JP2003055426A - Amine catalyst composition for production of polyurethane resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a process for producing a polyurethane resin without the contamination with a polycarbonate resin or vinyl chloride resin, and a catalyst composition used for it. SOLUTION: The catalyst composition used for the production of a polyurethane resin contains a compound represented by formula (1) (wherein R<1> , R<2> and R<3> are each independently H or a 1-4C alky; and R<4> is H, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl or 3-aminopropyl) and a compound represented by formula (2) (wherein R is H or a 1-4C alkyl; (m) is 2 to 10; (n) is 1 or 2; and the nitrogen atom forms a secondary amino group when (n) is 1), or contains a compound represented by formula (1), a compound represented by formula (2), and a compound represented by formula (3) (wherein R<1> , R<2> , R<3> , R<4> , R<5> , R<6> , R<7> and R<8> are each independently H or a 1-4C alkyl).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a catalyst composition for producing a soft, rigid, semi-rigid polyurethane resin and the like, and a method for producing a polyurethane resin using the same. More specifically, the present invention relates to a catalyst composition and a method for producing a polyurethane resin in which the contamination of a polycarbonate resin and a vinyl chloride resin used for automobile interior parts and the like is significantly suppressed.

[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 using them alone or in combination.

Particularly, tertiary amine compounds are widely used as tertiary amine catalysts for producing polyurethane resins because of their excellent productivity and moldability. For example, conventionally known triethylenediamine, N, N, N ′, N′-tetramethyl-1,6-hexanediamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″,
Compounds such as N ″ -pentamethyldiethylenetriamine, N-methylmorpholine, N-ethylmorpholine, and 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, since the above-mentioned tertiary amine catalyst remains in free form in the polyurethane resin product, it is pointed out that the tertiary amine discharged from the polyurethane resin is contaminated. . For example, deterioration and discoloration problems of vinyl chloride resins and polycarbonate resins used for automobile interior parts can be mentioned.

As a method for solving this problem with respect to these tertiary amine catalysts, for example, amine catalysts having primary and secondary amino groups or hydroxyalkyl groups capable of reacting with polyisocyanate in the molecule are used. A method for use has been proposed (see JP-A-46-4846, JP-B-61-31727, JP-B-57-14762, etc.). In the publication, these amine catalysts are said to be able to avoid the above problems because they are immobilized in the polyurethane resin skeleton in the form of reacting with polyisocyanate. However, in reality, amine catalysts having these reactive groups are provided. Most of them are not completely reacted and remain in a small amount in the polyurethane resin product. Further, there is a case where, although it is once reacted with polyisocyanate and fixed in the polyurethane resin skeleton, the bond is decomposed at a high temperature and a small amount of free amine is discharged. This small amount of amine contaminates the polycarbonate resin and vinyl chloride resin, which are extremely sensitive to strongly basic amines. Therefore, it was difficult to suppress contamination of these resins with the catalyst described in the above publication.

Further, a method of using a high molecular weight and low volatility amine catalyst having two dimethylamino groups and two active hydrogen groups in the molecule has been proposed (JP-A-63-26590).
9 and JP-A-64-4613). In the publication, these amine catalysts are said to be able to avoid the above problems, but it is difficult to use them alone because the moldability of the polyurethane resin is extremely poor.

Further, metal-based catalysts other than amine-based catalysts, such as organotin compounds, do not cause the above problems, but when used alone, productivity, physical properties and moldability deteriorate, and environmental problems due to tin are also taken into consideration. It is coming.

The present invention has been made in view of the above problems, and an object thereof is to provide a catalyst composition for producing a polyurethane resin and a method for producing the polyurethane resin, which can solve the problem of contamination of a polycarbonate resin or a vinyl chloride resin. Is to provide.

[0010]

[Means for Solving the Problems] The present inventors have made extensive studies to solve the above problems. As a result, it was found that, when a specific amine catalyst is used in combination during the production of a polyurethane resin, it is possible to solve the contamination problem of the polycarbonate resin or the vinyl chloride resin while maintaining the moldability and various physical properties of the polyurethane resin. I arrived.

