JP2007077240A - Catalyst composition for producing polyurethane resin and method for producing the polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst composition which gives a product having very little odor by improving curing properties, moldability and a low temperature adhesion strength as a solution forming a homogeneous liquid phase. <P>SOLUTION: A composition comprising (A) an amine compound expressed by general formula (1) [wherein A expresses a 8-18C alkyl; R<SB>1</SB>and R<SB>2</SB>independently express each a 1-6C alkyl], (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, and/or (C) triethylene diamine is used as the catalyst for producing polyurethane resins. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a catalyst composition for producing a polyurethane resin such as soft, hard, semi-rigid, and elastomer, and a method for producing a polyurethane resin using the catalyst composition.

  More specifically, the present invention relates to a catalyst composition having excellent characteristics in moldability, curability and surface adhesive strength at a low temperature and extremely low discharge of a volatile amine catalyst, and a method for producing a polyurethane resin using the catalyst. Is.

  The polyurethane resin is produced by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a crosslinking agent and the like. It has been conventionally known that a large number of metal compounds and tertiary amine compounds are used as catalysts for the production of this polyurethane resin. These catalysts are used singly or in combination and are widely used industrially.

  Among these catalysts, tertiary amine compounds are widely used as catalysts for producing polyurethane resins because of their excellent productivity and moldability. For example, conventionally known triethylenediamine, N, N-dimethylcyclohexylamine, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, N, N, N ′, N′-tetramethyl-1,6-hexane Examples thereof include diamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, triethylamine, N-methylmorpholine, N-ethylmorpholine and the like.

  In recent years, in order to improve cost reduction and foam productivity in polyurethane production, there is a strong demand for excellent curing speed for shortening the demolding time and excellent moldability for improving yield. The formation reaction of polyurethane foam mainly consists of two reactions: urethane group formation reaction (resinification reaction) by reaction of polyol and isocyanate, urea group formation by reaction of isocyanate and water, and carbon dioxide gas generation (foaming reaction) reaction. Thus, the catalyst has a great influence not only on the reaction rate but also on the foam curing rate, moldability, foam density reduction and physical properties.

  On the other hand, reduction of chlorofluorocarbons (so-called CFCs such as trichloromonofluoromethane and dichlorodifluoromethane) and hydrochlorofluorocarbons (so-called HCFCs such as dichloromonofluoroethane) that cause destruction of the ozone layer and improvement of the working environment Environmental issues such as the suppression of volatile substances from products and products are becoming a major concern. Currently, hydrofluorocarbons (tetrafluoroethane, 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-pentafluoro with little or no ozone layer destruction) So-called HFCs such as butane) are newly proposed and used as blowing agents.

  However, these HFCs are expensive and therefore disadvantageous in terms of cost when used in large amounts, and may be used only in small amounts due to their combustibility. Furthermore, since the surface curability of urethane is deteriorated, there are problems such as poor adhesion performance.

  In addition, low boiling point hydrocarbons that do not destroy the ozone layer (so-called HCs such as propane, butane, pentane, etc.) are considered to be promising as foaming agents, but the amount of use cannot be increased because they are highly combustible. There is a problem.

  For this reason, a study has been made on a prescription in which CFCs, HCFCs, HFCs, and HCs as foaming agents are reduced and the amount of water is increased. Further, the moldability is deteriorated, and the adhesive performance is remarkably deteriorated. For this reason, there is a strong demand for the development of a catalyst suitable for a formulation in which CFCs, HCFCs, HFCs and HCs are reduced and the amount of water is increased.

  However, the polyurethane production catalysts developed so far have various problems.

  For example, conventionally known tertiary amines have a strong amine odor, and are particularly low molecular weight N-methylmorpholine, N-ethylmorpholine, triethylamine, N, N, N ′, N′-tetramethylhexamethylenediamine. N, N-dimethylcyclohexylamine has a very strong irritating odor and significantly deteriorates the working environment due to the bad odor of the foaming process. In particular, when a large amount of a tertiary amine catalyst is used to increase the curing speed, there are problems such as causing eye itchiness. In addition, there is a problem that the polyurethane product itself has a bad odor or is scattered from the product to the outside to impair the value of the product.

  Conventionally known metal catalysts, such as organotin compounds, do not cause the above-mentioned problems, but when used alone, productivity, physical properties and moldability deteriorate, and environmental problems due to tin have been taken into account.

  In order to solve these problems, relatively high molecular weight amine catalysts have been proposed. As a relatively high molecular weight amine catalyst, aliphatic monoamines having 6 to 10 carbon atoms use CFCs as foaming agents and use less water, and cure speed, moldability, adhesive strength, and dimensional stability It is disclosed as an amine catalyst from which a polyurethane foam excellent in properties and the like can be obtained (Patent Document 1).

  In addition, the high molecular weight amine compound having a long-chain aliphatic monoamino group in the range of 11 to 14 carbon atoms has a low odor and volatility, and in a formulation in which the amount of water is increased without using CFCs as a blowing agent, the curing rate Further, it is disclosed as a catalyst for obtaining a polyurethane foam excellent in moldability, adhesive strength, dimensional stability, and the like (Patent Document 2).

  Specifically, Patent Document 1 discloses a third example such as triethylenediamine, N, N, N ′, N′-tetramethylalkylenediamine, polyN-methylpolyalkylenepolyamine in combination with aliphatic monoamines. It has been disclosed that the use of a secondary amine catalyst makes it possible to shorten the molding time without causing burns or cracks in the production of hard high density urethane.

