JP2010037488A - Amine catalyst composition for production of polyurethane resin and production method for polyurethane resin using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new catalyst composition and a production method using it for producing a polyurethane product with good producibility and moldability without causing any odor, toxicity, and environmental problems. <P>SOLUTION: The catalyst composition consists of an amine compound represented by a general formula (1) and an amine compound containing one kind or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group in its molecule. In the formula, X is a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group. Using this composition, a polyurethane resin is produced. <P>COPYRIGHT: (C)2010,JPO&INPIT

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 having almost no volatile amine catalyst or harmful metal catalyst during the production of the 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, see Non-Patent Document 1). In most cases, metal-based compounds are often used in combination with a tertiary amine catalyst, because the productivity and formability deteriorate, and are 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 above-mentioned tertiary amine catalyst generally has a strong bad odor, and the working environment at the time of producing the polyurethane resin is remarkably 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 above amine catalyst is said to be able to avoid the above problem because the amine catalyst is immobilized in the polyurethane resin skeleton in a form reacted with polyisocyanate, and certainly reduces the odor of the final resin product. Is effective, but these amine catalysts have a problem that the curability is lowered because the activity of the resinification reaction (reaction of polyol and isocyanate) is inferior. The method using the above-mentioned crosslinking agent is effective in reducing the odor of the final polyurethane resin product and improving the working environment during the production of the polyurethane resin, but the physical properties such as hardness of the polyurethane resin are insufficient.

  Patent Document 6 and Patent Document 7 describe examples in which an amine compound having a hydroxy group, a primary amino group, and a secondary amino group in a 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 of the odor, and does not mention any 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. It is getting worse, and the problems of toxicity and environmental problems caused by heavy metals remaining in the products are being 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 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 in order to solve the above problems, the present inventors, as a catalyst for producing a polyurethane resin, triethylenediamine having a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group in the molecule, a hydroxy group, When an amine compound having one or two or more substituents selected from the group consisting of a primary amino group and a secondary amino group is used in combination, a polyurethane product can be produced with almost no odor, toxicity or environmental problems. As a result, the present invention was 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] An amine compound having in its molecule one or more substituents selected from the group consisting of an amine compound represented by the following general formula (1), a hydroxy group, a primary amino group, and a secondary amino group A catalyst composition for producing a polyurethane resin.

［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。］
［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, X represents a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group. ]
[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] An amine compound represented by the following general formula (2), wherein an amine compound having one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group in the molecule The catalyst composition for producing a polyurethane resin as described in [1] or [2] above,

［式中、Ｒ_１〜Ｒ_８は各々独立して、水素原子、ヒドロキシ基、炭素数１〜１６のアルキル基、炭素数６〜１６のアリール基、炭素数１〜１０のヒドロキシアルキル基、炭素数１〜１０のアミノアルキル基、炭素数１〜１０のモノメチルアミノアルキル基、又は炭素数１〜１０のジメチルアミノアルキル基を表し、ｘは０〜１１の整数、ｙは０〜１１の整数、ａは０〜１０の整数、ｂは０〜１０の整数を表す。］
［４］一般式（２）において、Ｒ_１〜Ｒ_８が、各々独立して、水素原子、ヒドロキシ基、メチル基、ヒドロキシエチル基、ヒドロキシプロピル基、アミノエチル基、アミノプロピル基、モノメチルアミノエチル基、モノメチルアミノプロピル基、ジメチルアミノエチル基、又はジメチルアミノプロピル基を表すことを特徴とする上記［３］に記載のポリウレタン樹脂製造用の触媒組成物。

[Wherein R _{1 to} R ₈ are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, carbon Represents an aminoalkyl group having 1 to 10 carbon atoms, a monomethylaminoalkyl group having 1 to 10 carbon atoms, or a dimethylaminoalkyl group having 1 to 10 carbon atoms, x is an integer of 0 to 11, y is an integer of 0 to 11; a represents an integer of 0 to 10, and b represents an integer of 0 to 10. ]
[4] In General Formula (2), R _{1 to} R ₈ are each independently a hydrogen atom, a hydroxy group, a methyl group, a hydroxyethyl group, a hydroxypropyl group, an aminoethyl group, an aminopropyl group, or monomethylaminoethyl. The catalyst composition for producing a polyurethane resin according to the above [3], which represents a group, a monomethylaminopropyl group, a dimethylaminoethyl group, or a dimethylaminopropyl group.