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

[0012]

[Chemical 6]

(In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ is a hydrogen atom, a 2-hydroxyethyl group or a 2-hydroxypropyl group. Group, a 3-hydroxypropyl group or a 3-aminopropyl group) and the following general formula (2):

[0014]

[Chemical 7]

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. M is 2 to 10, n is 1 or 2, and when n is 1, the nitrogen atom is a secondary amino group. It is.)
A catalyst composition for producing a polyurethane resin, which comprises a compound represented by the above formula, a compound represented by the above general formula (1), a compound represented by the above general formula (2), and the following general formula (3)

[0016]

[Chemical 8]

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ ,
R ⁷ and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. And a catalyst composition for producing a polyurethane resin, which comprises a compound represented by the formula (1), and a method for producing a polyurethane resin, which comprises using the catalyst composition.

The present invention will be described in detail below.

The catalyst composition for producing a polyurethane resin of the present invention contains the compound represented by the general formula (1) and the compound represented by the general formula (2). The catalyst composition of the present invention may further contain a compound represented by the above general formula (3).

In the present invention, the compound represented by the above general formula (1) is an imidazole compound having a reactive group, but from the viewpoint of catalytic activity, R ¹ is a hydrogen atom or a methyl group, R ² and R ² . ³ is preferably hydrogen, and R ⁴ is preferably a 2-hydroxypropyl group, a 2-hydroxyethyl group or a 3-aminopropyl group. As the compound represented by the general formula (2), m = 2 to 3, n = 1 to 2, and R is preferably a hydrogen atom or a methyl group from the viewpoint of catalytic activity and easiness of production. Further, as the compound represented by the general formula (3), R ¹ , R ² ,
It is preferred that R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are all hydrogen.

Examples of the amine compound represented by the above general formula (1) of the present invention include imidazole, 2-methylimidazole, 1- (2'-hydroxypropyl) imidazole and 1- (2'-hydroxypropyl)-. 2-Methylimidazole, 1- (2'-hydroxyethyl) imidazole, 1- (2'-hydroxyethyl) -2-methylimidazole, 1- (3'-aminopropyl) imidazole, 1- (3'-aminopropyl) ) -2-Methylimidazole, 1- (3′-hydroxypropyl) imidazole, 1- (3′-hydroxypropyl) -2-methylimidazole and the like. Of these, 1- (2′-hydroxypropyl) -2-methylimidazole and 1- (3′-aminopropyl) -from the viewpoints of catalytic activity, ease of synthesis, and suppression of contamination of polycarbonate resin and vinyl chloride resin. 2-methylimidazole, 1- (2 '
-Hydroxypropyl) imidazole and 1- (3'-aminopropyl) imidazole are more preferable.

Examples of the amine compound represented by the above general formula (2) of the present invention include N, N-dimethylaminopropyl-N '-(2-hydroxyethyl) amine, N,
N-dimethylaminopropyl-N '-(2-hydroxypropyl) -N'-methylamine, N, N-dimethylaminopropyl-N', N'-bis (2-hydroxyethyl) amine, N, N-dimethyl Aminopropyl-N ',
N'-bis (2-hydroxypropyl) amine, N, N
-Dimethylaminoethyl-N ', N'-bis (2-hydroxyethyl) amine, N, N-dimethylaminoethyl-N', N'-bis (2-hydroxypropyl) amine and the like can be mentioned. Of these, N, N-dimethylaminopropyl-N ′, from the viewpoint of catalytic activity, ease of production, and suppression of contamination of polycarbonate resin and vinyl chloride resin.
N'-bis (2-hydroxyethyl) amine, N, N-
More preferred is dimethylaminopropyl-N ', N'-bis (2-hydroxypropyl) amine.

Examples of the amine compound represented by the above general formula (3) of the present invention include bis {2- (4- (morpholino) ethyl} ether and bis {2- (2,6-dimethyl-4-morpholino). ) Ethyl} ether and the like.

