JP2005105082A - Catalyst for producing flexible polyurethane foam and method for producing flexible polyurethane foam using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a catalyst for producing a flexible polyurethane foam having improved curing rate and moldability of foam and a slight smell and to provide a method for producing the flexible polyurethane foam. <P>SOLUTION: In the method for producing the flexible polyurethane by reacting a polyol with a polyisocyanate in the presence of an amine catalyst, a blowing agent and, if necessary, another auxiliary, the catalyst for producing the flexible polyurethane, comprising an amine compound containing an alkyl ether group and/or an aryl ether group in the molecule, is used as the amine catalyst. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a catalyst for producing a flexible polyurethane and a method for producing a flexible polyurethane foam using the catalyst. More specifically, a catalyst for producing a flexible polyurethane comprising an amine compound having an alkyl ether group and / or an aryl ether group in the molecule, and a soft, low odor, excellent in foam curing speed and moldability using the catalyst. The present invention relates to a method for producing polyurethane foam.

  Polyurethane foam is widely used as a flexible foam used for automobile seat cushions, mattresses, furniture, etc., a semi-rigid foam used for automobile instrument panels, headrests, armrests, etc., and a rigid foam used for electric refrigerators, building materials, etc. ing.

  In recent years, in the production of flexible polyurethane foams and semi-rigid polyurethane foams, in order to reduce costs and improve foam productivity, there is a strong demand for excellent curing speed that shortens the demolding time and excellent moldability that improves yield. ing. 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 reaction by reaction of isocyanate and water, and carbon dioxide gas generation reaction (foaming reaction). Thus, the catalyst has a great influence not only on the reaction rate but also on the curing rate, moldability and physical properties of the foam.

  Conventionally, organometallic catalysts and tertiary amine catalysts have been used as catalysts for polyurethane production, and it is already widely known that tertiary amine catalysts become excellent catalysts for polyurethane production. Among tertiary amine compounds, industrially utilized catalysts for polyurethane production include triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethyl). Aminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine and the like can be exemplified (for example, Patent Document 1 and Non-Patent Document 1). reference).

  Moreover, as a catalyst for producing a flexible polyurethane foam with less odor, it has a long-chain aliphatic monoamine such as N, N-dimethyldodecylamine, and an active hydrogen group capable of reacting with a long-chain aliphatic amino group and an isocyanate in the molecule. Compounds have been proposed (see, for example, Patent Document 2 and Patent Document 3).

Japanese Patent Laid-Open No. 01-168717

Japanese Patent Laid-Open No. 07-173242 Japanese Patent Laid-Open No. 07-070275 Keiji Iwata, "Polyurethane resin handbook", published by Nikkan Kogyo Shimbun, published in 1987, p. 118

  However, in the production of flexible polyurethane foam, the conventional tertiary amine catalyst has a strong amine odor. Particularly, N-methylmorpholine, N-ethylmorpholine, and triethylamine, which are relatively low amounts, have a very strong stimulating odor. , Significantly worsen the work environment. Further, when a large amount of these amine catalysts is used to increase the curing speed, there is a problem that it causes eye itchiness. In addition, the polyurethane product itself has problems such as leaving a bad odor and deteriorating the value of the product.

  In addition, long-chain aliphatic monoamines such as N, N-dimethyldodecylamine proposed as a catalyst for producing a flexible polyurethane foam with less odor, and active hydrogen groups capable of reacting with long-chain aliphatic amino groups and isocyanates in the molecule Although it is possible to obtain a flexible polyurethane foam having a low odor, the compound having a low catalytic activity or a problem in the moldability of the foam has been strongly desired to be improved.

  The present invention has been made in view of the above problems, and its purpose is to develop a polyurethane production catalyst and to use the catalyst to improve foam curing speed and moldability and to produce a soft odor. It is to provide a method for producing a polyurethane foam.

  As a result of diligent studies to solve the above problems, the present inventors have found a catalyst for producing a flexible polyurethane comprising an amine compound having an alkyl ether group and / or an aryl ether group in the molecule, and use this catalyst. As a result, it was found that a flexible polyurethane foam having excellent foam curing speed and moldability and less odor was obtained, and the present invention was completed.

