JP2003206329A - Imidazole catalyst for producing polyurethane resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a catalyst for producing a polyurethane resin capable of solving the problem of prior art even in a formulation using a large quantity of water as a blowing agent, and to provide a method for producing the polyurethane resin using the same. <P>SOLUTION: The polyurethane resin is produced using the catalyst containing a compound represented by general formula (1), wherein R<SP>1</SP>, R<SP>2</SP>and R<SP>3</SP>each independently denotes a hydrogen atom or a 1-4C linear or branched alkyl group; and R<SP>4</SP>denotes a 1-4C linear or branched alkylene group. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst for producing a polyurethane resin such as a soft, hard, semi-rigid or elastomer,
And a method for producing a polyurethane resin or polyurethane foam using the same. More particularly, it relates to catalysts and methods for making polyurethane resins or polyurethane foams that emit little volatile amines.

[0002]

Polyurethane resins are produced by reacting a polyol and a polyisocyanate in the presence of a catalyst and, if necessary, a foaming agent, a surfactant, a cross-linking agent and the like. Conventionally, it has been known to use many metal compounds and tertiary amine compounds as catalysts in the production of this polyurethane resin. These catalysts are widely used industrially by being used alone or in combination.

Of these catalysts, especially tertiary amine compounds are widely used as tertiary amine catalysts for producing polyurethane resins because of their excellent productivity and moldability. Examples of such compounds include conventionally known triethylenediamine, N, N, N ', N'-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N. ', N ", N"-
Examples include compounds such as pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, N, N-dimethylethanolamine.

Since the metal-based catalyst deteriorates in productivity and moldability, the metal-based catalyst is often used in combination with a tertiary amine catalyst in most cases and is rarely used alone.

[0005]

However, the above-mentioned tertiary amine catalysts generally have an unpleasant odor and have high volatility. This causes various problems in the foam manufacturing process. For example, the odor problem of volatile amines emitted from polyurethane foam products in automobiles, and in recent years, the volatile components in polyurethane foams have become a cause of deposition on automobile window glass and causing it to fog and reduce its commercial value. The problem is so-called fogging, and the problem of contamination of other materials by volatile amines discharged from polyurethane products.

In contrast to the above-mentioned conventional tertiary amine catalyst, for example, a method using an amine catalyst having primary and secondary amino groups or hydroxyalkyl groups capable of reacting with polyisocyanate in the molecule has been proposed. (See JP-A-46-4846, JP-B-61-31727, JP-B-57-14762, etc.). Tokusho Sho 6
Although there is a description in Japanese Patent Laid-Open No. 1-31727 that contamination of other materials can be prevented when such a catalyst is used,
These catalysts generally have a high volatility and an unpleasant odor, and have a problem in working environment.

Further, a ureido group (for example, NHC) is included in the molecule.
ONH ₂₎ How to use the specific amine catalyst having has been proposed (see JP-A-61-85431 Publication).
According to the publication, the specific amine catalyst having these ureido groups is less volatile than the amine catalyst lacking this functional group, and when these specific amine catalysts are used, contamination of other materials is prevented. There is a statement that it can be done. However, since the amine catalyst described in the same publication promotes both gelation (polyol-polyisocyanate) and foaming (water-polyisocyanate) reaction at the same time, when a large amount of water is used as a foaming agent, the amine catalyst does not react at the beginning of the reaction. The foaming reaction proceeds unnecessarily, causing problems such as narrowing the process range of moldability of the polyurethane foam.

The present invention has been made in view of the above problems, and an object thereof is to produce a polyurethane resin capable of solving the problems of the prior art even in a formulation using a large amount of water as a foaming agent. A catalyst and a method for producing a polyurethane resin using the catalyst.

[0009]

Means for Solving the Problems The present inventors have made extensive studies in order to solve the above problems. As a result, when an urea adduct of imidazole is used as an amine catalyst in the production of a polyurethane resin, a polyurethane resin having almost no volatility and odor can be obtained with good moldability and productivity, and a large amount of water is used as a foaming agent. The inventors have found that the above problems can be solved even in the prescription, and have completed the present invention.