  [5] The amine compound represented by the general formula (2) is N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N′-dimethylpropylenediamine, N, N. -Dimethylhexamethylenediamine, N, N'-dimethylhexamethylenediamine, trimethyldiethylenetriamine, trimethylethylenediamine, trimethylpropylenediamine, trimethylhexamethylenediamine, tetramethyldiethylenetriamine, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol Bis (3-dimethylaminopropyl) amine, N-methylpiperazine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, N, -Dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoisopropanol, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethyl-N ', N'-bis (2-hydroxypropyl) -1 , 3-propanediamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine N, N-dimethylaminohexanol, and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) propylenediamine selected from the group consisting of one or two or more amine compounds. The catalyst composition for producing a polyurethane resin according to the above [3] or [4].

  [6] An amine compound represented by the general formula (1), an amine compound having in the molecule one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group; The mixing ratio of [Amine compound represented by the general formula (1)] / [Hydroxy group, primary amino group, and secondary amino group selected from the group consisting of one or two or more substituents in the molecule Amine composition] = 1/99 to 99/1 (weight ratio), The catalyst composition for producing a polyurethane resin according to any one of the above [1] to [5].

  [7] The mixing ratio of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is [amine compound represented by the general formula (1)] / [general formula (2) The catalyst composition for producing a polyurethane resin according to any one of the above [3] to [5], wherein the amine compound represented by the formula: = 1/99 to 99/1 (weight ratio).

  [8] 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 [7].

  [9] The amount of the catalyst composition according to any one of [1] to [7] is in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyol. 9. The production method according to 8.

  The polyurethane resin produced using the catalyst composition of the present invention has almost no amine volatilized from the polyurethane resin. Therefore, the catalyst composition of the present invention can not only obtain a polyurethane product with good productivity and moldability, but also a window glass due to PVC discoloration of an automobile instrument panel caused by a normal amine catalyst, and migration of volatile components from foam. It is effective in preventing clouding phenomenon.

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

  The polyurethane resin production catalyst composition of the present invention comprises one or more selected from the group consisting of the amine compound represented by the general formula (1), a hydroxy group, a primary amino group, and a secondary amino group. It is a catalyst composition containing the amine compound which has a substituent in a molecule | numerator.

  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, the amine compound having in its molecule one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group is not particularly limited, but preferably Is an amine compound represented by the general formula (2).

The substituents R _{1 to} R ₈ of the amine compound represented by the general formula (2) are each independently a hydrogen atom, hydroxy group, methyl group, hydroxyethyl group, hydroxypropyl group, aminoethyl group, aminopropyl. Group, monomethylaminoethyl group, monomethylaminopropyl group, dimethylaminoethyl group, or dimethylaminopropyl group are preferred.

Specific examples of the amine compound represented by the general formula (2) include N, N-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N-dimethyltetramethylenediamine, and N, N-dimethylpentamethylene. Diamine, N, N-dimethylhexamethylenediamine, N, N-dimethylheptamethylenediamine, N, N-dimethyloctamethylenediamine, N, N-dimethylnonamethylenediamine, N, N-dimethyldecamethylenediamine, N-methyl Ethylenediamine, N-methylpropylenediamine, N-methyltetramethylenediamine, N-methylpentamethylenediamine, N-methylhexamethylenediamine, N-methylheptamethylenediamine, N-methyloctamethylenediamine, N-methylnonamethylenediamine, -Methyldecamethylenediamine, N-acetylethylenediamine, N-acetylpropylenediamine, N-acetyltetramethylenediamine, N-acetylpentamethylenediamine, N-acetylhexamethylenediamine, N-acetylheptamethylenediamine, N-acetyloctamethylene Diamine, N-acetylnonamethylenediamine, N-acetyldecamethylenediamine, N, N, N′-trimethyldiethylenetriamine, N, N, N ′, N ″ -tetramethyltriethylenetetramine, N, N, N ′, N Primary amine compounds such as ", N"'-pentamethyltetraethylenepentamine, N, N, N', N ", N"'N""-hexamethylpentaethylenehexamine,
N, N′-dimethylethylenediamine, N, N′-dimethylpropylenediamine, N, N′-dimethylhexamethylenediamine, trimethylethylenediamine, trimethylpropylenediamine, trimethyltetramethylenediamine, trimethylpentamethylenediamine, trimethylhexamethylenediamine, trimethyl Heptamethylenediamine, trimethyloctamethylenediamine, trimethylnonamethylenediamine, trimethyldecamethylenediamine, tetramethyldiethylenetriamine, pentamethyltriethylenetetramine, hexamethyltetraethylenepentamine, heptamethylpentaethylenehexamine, bis (N, N-dimethylamino) Propyl) amine, secondary amine compounds such as N-methylpiperazine,
N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyisopropanol, N, N, N′-trimethylaminoethylethanolamine, N, N -Dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoethanol, N, N-dimethylaminoethyl-N'-methylaminoethyl-N" -methylaminoisopropanol, N, N-dimethylaminoethoxyethoxyethanol N, N-dimethylaminoethoxyethoxyisopropanol, N, N-dimethyl-N ′-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, N, N— Dimethyl-N ′, N′-bis (2-H Droxypropyl) -1,3-propanediamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N, N, N′-trimethyl-N ′ -(2-hydroxyisopropyl) bis (2-aminoethyl) ether, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N, N-dimethylaminohexanol, 5-dimethylamino-3-methyl Alkanols such as -1-pentanol, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) propylenediamine, N, N, N′-trimethyl-N ′-(2-hydroxypropyl) propylenediamine Examples include amines.