  Further, in Patent Document 2, specifically, in combination with long-chain aliphatic monoamines, other resinification catalysts and foaming catalysts such as triethylenediamine, 1,8-diazabicyclo [5.4.0] are used. ] Using a tertiary amine compound such as undecene-7, bis (2-dimethylaminoethyl) ether, N, N, N ', N ", N" -pentamethyldiethylenetriamine, the curing rate and moldability of the foam And the adhesive strength can be improved. Furthermore, a method for producing a rigid polyurethane foam in combination with a tertiary amine compound having an active hydrogen group capable of reacting with an isocyanate, an organometallic compound and / or a carboxylic acid metal salt is disclosed.

JP 58-93715 A Japanese Patent Laid-Open No. 8-120044

  However, the above-described high molecular weight amine catalyst is relatively volatile than the conventional catalyst, but its catalytic activity is low. Therefore, it is necessary to use a large amount of the catalyst. There was a problem of scattering to the outside and contaminating other materials.

  Moreover, although these catalysts improved the moldability of the foam surface part, the curability was not sufficient. In addition, these high molecular weight amine catalysts are highly hydrophobic and are not compatible with other tertiary amines and foam stabilizers. Therefore, in the polyurethane production line, the catalyst is supplied to other containers, tanks and foaming equipment. There was a problem that it was disadvantageous in terms of cost because equipment such as a line was necessary.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a catalyst composition that improves the curability, moldability, and low-temperature adhesive strength of a polyurethane product, and provides an extremely low odor product. It is to provide a solution that forms a uniform liquid phase and does not cause phase separation.

  Furthermore, it is providing the manufacturing method of polyurethane resins, such as a soft, hard, semi-rigid, elastomer, using this catalyst composition.

  The present inventors diligently studied to solve various problems of known catalysts. As a result, surprisingly, (A) a long-chain aliphatic monoamine compound having 8 to 18 carbon atoms in the molecule, (B) a tertiary amine compound having a hydroxyalkyl group in the molecule, and / or (C) The present invention has found a novel fact that a catalyst composition comprising triethylenediamine improves the curability, moldability and low-temperature adhesive strength of a polyurethane resin, and gives a polyurethane product having an extremely low odor. Is completed.

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

  [1] (A) The following general formula (1)

［上記一般式（１）中、Ａは炭素数８〜１８のアルキル基を表し、Ｒ_１、Ｒ_２は各々独立して炭素数１〜６のアルキル基を表す。］
で示されるアミン化合物と、（Ｂ）分子内に少なくとも１つのヒドロキシアルキル基を有する第３級アミン化合物とからなるポリウレタン樹脂製造用の触媒組成物。

[In the general formula (1), A represents an alkyl group having 8 to 18 carbon atoms, and R ₁ and R ₂ each independently represents an alkyl group having 1 to 6 carbon atoms. ]
And (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, a catalyst composition for producing a polyurethane resin.

  [2] The mixing ratio of (A) the amine compound represented by the general formula (1) and (B) the tertiary amine compound having at least one hydroxyalkyl group in the molecule is 10 to 90/10 to 90 ( Weight%) range [however, the sum of (A) and (B) does not exceed 100 (wt%). The catalyst composition as described in [1] above, wherein

  [3] (A) The following general formula (1)

［上記一般式（１）中、Ａは炭素数８〜１８のアルキル基を表し、Ｒ_１、Ｒ_２は各々独立して炭素数１〜６のアルキル基を表す。］
で示されるアミン化合物と、（Ｂ）分子内に少なくとも１つのヒドロキシアルキル基を有する第３級アミン化合物、及び／又は（Ｃ）トリエチレンジアミンとからなるポリウレタン樹脂製造用の触媒組成物。

[In the general formula (1), A represents an alkyl group having 8 to 18 carbon atoms, and R ₁ and R ₂ each independently represents an alkyl group having 1 to 6 carbon atoms. ]
(B) A tertiary amine compound having at least one hydroxyalkyl group in the molecule and / or (C) a triethylenediamine catalyst composition for producing a polyurethane resin.

  [4] The mixing ratio of (A) the amine compound represented by the general formula (1), (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, and (C) triethylenediamine is 10 to 10. The range of 90/10 to 90 / 20-0 (% by weight) [however, the sum of (A), (B) and (C) does not exceed 100 (% by weight). The catalyst composition as described in [3] above, wherein

  [5] (A) The amine compound represented by the general formula (1) is dimethyloctylamine, dimethylnonylamine, dimethyldecylamine, dimethylundecylamine, dimethyldodecylamine, dimethyltridecylamine, dimethyltetradecylamine, dimethyl Any one of [1] to [4] above, which is one or more amine compounds selected from the group consisting of pentadecylamine, dimethylhexadecylamine, dimethylheptadecylamine and dimethyloctadecylamine. The catalyst composition as described in 1.

  [6] (B) A tertiary amine compound having at least one hydroxyalkyl group in the molecule is N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethyl-N ′. -Methylaminoethanol, N, N-dimethylaminopropyl-N'-methylaminoethanol, N, N, N'-trimethyl-N'-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N'- Methylaminoethyl-N ″ -methylaminoisopropanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- ( 2-hydroxyethyl) -N'-methylpiperazine, N, N-dimethylamino It is one or two or more amine compounds selected from the group consisting of xanol, 5-dimethylamino-3-methyl-1-pentanol, and 1- (2-hydroxypropyl) -2-methylimidazole. The catalyst composition according to any one of [1] to [5] above.