In the catalyst composition of the present invention, the amine compounds represented by the above general formulas (1) to (3) can be used in any proportion as necessary and are not particularly limited. From the viewpoint of suppressing pollution and maintaining moldability of the polyurethane resin, the amine compound represented by the general formula (1) is contained in an amount of 10 to 30% by weight, and the general formula (2) is used.
20 to 80% by weight of the amine compound represented by, and 0 to 50% by weight of the amine compound represented by the general formula (3).
Preference is given to using. From the viewpoint of suppressing the contamination of the vinyl chloride resin, it is preferable to keep the use of the amine compound represented by the general formula (3) to a minimum.

The compounds represented by the above general formulas (1) to (3), which are components of the catalyst composition of the present invention, can be easily produced by methods known in the literature. The compound represented by the general formula (1) is obtained by, for example, reacting 2-methylimidazole with acrylonitrile, and then amination by hydrogenation,
It is obtained by a reaction of 2-methylimidazole with propylene oxide or ethylene oxide. The compound represented by the general formula (2) can be obtained, for example, by reacting N, N-dimethylpropanediamine with propylene oxide. The compound represented by the general formula (3) can be obtained, for example, by a dehydration reaction of diethylene glycol and morpholine.

In the catalyst composition of the present invention, the compound represented by the general formula (1) and the compound represented by the general formula (2) react with polyisocyanate which is a raw material of polyurethane resin, and most of them react. It is immobilized in the polyurethane resin skeleton. Therefore, the compound represented by the general formula (1) and the compound represented by the general formula (2) hardly exist as free amines in the polyurethane resin. Further, the compound represented by the general formula (1) and the compound represented by the general formula (2) have low basicity and volatility as compared with a general tertiary amine catalyst. That is, the above general formula (1)
Polyurethane resin products using the catalyst composition of the present invention containing the compound represented by the formula (1) and the compound represented by the general formula (2) hardly cause the above-mentioned contamination of polycarbonate and vinyl chloride.

The compound represented by the general formula (3) is required to be used in order to increase the fluidity and the expansion ratio, but since it is low in basicity and volatility, it is comparatively used among the tertiary amine catalysts. It has the characteristic of not contaminating polycarbonate. Therefore, a catalyst composition containing the compound represented by the general formula (1) and the compound represented by the general formula (2), the compound represented by the general formula (1), and the compound represented by the general formula (2) By combining the compound represented by the formula (3) and the catalyst composition containing the compound represented by the general formula (3) in an arbitrary ratio, the catalyst performance (foaming, foaming,
(Resinization) can be easily derived, and at the same time, contamination of polycarbonate and vinyl chloride can be greatly suppressed. Usually, when the catalyst of the present invention is used for producing a polyurethane resin, the amount used is 100 parts by weight of the polyol used,
Although it is 0.01 to 10 parts by weight, the amount of catalyst used is 5 from the viewpoint of suppressing the contamination of polycarbonate resin and vinyl chloride resin.
Less than or equal to parts by weight is desirable.

In the method for producing a polyurethane resin using the catalyst composition of the present invention, a polyol and polyisocyanate are added to the catalyst composition and, if necessary, a foaming agent, a surfactant,
It is a method of obtaining a polyurethane resin product by reacting in the presence of a crosslinking agent and the like. Examples of the product include flexible polyurethane foam, semi-rigid polyurethane foam, rigid polyurethane foam and elastomer. Of these,
It is preferably applied to flexible and semi-rigid polyurethane foams.

The polyurethane resin produced according to the present invention hardly causes contamination of polycarbonate resin or vinyl chloride resin.

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

Examples of the polyether polyol include polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane and pentaerythritol, amines such as ethylenediamine, and alkanolamines such as ethanolamine and diethanolamine. A compound having at least two active hydrogen groups, such as, is used as a starting material, and an alkylene oxide represented by ethylene oxide or propylene oxide is added to the starting material to give, for example, Gu.
inter Oertel, “Polyurethane
Handbook ”(1985) Hanser P
ublishers (Germany), p. It can be produced by the method described in 42-53.

Examples of the polyester polyol include those obtained by the reaction of dibasic acid and glycol, and Keiji Iwata "Polyurethane Resin Handbook" (1987) Nikkan Kogyo Shimbun, Ltd. p. 117, wastes during nylon production, trimethylolpropane, pentaerythritol wastes, phthalic acid polyester wastes, polyester polyols obtained by treating waste products, and the like.

