JP2005105085A - Catalyst composition for producing polyurethane resin and method for producing polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a polyurethane resin, with which high productivity is attained by high-speed curing and a product resin has improved qualities and to obtain a low-toxicity catalyst. <P>SOLUTION: In the method for producing a polyurethane resin by reacting a polyol with an organic polyisocyanate, a catalyst composed of a bicyclic tertiary amine represented by general formula (1) and a quaternary ammonium salt compound represented by general formula (2) (R<SB>n</SB>is an alkyl group, a hydroxyalkyl group, an aminoalkyl group or the like; X is an organic acid group or an inorganic acid group) is used. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a catalyst composition for producing a polyurethane resin and a method for producing a polyurethane resin using the same. When the organic polyisocyanate is used, the catalyst composition of the present invention can produce a polyurethane resin excellent in curing speed, weather resistance, and coating film performance.

  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. Curing reaction proceeds even at room temperature, and it is possible to form a resin having a cross-linked structure, and it has excellent adhesion to substrates, flexibility, and weather resistance, so it can be used in automobiles, architecture, home appliances, heavy anticorrosion, plastic paints, and adhesives. It is widely used for such applications. In particular, aliphatic isocyanates are used as various top coatings that require weather resistance because the coating is not easily yellowed by light or heat, but they are polyols compared to aromatic isocyanates typified by TDI and MDI. The reaction rate with is very slow, so a more active catalyst is needed.

  Tertiary amine catalysts and metal catalysts are widely used as catalysts for polyurethane production, but organotin catalysts are mainly used as aliphatic isocyanate catalysts because of their high activity, mainly dibutyltin. Dilaurate (hereinafter sometimes referred to as DBTDL) or stannous octoate is frequently used (see Non-Patent Document 1, for example).

  Recently, transition metal complex catalysts have been studied as new catalysts, and in particular, studies on metal acetylacetonate catalysts have been actively conducted (for example, see Patent Document 1 and Non-Patent Document 2).

JP 2003-82052 A (Page 5, Table 1)

Tetsuo Yokoyama, “Structure / Physical Properties of Polyurethanes, Higher Functionality, and Application Development” published by Technical Information Association, 1998, page 325 R. A. Rigabue, “J. Mol. Catal. A. Chem.”, 2000, 157, 73

  However, many problems have been pointed out with the organotin catalysts currently used.

  For example, in recent years, toxicity problems of organotin catalysts have been pointed out. In particular, tributyltin contained as an impurity in DBTDL has become a problem of harmfulness to the human body as an environmental hormone. Already there is a movement to regulate the use of organotin catalysts in polyurethane production, mainly in Europe, so there is a strong demand for alternative catalysts for organotin catalysts.

  Further, metal acetylacetonate-based catalysts represented by iron acetylacetonate or copper acetylacetonate have low catalytic activity, and it is difficult to achieve a curing rate when using an organic tin catalyst.

  In addition, the combined use of a metal acetylacetonate catalyst and triethylenediamine significantly improves the catalytic activity compared to the use of metal acetylacetonate alone, but metal acetylacetonate is inexpensive and less toxic. Is required.

  As described above, in a method for producing a polyurethane resin using an organic polyisocyanate, there has been a demand for a catalyst that can improve high-speed curing of a coating film and physical properties of the coating film, and can replace an organic tin catalyst.

  In view of the above circumstances, the present inventors have conducted extensive studies on a polyurethane reaction catalyst that improves the curing rate of organic polyisocyanate. As a result, a specific bicyclic tertiary amine compound and a quaternary ammonium salt compound are used in combination. As a result, the present inventors have found a catalyst that can promote the reaction between an organic polyisocyanate and an alcohol very effectively and can substitute for an organic tin catalyst, and have completed the present invention.