  [7] 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 [6].

  [8] In the method for producing a rigid polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a foaming agent, the catalyst composition according to any one of the above [1] to [6] is used as a catalyst. A method for producing a rigid polyurethane foam, characterized in that:

  [9] In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a foaming agent, the catalyst composition according to any one of the above [1] to [6] is used as a catalyst. A method for producing a flexible polyurethane foam, comprising:

  Since the catalyst composition of the present invention forms a polyurethane foam having a lower odor than the conventional amine catalyst, the working environment is remarkably improved in the polyurethane production process, and the production foam itself does not leave a bad odor and is volatile from the foam. Can be reduced. In addition, it is possible to increase the curing rate of the foam and remarkably improve the adhesive strength of the surface.

  In addition, since the catalyst composition of the present invention forms a uniform liquid phase at room temperature and does not cause phase separation when mixed, equipment such as a catalyst supply line to a separate container, tank, or foaming device in a polyurethane production line Therefore, the present invention is extremely useful industrially.

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

  The catalyst composition of the present invention comprises (A) an amine compound represented by the above general formula (1), (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, and / or (C). It consists of triethylenediamine.

  (A) The amine compound represented by the above general formula (1) is an amine compound represented by the above general formula (1), and is not particularly limited, but specifically, dimethyloctylamine, dimethylnonylamine. , Dimethyldecylamine, dimethylundecylamine, dimethyldodecylamine, dimethyltridecylamine, dimethyltetradecylamine, dimethylpentadecylamine, dimethylhexadecylamine, dimethylheptadecylamine, dimethyloctadecylamine, diethyloctylamine, diethylnonylamine , Diethyldecylamine, diethylundecylamine, diethyldodecylamine, diethyltridecylamine, diethyltetradecylamine, diethylpentadecylamine, diethylhexadecylamine, diethylheptadecyl Min, diethyloctadecylamine, methylethyloctylamine, methylethylnonylamine, methylethyldecylamine, methylethylundecylamine, methylethyldodecylamine, methylethyltridecylamine, methylethyltetradecylamine, methylethylpentadecylamine, Examples include methyl ethyl hexadecyl amine, methyl ethyl heptadecyl amine, methyl ethyl diethyl octadecyl amine and the like.

  Among these amine compounds, dimethyloctylamine, dimethylnonylamine, dimethyldecylamine, dimethylundecylamine, dimethyldodecylamine, dimethyltridecylamine, dimethyltetradecylamine, dimethylpentadecylamine, dimethylhexadecylamine, dimethylhepta Decylamine and dimethyloctadecylamine are particularly preferred.

  (A) The amine compound represented by the general formula (1) is excellent in moldability and adhesive strength at low temperature, but has low catalytic activity and poor curability. When the main chain other than the present invention has 7 or less carbon atoms, the amine odor and volatility are high, and it is difficult to improve the working environment and reduce scattering from the foam. On the other hand, when the number of carbon atoms is 19 or more, the catalytic activity is remarkably lowered, the number of used parts of the catalyst is increased, and the curability is inferior.

  (A) The amine compound represented by the general formula (1) can be easily produced by methods known in the literature. Examples thereof include a method by reductive methylation of monoamine and amination of alcohol, a method by reaction of alkyl halide and dialkylamine, and the like.

  (B) The tertiary amine compound having at least one hydroxyalkyl group in the molecule is not particularly limited. Specifically, N, N-dimethylaminoethanol, N, N-dimethylaminoisopropanol N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyisopropanol, N, N-dimethylaminoethoxyethoxyethanol, N, N-dimethylaminoethoxyethoxyisopropanol, N, N-dimethylaminoethyl-N′- Methylaminoethanol, N, N-dimethylaminoethyl-N′-methylaminoisopropanol, N, N-dimethylaminopropyl-N′-methylaminoethanol, N, N-dimethylaminopropyl-N′-methylaminoisopropanol, N , N-dimethyl -N '-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N'-(2-hydroxyethyl) propanediamine, N, N, N'-trimethyl-N'-hydroxyethylbisaminoethyl ether, N , N, N′-trimethyl-N′-hydroxyisopropylbisaminoethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethanol, N, N-dimethylaminoethyl-N ′ -Methylaminoethyl-N "-methylaminoisopropanol, N, N-dimethylaminoethyl-N'-methylaminoethyl-N" -methylaminoethyl-N "'-methylaminoethanol, N, N-dimethylaminoethyl- N′-methylaminoethyl-N ″ -methylaminoethyl-N ″ ′-methylamino Sopropanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N ′ -Methylpiperazine, N, N-dimethylaminohexanol, 5-dimethylamino-3-methyl-1-pentanol, 1- (2'-hydroxyethyl) imidazole, 1- (2'-hydroxypropyl) imidazole, 1- Examples include alkanolamines such as (2′-hydroxyethyl) -2-methylimidazole and 1- (2′-hydroxypropyl) -2-methylimidazole.

  Of these, N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethyl-N′-methylaminoethanol, N, N-dimethylaminopropyl- are high in catalytic activity. N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxyethyl) -N′-methylpiperazine, N , N-dimethylaminohexanol, and 5-dimethylamino-3-methyl 1-pentanol, 1- (2-hydroxypropyl) -2-methylimidazole are particularly preferred.

