamine.

  [3] The catalyst for producing a polyurethane resin as described in [1] or [2] above, wherein the amine compound represented by the general formula (2) is 3-quinuclidinol or 3-hydroxymethylquinuclidine. Composition.

  [4] The catalyst composition according to any one of the above [1] to [3], which does not contain lead, tin, mercury, or a compound thereof.

  [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] The amount of the catalyst composition according to any one of [1] to [4] above is in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyol. [5] The production method according to [5].

  The polyurethane resin produced using the catalyst composition of the present invention has little amine volatilized from the polyurethane resin. In addition, the catalyst composition of the present invention does not require the use of a metal catalyst containing lead, tin, mercury and their compounds. Therefore, the catalyst composition of the present invention not only can obtain polyurethane products with good productivity and moldability, but also does not cause odor problems, toxicity and environmental problems, and moreover it is an automobile instrument caused by a normal amine catalyst. It is effective for preventing panel fogging and fogging of window glass due to volatile component migration from foam.

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

  The catalyst composition for producing a polyurethane resin of the present invention is a catalyst composition comprising an amine compound represented by the general formula (1) and an amine compound represented by the general formula (2). The catalyst composition of the present invention does not need to use a metal-based catalyst containing lead, tin, mercury and their compounds.

  In the present invention, examples of the amine compound represented by the general formula (1) include hydroxytriethylenediamine, hydroxymethyltriethylenediamine, hydroxyethyltriethylenediamine, and the like. Hydroxymethyltriethylenediamine is preferred.

  The compound represented by the general formula (1) can be produced by a known method. For example, it can be produced by reacting a dibromocarboxylic acid ester corresponding to piperazine at an appropriate molar ratio and reducing the resulting ester.

  In the present invention, examples of the amine compound represented by the general formula (2) include 3-quinuclidinol, 3-hydroxymethyl quinuclidine, 3-methyl-3-hydroxymethyl quinuclidine, 4-hydroxymethyl quinuclidine. Although gin etc. are mentioned, since it is industrially available, 3-quinuclidinol and 3-hydroxymethyl quinuclidine are preferable.

  In the present invention, the amine compound represented by the above general formula (1) and the amine compound represented by the above general formula (2) used as a catalyst composition may be added in advance during the reaction. It may be added at the same time during the reaction. Moreover, when mixing them, it can also be melt | dissolved and used for a solvent. Although it does not specifically limit as a solvent, For example, alcohol, such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, and 2-methyl-1,3-propanediol, toluene, xylene, mineral terpene, Hydrocarbons such as mineral spirits, esters such as ethyl acetate, butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, N, N-dimethylformamide, N, N-dimethylacetamide Examples include solvable organic solvents such as amides, β-diketones such as acetylacetone and fluorinated substituents thereof, chelating solvents such as ketoesters such as methyl acetoacetate and ethyl acetoacetate, and water. .

  Next, the manufacturing method of the polyurethane resin of this invention is demonstrated.

  The method of the present invention is characterized in that a polyol and an isocyanate are reacted in the presence of the above-described catalyst composition of the present invention and, if necessary, a foaming agent, a surfactant, a flame retardant, a crosslinking agent and the like. .

  In the method of the present invention, the amount of the catalyst composition of the present invention is usually in the range of 0.01 to 30 parts by weight, preferably 0.1 to 20 parts by weight, based on 100 parts by weight of the polyol used. Range. If the amount is less than 0.01 parts by weight, the effect of the catalyst may not be obtained. On the other hand, when it exceeds 30 parts by weight, not only the effect of increasing the catalyst is not obtained, but also the physical properties of the polyurethane resin may be deteriorated.

  Examples of the polyol used in the method 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.

  In the method of the present invention, the polyether polyol used is not particularly limited. For example, a compound having at least two active hydrogen groups (ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentane). Examples thereof include polyhydric alcohols such as erythritol, amines such as ethylenediamine, alkanolamines such as ethanolamine and diethanolamine, etc.) and starting materials thereof and alkylene oxides (such as ethylene oxide and propylene oxide). [For example, Gunter Oertel, “Polyurethane Handbook” (1985) Hanser Publishers (Germany), p. See method according to 42-53].