That is, the present invention
1) The following general formula (1)

（式中、ｎは少なくとも１以上３以下の値を示す整数である。）で示される二環式第三級アミン化合物と四級アンモニウム塩化合物からなるポリウレタン樹脂製造用触媒組成物、
２）二環式第三級アミン化合物が、１，８−ジアザビシクロ[５，４，０]ウンデセン−７及び／又は１，５−ジアザビシクロ[４，３，０]ノネン−５である上記１）に記載のポリウレタン製造用触媒組成物、
３）四級アンモニウム塩化合物が、下記一般式（２）

(Wherein n is an integer having a value of at least 1 and no greater than 3), a catalyst composition for producing a polyurethane resin comprising a bicyclic tertiary amine compound and a quaternary ammonium salt compound,
2) The above 1) wherein the bicyclic tertiary amine compound is 1,8-diazabicyclo [5,4,0] undecene-7 and / or 1,5-diazabicyclo [4,3,0] nonene-5 A catalyst composition for producing polyurethane according to claim 1,
3) A quaternary ammonium salt compound is represented by the following general formula (2)

（式中、Ｒ_１〜Ｒ_４は各々独立した炭素数１〜１８のアルキル基、炭素数１〜１８のアリール基、炭素数１〜１２のヒドロキシアルキル基、炭素数１〜１２のアミノアルキル基、炭素数１〜１２のモノメチルアミノアルキル基、炭素数１〜１２のジメチルアミノアルキル基である、又は下式（３）

Wherein R _{1 to} R ₄ are each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, and an aminoalkyl group having 1 to 12 carbon atoms. , A monomethylaminoalkyl group having 1 to 12 carbon atoms, a dimethylaminoalkyl group having 1 to 12 carbon atoms, or the following formula (3)

（式中、Ｒ_５〜Ｒ_１１は各々独立して、水素原子、炭素数１〜１６のアルキル基、炭素数１〜１６のアリール基、炭素数１〜６のジメチルアミノアルキル基、又は炭素数１〜１６のアルコキシアルキル基を表し、ｎは１〜１１の整数、ａは０〜１０の整数を表す。ただし、Ｒ_９とＲ_５又はＲ_６とが結合して５〜７員環を形成しても良い。）である、又は下式（４）

(In the formula, R _{5 to} R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an aryl group having 1 to 16 carbon atoms, a dimethylaminoalkyl group having 1 to 6 carbon atoms, or a carbon number. Represents an alkoxyalkyl group of 1 to 16, n represents an integer of 1 to 11, and a represents an integer of 0 to 10. However, R ₉ and R ₅ or R ₆ are bonded to form a 5- to 7-membered ring. Or the following formula (4)