  (B) The tertiary amine compound having at least one hydroxyalkyl group in the molecule reacts with the isocyanate and is incorporated into the foam, so that the amount of volatilization from the foam can be reduced. However, there is a problem that moldability and adhesive strength at low temperature are lowered.

  (B) A tertiary amine compound having at least one hydroxyalkyl group in the molecule can be easily produced by methods known in the literature. Examples thereof include a method by amination of alcohol and a method by reductive methylation of amino alcohols.

  In the catalyst composition of the present invention, (A) an amine compound represented by the above general formula (1), (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, and / or (C) tri The mixing ratio of ethylenediamine is usually in the range of 10-90 / 10-90 / 20-0 (wt%), preferably in the range of 30-90 / 10-70 / 5-15 (wt%), The sum of (A), (B) and (C) does not exceed 100 (% by weight).

  For example, (A) When the ratio of the amine compound represented by the general formula (1) is increased, the moldability and the adhesive strength at low temperature are improved, but the catalytic activity is decreased, so that the amount used is increased and the curability is increased. Inferiority causes a problem of lowering productivity.

  In addition, when the ratio of the tertiary amine compound having at least one hydroxyalkyl group in the molecule (B) increases, it is possible to reduce the amount of amine catalyst volatilization from the foam, and the curability is also improved. There is a problem that moldability and adhesive strength at low temperatures are lowered.

  Furthermore, when the ratio of (C) triethylenediamine is increased, the catalytic activity as the catalyst composition is improved, so that the amount of the catalyst used can be reduced and the curability is improved, but the moldability and adhesion at low temperature are improved. Strength decreases.

  That is, even if the amine compounds of (A), (B), and (C) are used alone in the production of polyurethane resin, the amount of volatile amine increases, curability and moldability become a problem. The effect of this invention is not achieved, and the effect of this invention is achieved only by using (A) and (B) and / or (C) together.

  The catalyst composition of the present invention is used as a catalyst in a method for producing a polyurethane resin, and is particularly preferably used in a method for producing a rigid polyurethane foam, a semi-rigid polyurethane foam, and a flexible polyurethane foam.

Rigid polyurethane foam has a highly crosslinked closed cell structure, is a non-reversible deformable foam, and has completely different properties from flexible and semi-rigid foams [Gunter Oeltel, “Polyurethane Handbook” (1985 edition) Hanser Publishers (Germany) p. 234-313, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. 224-283 etc.]. In addition, the physical properties of the rigid polyurethane foam are not particularly limited, but generally, the density is in the range of ²⁰ to 100 kg / m ³ and the compressive strength is in the range of 0.5 to 10 kgf / cm ² (50 to 1000 kPa). It is.

In contrast, flexible polyurethane foam is a reversibly deformable foam that generally has an open cell structure and exhibits high air permeability [Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany) p. 161-233, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. 150-221 etc.]. In addition, the physical properties of the flexible polyurethane foam is not particularly limited because it differs depending on the chemical structure such as the polyol, isocyanate and the like, the chemical amount of the foaming agent and the chemical factor such as the isocyanate index, and the cell structure. Generally, the density is 10 to 100 kg / m ³ (JIS K 6401), the compressive strength (IDL 25%) is 2 to 80 kgf (20 to 800 N) (JIS K 6401), and the elongation is 80 to 500% (JIS K). 6301) [Gunter Oertel, “Polyurethane Handbook” (1985 edition) Hanser Publishers (Germany) p. 184-191 and p. 212-218, Keiji Iwata “Polyurethane Resin Handbook” (1987 first edition), Nikkan Kogyo Shimbun, p. 160-166 and p. 186-191].

Semi-rigid polyurethane foam, which has higher foam density and compressive strength than flexible polyurethane foam, has an open cell structure similar to flexible polyurethane foam and is a reversibly deformable foam that exhibits high breathability and is used. Since the polyol and isocyanate raw materials are the same as the flexible polyurethane foam, they are generally classified into flexible polyurethane foams [Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany) p. 223-233, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. 211-221]. The physical properties of the semi-rigid polyurethane foam are not particularly limited, but generally, the density is 40 to 800 kg / m ³ and the 25% compressive strength is 0.1 to ² kgf / cm ² (9.8). ˜200 kPa) and the elongation is in the range of 40 to 200%.

  The method for producing a polyurethane resin of the present invention is characterized by reacting a polyol and a polyisocyanate in the presence of the above-described catalyst composition of the present invention.

  As the polyol used in the method for producing the polyurethane resin of the present invention, generally known polyester polyols, polyether polyols, polymer polyols and mixtures thereof can be used. Known polyester polyols include those obtained from the reaction of dibasic acids and hydroxy compounds (glycols, etc.), polyester polyols starting from DMT residue, phthalic anhydride, wastes from the production of nylon, TMP, pentaerythritol Examples include wastes, wastes of phthalic polyesters, polyester polyols obtained by treating and inducing wastes [for example, Keiji Iwata “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, p. 116-117]. In addition to the above, examples include phthalic acid, isophthalic acid, terephthalic acid, phthalic anhydride, wastes thereof, and those obtained by esterifying aromatic dicarboxylic acid or its derivatives from waste products. Specific examples of the dibasic acid used as a raw material for the polyester polyol include adipic acid, phthalic acid, succinic acid, azelaic acid, sebacic acid, and ricinoleic acid.