Examples of the polymer polyol include polymer polyols obtained by reacting the above polyether polyol with an ethylenically unsaturated monomer such as butadiene, acrylonitrile, styrene and the like in the presence of a radical polymerization catalyst.

Examples of flame-retardant polyols include phosphorus-containing polyols obtained by adding alkylene oxides to phosphoric acid compounds, halogen-containing polyols obtained by ring-opening polymerization of epichlorohydrin or trichlorobutylene oxide,
Examples thereof include phenol polyol.

The molecular weight (Mw) of these polyols is 62.
-15,000 can be used. As the flexible polyurethane foam, one having a molecular weight (Mw) of 1000 to 15000 is used, and preferably a molecular weight (Mw) of 3000.
˜15,000 polyether polyols and polymer polyols. More preferred is a flexible polyurethane foam which is used in combination with a polyether polyol and a polymer polyol.

The polyisocyanate used in the present invention may be any known one, for example, aromatic polyisocyanate such as toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), naphthylene diisocyanate, xylylene diisocyanate, hexahexadiene, etc. Aliphatic polyisocyanates such as methylene diisocyanate, alicyclic polyisocyanates such as dicyclohexyl diisocyanate, isophorone diisocyanate and mixtures thereof can be mentioned. Examples of TDI and its derivatives include a mixture of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate or a terminal isocyanate prepolymer derivative of TDI.
As MDI and its derivative, a mixture of MDI and its polymer polyphenyl-polymethylene diisocyanate,
And / or diphenylmethane diisocyanate derivatives having terminal isocyanate groups. Of these organic polyisocyanates, TDI and MDI are preferably used.

The ratio of the polyisocyanate and the polyol to be used is not particularly limited, but in terms of the isocyanate index (isocyanate group / active hydrogen group capable of reacting with the isocyanate group), it is generally a soft foam or a semi-rigid foam. Generally 60 to 1 in manufacturing
It is in the range of 30 and generally in the range of 60 to 400 in the production of rigid foams and urethane elastomers.

The catalyst used in the method for producing a polyurethane of the present invention is the above-mentioned catalyst composition of the present invention, but other catalysts may be used in combination within the scope of the present invention. . Examples of other catalysts include conventionally known organic metal catalysts, tertiary amines and quaternary ammonium salts.

Examples of the organometallic catalysts include stannous 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 any 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, 3-quinuclidinol and the like can be mentioned.

The quaternary ammonium salts may be conventionally known ones, for example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium hydroxides such as tetramethylammonium hydroxide, and tetraalkylammonium hydroxide. Examples thereof include tetraalkylammonium organic acid salts such as methylammonium 2-ethylhexanoate, 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 / or a low boiling point organic compound. Examples of the low boiling point organic compound include low boiling point hydrocarbon compounds and halogenated hydrocarbon compounds. As such a hydrocarbon compound, known methane, ethane, propane, butane, pentane, hexane and the like can be used.
As the halogenated hydrocarbon, conventionally known halogenated methane, halogenated ethanes, fluorinated hydrocarbons and the like can be used, and specifically, methylene chloride and HCFC-141.
b, HFC-245fa, HFC-356mfc and the like. In using these foaming agents, water and the low boiling point organic compound may be used alone or in combination. A particularly preferred blowing agent is water. The amount used may vary depending on the density of the intended product, but is usually 0.1 part by weight or more, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the polyol.

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 or the like, a low molecular weight amine polyol such as diethanolamine, triethanolamine or polyamine, for example,
Examples thereof include ethylenediamine, xylylenediamine, and methylenebisorthochloroaniline. Of these, diethanolamine and triethanolamine are preferable.

In the method of the present invention, if necessary,
Further, coloring agents, flame retardants, antiaging agents, communicating agents, and other known additives can be used. 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. For flexible foams, for example, beds as cushions, car seats, mattresses, etc. In semi-rigid foam, for example, automobile-related instrument panels, headrests, steering wheels, etc. For rigid foam, for example, freezer, refrigerator,
Examples include heat insulating building materials.

Hereinafter, description will be given based on Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1 to 2 and Comparative Examples 1 to 9 Examples of producing flexible polyurethane foams using the catalysts and catalyst compositions of the present invention and the catalysts of Comparative Examples will be shown.