  In the method of the present invention, the polyester polyol to be used is not particularly limited, and examples thereof include those obtained from the reaction of dibasic acid and glycol, wastes from the production of nylon, trimethylolpropane, and pentaerythritol. Wastes of phthalic polyester, polyester polyols obtained by treating and inducing waste products [for example, Keiji Iwata “Polyurethane Resin Handbook” (1987) Nikkan Kogyo Shimbun, p. See description of 117. ].

  In the method of the present invention, the polymer polyol to be used is not particularly limited. For example, radical polymerization of the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.). Examples include polymer polyols reacted in the presence of a catalyst.

  In the method of the present invention, the flame retardant polyol to be used is not particularly limited. For example, a phosphorus-containing polyol obtained by adding alkylene oxide to a phosphoric acid compound, epichlorohydrin, or trichlorobutylene oxide is opened. Examples thereof include halogen-containing polyols and phenol polyols obtained by polymerization.

  In the method of the present invention, a polyol having an average hydroxyl value in the range of 20 to 1000 mgKOH / g is usually used, but an average hydroxyl value in the range of 20 to 100 mgKOH / g is used for a soft polyurethane resin or a semi-rigid polyurethane resin. As the hard polyurethane resin, those having an average hydroxyl value in the range of 100 to 800 mgKOH / g are preferably used.

  The polyisocyanate used in the present invention may be a conventionally known polyisocyanate and is not particularly limited. For example, toluene diisocyanate (hereinafter sometimes referred to as TDI), diphenylmethane diisocyanate (hereinafter referred to as MDI). ), Aromatic polyisocyanates such as naphthylene diisocyanate, xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate, and mixtures thereof Examples include the body. Among these, TDI and its derivatives, or MDI and its derivatives are preferable, and these may be used alone or in combination.

  Examples of TDI and derivatives thereof include a mixture of 2,4-TDI and 2,6-TDI, a terminal isocyanate prepolymer derivative of TDI, and the like. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate, and a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  Among these isocyanates, TDI and its derivatives and / or MDI and its derivatives are preferably used for soft polyurethane resins and semi-rigid polyurethane resin products. As the rigid polyurethane resin, a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate is preferably used.

  The mixing ratio of these polyisocyanates and polyols is not particularly limited, but generally expressed as an isocyanate index ([isocyanate group] / [active hydrogen group capable of reacting with isocyanate group] (molar ratio) × 100). A range of 60 to 400 is preferred.

  In the method of the present invention, as the catalyst, in addition to the catalyst composition of the present invention described above, as other catalysts, organometallic catalysts, carboxylic acid metal salt catalysts, tertiary amine catalysts, quaternary ammonium salt catalysts. Etc. may be used in combination without departing from the spirit of the present invention.

  The organometallic catalyst may be a conventionally known one and is not particularly limited, and examples thereof include nickel naphthenate and cobalt naphthenate.

  The carboxylic acid metal salt catalyst may be a conventionally known catalyst and is not particularly limited, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono- and dicarboxylic acids such as benzoic acid and phthalic acid. Etc. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  The tertiary amine catalyst may be a conventionally known one, and is not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetra Methylpropylenediamine, 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, 1 , 8-diazabicyclo [5.4.0] undecene-7, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, dimethylcyclo Xylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, etc. And tertiary amine compounds.

  The quaternary ammonium salt catalyst may be a conventionally known one, and is not particularly limited. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium water such as tetramethylammonium hydroxide salts, and the like. Examples thereof include tetraalkylammonium organic acid salts such as oxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  In the method of the present invention, the catalyst composition of the present invention can be used alone or mixed with the above-mentioned other catalysts. However, if necessary, dipropylene glycol, ethylene glycol, A solvent such as 1,4-butanediol or water can be used. The amount of the solvent is not particularly limited, but is preferably 3 times or less by weight based on the total amount of the catalyst. If it exceeds 3 times by weight, the physical properties of the resulting foam may be affected, and it is not preferable for economic reasons. The catalyst composition thus adjusted may be used by adding to the polyol, or individual components may be added separately to the polyol, and there is no particular limitation.

  In the method of the present invention, a foaming agent can be used if necessary. The foaming agent is not particularly limited, and examples thereof include 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3,3,3-heptafluoro Fluorocarbon compounds such as propane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low boiling point hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, and acetone, and a mixture is used. be able to. As the low-boiling hydrocarbons, hydrocarbons having a boiling point of usually −30 to 70 ° C. are usually used, and specific examples thereof include propane, butane, pentane, cyclopentane, hexane, and mixtures thereof.