（式中、Ｒ_５、Ｒ_６、Ｒ_７、Ｒ_８、Ｒ_１０、Ｒ_１１、ｎ及びａは上記定義に同じ。）である、又は、Ｒ_１〜Ｒ_４のうちのいずれか２個が炭素、窒素、又は酸素原子を介してヘテロ環を形成しているものであり、Ｘは有機酸基、又は無機酸基）で表わされる四級アンモニウム塩化合物である上記１）に記載のポリウレタン製造用触媒組成物、
４）上記一般式（２）において、Ｒ_１〜Ｒ_４が各々独立して、水素、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ノニル基、デシル基、ウンデシル基、ドデシル基、トリデシル基、テトラデシル基、ヘプタデシル基、ヘキサデシル基、ヘプタデシル基、オクタデシル基、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、ジメチルアミノプロピル基、ジメチルアミノエタノールエチル基、又はジメチルアミノエチルアミノエチ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製造用触媒組成物、
５）上記一般式（２）において、四級アンモニウムが、テトラメチルアンモニウム、メチルトリエチルアンモニウム、エチルトリメチルアンモニウム、ブチルトリメチルアンモニウム、ヘキシルトリメチルアンモニウム、オクチルトリメチルアンモニウム、デシルトリメチルアンモニウム、ドデシルトリメチルアンモニウム、テトラデシルトリメチルアンモニウム、ヘキサデシルトリメチルアンモニウム、オクタデシルトリメチルアンモニウム、（２−ヒドロキシプロピル）トリメチルアンモニウム、ヒドロキシエチルトリメチルアンモニウム、１−メチル−１−アザニア−４−アザビシクロ［２，２，２］オクタニウム、又は１，１−ジメチル−４−メチルピペリジニウムを表すことを特徴とする上記３）に記載のポリウレタン製造用触媒組成物、
６）上記一般式（２）において、有機酸基が、ギ酸基、酢酸基、２−エチルヘキサン酸基、又はメチル炭酸基、無機酸基が、ハロゲン基、水酸基、炭酸水素基、又は炭酸基を表すことを特徴とする上記３）乃至５）に記載のポリウレタン製造用触媒組成物、
７）ポリオールと有機ポリイソシアナートを、触媒及び必要に応じて添加剤の存在下で反応させポリウレタン樹脂を製造する方法において、触媒として上記１）乃至６）のいずれかに記載のポリウレタン製造用触媒組成物を用いることを特徴とするポリウレタン樹脂の製造方法、
８）ポリオールと有機ポリイソシアナートを、触媒、発泡剤及び必要に応じて他の添加剤の存在下に反応させてポリウレタンフォームを製造する方法において、触媒として上記１）乃至６）のいずれかに記載のポリウレタン製造用触媒組成物を用いることを特徴とするポリウレタンフォームの製造方法、
９）二環式第三級アミン化合物と四級アンモニウム塩化合物との混合比率が、二環式第三級アミン化合物／四級アンモニウム塩化合物のモル比が２０〜０．０５であることを特徴とする上記７）又は８）に記載の製造方法、
１０）触媒組成物の使用量が、ポリオール１００重量部に対して０．００１〜２０重量部であることを特徴とする上記７）乃至９）に記載の製造方法、である。

(Wherein R ₅ , R ₆ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , n and a are the same as defined above), or any two of R _{1 to} R ₄ are The polyurethane production according to 1) above, wherein a heterocyclic ring is formed through a carbon, nitrogen, or oxygen atom, and X is a quaternary ammonium salt compound represented by an organic acid group or an inorganic acid group). Catalyst composition,
4) In the general formula (2), R _{1 to} R ₄ are each independently hydrogen, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Decyl, undecyl, dodecyl, tridecyl, tetradecyl, heptadecyl, hexadecyl, heptadecyl, octadecyl, hydroxyethyl, hydroxypropyl, aminoethyl, aminopropyl, monomethylaminoethyl, monomethylamino The catalyst composition for producing polyurethane according to 3) above, which represents a propyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a dimethylaminoethanolethyl group, or a dimethylaminoethylaminoethyl group,
5) In the above general formula (2), quaternary ammonium is tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethyl Ammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, or 1,1- 3. The polyurethane production catalyst according to 3) above, which represents dimethyl-4-methylpiperidinium. Narubutsu,
6) In the above general formula (2), the organic acid group is a formic acid group, an acetic acid group, a 2-ethylhexanoic acid group, or a methyl carbonate group, and an inorganic acid group is a halogen group, a hydroxyl group, a hydrogen carbonate group, or a carbonate group. The catalyst composition for producing polyurethane according to 3) to 5) above, wherein
7) In the method for producing a polyurethane resin by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and optionally an additive, the catalyst for producing a polyurethane according to any one of the above 1) to 6) as a catalyst A method for producing a polyurethane resin, characterized by using a composition;
8) In the process for producing a polyurethane foam by reacting a polyol and an organic polyisocyanate in the presence of a catalyst, a foaming agent and, if necessary, other additives, any of the above 1) to 6) as a catalyst. A method for producing a polyurethane foam, characterized by using the catalyst composition for polyurethane production described
9) The mixing ratio of the bicyclic tertiary amine compound and the quaternary ammonium salt compound is such that the molar ratio of bicyclic tertiary amine compound / quaternary ammonium salt compound is 20 to 0.05. The production method according to 7) or 8) above,
10) The production method according to 7) to 9) above, wherein the amount of the catalyst composition used is 0.001 to 20 parts by weight with respect to 100 parts by weight of the polyol.