Premix A was prepared by mixing the polyol, water, cross-linking agent and foam stabilizer at the raw material mixing ratio shown in Table 2. 86.6 g of Premix A was placed in a 300 ml polyethylene cup, and the catalyst of the present invention and the catalyst of Comparative Example shown in Table 1 were added in amounts such that the reactivity was 60 seconds at the following rise time, and the temperature was adjusted to 20 ° C. did. A polyisocyanate solution (crude MDI) whose temperature was adjusted to 20 ° C. in a separate container was put into a cup of Premix A in an amount such that the isocyanate index {isocyanate group / OH group (molar ratio) × 100)} was 70, and quickly. 6000r with a stirrer
Stirred at pm for 5 seconds. The mixed solution with mixing and stirring was transferred to a 2 l polyethylene cup whose temperature was adjusted to 40 ° C., and the reactivity during foaming was measured. Next, increase the raw material scale and perform the same operation to adjust the temperature to 50 ° C.
(35 x 10 x 10 cm aluminum) with a total foam density of 4
The mixed solution was put into the container so that the pressure was 5 kg / m ³ and the container was capped to perform foam molding. The foam was demolded 3 minutes after the mixture was added. From molded foam to total density of foam, core density, formability of foam, degree of cell communication (immediately after demolding 1
Second ILD-2nd ILD), foam hardness, tensile strength, permanent compression strain, polycarbonate contamination degree, and vinyl chloride contamination degree were measured and compared. The results are shown in Table 3.

[0050]

[Table 1]

[0051]

[Table 2]

[0052]

[Table 3]

The measuring method of each measurement item is as follows.

Reactivity measurement items Cream time: Foaming start time, foam rising start time is visually measured Gel time: Reaction progresses to change from liquid material to resinous material Rise time: foam Visually measure the time when the rise stops.

Foam core density: The center portion of the molded foam foam was cut into a size of 20 × 20 × 6 cm, and the size and weight were accurately measured to calculate the core density.

Formability of foam: The cell roughness on the surface of the molded foam was visually observed and evaluated as the formability as follows: ∘: Almost no cell inferior ○: Cell inferior in part △: Cell roughness is about half of the surface area: Cell roughness is on the entire surface area.

Cell communication: The 65% compressive strength of the foam immediately after demolding from the mold was continuously measured 10 times, and the difference between the compressive strength value at the first time and the compressive strength value at the second time was calculated. Evaluated as ◯: 0 to 0.3 kN / m ² (cells are completely in communication) Δ: 1.5 to 3.0 kN / m ² (some cells are not in communication) ×: 6.0 kN / M ² or more (cells are not connected).

Foam hardness: 65% compressive strength of the foam immediately after demolding was continuously measured 10 times,
The tenth compression strength was determined.

Tensile strength of foam: A foam measuring 1 × 1 × 10 cm was cut from the foam whose core density was measured, and the tensile strength was measured. -Permanent compression set of foam: A foam measuring 5 x 5 x 2.5 cm was cut from the foam whose core density was measured, and the permanent set (dry set) of 50% compression at 50 ° C x 22 hr was measured.

Polycarbonate resin contamination degree: 6 g of foam was cut from the foam whose core density was measured, and this was placed in a 1 liter separable flask together with 100 g in a 100 ml beaker, and polycarbonate resin (manufactured by Mitsubishi Engineering) 3x3x
Suspend 0.2 cm in the air, close the lid and seal it at 80 ° C.
After standing under the condition of 100 hr, the degree of contamination of the polycarbonate resin was visually confirmed, and the color change and the surface solubility were evaluated as follows.

.Change in color ◎: No cloudiness ○: Slightly cloudy △: More than half white turbid X: Completely cloudy.

Surface solubility: Only those having a small change in color were evaluated as follows.

⊚: No dissolution ○: slightly dissolved △: The surface is sticky X: completely dissolved.