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

[0011]

[Chemical 3] (In the above formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and R ⁴ is a direct alkyl group having 1 to 4 carbon atoms. A catalyst for producing a polyurethane resin comprising a compound represented by a chain or branched alkylene group), and a method for producing a polyurethane resin or polyurethane foam using the same.

The present invention will be described in detail below.

The catalyst of the present invention comprises the compound represented by the above general formula (1). The catalyst of the present invention is obtained by further adding the compound represented by the general formula (1) to the following general formula (2).

[0014]

[Chemical 4] (In the above formula, R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and R ⁸ is a direct alkyl group having 1 to 4 carbon atoms. It represents a chain or a branched alkylene group).

The catalyst of the present invention contains 50 to 100% by weight of the compound of the general formula (1) based on the total amount of the compound of the general formula (1) and the compound of the general formula (2). , And 0 to 50% by weight of the compound of the general formula (2)
It is preferable to contain. When the amount of the compound of the general formula (1) is less than 50% by weight, the catalytic activity is low and the productivity of the polyurethane resin may decrease.

In the present invention, as the compound represented by the general formula (1), R ¹ is a hydrogen atom or a methyl group, and R ² and R ³ are hydrogen from the viewpoint of catalytic activity and easiness of production. And R ⁴ is preferably a propylene group.
Further, as the compound represented by the general formula (2), R ⁵ is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are hydrogen, and R ⁸ is R ⁸ from the viewpoint of catalytic activity and easiness of production. It is preferably a propylene group.

Specific examples of the amine compound represented by the above general formula (1) of the present invention include 1- {3 '-(imidazolinyl) propyl} urea and 1- {3'-(2 "-methylimidazo). Linyl) propyl} urea, 1- {2 '-(imidazolinyl) ethyl} urea, 1- {2'-(2 "-methylimidazolinyl) ethyl} urea, 1- {2 '-(imidazolinyl) -1 '-Methylethyl} urea, 1-
{2 '-(2 "-methylimidazolinyl) -1'-methylethyl} urea, etc. Of these, 1- {3'-(imidazolinyl) propyl} urea is preferred from the viewpoint of ease of synthesis. , 1- {3 ′-(2 ″ -methylimidazolinyl) propyl} urea is more preferred.

Specific examples of the amine compound represented by the above general formula (2) of the present invention include 1,3-bis {3'-
(Imidazolinyl) propyl} urea, 1,3-bis {3 '-(2 "-methylimidazolinyl) propyl} urea, 1,3-bis {2'-(imidazolinyl) ethyl}
Urea, 1,3-bis {2 '-(2 "-methylimidazolinyl) ethyl} urea, 1,3-bis {2'-(imidazolinyl) -1'-methylethyl} urea, 1,3-bis {2 '-(2 "-methylimidazolinyl) -1'-methylethyl} urea and the like can be mentioned. Of these, 1,3-bis {3 ′-(imidazolinyl) propyl} urea and 1,3-bis {3 ′-(2 ″ -methylimidazolinyl) propyl} urea are preferred from the viewpoint of ease of synthesis. More preferable.

The compounds represented by the above general formula (1) and the above general formula (2) are obtained by, for example, heating urea and 1- (3'-aminopropyl) imidazole at an appropriate molar ratio to react them. Can be manufactured by. Therefore, the catalyst composition of the present invention may contain up to 20% by weight of unreacted urea. The compound represented by the general formula (1) and the compound represented by the general formula (2) can be individually isolated by chromatography, recrystallization, sublimation or the like.

When the catalyst of the present invention is used for producing a polyurethane resin, the amount used is usually 0.01 to 10 parts by weight, based on 100 parts by weight of the polyol used.
When the amount of the catalyst is large, the amount of the catalyst incorporated as a terminator into the polyurethane resin is large, and thus the physical properties (functionality) of the resin may be deteriorated.
5 to 5 parts by weight.