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

  The catalyst composition for producing a polyurethane resin of the present invention comprises a catalyst composition comprising a bicyclic tertiary amine compound represented by the general formula (1) and a quaternary ammonium salt compound represented by the general formula (2). Become. The general formula (1) comprises a 5-membered ring and a 6-membered ring when n is 1, and a 7-membered ring and a 6-membered ring when n is 3.

  In the present invention, the bicyclic tertiary amine compound represented by the general formula (1) is not particularly limited. For example, 1,8-diazabicyclo [5,4,0] undecene-7, 1,5-diazabicyclo [4,3,0] nonene-5, 1,8-diazabicyclo [5,3,0] decene-7, 1,4-diazabicyclo [3,3,0] octene-4 It is done. Among these, 1,8-diazabicyclo [5,4,0] undecene-7 and / or 1,5-diazabicyclo [4,3,0] nonene-5 are excellent in catalytic activity and industrially available. Is preferred.

  In the present invention, the quaternary ammonium salt compound represented by the general formula (2) is not particularly limited, but as the quaternary ammonium constituting the quaternary ammonium salt compound represented by the general formula (2), For example, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, propyltrimethylammonium, butyltrimethylammonium, pentyltrimethylammonium, hexyltrimethylammonium, heptyltrimethylammonium, octyltrimethylammonium, nonyltrimethylammonium, decyltrimethylammonium, undecyl Trimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, tetradecyltrimethylammonium, Aliphatic ammonium compounds such as butadecyltrimethylammonium, hexadecyltrimethylammonium, heptadecyltrimethylammonium and octadecyltrimethylammonium, hydroxyammonium compounds such as (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium and trimethylaminoethoxyethanol, 1 -Alicyclic such as methyl-1-azania-4-azabicyclo [2,2,2] octanium, 1,1-dimethyl-4-methylpiperidinium, 1-methylmorpholinium, 1-methylpiperidinium An ammonium compound etc. are mentioned. Among these, since it has excellent catalytic activity and is industrially available, tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetra Decyltrimethylammonium, hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, 1,1 -Dimethyl-4-methylpiperidinium is preferred.

  Examples of the acid constituting the quaternary ammonium salt compound represented by the general formula (2) include formic acid group, acetic acid group, 2-ethylhexanoic acid group, succinic acid group, malonic acid group, succinic acid group, and glutar. Organic acids such as acid groups, adipic acid groups, benzoic acid groups, toluic acid groups, ethyl benzoic acid groups, methyl carbonate groups, phenol groups, alkylbenzene sulfonic acid groups, toluene sulfonic acid groups, benzene sulfonic acid groups, and phosphate ester groups And inorganic acid groups such as a group, a halogen group, a hydroxyl group, a hydrogen carbonate group, and a carbonate group. Among these, a formic acid group, an acetic acid group, a 2-ethylhexanoic acid group, a methyl carbonate group, a halogen group, a hydroxyl group, a hydrogen carbonate group, and a carbonate group are preferable because of excellent catalytic activity and industrial availability.

  In the present invention, the mixing ratio of the bicyclic tertiary amine compound represented by the general formula (1) and the quaternary ammonium salt compound represented by the general formula (2) is not particularly limited. Usually, the mixing ratio is adjusted so that the molar ratio of the bicyclic tertiary amine compound / quaternary ammonium salt compound is in the range of 20 to 0.05. If the molar ratio exceeds this range, the synergistic effect of the two catalysts may not be obtained, and satisfactory performance may not be exhibited in terms of coating film properties and catalyst activity.

  When the catalyst composition of the present invention is used for producing a polyurethane resin, the amount used is 0.001 to 20 parts by weight, preferably 0.01 to 10 parts by weight, when the polyol used is 100 parts by weight. Part range. If the amount is less than 0.001 part by weight, the reaction rate becomes extremely slow, and the satisfactory performance may not be exhibited in terms of physical properties of the coating film. On the other hand, if it exceeds 20 parts by weight, the effect of increasing the catalyst may not be obtained.