  Known polyether polyols include, for example, polyhydric alcohols such as glycol, glycerin, pentaerythritol, trimethylolpropane, sorbitol, and sucrose, aliphatic amine compounds such as ammonia, ethylenediamine, and ethanolamine, toluenediamine, and diphenylmethane. It is obtained by adding ethylene oxide or propylene oxide to aromatic amine compounds such as -4,4'-diamine and / or mixtures thereof. Known polymer polyols include polymer polyols obtained by reacting the polyether polyols with ethylenically unsaturated monomers such as butadiene, acrylonitrile, styrene, etc. in the presence of a radical polymerization catalyst.

  Of these polyols, polyether and / or polyester polyols are preferred in the method for producing a rigid polyurethane foam. The average functionality of the polyol is preferably in the range of 4 to 8, and the average hydroxyl value is preferably in the range of 200 to 800 mgKOH / g, more preferably in the range of 300 to 700 mgKOH / g.

  In the method for producing a flexible polyurethane foam and a semi-rigid polyurethane foam, a polyether polyol and / or a polymer polyol is preferred as the polyol. Of these, the average molecular weight of the polyether polyol is more preferably in the range of 3,000 to 15,000.

  The polyisocyanate used in the method for producing the polyurethane resin of the present invention may be a known polyisocyanate, and is not particularly limited. Specifically, toluene diisocyanate (TDI), 4,4′- or Aromatic polyisocyanates such as 4,2′-diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, aliphatic polyisocyanates such as hexamethylene diisocyanate, or the like Examples include free isocyanate-containing prepolymers obtained by the reaction of diol with polyol, modified polyisocyanates such as carbodiimide modification, and mixed polyisocyanates thereof.

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

  Among these polyisocyanates, MDI or a derivative of MDI is preferable in the method for producing a rigid polyurethane foam, and these may be used as a mixture. In the method for producing a flexible polyurethane foam, TDI and its derivative or MDI and its derivative are preferable as polyisocyanate, and these may be mixed and used.

  Although it does not specifically limit as a physical foaming agent used for the manufacturing method of the polyurethane resin of this invention, It is a low boiling-point organic compound mainly. Examples of known low-boiling organic compounds include hydrocarbon-based and halogenated hydrocarbon-based compounds. Examples of the hydrocarbon-based low boiling point organic compound include known methane, ethane, propane, butane, pentane, hexane, and the like. Examples of the halogenated hydrocarbon-based low boiling point organic compounds include known halogenated methanes, halogenated ethanes, and fluorinated hydrocarbons. Specifically, methylene chloride, HCFC-141b, HFC-245fa, HFC-365mfc and the like are exemplified. Moreover, gas, such as air, nitrogen, a carbon dioxide, etc. can be used as a foaming agent.

  Examples of the chemical foaming agent used in the method for producing a polyurethane resin of the present invention include those that generate gas by being reacted with a polyurethane resin component or reacting with heat or the like. Specifically, water, organic acid, Examples thereof include inorganic acids such as boric acid, alkali carbonates, cyclic carbonates, dialkyl carbonates and the like.

  Of these, the foaming agent is preferably water alone or a mixture of water and the above physical foaming agent. The amount of water is usually in the range of 2 to 15 parts by weight, more preferably in the range of 2 to 10 parts by weight with respect to 100 parts by weight of the polyol. When water is used excessively, the foam curing rate is slowed, the foaming process range is narrowed, the foam density is reduced, and the moldability is deteriorated. The amount of the physical blowing agent used in combination with water is appropriately selected depending on the desired foam density and is not particularly limited, but is usually 40 parts by weight or less, preferably 100 parts by weight or less of polyol. Is 30 parts by weight or less.

  The amount used when the catalyst composition of the present invention is used in the method for producing a polyurethane resin is usually in the range of 0.01 to 15 parts by weight, preferably 100 to 15 parts by weight of the polyol used. It is in the range of 0.05 to 10 parts by weight. Excessive use of the catalyst composition is not preferable because the curability and productivity of the polyurethane resin are improved, but the amount of volatile amine is increased.

  The catalyst used in the method for producing a polyurethane resin of the present invention is the catalyst composition of the present invention, but other catalysts can be used in combination without departing from the gist of the present invention. Examples of such a catalyst include conventionally known organometallic catalysts, tertiary amines, and quaternary ammonium.

  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.

  Tertiary amines include, for example, 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, 1,8-diazabicyclo [5.4.0] undecene-7, Triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, N, N′-dimethyl Piperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethyl There may be mentioned tertiary amine compounds such as aminopropylimidazole.

  Among these tertiary amine compounds, N, N, N ′, N′-tetramethylhexamethylenediamine, dimethylcyclohexylamine, bis (2-dimethylaminoethyl) ether, N, N are used because of their high catalytic activity. N ′, N ″, N ″ -pentamethyldipropylenetriamine is particularly preferred.

  Examples of the quaternary ammonium salts include tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, tetramethylammonium acetate, tetramethylammonium 2-ethylhexane. Examples include tetraalkylammonium organic acid salts such as acid salts, and hydroxyalkylammonium organic acid salts such as 2-hydroxypropyltrimethylammonium formate and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  In the method for producing a polyurethane resin of the present invention, the above-mentioned organometallic catalyst, tertiary amine compounds, quaternary ammonium salts and the like are not essential, but the amount used in combination of these is 100 parts by weight of polyol. On the other hand, it is usually in the range of 0.01 to 5 parts by weight.