The catalyst of the present invention has extremely low volatility and odor. Further, it reacts with polyisocyanate, which is a polyurethane resin raw material, and is fixed in the polyurethane resin skeleton. That is, when the catalyst of the present invention is used, the working environment of polyurethane production is improved, and further, in the polyurethane resin product, it is possible to prevent the above-mentioned various problems such as odor and fogging due to volatile amines. .

The method for producing a polyurethane resin using the catalyst of the present invention comprises reacting a polyol and a polyisocyanate in the presence of the catalyst of the present invention and, if necessary, a foaming agent, a surfactant, a crosslinking agent and the like. It is a method for obtaining a polyurethane resin product. Examples of products include flexible polyurethane foams, semi-rigid polyurethane foams and rigid polyurethane foams produced using a foaming agent, and elastomer products that do not use a foaming agent. The method of the present invention is
Among these, it is preferably applied to flexible polyurethane foam, semi-rigid polyurethane foam and rigid polyurethane foam produced by using a foaming agent.

As the polyol used in the method for producing the polyurethane resin of the present invention, conventionally known polyether polyol, polyester polyol, polymer polyol, and flame-retardant polyol such as phosphorus-containing polyol and halogen-containing polyol can be used. . These polyols can be used alone or in an appropriate mixture and used together.

In the method of the present invention, examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and pentaerythritol, amines such as ethylenediamine, ethanolamine and diethanolamine. A compound having at least two active hydrogen groups, such as alkanolamines, is used as a starting material, and an addition reaction of this with an alkylene oxide represented by ethylene oxide or propylene oxide,
For example, Gunter Oertel, “Polyur
ethane Handbook "(1985 version)
Hanser Publishers (Germany) No. 4
It can be produced by the method described on pages 2-53.

In the method of the present invention, as the polyester polyol, those obtained from the reaction of dibasic acid and glycol, and further, Keiji Iwata, “Polyurethane Resin Handbook” (first edition in 1987), Nikkan Kogyo Shimbun, 11
Examples thereof include wastes during nylon production, trimethylolpropane, pentaerythritol wastes, phthalic acid polyester wastes, and polyester polyols obtained by treating wastes described on page 7.

In the method of the present invention, as the polymer polyol, for example, the above polyether polyol and an ethylenically unsaturated monomer such as butadiene, acrylonitrile, styrene, etc. are reacted in the presence of a radical polymerization catalyst. A coalesced polyol is mentioned.

In the method of the present invention, examples of the flame-retardant polyol include a phosphorus-containing polyol obtained by adding an alkylene oxide to a phosphoric acid compound, a halogen-containing polyol obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide, Examples thereof include phenol polyol.

The molecular weight (Mw) of these polyols is 62 to 15,000.

In the case of flexible polyurethane foams,
Those having a molecular weight (Mw) of 1000 to 15000 are used, but preferably, the molecular weight (Mw) is 3000 to 15
000 polyether polyols and polymer polyols. When the molecular weight is less than 3000, the physical properties (elasticity) may be inferior, so that the molecular weight of 3000 or more is desirable. More preferred is a flexible polyurethane foam which is used in combination with a polyether polyol and a polymer polyol. Polymer polyols have the effect of increasing the strength (hardness, elasticity) of the resin, and molecular design (hardness,
Elasticity) becomes easy.

In the case of rigid polyurethane foam,
Usually, those having a molecular weight (Mw) of 62 to 8000 are used, but preferably the molecular weight (Mw) is 62 to 1500.
Is a polyether polyol. As a polyol for rigid polyurethane foam, there are many functional groups (4 to
8), low molecular weight ones are preferred.

The polyisocyanate used in the present invention may be any conventionally known one, for example, aromatic polyisocyanates such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate and xylylene diisocyanate. And aliphatic polyisocyanates such as hexamethylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate and isophorone diisocyanate, and mixtures thereof. Examples of TDI and its derivatives include 2,4-toluene diisocyanate and 2,
Mention may be made of mixtures of 6-toluene diisocyanates or terminal isocyanate prepolymer derivatives of TDI. Examples of MDI and its derivative include a mixture of MDI and its polymer polyphenyl-polymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group. Of these polyisocyanates, TDI and MDI
Is preferably used.