  In the present invention, the bicyclic tertiary amine compound represented by the general formula (1) and the quaternary ammonium salt compound represented by the general formula (2) used as the catalyst composition were prepared by mixing in advance. A thing may be added at the time of reaction, and may be added simultaneously at the time of reaction. Further, it can be used by dissolving in a solvent when mixing. Although the solvent is not particularly limited, for example, alcohols such as ethylene glycol, diethylene glycol, dipropylene glycol, propylene glycol, butanediol, hydrocarbons such as toluene, xylene, mineral terpenes, mineral spirits, ethyl acetate, Esters such as butyl acetate, methyl glycol acetate and cellosolve acetate, ketones such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, organic solvents of amides such as N, N-dimethylformamide and N, N-dimethylacetamide, acetylacetone and its Examples include chelatable solvents such as β-diketones such as fluorinated substituents, and ketoesters such as methyl acetoacetate and ethyl acetoacetate.

  In addition to the catalyst composition of the present invention comprising the bicyclic tertiary amine compound and the quaternary ammonium salt compound represented by the general formula (1) as a catalyst in the method for producing a polyurethane resin of the present invention, the present invention Other organometallic catalysts and tertiary amine catalysts may be used in combination without departing from the spirit of the present invention.

  The other organometallic catalyst may be a conventionally known organometallic as a catalyst for polyurethane production, and is not particularly limited. Specifically, stannous diacetate, stannous dioctoate, stannous dioleate, stannous And organic tin catalysts such as dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, and dioctyltin dilaurate. Of these, preferred compounds are organotin catalysts, and more preferred are stannous dioctate and dibutyltin dilaurate. In the method for producing a polyurethane resin of the present invention, the use amount of the organotin catalyst can be greatly reduced by using the catalyst composition of the present invention.

  Further, the other tertiary amine catalyst may be a conventionally known tertiary amine catalyst as a catalyst for polyurethane production, and is not particularly limited. Specifically, triethylenediamine, 2-methyltriethylenediamine, 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′-tetramethyl Hexamethylenediamine, bis (2-dimethylaminoethyl) ether, dimethylethanolamine, dimethylisopropanolamine, dimethylamino Noethoxyethanol, N, N-dimethyl-N ′-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N ′-(2-hydroxyethyl) propanediamine, bis (dimethylaminopropyl) amine, bis (dimethyl) Aminopropyl) isopropanolamine, 3-quinuclidinol, N, N, N ′, N′-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8- Diazabicyclo [5.4.0] undecene-7, N-methyl-N ′-(2-dimethylaminoethyl) piperazine, N, N′-dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, 1-methylimidazole, 1,2-dimethylimidazole, 1- Sobutyl-2-methylimidazole, 1-dimethylaminopropylimidazole, N, N-dimethylhexanolamine, N-methyl-N ′-(2-hydroxyethyl) piperazine, 1- (2-hydroxyethyl) imidazole, 1- ( 2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, quinuclidine, 2-methylquinuclidine and the like.

  In the present invention, when other organometallic catalyst or tertiary amine catalyst is used, the amount used is usually 0.0001 to 20 parts by weight, more preferably 0 when the polyol is 100 parts by weight. 0.001 to 10 parts by weight.

  In the method for producing a polyurethane resin of the present invention, the polyol used is not particularly limited. For example, conventionally known polyether polyol, polyester polyol, polycarbonate polyol, acrylic polyol, polybutadiene polyol, polyolefin Polyol, caprolactone-modified polyol, polyesteramide polyol, polyurethane polyol, epoxy polyol, epoxy-modified polyol, alkyd-modified polyol, castor oil, fluorine-containing polyol and the like can be used. These polyols can be used alone or in combination as appropriate.

  Examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, tetramethylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, and aliphatic amine compounds such as ethylenediamine. Starting compounds, compounds having at least two active hydrogen groups such as aromatic amine compounds such as toluene diamine and diphenylmethane-4,4-diamine, alkanolamines such as ethanolamine and diethanolamine, etc. By adding an alkylene oxide represented by ethylene oxide or propylene oxide to this, for example, Gunter Oertel, “Polyurethane Handbook” (1985 edition) Hanser Publishers (Germany), p. It can manufacture by the method as described in 42-53.