  In the method for producing a polyurethane resin of the present invention, an organic carboxylate of an amine compound represented by the general formula (1), an organic carboxylic acid of a tertiary amine compound having at least one hydroxyalkyl group in the molecule A salt, an organic carboxylate salt of triethylenediamine, and a conventionally known organic carboxylate salt of the above-mentioned tertiary amine compound can be appropriately used as a catalyst or a cocatalyst without departing from the gist of the present invention.

  In the production method of the polyurethane resin of the present invention, the catalyst composition of the present invention can be used alone or mixed with the above-mentioned conventionally known catalyst, but a solvent is used when preparing the mixture. Can do. Examples of the solvent include dipropylene glycol, ethylene glycol, 1,4-butanediol, water, and the like. The amount of the solvent is not particularly limited, but is preferably 70% by weight or less based on the total amount of the catalyst. In the method for producing a polyurethane resin of the present invention, the catalyst thus prepared may be used by adding it to a polyol, or a conventionally known catalyst used in combination with each component of the catalyst composition of the present invention. It may be added separately to the polyol and is not particularly limited.

  In the method for producing a polyurethane resin of the present invention, a foam stabilizer can be used as an auxiliary agent if necessary. The foam stabilizer is not particularly limited as long as it is a conventionally known foam stabilizer. For example, nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers are used. Agent, or a mixture thereof. The amount used is usually in the range of 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, if necessary, a crosslinking agent or a chain extender can be used as an auxiliary agent. Examples of the crosslinking agent or chain extender include low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and glycerin, low molecular weight amine polyols such as diethanolamine and triethanolamine, or ethylenediamine. And polyamines such as xylylenediamine and methylenebisorthochloroaniline.

  In the method for producing the polyurethane resin of the present invention, a colorant, a flame retardant, an anti-aging agent and other known additives may be used as necessary. The types and amounts of these additives can be used as long as they are usually used.

  The product produced by the method for producing a polyurethane resin of the present invention can be used for various applications. In the case of a flexible polyurethane foam, for example, a bed as a cushion, a car seat, a mattress and the like can be mentioned. In the case of a semi-rigid polyurethane foam, for example, an automobile-related instrument panel, a headrest, a handle, and the like can be given. In the case of a rigid foam, for example, a freezer, a refrigerator, a heat insulating building material and the like can be mentioned. In the case of an elastomer product, examples thereof include an adhesive, a flooring material, and a waterproof material.

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

Examples 1-11 and Comparative Examples 1-13
The example which manufactured the rigid polyurethane foam using the catalyst composition of this invention and the catalyst of a comparative example is shown below.

(1) Compatibility of catalyst composition In a 200 ml glass sample bottle, the catalysts shown in Table 3 having the compositions shown in Tables 1 and 2 were weighed so that the total amount thereof was 100 g. Next, they were mixed well and dissolved, and then the temperature of the catalyst mixture was adjusted to about 20 ° C., and the compatibility was determined as follows: ○: Uniform transparent solution, x: crystals precipitated.

  Their compositions and results are shown in Tables 1 and 2 together. In addition, the explanation of the catalyst abbreviations in Tables 1 and 2 is also shown in Table 3.

  As is clear from Examples 1 to 11, the catalyst composition of the present invention is a uniform transparent solution and does not undergo phase separation. On the other hand, the catalyst compositions shown in Comparative Example 7, Comparative Example 9, and Comparative Example 10 do not dissolve uniformly, but turbidity, phase separation, crystal precipitation, and the like occur.

(2) Reactivity of foamed foam, physical properties of foam Using the catalyst compositions or catalysts shown in Tables 1 and 2, rigid polyurethane foam formulations shown in Table 4 were carried out, and their reactivity and foam physical properties were evaluated.

  That is, polyol, water, flame retardant, and foam stabilizer were premixed in advance. 43.2 g of the premix solution was weighed into a 300 ml polyethylene cup, and then the catalyst composition or catalyst shown in Tables 1 and 2 was added in an amount such that the respective reactivity was about 30 seconds with the gel time defined below. Further, after adding a predetermined amount of foaming agent to the premix solution, it was mixed uniformly while adjusting the temperature to 10 ° C.

  In a separate container, weigh the polyisocyanate liquid whose temperature is adjusted to 10 ° C. by an amount such that the isocyanate index {isocyanate group / OH group (molar ratio) × 100)} is 110, and put it in the polyethylene cup. The mixture was stirred at 8000 rpm for 3 seconds. This mixed solution was transferred to a 2 L polyethylene cup whose temperature was adjusted to 20 ° C., and the reactivity during foaming was measured.

Next, the raw material scale is increased, and the foam core density is about 30 kg / m ³ in a mold (inner dimensions, made of aluminum of 25 × 25 × 8 cm) whose temperature is adjusted to 20 ° C. by the same operation as above. The premix solution and the catalyst composition or a mixed solution of the catalyst and the polyisocyanate solution was put into a lid and subjected to foam molding. The foam was removed 10 minutes after the start of stirring. From the molded foam, the adhesive strength of the foam, the core density of the foam and the odor of the foam were measured and compared.

  These results are shown in Tables 1 and 2 together. The measurement method for each measurement item is as follows.

・ Reactivity measurement item Cream time: Measure the time when foam starts to rise visually Gel time: Measure the time when reaction proceeds and change from liquid to resinous material Rise time: Time when foam rise stops Measured visually.