In the method of the present invention, the ratio of the polyisocyanate and the polyol to be used is not particularly limited, but is generally represented by an isocyanate index (isocyanate group / active hydrogen group capable of reacting with isocyanate group). In the production of flexible foam and semi-rigid foam, it is generally in the range of 60 to 130, and in the production of rigid foam and urethane elastomer, it is generally in the range of 60 to 400.

The catalyst used in the method for producing the polyurethane of the present invention is a catalyst containing the compound represented by the above general formula (1), but other catalysts may be used within the scope of the effects of the present invention. A catalyst can be used in combination. Examples of such other catalysts include conventionally known organic metal catalysts, tertiary amines and quaternary ammonium salts.

Examples of the organometallic catalyst include stannas diacetate, stannas dioctoate, stannas dioleate, stannas dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, dioctyltin dilaurate, Examples thereof include lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate and the like.

The tertiary amines may be conventionally known ones, 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 '
-Dimethylpiperazine, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1 And tertiary amine compounds such as dimethylaminopropylimidazole. Further, a tertiary amine compound having a reactive group other than the present invention can also be used, and examples thereof include dimethylethanolamine, dimethylisopropanolamine, N, N-dimethylhexanolamine, dimethylaminoethoxyethanol, N, N-dimethyl-N. '-(2-hydroxyethyl) ethylenediamine, N, N-dimethyl-N'-
(2-hydroxyethyl) propanediamine, N-methyl-N '-(2-hydroxyethyl) piperazine, bis (dimethylaminopropyl) amine, bis (dimethylaminopropyl) isopropanolamine, 1- (2-hydroxyethyl) imidazole , 1- (2-hydroxypropyl) imidazole, 1- (2-hydroxyethyl) -2-methylimidazole, 1- (2-hydroxypropyl) -2-methylimidazole, 3-quinuclidinol and the like.

As the quaternary ammonium salt, conventionally known tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxide such as tetramethylammonium hydroxide, and tetramethylammonium 2-ethylhexanoic acid. Examples thereof include tetraalkylammonium organic acid salts such as salts, 2-hydroxypropyltrimethylammonium formate, and 2-hydroxypropyltrimethylammonium 2-ethylhexanoate.

The blowing agent used in the method for producing a polyurethane resin of the present invention is water and a low boiling point organic compound. The low boiling point organic compound is a hydrocarbon-based or halogenated hydrocarbon-based compound. As the hydrocarbon compound, conventionally known methane, ethane, propane, butane, pentane,
Hexane etc. can be used. As the halogenated hydrocarbon compound, conventionally known halogenated methane, halogenated ethanes, fluorinated hydrocarbons can be used, and specifically,
Methylene chloride, HCFC-141b, HFC-245f
a, HFC-356mfc, etc. can be used. In the use of these foaming agents, water and the low boiling point organic compound may be used alone or in combination, but water is a particularly preferable foaming agent in terms of environment. The amount used may vary depending on the density of the intended product, but normally 100
The amount is 0.1 part by weight or more, and preferably 0.5 to 10 parts by weight with respect to parts by weight.

If necessary in the present invention, a surfactant can be used. The surfactant used in the present invention is a conventionally known organic silicone surfactant, and the amount thereof is 0.1 to 10 parts by weight with respect to 100 parts by weight of the polyol.

In the present invention, a crosslinking agent or a chain extender can be added if necessary. As the cross-linking agent or chain extender, a low molecular weight polyhydric alcohol (for example, ethylene glycol, 1,4-butanediol, glycerin, etc.), a low molecular weight amine polyol (for example, diethanolamine, triethanolamine, etc.), a low molecular weight The polyamines (for example, ethylenediamine, xylylenediamine, methylenebisorthochloroaniline, etc.) can be mentioned. Of these, diethanolamine,
Triethanolamine is preferred.