  Among these amine compounds, N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N′-dimethylpropylenediamine, N, N—is high in catalytic activity. Dimethylhexamethylenediamine, N, N′-dimethylhexamethylenediamine, trimethyldiethylenetriamine, trimethylethylenediamine, trimethylpropylenediamine, trimethylhexamethylenediamine, tetramethyldiethylenetriamine, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol, Bis (3-dimethylaminopropyl) amine, N-methylpiperazine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethyl-N ′, N′-bis (2-hydroxy Propyl) -1,3-propanediamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N, N-bis (3-dimethylaminopropyl)- One or more amine compounds selected from the group consisting of N-isopropanolamine, N, N-dimethylaminohexanol, and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) propylenediamine Particularly preferred.

  The amine compound represented by the general formula (2) used in the catalyst composition of the present invention can be easily produced by methods known in the literature. For example, a method of reaction of diol and diamine, a method of amination of alcohol, a method of reductive methylation of monoamino alcohol or diamine, a method of reaction of amine compound and alkylene oxide, and the like can be mentioned.

  In the present invention, an amine having one or more substituents selected from the group consisting of the amine compound represented by the general formula (1) and a hydroxy group, a primary amino group, and a secondary amino group in the molecule. The mixing ratio with the compound is not particularly limited, but is usually a kind selected from the group consisting of an amine compound represented by the general formula (1), a hydroxy group, a primary amino group, and a secondary amino group Or the weight ratio of the amine compound having two or more substituents in the molecule ([amine compound represented by the general formula (1)] / [from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group The mixing ratio is adjusted so that the amine compound having one or two or more selected substituents in the molecule is usually in the range of 1/99 to 99/1. More preferably, it is the range of 5 / 95-95 / 5. If the weight ratio exceeds this range, the synergistic effect of both catalysts may not be obtained, and satisfactory performance may not be exhibited in terms of physical properties and catalytic activity of the polyurethane resin.

  In the present invention, the mixing ratio of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is not particularly limited. The weight ratio of the amine compound represented by formula (2) to the amine compound represented by formula (2) ([amine compound represented by formula (1)] / [amine compound represented by formula (2)] ) Is in the range of 1/99 to 99/1. More preferably, it is the range of 5 / 95-95 / 5. If the weight ratio exceeds this range, the synergistic effect of both catalysts may not be obtained, and satisfactory performance may not be exhibited in terms of physical properties and catalytic activity of the polyurethane resin.

  In the present invention, the amine compound represented by the above general formula (1) used in the catalyst composition, and one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group In the molecule, the amine compound prepared by mixing in advance may be added during the reaction, or may be added simultaneously 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 for producing a polyurethane resin of the present invention comprises reacting a polyol and an isocyanate 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. Its features.

  In the method for producing a polyurethane resin 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 100 parts by weight of the polyol used. It is in the range of ˜20 parts by weight. 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.

  In the method for producing a polyurethane resin of the present invention, examples of the polyol used 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 for producing a polyurethane resin of the present invention, the polyether polyol to be used is not particularly limited, but for example, a compound having at least two active hydrogen groups (ethylene glycol, propylene glycol, glycerin, triglyceride). Examples include polyhydric alcohols such as methylolpropane and pentaerythritol, amines such as ethylenediamine, alkanolamines such as ethanolamine and diethanolamine, etc.) as starting materials and alkylene oxides (such as ethylene oxide and propylene oxide) (For example, Gunter Oertel, “Polyurethane Handbook” (1985) Hans Publisher). Company (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 for producing a polyurethane resin of the present invention, the polymer polyol used is not particularly limited. For example, the polyether polyol and an ethylenically unsaturated monomer (for example, butadiene, acrylonitrile, styrene, etc.). ) In the presence of a radical polymerization catalyst.