Degree of contamination with vinyl chloride resin: The foam whose foam core density was measured was cut into 7 × 7 × 3 cm, charged into a 3 liter separable flask, and vinyl chloride having a diameter of 10 cm and a height of 12 cm from the foam. A resin sheet (# 5620 Plus Tech Co., white, pigment-free sheet) is hung, the lid is closed and sealed at 80 ° C x 2
After standing under the condition of 00 hr, the degree of contamination of the vinyl chloride resin was visually confirmed, and the color change was evaluated as follows.

・ Change in color ◎: No discoloration ○: slightly yellowing △: discolored to yellow X: Discolored to red.

Example 1 is an example in which 25% by weight of the reactive imidazole compound (1) and 75% by weight of the compound (2) were combined, but the contamination of the polycarbonate resin and the vinyl chloride resin can be suppressed, and the moldability of the foam can be improved. , It is possible to maintain various physical properties.

Although Example 2 is an example in which 25% by weight of the reactive imidazole compound (1), 25% by weight of the compound (2) and 50% by weight of the compound (3) are combined, contamination of the polycarbonate resin can be suppressed.

Comparative Example 1 is an example in which triethylenediamine and bis (2-dimethylaminoethyl) -ether, which are generally used for producing flexible foams, are combined.
Violently contaminates polycarbonate resin and vinyl chloride resin.

Comparative Example 2 is an example in which the non-reactive imidazole compound was used alone, but the polycarbonate resin and vinyl chloride resin were severely contaminated.

Comparative Example 3 is an example in which the reactive imidazole compound (1) was used alone, but the unreacted compound (1) remained in the foam due to the large amount of use, so that the polycarbonate resin was slightly dissolved. , Also yellow the vinyl chloride resin.

Comparative Example 4 is an example in which the reactive compound (2) was used alone, but did not contaminate the polycarbonate resin and vinyl chloride resin at all. However, the moldability and the permanent compression strain are significantly deteriorated.

Comparative Example 5 is an example in which 50% by weight of the reactive imidazole compound (1) and 50% by weight of the compound (3) are combined, but the polycarbonate resin and the vinyl chloride resin are contaminated.

Comparative Example 6 is 50% by weight of the reactive compound (2).
And 50% by weight of compound (3) are combined,
Formability of the foam deteriorates.

Comparative Example 7 is an example in which a reactive tertiary amine compound was used, but the polycarbonate resin was severely contaminated.

Comparative Example 8 is an example in which 67% by weight of the reactive imidazole compound (1) and 33% by weight of the reactive tertiary amine compound are combined, but the polycarbonate resin is contaminated.

Comparative Example 9 is 67% by weight of the reactive compound (2).
And 33% by weight of a reactive type tertiary amine compound are combined, but the polycarbonate resin is contaminated.

[0077]

The catalyst composition of the present invention is capable of solving the problem of contamination of vinyl chloride resin and polycarbonate resin, facilitating adjustment of reactivity, and maintaining moldability and foam physical properties. Therefore, it is extremely effective in the production of flexible, rigid, semi-rigid polyurethane foams, etc., which require suppression of contamination of vinyl chloride resin or polycarbonate resin.

Claims (4)

[Claims] 1. The following general formula (1): (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ is a hydrogen atom, 2-
Hydroxyethyl group, 2-hydroxypropyl group, 3-
It represents a hydroxypropyl group or a 3-aminopropyl group. ) And a compound represented by the following general formula (2): (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. M represents 2 to 10, n represents 1 or 2, and when n is 1, the nitrogen atom is a secondary amino group. ) A catalyst composition for producing a polyurethane resin, which comprises a compound represented by 2. The following general formula (1): (In the formula, R ¹ , R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ is a hydrogen atom, 2-
Hydroxyethyl group, 2-hydroxypropyl group, 3-
It represents a hydroxypropyl group or a 3-aminopropyl group. ), A compound represented by the following general formula (2): (In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. M represents 2 to 10, n represents 1 or 2, and when n is 1, the nitrogen atom is a secondary amino group. ) And a compound represented by the following general formula (3): (In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). A catalyst composition for producing a polyurethane resin, comprising a compound. 3. 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 1 or 2. 4. A polyol and a polyisocyanate,
A method for producing a polyurethane resin, which comprises reacting with water and / or a low boiling point organic compound as a blowing agent in the presence of the catalyst composition according to claim 1 or 2.