In the present invention, a colorant, a flame retardant, an antiaging agent, other known additives and the like can be used if necessary. The types and amounts of these additives can be sufficiently used within the range usually used as long as they do not depart from known formats and procedures.

The product produced by the method for producing a polyurethane resin of the present invention can be used for various purposes. Examples of the flexible foam include beds as cushions, car seats, mattresses, and the like. Examples of the semi-rigid foam include automobile-related instrument panels, headrests, handles, and the like. Examples of the rigid foam include a freezer, a refrigerator, and a heat insulating building material. Examples of elastomer products include adhesives, flooring materials, and waterproof materials.

The present invention will be described below based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

[0043]

EXAMPLES Preparation Example 1 Preparation of 60% Solution of 1- {3 ′-(2 ″ -Methylimidazolinyl) propyl} urea Composition 1- (3′-Aminopropyl) -2-methylimidazole (139.2 g) Add 60.0 g of urea and add 160
React at 10 ℃ for 10 hours, after reaction, remove volatile components,
-{3 '-(2 "-methylimidazolinyl) propyl}
A composition containing urea and 1,3-bis {3 '-(2 "-methylimidazolinyl) propyl} urea 176.1.
g was obtained. To this, 117.4 g of dipropylene glycol was added to prepare a 60% solution of 1- {3 ′-(2 ″ -methylimidazolinyl) propyl} urea composition (IZUM),
It was used in the following foaming experiments. Table 1 shows the composition of this solution.

[0044]

[Table 1] Preparation Example 2 Preparation of 1- {3 ′-(2 ″ -methylimidazolinyl) propyl} urea 60% solution The reaction solution obtained in the same manner as in the above Reaction Example was separated by liquid chromatography to give 1- {. 3 '-(2 "-methylimidazolinyl) propyl} urea was obtained. Dipropylene glycol was added thereto to prepare a 60% solution of 1- {3 ′-(2 ″ -methylimidazolinyl) propyl} urea (IZU), which was used in the following foaming experiment.

Both of the above catalyst compositions were diluted with a dipropylene glycol solution to prevent crystallization.
The weight ratio of the solvent species and the solvent is not limited to this preparation example.

Examples 1 to 2 and Comparative Examples 1 to 6 Examples in which a flexible polyurethane foam (ester slab formulation) is produced by using the catalyst of the present invention and the catalyst of Comparative Example will be shown.

The catalyst used was a 60% solution (IZUM) of the 1- {3 '-(2 "-methylimidazolinyl) propyl} urea composition obtained in Preparation Example 1 in Example 1, and in Example 2 Using the 60% solution of 1- {3 ′-(2 ″ -methylimidazolinyl) propyl} urea obtained in Preparation Example 2 (IZU),
In Comparative Examples 1 to 6, dimethylbenzylamine (D
B), N-ethylmorpholine (NEM), 1- (3'-
Aminopropyl) imidazole (API), 1- (2 '
-Hydroxypropyl) imidazole (HPI), dimethylaminopropylamine (DMAPA) and 3- (dimethylamino) propyl-1-urea (DMAPU) were used respectively. These are also shown in Table 2.

[0048]

[Table 2] A premix A was prepared by mixing the polyol, water, the cross-linking agent, and the foam stabilizer at the raw material mixing ratio shown in Table 3.

[0049]

[Table 3] Premix A (447.4 g) was added in an amount of 60 seconds in 2 liter polyethylene couple time, and the temperature was adjusted to 25 ° C. 192.6 g of the polyisocyanate solution (T-80) whose temperature was adjusted to 25 ° C. in a separate container was put into the cup of Premix A, and quickly stirred with a stirrer at 6000 rpm for 5 seconds. The mixed solution with mixing and stirring was put into a mold (internal size, made of aluminum of 25 × 25 × 25 cm, without upper lid) whose temperature was adjusted to 40 ° C., and foam molding was performed. The foam was demolded 20 minutes after the mixture was added. From the molded foam, the core density of the foam and the odor of the foam were measured and compared. Also, the odor of the catalyst was measured. The results are shown in Table 4.