  That is, the present invention relates to a catalyst for producing a flexible polyurethane comprising an amine compound having an alkyl ether group and / or an aryl ether group in the molecule, a polyol and a polyisocyanate, an amine catalyst, a blowing agent, and, if necessary, other In the method for producing a flexible polyurethane foam by reacting in the presence of an auxiliary agent, the above-mentioned catalyst for producing a flexible polyurethane is used as the amine catalyst.

  Hereinafter, the present invention will be described in detail.

In the present invention, the flexible polyurethane foam refers to 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 generally refers to a reversibly deformable foam having an open cell structure and exhibiting high air permeability. The physical properties of the flexible urethane foam are not particularly limited, but in general, the density is in the range of 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 flexible polyurethane foam of the present invention includes a semi-rigid polyurethane foam from the raw materials used and the physical properties of the foam. Semi-rigid polyurethane foams are described by Gunter Oertel, “Polyurethane Handbook” (1985 edition), Hanser Publishers (Germany), p. 223-233, Keiji Iwata, "Polyurethane resin handbook" (1987 first edition), Nikkan Kogyo Shimbun, p. As described in 211 to 221, the foam density and compressive strength are higher than that of the flexible polyurethane foam, but it has an open cell structure like the flexible polyurethane foam and is a reversibly deformable foam exhibiting high air permeability. . 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. Although the physical properties of the semi-rigid urethane foam are not particularly limited, 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 a range.

  The amine catalyst in the present invention is an amine catalyst composed of an amine compound having an alkyl ether group and / or an aryl ether group in the molecule.

  The catalyst for producing the flexible polyurethane of the present invention is not particularly limited as long as it is an amine compound having an alkyl ether group and / or an aryl ether group in the molecule. For example, the following general formula (1)

（式中、Ｒ_１〜Ｒ_７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、Ａは炭素数１〜１６のアルキル基、炭素数１〜１６のアリール基を表し、ｎは１〜１１の整数、ｍは１〜１１の整数を表し、ａは０〜１０の整数、ｂは１〜１０の整数を表す。ただし、Ｒ_５とＲ_１又はＲ_２とが結合して５〜７員環を形成しても良い。）
で示されるアミン化合物、下記一般式（２）

(Wherein R _{1 to} R ₇ 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) 1 to 16 alkoxyalkyl groups, A represents an alkyl group having 1 to 16 carbon atoms and an aryl group having 1 to 16 carbon atoms, n represents an integer of 1 to 11, m represents an integer of 1 to 11, a represents an integer of 0 to 10, and b represents an integer of 1 to 10. However, R ₅ and R ₁ or R ₂ may combine to form a 5- to 7-membered ring.
An amine compound represented by the following general formula (2)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（３）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (3)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（４）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (4):

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（５）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (5)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物からなる群より選ばれる１種又は２種以上のアルキルエーテル基及び／又はアリールエーテル基を分子中に有するアミン化合物が好適な化合物として挙げられる。

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound having in the molecule thereof one or more alkyl ether groups and / or aryl ether groups selected from the group consisting of amine compounds represented by the formula:

  In the amine compounds represented by the general formulas (2) to (5), the following general formula (6)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（７）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (7)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（８）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (8)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（９）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (9)

で示されるアミン化合物からなる群より選ばれる１種又は２種以上のアルキルエーテル基及び／又はアリールエーテル基を分子中に有するアミン化合物が好ましい。

An amine compound having in the molecule one or more alkyl ether groups and / or aryl ether groups selected from the group consisting of amine compounds represented by

Among these, as the catalyst for producing the flexible polyurethane of the present invention, in the amine compounds represented by the general formulas (1) to (9), the substituents R _{1 to} R ₇ are each independently a hydrogen atom. Represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 1 to 10 carbon atoms, a dimethylaminoalkyl group having 1 to 6 carbon atoms, or an alkoxyalkyl group having 1 to 10 carbon atoms, and n is an integer of 1 to 11 , M represents an integer of 1 to 11, a is an integer of 0 to 5, and b represents an integer of 1 to 5 (provided that R ₅ and R ₁ or R ₂ are bonded to form a 5- to 7-membered ring. An amine compound represented by (which may be formed) is preferred.