-Evaluation item of foam physical properties Foam core density: The center part of the molded foam was cut into a size of 20 × 20 × 5 cm, and the core density was calculated by accurately measuring the size and weight.

    Foam adhesive strength: A 5 × 5 cm SUS304 plate was set in advance on the upper lid of the mold, and the SUS304 plate was bonded to the foam foamed in the mold. One hour after foaming, the 90 ° peel strength of the set SUS304 plate was measured and used as the adhesive strength of the foam.

Foam odor: Cut a 5 × 5 × 5 cm size foam from the foam core density measured, put it in a mayonnaise bottle, cover it, and let the five people smell the foam. The strength was determined as follows. ◎: Almost no odor, ○: Slightly odor, △: Odor, x: Strong odor.

-Reactivity of foamed foam As is clear from Comparative Examples 1 to 3, (A) the amine compound alone represented by the above general formula (1) has a low catalytic activity, so that it is necessary to increase the amount of catalyst used. On the other hand, as is clear from the examples, the catalyst composition of the present invention has high catalytic activity, so that the amount of catalyst used can be reduced.

-Foam physical properties Foam core density: The foam core density in Examples 1 to 11 is about 10 to 20% lower than the foam core density in Comparative Examples 1 to 3 and Comparative Examples 7 to 12. This indicates that the catalyst composition of the present invention is effective for reducing the density of the foam.

  Adhesive strength: The rigid polyurethane foams obtained in Comparative Examples 4 to 6, Comparative Examples 8 to 11 and Comparative Example 13 have poor foam surface curability and low adhesive strength. On the other hand, as is clear from Examples 1 to 11, the hard polyurethane foam obtained using the catalyst composition of the present invention has excellent adhesive strength because the foam has excellent surface curability.

  Foam odor: Since the rigid polyurethane foams obtained in Comparative Examples 1 to 3 and Comparative Examples 7 to 12 have high amine catalyst volatility, the odor remains in the foam. On the other hand, as is clear from Examples 1 to 10, the rigid polyurethane foam obtained using the catalyst composition of the present invention has little odor because the foam has few volatile amine catalysts.

実施例１２〜実施例１６及び比較例１４〜比較例１９
本発明の触媒組成物及び比較例の触媒を用い軟質ポリウレタンフォームを製造した例を以下に示す。

Examples 12 to 16 and Comparative Examples 14 to 19
The example which manufactured the flexible polyurethane foam using the catalyst composition of this invention and the catalyst of a comparative example is shown below.

(1) Compatibility of catalyst composition The catalyst shown in Table 3 was weighed out in a 200 ml glass sample bottle with the composition shown in Table 6 so that the total amount thereof was 100 g. Next, they were mixed well and dissolved, and then the temperature of the catalyst mixture was adjusted to about 20 ° C., and the compatibility was determined as follows: ○: Uniform transparent solution, x: crystals precipitated.

  Their compositions and results are also shown in Table 5. In addition, Table 3 shows explanations of catalyst abbreviations in Table 5.

  As is clear from Examples 12 to 16, the catalyst composition of the present invention forms a uniform transparent solution. In contrast, in the catalyst composition shown in Comparative Example 17, precipitation of crystals occurred.

(2) Reactivity of catalyst composition, etc. The rigid polyurethane foam formulation shown in Table 6 was carried out using the catalyst composition or catalyst shown in Table 5,
Their reactivity and foam physical properties were evaluated.

  That is, the polyol, water, triethanolamine, and the foam stabilizer were premixed in advance. 107.5 g of the premix solution was weighed into a 300 ml polyethylene cup, and then the catalyst composition or catalyst shown in Table 5 was added in an amount such that each reactivity was about 70 seconds with the rise time described above. The temperature of this premix solution was adjusted to 25 ° C.

  In a separate container, weigh the polyisocyanate liquid whose temperature is adjusted to 25 ° C. by an amount such that the isocyanate index {isocyanate group / OH group (molar ratio) × 100)} is 105, and place it in the polyethylene cup. The mixture was stirred at 3000 rpm for 5 seconds. This mixed solution was transferred to a 2 L polyethylene cup whose temperature was adjusted to 40 ° C., and the reactivity during foaming was measured.

Next, the raw material scale is raised, and the foam density becomes about 55 kg / m ³ in a mold (inner dimensions, made of aluminum of 30 × 30 × 2.5 cm) whose temperature is adjusted to 30 ° C. by the same operation as above. As described above, the premix liquid and the catalyst composition or the mixed liquid of the catalyst and the polyisocyanate liquid were added, and the foamed molding was performed with the lid. The demoldable time from the start of stirring to demolding was evaluated. Moreover, the moldability and the odor of the foam were measured and compared from the molded foam. These results are also shown in Table 5. The measurement method for each measurement item is as follows.

  The reactivity of the foamed foam, the core density of the foam and the odor were evaluated by the same method as in Example 1.

  -Demolding time: 4 minutes, 4 minutes 30 seconds, 5 minutes and 30 seconds after the start of stirring, the demolding time was changed at 30-second intervals to demold the molded foam, and the appearance and hardness of the molded foam were evaluated. When the skin part of the molded foam was peeled off or deformed when the end part of the foam was pressed, it was determined that the mold could not be removed, and an evaluation after 30 seconds was performed. The time when the end of the foam was not deformed without the peeling of the skin part was defined as the demolding time.

-Formability of the foam: The appearance of the molded foam evaluated for demolding time was determined as follows: ◎: No void, ○: Slightly void, ×: Over the void.