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

  In the method for producing a polyurethane resin of the present invention, a polyol having an average hydroxyl value in the range of 20 to 1000 mgKOH / g can be used. For a soft polyurethane resin or a semi-rigid polyurethane resin, an average hydroxyl value in the range of 20 to 100 mgKOH / g. 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 is not particularly limited as long as it is a conventionally known polyisocyanate. For example, toluene diisocyanate (hereinafter sometimes referred to as TDI), diphenylmethane diisocyanate (hereinafter referred to as MDI). ), Aromatic polyisocyanates such as naphthylene diisocyanate and xylylene diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and these And the like. 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 when expressed in terms of isocyanate index ([isocyanate group] / [active hydrogen group capable of reacting with isocyanate groups]), generally the range is 60 to 400. preferable.

  In the method for producing a polyurethane resin of the present invention, the catalyst is one or more selected from the group consisting of the amine compound represented by the general formula (1), a hydroxy group, a primary amino group, and a secondary amino group. In addition to the catalyst composition of the present invention comprising an amine compound having a substituent in the molecule, other organometallic catalysts, carboxylic acid metal salt catalysts, and tertiary amine catalysts are within the scope of the present invention. A quaternary ammonium salt catalyst may be used in combination.

  The organometallic catalyst is not particularly limited as long as it is a conventionally known one. For example, stannous diacetate, stannous dioctoate, stannous dioleate, stannous dilaurate, dibutyltin oxide, dibutyltin diester Examples include acetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, and the like.

  The carboxylic acid metal salt catalyst may be any conventionally known one, 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 is not particularly limited as long as it is conventionally known. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N ′ can be used. -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 1,8-diazabicyclo [5.4.0] undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethyl Piperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethyl And tertiary amine compounds such as aminopropylimidazole.

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

  In the method for producing the polyurethane resin of the present invention, the catalyst composition of the present invention can be used alone or mixed with the above-mentioned other catalyst. A solvent such as ethylene glycol, 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 for producing a polyurethane resin 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 One or two selected from the group consisting of chlorofluorocarbons such as propane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low boiling point hydrocarbons, water, liquefied carbon dioxide, dichloromethane, formic acid, and acetone Thus, a mixture of these can be used. 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 for producing a polyurethane resin of the present invention, a surfactant can be used as a foam stabilizer if necessary. 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 for producing a polyurethane resin of the present invention, a crosslinking agent or a chain extender can be used if necessary. 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 for producing a polyurethane resin of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant used include reactive flame retardants such as phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide, tricresyl Tertiary phosphates such as phosphate, halogen-containing tertiary phosphates such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate, halogens such as dibromopropanol, dibromoneopentyl glycol, 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 for producing a polyurethane resin of the present invention, if necessary, a colorant, an antioxidant, 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 for producing the polyurethane resin of the present invention is carried out 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 polyurethane resin products include elastomers that do not use a foaming agent, polyurethane foams that use a foaming agent, and the like, and the method for producing a polyurethane resin of the present invention is suitably used for producing such polyurethane foam products. .

  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 includes a flexible polyurethane foam car sheet, semi-rigid foam used as an automotive interior material. It is particularly suitably used for the manufacture of insulation panels made of rigid polyurethane 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, 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 not limitedly interpreted only to these Examples.

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 nitrogen substitution, ethyl 2,3-dibromopropionate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) diluted with toluene was added to the mixture with stirring, and an aging reaction was performed at 100 ° C. for 24 hours. The precipitated hydrochloride of triethylamine 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 a 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. Take 148.1 g of Premix A in a 500 ml polyethylene cup and use 2-hydroxymethyltriethylenediamine and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether as a catalyst. The mixture was added at the mixing ratio shown in 2, and 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 time when the foam starts to rise are visually measured.
Gel time: Measures the time required for the reaction to progress to a resinous substance from a liquid substance.
Rise time: Measure the time when the rising of the foam stops 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.

  ◎: Almost no odor, ○: Slight, △: Odor, ×: Strong odor.

実施例２〜実施例６．
Ｎ，Ｎ，Ｎ’−トリメチル−Ｎ’−（２−ヒドロキシエチル）ビス（２−アミノエチル）エーテルの代わりに表２に示したアミン化合物を使用した以外は、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 6.
The same procedure as in Example 1 was used except that the amine compound shown in Table 2 was used instead of N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether. It was. The results are shown in Table 2.

Comparative Example 1
Example 1 except that L33 and TOYOCAT-ET were used in place of 2-hydroxymethyltriethylenediamine and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether The same method was used. The results are shown in Table 2.