The substituents R _{1 to} R ₇ of the amine compound represented by the general formula (1) to the general formula (9) are each independently a hydrogen atom, a methyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a methoxy group. An ethyl group, methoxypropyl group, methoxyisopropyl group, ethoxyethyl group, ethoxypropyl group, ethoxyisopropyl group, propoxyethyl group, propoxypropyl group, propoxyisopropyl group, butoxyethyl group, butoxypropyl group, or butoxyisopropyl group is preferable. (However, R ₅ and R ₁ or R ₂ may combine to form a 5- to 7-membered ring). The substituent A is preferably a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a phenyl group or a benzyl group, and particularly preferably a methyl group or an ethyl group.

In the amine compound represented by the general formula (1), the amine compound in which R ₅ and R ₁ or R ₂ are bonded to form a 5- to 7-membered ring includes the following general formula (10)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（１１）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (11)

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物、下記一般式（１２）

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (12):

（式中、Ｒ_１、Ｒ_６、Ｒ_７、Ａ、ｍ及びｂは上記定義に同じ。）
で示されるアミン化合物等が例示される。

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
The amine compound etc. which are shown are illustrated.

  In the present invention, the catalyst for producing the flexible polyurethane is not particularly limited as long as it falls under the amine compound described above, and specifically, N, N-dimethylaminoethyl methyl ether, N, N— Dimethylaminoethyl ethyl ether, N, N-dimethylaminopropyl methyl ether, N, N-dimethylaminopropyl ethyl ether, N, N-dimethylaminobutyl methyl ether, N, N-dimethylaminobutyl ethyl ether, N, N- Dimethylaminopentyl methyl ether, N, N-dimethylaminopentyl ethyl ether, N, N-dimethylaminohexyl methyl ether, N, N-dimethylaminohexyl ethyl ether, N, N-dimethylaminoheptyl methyl ether, N, N- Dimethylaminoheptyleth Ether, N, N-dimethylaminooctylmethyl ether, N, N-dimethylaminooctylethyl ether, N, N-dimethylaminononylmethyl ether, N, N-dimethylaminononylethyl ether, N, N-dimethylaminodecylmethyl Ether, N, N-dimethylaminodecyl ethyl ether, N, N-dimethylaminoethoxyethyl methyl ether, N, N-dimethylaminoethoxyethyl ethyl ether, N, N-dimethylaminoethoxyisopropyl methyl ether, N, N-dimethyl Aminoethoxyisopropyl ethyl ether, N, N-dimethylaminoethoxyethoxyethyl methyl ether, N, N-dimethylaminoethoxyethoxyethyl ethyl ether, N, N-dimethylaminoethoxyethoxyisopropyl Methyl ether, N, N-dimethylaminoethoxyethoxyisopropyl ethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl methyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl ethyl ether, N, N-dimethylaminoethyl-N′-methylaminoisopropyl methyl ether, N, N-dimethylaminoethyl-N′-methylaminoisopropyl ethyl ether, N, N-dimethylaminopropyl-N′-methylaminoethyl methyl ether N, N-dimethylaminopropyl-N′-methylaminoethyl ethyl ether, N, N-dimethylaminopropyl-N′-methylaminoisopropyl methyl ether, N, N-dimethylaminopropyl-N′-methylaminoisopropylethyl Ether, N, N, N′-trimethyl-N′-methoxyethylbisaminoethyl ether, N, N, N′-trimethyl-N′-ethoxyethylbisaminoethyl ether, N, N, N′-trimethyl-N '-Methoxyisopropylbisaminoethyl ether, N, N, N'-trimethyl-N'-ethoxyisopropylbisaminoethyl ether, N, N-dimethylaminoethyl-N'-methylaminoethyl-N "-methylaminoethylmethyl Ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethyl ethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropylmethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ Methylaminoisopropyl ethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethyl-N ″ ′-methylaminoethyl methyl ether, N, N-dimethylaminoethyl-N′-methyl Aminoethyl-N ″ -methylaminoethyl-N ″ ′-methylaminoethyl ethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethyl-N ″ ′-methylaminoisopropylmethyl Ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoethyl-N ″ ′-methylaminoisopropylethyl ether, N, N-bis (3-dimethylaminopropyl) -N-isopropyl Methyl ether, N, N-bis (3-dimethylaminopropyl) -N-isopropylethyl ether, N- (2-methoxyethyl) -N'-methylpiperazine, N- (2-ethoxyethyl) -N'-methylpiperazine, 5-dimethylamino-3-methyl-1-pentylmethyl Ether, 5-dimethylamino-3-methyl-1-pentylethyl ether, 1- (2′-methoxyethyl) -3-methylpyrrolidine, 1- (2′-ethoxyethyl) -3-methylpyrrolidine, 1- ( 2'-methoxyethyl) -3-ethylpyrrolidine, 1- (2'-ethoxyethyl) -3-ethylpyrrolidine, 1- (2'-methoxyethyl) -4-methylpiperidine, 1- (2'-ethoxyethyl) ) -4-methylpiperidine, 1- (2′-methoxyethyl) -4-ethylpiperidine, 1- (2′-ethoxyethyl) -4-ethylpipe Gin, 1- (2′-methoxyethyl) -4-methylhexamethyleneimine, 1- (2′-ethoxyethyl) -4-methylhexamethyleneimine, 1- (2′-methoxyethyl) -4-ethylhexa Methyleneimine, 1- (2′-ethoxyethyl) -4-ethylhexamethyleneimine, 1- (2′-methoxyethyl) imidazole, 1- (2′-ethoxyethyl) imidazole, 1- (2′-methoxyethyl) ) -2-methylimidazole, 1- (2′-ethoxyethyl) -2-methylimidazole, 1- (2′-methoxypropyl) -2-methylimidazole, 1- (2′-ethoxypropyl) -2-methyl Examples include imidazole.