-Reactivity of foamed foam As is clear from Comparative Examples 14 and 15, (A) a long-chain aliphatic monoamine compound having 8 to 18 carbon atoms in the molecule, or (B) a hydroxyalkyl group in the molecule. Since the tertiary amine compound alone has low catalytic activity, it is necessary to increase the amount of catalyst used. As is clear from Comparative Example 19, (A) a long-chain aliphatic monoamine compound having 8 to 18 carbon atoms in the molecule and (B) a tertiary amine compound having a hydroxyalkyl group in the molecule or (C ) The catalyst composition with an amine compound other than triethylenediamine also has a low catalytic activity, so that it is necessary to increase the amount of catalyst used. On the other hand, as apparent from Examples 13 to 16, the catalyst composition of the present invention has high catalytic activity, and thus the amount of catalyst used can be reduced.

Foam properties Demolding time: As is clear from Comparative Examples 14 and 15, (A) a long-chain aliphatic monoamine compound having 8 to 18 carbon atoms in the molecule, or (B) a hydroxyalkyl group in the molecule A tertiary amine compound alone having a long demolding time. As is clear from Comparative Example 19, (A) a long-chain aliphatic monoamine compound having 8 to 18 carbon atoms in the molecule and (B) a tertiary amine compound having a hydroxyalkyl group in the molecule or (C ) The catalyst composition of amine compounds other than triethylenediamine also has a long demolding time. On the other hand, as is clear from Examples 12 to 16, the catalyst composition of the present invention can greatly shorten the demolding time.

  Moldability: In the foams obtained in Comparative Example 15, Comparative Example 16, and Comparative Example 18, many voids are generated on the foam surface portion. As is clear from Comparative Example 19, (A) a long-chain aliphatic monoamine compound having 8 to 18 carbon atoms in the molecule and (B) a tertiary amine compound having a hydroxyalkyl group in the molecule or (C ) In the foam foamed using a catalyst composition with an amine compound other than triethylenediamine, voids are generated on the entire surface of the foam. On the other hand, as is clear from Examples 12 to 16, foam-molded foams using the catalyst composition of the present invention have greatly improved moldability.

  Foam odor: Since the foams obtained in Comparative Example 14, Comparative Example 16, and Comparative Example 17 have high volatility of the amine catalyst, the odor remains in the foam. On the other hand, as is clear from Examples 12 to 16, foams molded using the catalyst composition of the present invention can greatly reduce odor.

Claims (9)

(A) The following general formula (1)

[In the general formula (1), A represents an alkyl group having 8 to 18 carbon atoms, and R ₁ and R ₂ each independently represents an alkyl group having 1 to 6 carbon atoms. ]
And (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, a catalyst composition for producing a polyurethane resin. (A) The mixing ratio of the amine compound represented by the general formula (1) and (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule is 10 to 90/10 to 90 (wt%). [However, the sum of (A) and (B) does not exceed 100 (% by weight). The catalyst composition according to claim 1, wherein (A) The following general formula (1)

[In the general formula (1), A represents an alkyl group having 8 to 18 carbon atoms, and R ₁ and R ₂ each independently represents an alkyl group having 1 to 6 carbon atoms. ]
(B) A tertiary amine compound having at least one hydroxyalkyl group in the molecule and / or (C) a triethylenediamine catalyst composition for producing a polyurethane resin. (A) The mixing ratio of the amine compound represented by the general formula (1), (B) a tertiary amine compound having at least one hydroxyalkyl group in the molecule, and (C) triethylenediamine is 10 to 90/10. The range of ˜90 / 20 to 0 (% by weight) [However, the sum of (A), (B) and (C) does not exceed 100 (% by weight). The catalyst composition according to claim 3, wherein (A) The amine compound represented by the general formula (1) is dimethyloctylamine, dimethylnonylamine, dimethyldecylamine, dimethylundecylamine, dimethyldodecylamine, dimethyltridecylamine, dimethyltetradecylamine, dimethylpentadecylamine. 5. The catalyst according to claim 1, which is one or more amine compounds selected from the group consisting of dimethylhexadecylamine, dimethylheptadecylamine and dimethyloctadecylamine. Composition. (B) A tertiary amine compound having at least one hydroxyalkyl group in the molecule is N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethyl-N′-methylamino Ethanol, N, N-dimethylaminopropyl-N′-methylaminoethanol, N, N, N′-trimethyl-N′-hydroxyethylbisaminoethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl -N "-methylaminoisopropanol, N, N-bis (3-dimethylaminopropyl) -N-isopropanolamine, N- (3-dimethylaminopropyl) -N, N-diisopropanolamine, N- (2-hydroxy Ethyl) -N'-methylpiperazine, N, N-dimethylaminohexa And one or more amine compounds selected from the group consisting of 5-dimethylamino-3-methyl-1-pentanol and 1- (2-hydroxypropyl) -2-methylimidazole. The catalyst composition according to any one of claims 1 to 5, characterized in that: 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 6. In the method for producing a rigid polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a foaming agent, the catalyst composition according to any one of claims 1 to 6 is used as a catalyst. A method for producing a rigid polyurethane foam. In the method for producing a flexible polyurethane foam by reacting a polyol and a polyisocyanate in the presence of a catalyst and a foaming agent, the catalyst composition according to any one of claims 1 to 6 is used as a catalyst. A method for producing a flexible polyurethane foam.