Comparative Example 2
Except for using N, N-dimethylaminoethanol instead of 2-hydroxymethyltriethylenediamine and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether The same procedure as in Example 1 was used. The results are shown in Table 2.

  Examples 1 to 6 are examples in which the catalyst composition of the present invention was used, but the catalyst activity was high, and the amine catalyst odor was almost absent from the foam. When L33 and TOYOCAT-ET which are generally used as urethane catalysts are used (Comparative Example 1), the odor of the amine catalyst is confirmed from the foam, the PVC discoloration of the automobile instrument panel caused by the amine catalyst, the fogging phenomenon of the window glass Could not be prevented.

  On the other hand, when N, N-dimethylaminoethanol, which is a reactive catalyst, is used alone (Comparative Example 2), the catalytic activity is low, the odor of the amine catalyst is confirmed from the foam, and the automotive instrument panel caused by the amine catalyst PVC discoloration and fogging of the window glass could not be prevented.

Claims (9)

It consists of an amine compound represented by the following general formula (1) and an amine compound having in its molecule one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group. A catalyst composition for producing a polyurethane resin.

[Wherein, X represents a hydroxy group, a hydroxymethyl group, or a hydroxyethyl group. ] The catalyst composition for producing a polyurethane resin according to claim 1, wherein the amine compound represented by the general formula (1) is 2-hydroxymethyltriethylenediamine. The amine compound having in the molecule one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group is an amine compound represented by the following general formula (2). A catalyst composition for producing a polyurethane resin according to claim 1 or 2, characterized in that:

[Wherein R _{1 to} R ₈ are each independently a hydrogen atom, a hydroxy group, an alkyl group having 1 to 16 carbon atoms, an aryl group having 6 to 16 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, carbon Represents an aminoalkyl group having 1 to 10 carbon atoms, a monomethylaminoalkyl group having 1 to 10 carbon atoms, or a dimethylaminoalkyl group having 1 to 10 carbon atoms, x is an integer of 0 to 11, y is an integer of 0 to 11; a represents an integer of 0 to 10, and b represents an integer of 0 to 10. ] In the general formula (2), R _{1 to} R ₈ are each independently a hydrogen atom, a hydroxy group, a methyl group, a hydroxyethyl group, a hydroxypropyl group, an aminoethyl group, an aminopropyl group, a monomethylaminoethyl group, or a monomethyl group. The catalyst composition for producing a polyurethane resin according to claim 3, which represents an aminopropyl group, a dimethylaminoethyl group, or a dimethylaminopropyl group. The amine compound represented by the general formula (2) is N, N-dimethylethylenediamine, N, N′-dimethylethylenediamine, N, N-dimethylpropylenediamine, N, N′-dimethylpropylenediamine, N, N-dimethylhexa. Methylenediamine, N, N′-dimethylhexamethylenediamine, trimethyldiethylenetriamine, trimethylethylenediamine, trimethylpropylenediamine, trimethylhexamethylenediamine, tetramethyldiethylenetriamine, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol, bis ( 3-dimethylaminopropyl) amine, N-methylpiperazine, N, N-dimethylaminoethoxyethanol, N, N, N′-trimethylaminoethylethanolamine, N, N-di Tylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethyl-N ′, N′-bis (2-hydroxypropyl) -1, 3-propanediamine, N, N, N′-trimethyl-N ′-(2-hydroxyethyl) bis (2-aminoethyl) ether, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, It is one or two or more types of amine compounds selected from the group consisting of N, N-dimethylaminohexanol and N, N, N′-trimethyl-N ′-(2-hydroxyethyl) propylenediamine. A catalyst composition for producing a polyurethane resin according to claim 3 or 4. Mixing ratio of the amine compound represented by the general formula (1) and the amine compound having in the molecule one or more substituents selected from the group consisting of a hydroxy group, a primary amino group, and a secondary amino group Is an amine compound having in its molecule one or more substituents selected from the group consisting of [hydroxyl group, primary amino group, and secondary amino group] The catalyst composition for producing a polyurethane resin according to any one of claims 1 to 5, wherein = 1/99 to 99/1 (weight ratio). The mixing ratio of the amine compound represented by the general formula (1) and the amine compound represented by the general formula (2) is represented by [amine compound represented by the general formula (1)] / [general formula (2). The catalyst composition for producing a polyurethane resin according to any one of claims 3 to 5, wherein the amine compound] = 1/99 to 99/1 (weight ratio). 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 7. The amount of the catalyst composition according to any one of claims 1 to 7 is in the range of 0.01 to 30 parts by weight with respect to 100 parts by weight of the polyol. Production method.