[0050]

[Table 4] The measuring method of each measurement item is as follows.

<Measurement Items of Reactivity> Cream Time: Visually measure foaming start time and foaming start time Gel time: Measure time when reaction proceeds to change from liquid material to resinous material Rise time: foam Visually measure the time at which the rise of the stops.

<Catalyst Odor> 10 g of the catalyst was placed in a 20 ml sample bottle, and the distance between the sample and the nose was opened 10 cm on 10 monitors, and the smell was smelled and the intensity of the smell was measured. No odor △: With odor ×: With strong odor

<Foam core density> The center of the molded foam is cut into a size of 20 × 20 × 20 cm,
The size and weight were accurately measured to calculate the core density.

<Repulsion Elasticity> A predetermined piece having a size of 20 × 20 × 5 cm was cut from the foam whose foam core density was measured to obtain a test piece, and JIS K6401-1 was used.
The impact resilience test was carried out according to 980, and the impact resilience was measured.

<Hardness of foam (CLD)> JIS K6 was used as a test piece of foam whose foam core density was measured.
A hardness test was carried out according to 401-1980, and the 25% compressive strength and 65% compressive strength of the core portion of the foam were measured.

That is, JIS K6401-1980
Place the test piece flat on the table of the tester according to
A 0 cm circular pressure plate was placed on the upper surface of the test piece, and the thickness was measured when the load was 0.5 kgf (4.9 N).
This was the initial thickness. Next, after pushing in the circular pressure plate by 75% of the initial thickness, immediately removing the load, immediately again pushing in the circular pressure plate by 25% of the original thickness, and after standing still, 20
The load in seconds was read. Furthermore, after pressing the circular pressure plate 75% of the initial thickness, the load was immediately removed, and immediately again, the circular pressure plate was pressed 65% of the initial thickness, and the load at 20 seconds after rest was read. The foam hardness was calculated using the following formula, and the foam hardness when 25% of the initial thickness was indented was 25% compressive strength, and the foam hardness when it was indented 65% of the initial thickness was 65% compressive strength. did.

Foam hardness (N / m ² ) = load (N) obtained by using a circular pressure plate / area of the foam portion grounded on the circular pressure plate (m ² ) <foam elongation> measuring foam core density A predetermined foam having a size of 1 × 1 × 10 cm was cut from the foam to give a test piece, which was subjected to a tensile test according to JIS K7311-1995 to measure its elongation.

<Tensile Strength of Foam> A predetermined piece having a size of 1 × 1 × 10 cm was cut from the foam whose foam core density was measured to obtain a test piece, and JIS K731 was used.
A tensile test was carried out according to 1-1995, and the tensile strength was measured and used as the tensile strength of the foam.

<Tear Strength of Foam> A predetermined piece having a size of 1 × 1 × 10 cm was cut from the foam whose density was measured to obtain a test piece, and JIS K731 was used.
The tear strength was measured according to 1-1995 and the tear strength of the foam was measured.

<Moisture and heat permanent compression strain> A foam having a size of 5 x 5 x 2.5 cm was cut from a foam whose core density was measured to obtain a test piece, and JIS K6401-198 was used.
In accordance with 0, a thermal aging test of 50 ° C. × 22 hr, humidity 95%, 50% compression was carried out, and the hardness reduction rate was measured to be a wet heat permanent compression strain.

<Form scorch> The presence or absence of foam coloring (burning) was measured by visually observing the center of the molded foam. O: No foam coloring X: Foam coloring.

<Foam Odor> A foam measuring 5 × 5 × 5 cm was cut from the foam whose core density was measured, placed in a mayonnaise bottle and covered with a lid, and then 10 monitors smelled the foam. The strength of odor was measured. ○: Almost no odor △: Slight odor ×: Strong odor

Examples 1 and 2 are examples using the catalyst of the present invention, but the odor of the amine catalyst is almost zero. In addition, no scorch is generated and the foam has no amine odor.