The amount of the foaming agent used is determined according to the desired density and foam physical properties. Specifically, the foam density obtained is usually 5 to 1000 kg / m ³ , preferably 10 to 500 kg / m ^3. Selected as

  In the method of the present invention, if necessary, a surfactant can be used as a foam stabilizer. Examples of the surfactant to be used include conventionally known organosilicone surfactants, and specifically, nonionic systems such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Surfactant or a mixture thereof is exemplified. Their use amount is usually 0.1 to 10 parts by weight per 100 parts by weight of polyol.

  In the method of the present invention, if necessary, a crosslinking agent or a chain extender can be used. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine and xylylene. Examples include polyamines such as range amine and methylene bisorthochloroaniline.

  In the method of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant include reactive flame retardants such as phosphorus-containing polyols typified by propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl phosphate, and the like. And other halogen-containing tertiary phosphates such as tris (2-chloroethyl) phosphate and tris (chloropropyl) phosphate, and halogens such as dibromopropanol, dibromoneopentyl glycol and tetrabromobisphenol A Examples include organic compounds, inorganic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount is not particularly limited and varies depending on the required flame retardancy, but is usually 4 to 20 parts by weight with respect to 100 parts by weight of the polyol.

  In the method of the present invention, if necessary, a colorant, an anti-aging agent, and other conventionally known additives can be used. The type and amount of these additives may be within the normal usage range of the additive used.

  The method of the present invention is performed by rapidly mixing and stirring the mixed solution in which the raw materials are mixed, and then injecting the mixture into a suitable container or mold to perform foam molding. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, high-pressure, low-pressure and spray-type devices can be used.

  Examples of the polyurethane resin product obtained by the method of the present invention include an elastomer that does not use a foaming agent, a polyurethane foam that uses a foaming agent, and the like. It is suitably used for production.

  Examples of polyurethane foam products include flexible polyurethane foam, semi-rigid polyurethane foam, and rigid polyurethane foam. The polyurethane resin production method of the present invention is a flexible polyurethane foam car sheet used as an automobile interior material, semi-rigid polyurethane. It is particularly preferably used for the production of insulation panels made of foam instrument panels and handles and rigid polyurethane foam.

In the present invention, the flexible polyurethane foam generally refers to a reversibly deformable foam having an open cell structure and exhibiting high air permeability [Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers ( Germany), p. 161-233, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. See description of 150-221. ]. The physical properties of the flexible urethane foam are not particularly limited. Generally, the density is 10 to 100 kg / m ³ , the compressive strength (ILD 25%) is 200 to 8000 kPa, and the elongation is 80 to 500%. It is.

The semi-rigid polyurethane foam is a reversibly deformable foam having an open cell structure and high air permeability like the flexible polyurethane foam, although the foam density and compressive strength are higher than those of the flexible polyurethane foam. Oertel, "Polyurethane Handbook" (1985 edition) Hanser Publishers (Germany), p. 223-233, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 211-221. ]. Moreover, since the polyol and isocyanate raw material to be used are the same as that of the flexible polyurethane foam, it is generally classified as a flexible polyurethane foam. The physical properties of the semi-rigid urethane foam are not particularly limited, but generally, the density is 40 to 800 kg / m ³ , the compressive strength (ILD 25%) is 10 to 200 kPa, and the elongation is 40 to 200%. It is. In the present invention, the flexible polyurethane foam may include a semi-rigid polyurethane foam from the raw materials used and the physical properties of the foam.

Further, the rigid polyurethane foam refers to a foam having a highly crosslinked closed cell structure and cannot be reversibly deformed [Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany), p. 234-313, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. See description of 224-283. ]. The physical properties of the rigid urethane foam are not particularly limited, but are generally in the range of a density of 10 to 100 kg / m ³ and a compressive strength of 50 to 1000 kPa.