  Examples of polyester polyols include condensates of polyhydric alcohols with polybasic acids such as maleic anhydride, fumaric acid, itaconic anhydride, itaconic acid, adipic acid, and isophthalic acid, and Keiji Iwata, “Polyurethane Resin Handbook”. (1987 first edition) Nikkan Kogyo Shimbun, p. 117, wastes from the production of nylon, trimethylolpropane, pentaerythritol wastes, phthalic polyester wastes, polyester polyols obtained by treating waste products, and the like.

  In the method for producing a polyurethane resin of the present invention, the average molecular weight of the polyol is preferably in the range of 200 to 10,000. If the average molecular weight is less than 200, the distance between cross-linking points is short, the flexibility when used as a coating film is not sufficient, the crack resistance may be insufficient, and if it exceeds 10,000, the cross-linking density becomes low, When the coating film is used, the toughness and hardness are insufficient, and the effects of the present invention may not be exhibited.

  In the method for producing a polyurethane resin of the present invention, the organic polyisocyanate used is not particularly limited, and examples thereof include toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, and xylylene diisocyanate. Examples include aromatic isocyanates, aliphatic isocyanates such as hexamethylene diisocyanate, alicyclic isocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof. Of these, aliphatic isocyanates are preferable for the purpose of providing excellent coating film properties and weather resistance. Examples of aliphatic isocyanates include conventionally known linear aliphatic systems, cycloaliphatic systems, Specific examples include isocyanates such as alicyclic systems, such as hexamethylene diisocyanate (HDI), hydrogenated diphenylmethane diisocyanate (H-MDI), and hydrogenated xylylene diisocyanate (H-XDI). ), Isophorone diisocyanate (IPDI), norbornane diisocyanate (NBDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), L-lysine diisocyanate (LDI), 1,6,11-undecane Isocyanates such as triisocyanates or dimer-modified, trimer-modified, bures of these isocyanates Modified compounds, allophanate modified products, block isocyanates of these organic polyisocyanate compounds, and NCO group-terminated prepolymers that are a reaction product with the aforementioned active hydrogen-containing compounds can be used alone or in combination. . Examples of the block isocyanate include alcohols such as ethanol, isopropanol and n-butanol, phenols such as phenol and p-nitrophenol, lactams such as ε-caprolactam, oximes such as acetooxime and methylethylketoxime, and malon. An active methylene-containing compound such as diethyl acid, ethyl acetoacetate, acetylacetone or the like is used to block an active isocyanate group.

  In the method for producing a polyurethane resin of the present invention, the isocyanate index is not particularly limited, but is usually in the range of 50 to 800, more preferably in the range of 70 to 400. If it is 70 or less, the crosslinking density is low and the resin strength may be lowered. If it is 400 or more, the unreacted isocyanate group remains, and thus the drying property of the coating film may be deteriorated.

  In the method of the present invention, a foaming agent can be used as necessary. Although it does not specifically limit as a foaming agent, For example, HCFCs, such as 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 It is one or more selected from HFCs such as 3-heptafluoropropane (HFC-227ea), hydrofluoroethers such as HFE-254pc, low-boiling hydrocarbons, and water, and a mixture 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.

In the method of the present invention, the amount of the foaming agent used is determined according to the desired density and physical properties of the foam. Specifically, the foam density to be obtained is usually 5 to 200 kg / m ³ , preferably 10 to 10 kg. It is selected to be 100 kg / m ³ .

  In the method for producing a polyurethane resin of the present invention, additives can be used as necessary. Such additives include crosslinking agents or chain extenders, pigments, colorants, flame retardants, anti-aging agents, antioxidants, fillers, thickeners, thickeners, plasticizers, sagging inhibitors, Examples thereof include precipitation inhibitors, antifoaming agents, UV absorbers, solvents, thixotropic agents, adsorbents, and other known additives. As long as the types and amounts of such additives do not deviate from the known formats and procedures, they can be used within the range normally used.