  Among these amine compounds, N, N-dimethylaminoethyl methyl ether, N, N-dimethylaminoethyl ethyl ether, N, N-dimethylaminopropyl methyl ether, N, N-dimethylamino have high catalytic activity. Propyl ethyl ether, N, N-dimethylaminobutyl methyl ether, N, N-dimethylaminobutyl ethyl ether, N, N-dimethylaminopentyl methyl ether, N, N-dimethylaminopentyl ethyl ether, N, N-dimethylamino Hexyl methyl ether, N, N-dimethylaminohexyl ethyl ether, N, N-dimethylaminoethoxyethyl methyl ether, N, N-dimethylaminoethoxyethyl ethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl Me Tyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl ethyl ether, N, N-dimethylaminopropyl-N′-methylaminoethyl methyl ether, N, N-dimethylaminopropyl-N′-methylaminoethyl Ethyl ether, N, N, N′-trimethyl-N′-methoxyethyl bisaminoethyl ether, N, N, N′-trimethyl-N′-ethoxyethyl bisaminoethyl ether, N, N-dimethylaminoethyl-N '-Methylaminoethyl-N ″ -methylaminoisopropylmethyl ether, N, N-dimethylaminoethyl-N′-methylaminoethyl-N ″ -methylaminoisopropylethyl ether, N, N-bis (3-dimethylaminopropyl) ) -N-isopropylmethyl ether, N, N-bis ( -Dimethylaminopropyl) -N-isopropylethyl ether, N- (2-methoxyethyl) -N'-methylpiperazine, N- (2-ethoxycyethyl) -N'-methylpiperazine, 5-dimethylamino-3- Methyl-1-pentylmethyl ether and 5-dimethylamino-3-methyl-1-pentylethyl ether are particularly preferred.

  The amine compounds represented by the general formulas (1) to (9) used as the catalyst for producing the flexible polyurethane of the present invention can be easily produced by methods known in the literature. Examples thereof include a method of etherification of a dialkylamino alcohol or a reaction between a alkyl ether containing a halogen group and a dialkylamine.

  The catalyst for producing a flexible polyurethane according to the present invention is used as an amine catalyst in a method for producing a polyurethane foam by reacting a polyol and a polyisocyanate in the presence of an amine catalyst, a foaming agent and, if necessary, other auxiliary agents. Is done.

  In the method of the present invention, the amine catalyst is used in an amount of usually 0.01 to 20 parts by weight, preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the polyol used. If the amount is less than 0.01 parts by weight, the moldability of the foam deteriorates, and a sufficient effect speed may not be obtained. On the other hand, when it exceeds 20 parts by weight, not only the effect of increasing the catalyst is not obtained, but also the fluidity and moldability of the foam may be deteriorated.