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

Synthesis Example 1
Piperazine (43.1 g, 0.5 mol) and triethylamine (151.8 g, 1.5 mol) were charged into a 2 L separable flask and diluted with toluene. After substitution with nitrogen, ethyl 2,3-dibromopropionate (manufactured by Tokyo Chemical Industry Co., Ltd.) diluted with toluene was added to the mixture with stirring, and an aging reaction was carried out at 100 ° C. for 24 hours. The precipitated triethylamine hydrochloride was removed by filtration, and the resulting reaction solution was concentrated to synthesize an ester. This ester was dissolved in tetrohydrofuran and added to a tetrohydrofuran solution of lithium aluminum hydride with stirring in an ice bath. After reacting at room temperature for 2 hours, water and 15% aqueous sodium hydroxide solution were added to stop the reaction, and insoluble materials were removed by filtration. The reaction mixture was concentrated and extracted and washed with ethyl acetate. Ethyl acetate was removed to obtain 48 g of 2-hydroxymethyltriethylenediamine as the target compound (yield 68%).

Example 1.
A premix A was prepared using the polyol, cell opener, crosslinking agent, foam stabilizer, and water in the raw material blending ratio shown in Table 1. 148.1 g of Premix A was taken in a 500 ml polyethylene cup, and a 33.3 wt% dipropylene glycol solution of 2-hydroxymethyltriethylenediamine and 3-quinuclidinol (reagent product, manufactured by Aldrich Co.) was used as a catalyst in the mixing ratio shown in Table 2. The temperature was adjusted to 20 ° C. In a separate container, the isocyanate liquid whose temperature is adjusted to 20 ° C. is added in an amount in which the isocyanate index [= isocyanate group / OH group (molar ratio) × 100] is 100 in a premix A cup, and quickly stirred with a stirrer. 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 60 ° C., and the reactivity during foaming was measured. Moreover, foam density was measured and compared from the obtained molded foam. The results are shown in Table 2. The measurement method for each measurement item is as follows.

(1) Measurement items for reactivity.
Cream time: The foaming start time and the foam start time were measured visually.
Gel time: The time required for the reaction to progress to a resinous substance from a liquid substance was measured.
Rise time: The time for the rising of the foam to stop was measured visually.

(2) Foam core density.
The center part of the molded mold was cut into a size of 7 × 7 × 5 cm, and the core density was calculated by accurately measuring the size and weight.

(3) Foam odor.
A 5 × 5 × 5 cm size foam was cut from the foam of which the foam core density was measured, placed in a mayonnaise bottle, and capped. After the bottle was heated at 80 ° C. for 1 hour, the bottle was cooled to room temperature, and the smell of the foam was smelled on 10 monitors, and the intensity of the smell was measured.

A: Almost no odor.
○: Slightly present.
Δ: Odor is present.
X: There is a strong odor.

実施例２〜実施例５．
配合比を変更した以外は、実施例１と同じ手法を用いた。結果をあわせて表２に示す。

Example 2 to Example 5.
The same method as in Example 1 was used except that the blending ratio was changed. The results are shown in Table 2.

Comparative Examples 1 to 3
The same method as in Example 1 was used except that foaming was performed at the raw material blending ratio shown in Table 2. The results are also shown in Table 2.

  Examples 1 to 5 are examples using the catalyst composition of the present invention, but there was almost no odor of the amine catalyst from the foam. Further, by using 2-hydroxymethyltriethylenediamine and 3-quinuclidinol in combination, the catalytic activity is improved as compared to the single use (Comparative Example 2 and Comparative Example 3), and the catalyst system has excellent curability. It was. Further, when a 33.3% dipropylene glycol solution (product name: TEDA-L33, manufactured by Tosoh Corporation), which is generally used as a urethane catalyst, was used (Comparative Example 1), the odor of the amine catalyst was confirmed from the foam. Thus, the PVC discoloration of the automobile instrument panel and the fogging phenomenon of the window glass caused by the amine catalyst could not be prevented.

Claims (5)

An amine compound selected from the group consisting of 2-hydroxymethyltriethylenediamine and 3-quinuclidinol, 3-hydroxymethylquinuclidine, 3-methyl-3-hydroxymethylquinuclidine, and 4-hydroxymethylquinuclidine; A catalyst composition for producing a polyurethane resin. The catalyst composition for producing a polyurethane resin according to claim 1 , comprising an amine compound selected from the group consisting of 2-hydroxymethyltriethylenediamine , 3-quinuclidinol, and 3-hydroxymethylquinuclidine. . The catalyst composition according to claim 1 or 2 , which does not contain lead, tin, mercury, and compounds thereof. 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 3 and a foaming agent. The amount of the catalyst composition according to any one of claims 1 to 3, according to claim 4, characterized in that in the range of 0.01 to 30 parts by weight per 100 parts by weight of the polyol Manufacturing method.