On the other hand, Comparative Examples 1 and 2 are examples of tertiary amine catalysts having no reactive group in the molecule which are generally used in the ester slab formulation, but have an extremely unpleasant amine odor. To do. Also, the foam has an unpleasant amine odor. Comparative Examples 3 to 5 are examples of amine catalysts having a primary amino group or a secondary hydroxyl group in the molecule, but the amine catalyst has an odor. Further, in Comparative Example 5, the foaming reaction (water-isocyanate reaction) at the initial stage of foaming proceeds more than necessary, so scorch is generated. Comparative Example 6 is an example of an amine catalyst having an ureido group (NHCONH ₂ ) in the molecule,
Since the foaming reaction in the initial stage of foaming proceeds more than necessary, scorch occurs.

[0065]

EFFECTS OF THE INVENTION The catalyst of the present invention reacts with polyisocyanate, which is a raw material of polyurethane resin, and ureido group, and with polyisocyanate and urea group, and is fixed in the polyurethane resin skeleton, and the catalyst does not migrate to the resin surface or the like.
PVC in automotive instrument panel due to catalyst migration
It is effective in preventing tarnishing of window glass due to discoloration and migration of volatile components from foam. It also provides an excellent polyurethane foam even in a formulation that uses a large amount of water as a foaming agent. Further, since it has almost no catalytic odor and the odor of the produced polyurethane resin is reduced and contributes greatly to the improvement of the environment at the foaming site, it is extremely effective in the production of polyurethane such as soft, hard, semi-hard, and elastomer.

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 4J034 BA02 DF01 DF16 DF17 DF22                       DG02 DG03 DG04 DG23 DG28                       DP13 DP18 DP19 HA07 HA13                       HA14 HC03 HC12 HC13 HC22                       HC33 HC61 HC64 HC67 HC71                       HC73 KC17 KC18 KC35 KD02                       KD11 KD12 KD27 KE02 NA01                       NA02 NA03 NA08 QA03 QA05                       QB14 QB15 QB16 QB19 QC01                       RA03 RA08 RA10 RA12 RA14

Claims (8)

[Claims] 1. The following general formula (1): (In the above formula, R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and R ⁴ is a direct alkyl group having 1 to 4 carbon atoms. A catalyst for producing a polyurethane resin, which comprises a compound represented by a chain or branched alkylene group. 2. A compound represented by the general formula (1) is R ¹
Is a hydrogen atom or a methyl group, R ² and R ³ are hydrogen, and R ⁴ is a propylene group, The catalyst for producing a polyurethane resin according to claim 1. 3. A compound represented by the following general formula (2): (In the above formula, R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 4 carbon atoms, and R ⁸ is a direct alkyl group having 1 to 4 carbon atoms. A catalyst for producing a polyurethane resin according to claim 1 or 2, which comprises a compound represented by a chain or branched alkylene group. 4. The compound represented by the general formula (2) is R ⁵
Is a hydrogen atom or a methyl group, R ⁶ and R ⁷ are hydrogen, and R ⁸ is a propylene group, The catalyst for producing a polyurethane resin according to claim 3. 5. A polyol and a polyisocyanate,
A method for producing a polyurethane resin, which comprises reacting in the presence of the catalyst according to claim 1 or 2. 6. A polyol and a polyisocyanate,
A method for producing a polyurethane foam, which comprises reacting water and a low boiling point organic compound as a blowing agent in the presence of the catalyst according to claim 1 or 2. 7. A polyol and a polyisocyanate,
A method for producing a polyurethane resin, which comprises reacting in the presence of the catalyst composition according to claim 3 or 4. 8. A polyol and a polyisocyanate,
A method for producing a polyurethane foam, which comprises reacting in the presence of the catalyst composition according to claim 3 or claim 4 with water and a low boiling point organic compound as a blowing agent.