  The amine catalyst used in the method for producing a polyurethane of the present invention is the above-described catalyst for producing a flexible polyurethane of the present invention, but other catalysts may be used in combination without departing from the present invention. it can. Examples of other catalysts include conventionally known organometallic catalysts, carboxylic acid metal salts, tertiary amines and quaternary ammonium salts.

  The organometallic catalyst may be any conventionally known one, and is not particularly limited. 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 is not particularly limited as long as it is a conventionally known metal salt, 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 amines may be any conventionally known ones and are not particularly limited. 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 Perazine, 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.

  The quaternary ammonium salts are not particularly limited as long as they are conventionally known. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium water such as tetramethylammonium hydroxide salts, and the like. Examples thereof include tetraalkylammonium organic acid salts such as oxide, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

  The amine catalyst of the present invention can be used alone or in combination with other catalysts as described above, but dipropylene glycol, ethylene glycol, 1,4-butanediol can be used for mixing adjustment if necessary. Alternatively, a solvent such as 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, it will affect the physical properties of the foam, which is not preferred for economic reasons. The catalyst adjusted in this way may be used by adding to the polyol, or various amine catalysts may be added separately to the polyol, and is not particularly limited.

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

  Examples of the polyether polyol used in the method of the present invention include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, and aliphatic amines such as ethylenediamine. Starting compounds such as aromatic amines such as toluenediamine and diphenylmethane-4,4-diamine and alkanolamines such as diethanolamine and the like as starting materials. By the addition reaction of alkylene oxide typified by propylene oxide, for example, Gunter Oertel, "Polyurethane Handbook" (1985 edition) Hanser Public hers, Inc. (Germany), p. What was manufactured by the method of 42-53 is mentioned.

  Examples of the polyester polyol used in the method of the present invention include those obtained from the reaction of dibasic acid and glycol, 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 of the present invention, the polymer polyol used is, for example, a polymer polyol obtained by reacting the polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, styrene or the like in the presence of a radical polymerization catalyst. Is mentioned.

  Examples of the flame retardant polyol used in the method of the present invention include a phosphorus-containing polyol obtained by adding alkylene oxide to a phosphoric acid compound, a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, A phenol polyol etc. are mentioned.

  In the method of the present invention, a polyol having an average hydroxyl value of 20 to 100 mgKOH / g is preferred, and a polyol of 20 to 80 mgKOH / g is particularly preferably used.

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

  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 polyphenyl polymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  The mixing ratio of these polyisocyanates and polyols is not particularly limited, but generally 60 to 400 is preferable in terms of isocyanate index (isocyanate group / active hydrogen group capable of reacting with isocyanate group).

  As the blowing agent used in the method of the present invention, it is preferable to use one or more selected from the group consisting of water, low-boiling hydrocarbons, chlorofluorocarbon compounds, air, nitrogen and carbon dioxide.

  Examples of low-boiling hydrocarbons include propane, n-butane, i-butane, n-pentane, i-pentane, cyclopentane, n-hexane, cyclohexane, and chlorofluorocarbon compounds such as 1,1-dichloro-1-fluoro. HCFCs such as ethane (HCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), chlorodifluoromethane (HCFC-22), 1,1,1,3,3-pentafluoropropane (HFC) -245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1,2,3, HFCs such as 3,3-heptafluoropropane (HFC-227ea), 1,1,1-trifluoroethyl difluoromethyl ether (HFE-245mf), 1,1,2,2-tetrafluoroethyl methyl ether (HFE-254pc), 1,1,2,2-tetrafluoroethyl-1,1,1-trifluoroethyl ether (HFE- HFEs such as 347pc-f). Among these, as low-boiling hydrocarbons, n-butane, i-butane, n-pentane, i-pentane, cyclopentane, n-hexane, cyclohexane, and chlorofluorocarbon compounds are 1,1-dichloro-1-fluoro. Ethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1,1 , 2-tetrafluoroethane (HFC-134a) is preferred.

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 10 to 200 kg / m ³ , preferably 20 to 100 kg / m ^3. Selected as

  In the method of the present invention, auxiliary agents other than those described above can be used if necessary. Examples of other auxiliaries include foam stabilizers, crosslinking agents, chain extenders, flame retardants, and the like.