  In the method of the present invention, the crosslinking agent or chain extender may be a low molecular weight polyhydric alcohol (for example, ethylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexanediol, glycerin, etc. ), Low molecular weight amine polyols (eg, diethanolamine, triethanolamine, etc.), polyamines (eg, ethylenediamine, diethylenetriamine, piperazine, N-aminoethylpiperazine, xylylenediamine, methylenebisorthochloraniline, etc.), etc. .

  In the method of the present invention, a solvent can be used to dissolve and dilute raw materials such as isocyanate and polyol. Examples of such solvents include hydrocarbons such as toluene, xylene and mineral terpenes, 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, Examples thereof include organic solvents of amides such as N-dimethylformamide and N, N-dimethylacetamide.

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

  The catalyst composition of the present invention has a high catalytic activity in the urethane formation reaction, can improve the production rate of polyurethane products, and can be substituted for an organic tin catalyst, so that it is extremely effective industrially.

Example 1
In a 200 ml Erlenmeyer flask substituted with nitrogen, 0.005 g (0.03 mmol) of 1,8-diazabicyclo [5,4,0] undecene-7 (DBU) as a bicyclic tertiary amine compound, a quaternary ammonium salt compound Methyltriethylammonium methyl carbonate 0.006 g (0.03 mmol) and diethylene glycol (DEG) 1.10 g (10.4 mmol) were weighed, and 50 ml of N, N-dimethylformamide (DMF) was added. A DMF solution was prepared. Further, 1.42 g (10.4 mmol) of hexamethylene diisocyanate (HDI) was weighed into a 100 ml Erlenmeyer flask purged with nitrogen, and 50 ml of N, N-dimethylformamide (DMF) was added thereto, and HDI-DMF was added. A solution was prepared. The DEG-DMF solution and the HDI-DMF solution were each stirred at 30 ° C. for 30 minutes, and then the HDI-DMF solution was added to the DEG-DMF solution and the reaction was started while stirring. About 10 ml of the reaction solution is collected every 20 to 30 minutes after the start of the reaction, unreacted isocyanate is reacted with an excess of di-n-butylamine (DBA) solution, and the remaining DBA is treated with 0.5N hydrochloric acid aqueous standard solution. The amount of unreacted isocyanate was quantified by back titration.

The reaction rate constant (l ² / eq · mol · h) was determined on the assumption that the reaction between isocyanate and alcohol was first order at each concentration. The results are shown in Table 1.

Example 2 to Example 8
The same procedure as in Example 1 was used, except that a bicyclic tertiary amine compound and a quaternary ammonium salt compound were used as catalysts in the mixing ratio shown in Table 1. The results are shown in Table 1.

Comparative Examples 1 to 9
The same procedure as in Example 1 was used except that a bicyclic tertiary amine compound, a quaternary ammonium salt compound or DBTDL was used as a catalyst. The results are shown in Table 1.

表１から明らかなように、実施例１〜８では、特定の二環式第三級アミン化合物と四級アンモニウム塩化合物を組み合わせることにより、それらの単独系（比較例１〜８）より著しい触媒活性の向上が見られ、ウレタン形成反応を相乗的に促進する。また、スズ触媒であるＤＢＴＤＬに匹敵する触媒活性（比較例９）を発現する。

As is apparent from Table 1, in Examples 1 to 8, a combination of a specific bicyclic tertiary amine compound and a quaternary ammonium salt compound resulted in a catalyst that was more remarkable than those single systems (Comparative Examples 1 to 8). The activity is improved and the urethane formation reaction is synergistically promoted. Moreover, the catalyst activity (Comparative Example 9) comparable to DBTDL which is a tin catalyst is expressed.

Claims (10)

The following general formula (1)

(Wherein n is an integer having a value of at least 1 and no greater than 3) A catalyst composition for producing a polyurethane resin, comprising a bicyclic tertiary amine compound and a quaternary ammonium salt compound. The bicyclic tertiary amine compound is 1,8-diazabicyclo [5,4,0] undecene-7 and / or 1,5-diazabicyclo [4,3,0] nonene-5. A catalyst composition for producing polyurethane. The quaternary ammonium salt compound is represented by the following general formula (2)

Wherein R _{1 to} R ₄ are each independently an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 12 carbon atoms, and an aminoalkyl group having 1 to 12 carbon atoms. , A monomethylaminoalkyl group having 1 to 12 carbon atoms, a dimethylaminoalkyl group having 1 to 12 carbon atoms, or the following formula (3)

(In the formula, R _{5 to} R ₁₁ are each independently a hydrogen atom, an alkyl group having 1 to 16 carbon atoms, an aryl group having 1 to 16 carbon atoms, a dimethylaminoalkyl group having 1 to 6 carbon atoms, or a carbon number. Represents an alkoxyalkyl group of 1 to 16, n represents an integer of 1 to 11, and a represents an integer of 0 to 10. However, R ₉ and R ₅ or R ₆ are bonded to form a 5- to 7-membered ring. Or the following formula (4)

(Wherein R ₅ , R ₆ , R ₇ , R ₈ , R ₁₀ , R ₁₁ , n and a are the same as defined above), or any two of R _{1 to} R ₄ are A heterocycle is formed through a carbon, nitrogen, or oxygen atom, and X is an organic acid group or an inorganic acid group. 2. The catalyst composition for producing polyurethane according to claim 1, which is a quaternary ammonium salt compound represented by formula (1). In the general formula (2), R _{1 to} R ₄ are each independently hydrogen, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, heptadecyl group, hexadecyl group, heptadecyl group, octadecyl group, hydroxyethyl group, hydroxypropyl group, aminoethyl group, aminopropyl group, monomethylaminoethyl group, monomethylaminopropyl group It represents a dimethylaminoethyl group, a dimethylaminopropyl group, a dimethylaminoethanolethyl group, or a dimethylaminoethylaminoethyl group, The catalyst composition for producing polyurethane according to claim 3. In the general formula (2), quaternary ammonium is tetramethylammonium, methyltriethylammonium, ethyltrimethylammonium, butyltrimethylammonium, hexyltrimethylammonium, octyltrimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tetradecyltrimethylammonium, Hexadecyltrimethylammonium, octadecyltrimethylammonium, (2-hydroxypropyl) trimethylammonium, hydroxyethyltrimethylammonium, 1-methyl-1-azania-4-azabicyclo [2,2,2] octanium, or 1,1-dimethyl- The catalyst composition for producing polyurethane according to claim 3, which represents 4-methylpiperidinium. . In the general formula (2), the organic acid group represents a formic acid group, an acetic acid group, a 2-ethylhexanoic acid group, or a methyl carbonate group, and an inorganic acid group represents a halogen group, a hydroxyl group, a hydrogen carbonate group, or a carbonate group. 6. The catalyst composition for producing a polyurethane according to claim 3, wherein the catalyst composition is a polyurethane composition. The method for producing a polyurethane resin by reacting a polyol and an organic polyisocyanate in the presence of a catalyst and, if necessary, an additive, as a catalyst, a catalyst composition for producing a polyurethane according to any one of claims 1 to 6. A method for producing a polyurethane resin, comprising using a product. 7. The method for producing a polyurethane foam by reacting a polyol and an organic polyisocyanate in the presence of a catalyst, a foaming agent and, if necessary, other additives, as a catalyst according to any one of claims 1 to 6. A process for producing a polyurethane foam, characterized by using a catalyst. The mixing ratio of the bicyclic tertiary amine compound and the quaternary ammonium salt compound is characterized in that the molar ratio of bicyclic tertiary amine compound / quaternary ammonium salt compound is 20 to 0.05. The manufacturing method of Claim 7 or Claim 8. 10. The production method according to claim 7, wherein the amount of the catalyst composition used is 0.001 to 20 parts by weight with respect to 100 parts by weight of the polyol.