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

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

  In the method of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant 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 is usually 4 to 20 parts by weight with respect to 100 parts by weight of polyol, although it varies depending on the required flame retardancy.

  In the present invention, colorants, anti-aging agents, and other conventionally known additives can be used as necessary. The type and amount of these additives may be within the normal usage range of the additive used.

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

  The product produced by the method of the present invention can be used in various applications. For example, an automobile seat cushion, a mattress, furniture, an automobile instrument panel, a headrest, an armrest, and the like can be given.

  According to the method of the present invention, by using an amine compound having an alkyl ether group or an aryl ether group in the molecule, it is excellent in foam curing speed and moldability without damaging the physical properties of the foam, and has a soft odor. Polyurethane foam can be produced.

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

In the following examples and comparative examples, the measurement method for each measurement item is as follows.
-Reactive measurement item Cream time: The time when the foam starts to rise is 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.
-Foam core density Free foaming was performed in a 2 liter polyethylene cup, the center of the foam was cut into 10 x 6 x 6 cm dimensions, and the core density was calculated by accurately measuring the dimensions and weight. .
-Foam curing speed The foam foamed using an aluminum mold of 29.5 x 30.5 x 2.5 cm was removed after 2 minutes, and 5 at intervals of 20 seconds with an approximately 2.5 kg marker (20 mmφ). The compression was repeated for 2 seconds. The time when the mark on the foam disappeared was defined as the foam curing rate.
-Formability of foam The foam foamed using the aluminum mold was evaluated for the size of voids, skin roughness, skin peeling, etc. generated in the foam in the following three stages.

1: Almost 2: Moderate 3: Large • Foam odor Ten panelists sniffed the foam foamed using the aluminum mold, and the amine odor of the foam was evaluated in the following four stages.

Large: Everyone feels strong odor Medium: More than 4 out of 10 feel weak odor Small: Less than 3 out of 10 feel weak odor None: Everyone feels no odor Examples 1 to 6 and comparison Example 1 to Comparative Example 8
Premix B was prepared with the raw material blending ratio shown in Table 1 for polyol, foaming agent, foam stabilizer and auxiliary agent. 99.4 g of Premix B was taken in a 300 ml polyethylene cup, and the catalyst shown in Table 1 was added in an amount such that each reactivity was 40 seconds with the following gel time, and the temperature was adjusted to 20 ° C. Put the polyisocyanate liquid (NE-112) whose temperature was adjusted to 20 ° C. in a separate container into the cup of Premix B by an amount such that the isocyanate index {isocyanate group / OH group (molar ratio) × 100)} is 100, The mixture was quickly stirred at 6000 rpm for 5 seconds with a stirrer. The mixed and stirred liquid mixture was transferred to a 2 liter polyethylene cup whose temperature was adjusted to 30 ° C., and the reactivity during foaming was measured. The core density of the foam was measured from the obtained molded foam. Next, the raw material scale was increased, and the mixture was put into a mold whose temperature was adjusted to 30 ° C. by the same operation, and foam molding was performed. The foam was demolded 2 minutes after the mixed solution was added. From the molded foam, the foam curing rate, moldability and odor were evaluated. The results are shown in Table 2.

表２から明らかなように、本発明のアミン化合物を触媒として使用することで、硬化速度及び成型性に優れ、臭気の少ないフォームを製造することができる。

As is apparent from Table 2, by using the amine compound of the present invention as a catalyst, a foam having excellent curing speed and moldability and less odor can be produced.

  That is, Examples 1 to 6 are examples in which a flexible polyurethane foam was produced using the catalyst of the present invention. These are all excellent in curing speed and moldability, and are flexible urethane foams with less odor. Can be obtained.

On the other hand, Comparative Examples 1 to 4 and Comparative Examples 7 to 8 are examples of tertiary amine catalysts that do not have an alkyl ether group or an aryl ether group in the molecule, but have a curing rate and moldability. The form is inferior. Comparative Examples 5 to 6 are examples of catalysts that are often used as catalysts for producing flexible polyurethane foams. However, although the curing speed and moldability are excellent, the foam has a strong odor and is in terms of working environment. There's a problem.

Claims (14)

A catalyst for producing a flexible polyurethane comprising an amine compound having an alkyl ether group and / or an aryl ether group in the molecule. An amine compound having an alkyl ether group and / or an aryl ether group in the molecule is represented by the following general formula (1):

(Wherein R _{1 to} R ₇ 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) 1 to 16 alkoxyalkyl groups, A represents an alkyl group having 1 to 16 carbon atoms and an aryl group having 1 to 16 carbon atoms, n represents an integer of 1 to 11, m represents an integer of 1 to 11, a represents an integer of 0 to 10, and b represents an integer of 1 to 10. However, R ₅ and R ₁ or R ₂ may combine to form a 5- to 7-membered ring.
An amine compound represented by the following general formula (2)

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (3)

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (4):

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (5)

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
The catalyst for producing a flexible polyurethane according to claim 1, wherein the catalyst is one or more selected from the group consisting of amine compounds represented by formula (1). The amine compound represented by the general formula (2) to the general formula (5) is represented by the following general formula (6).

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (7)

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (8)

(In the formula, R ₁ , R ₆ , R ₇ , A, m and b are the same as defined above.)
An amine compound represented by the following general formula (9)

The catalyst for producing a flexible polyurethane foam according to claim 2, wherein the catalyst is an amine compound represented by the formula: In the amine compounds represented by general formula (1) to general formula (5), R _{1 to} R ₇ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 1 to 10 carbon atoms. Represents a dimethylaminoalkyl group having 1 to 6 carbon atoms or an alkoxyalkyl group having 1 to 10 carbon atoms, n represents an integer of 1 to 11, m represents an integer of 1 to 11, and a represents an integer of 0 to 5 , B represents an integer of 1 to 5 (provided that R ₅ and R ₁ or R ₂ may combine to form a 5- to 7-membered ring). The soft polyurethane production catalyst as described in 1. In the amine compound represented by the general formula (1) to the general formula (5), R _{1 to} R ₇ are each independently a hydrogen atom, a methyl group, a dimethylaminoethyl group, a dimethylaminopropyl group, a methoxyethyl group, It is characterized by being represented by methoxypropyl group, methoxyisopropyl group, ethoxyethyl group, ethoxypropyl group, ethoxyisopropyl group, propoxyethyl group, propoxypropyl group, propoxyisopropyl group, butoxyethyl group, butoxypropyl group, butoxyisopropyl group The catalyst for manufacturing a flexible polyurethane according to any one of claims 2 to 4. In the amine compound represented by the general formula (1) to the general formula (5), A is a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, a phenyl group, or a benzyl group. The catalyst for manufacturing a flexible polyurethane according to any one of claims 2 to 5. In the method for producing a polyurethane foam by reacting a polyol and a polyisocyanate in the presence of an amine catalyst, a foaming agent, and, if necessary, other auxiliary agents, any one of claims 1 to 6 as an amine catalyst. A method for producing a flexible polyurethane foam, comprising using the catalyst for producing a flexible polyurethane described in 1. The method for producing a flexible polyurethane foam according to claim 7, wherein one or more selected from the group consisting of water, low-boiling hydrocarbons, and chlorofluorocarbon compounds are used as the foaming agent. The low-boiling hydrocarbon is a compound selected from the group consisting of n-butane, i-butane, n-pentane, i-pentane, cyclopentane, n-hexane and cyclohexane. A method for producing a flexible polyurethane foam. The fluorocarbon compounds are 1,1-dichloro-1-fluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-penta The method for producing a flexible polyurethane foam according to claim 8, which is a compound selected from the group consisting of fluorobutane (HFC-365mfc) and 1,1,1,2-tetrafluoroethane (HFC-134a). . The method for producing a flexible polyurethane foam according to any one of claims 7 to 10, wherein the amount of the amine catalyst used is 0.01 to 20 parts by weight with respect to 100 parts by weight of the polyol. The method for producing a flexible polyurethane foam according to any one of claims 7 to 11, wherein a foam stabilizer is used as an auxiliary agent. The method for producing a flexible polyurethane foam according to any one of claims 7 to 12, wherein a crosslinking agent and / or a chain extender is used as an auxiliary agent. The method for producing a flexible polyurethane foam according to any one of claims 7 to 13, wherein a flame retardant is used as an auxiliary agent.