JP2003201397A - One-pack moisture-curing urethane resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a one-pack moisture-curing urethane resin composition which excels in the balance of storage stability and curability and does not cause sick house syndromes. <P>SOLUTION: The one-pack moisture-curing urethane resin composition comprises 100 pts.mass urethane prepolymer having two or more isocyanate groups in the molecule and 0.1-30 pts.mass malonate compound having a molecular weight of ≥200. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a one-component moisture-curable urethane resin composition which is suitable for use in adhesives, sealants, coating agents, etc. for construction and automobiles.

[0002]

2. Description of the Related Art A one-part moisture-curable urethane resin composition is
When an amine-based latent curing agent or an isocyanate group active catalyst is used, the storage stability tends to decrease. In response to such problems, active methylene compounds such as malonate compounds are known to improve storage stability (see, for example, Patent Document 1). However, many malonate compounds are volatile organic compounds, and when a resin composition containing them is used for building purposes, problems such as sick house syndrome may occur. Further, in Patent Document 2, when the malonate compound is used in combination with a relatively highly active catalyst having a structure such as a dimethylamino group, the catalytic activity is lowered. Therefore, by adding cyclopentadiene instead of the malonate compound, storage It is proposed to ensure stability. However, malonate compounds and cyclopentadiene, which are highly volatile, not only pose a problem by themselves, but when they are contained, the tack free time is delayed during long-term storage.

Further, in Patent Document 3, in order to suppress an increase in viscosity of the urethane prepolymer and improve storage stability, a storage stability is improved by adding a tertiary phosphine compound in place of a malonate compound such as diethyl malonate. It is proposed to secure the sex. However,
The addition of the tertiary phosphine compound has a sufficient effect only when an amine catalyst having high activity is used, and the effect is insufficient in other cases.

On the other hand, when the one-pack moisture-curable urethane resin composition is used as an adhesive for construction, automobiles, etc., it is essential that it has high adhesiveness and does not contain volatile substances. Has become.

[0005]

[Patent Document 1] Japanese Patent Laid-Open No. 11-269244

[Patent Document 2] Japanese Patent Laid-Open No. 11-286674

[Patent Document 3] Japanese Patent Application Laid-Open No. 2000-169699

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a one-part moisture-curable urethane resin composition which has an excellent balance between storage stability and curability and does not cause problems such as sick house syndrome. With the goal.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a malonate compound having a specific structure has no volatility and, when added to a urethane resin composition, the composition of the composition It was found that it is effective in maintaining storage stability. In addition, further research has shown that the malonate compound having a specific structure is more effective in suppressing the curability after storage as compared with the case where a low molecular weight malonate compound such as diethyl malonate is added. Heading, completed the present invention.

That is, according to the present invention, 100 parts by mass of a urethane prepolymer having two or more isocyanate groups in one molecule and a malonate compound having a molecular weight of 200 or more 0.1 to 0.1 are used.
A one-component moisture-curable urethane resin composition containing 30 parts by mass is provided.

The malonate compound is one or more of divalent to tetravalent polyols and the following formula (1)

[0010]

[Chemical 4]

[In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 18 carbon atoms and optionally having a heteroatom. ] A malonate compound obtained by transesterification with one or more malonate compounds represented by

The malonate compound has the following formula (2):

[0013]

[Chemical 5]

[In the formula, R ^3's independently of each other have 1 to 1 carbon atoms.
A hydrocarbon group which may have 18 heteroatoms, R ⁴
Represents a divalent polyol residue having 1 to 18 carbon atoms and optionally having a hetero atom, and n represents an integer of 1 to 20. n is 2
When the integers are the above, the n R ^{4 s} may be the same or different. ] Or a malonate compound represented by the following formula (3)

[0015]

[Chemical 6]

[In the formula, R ⁵ represents a hydrocarbon group having 1 to 18 carbon atoms and optionally having a hetero atom. ] It is preferable that it is a malonate compound which has at least 1 benzyl ester group represented by these.

The present invention also provides a wood adhesive comprising the above-mentioned one-component moisture-curable urethane resin composition.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The one-part moisture-curable urethane resin composition of the present invention (hereinafter, also simply referred to as "the composition of the present invention") will be described in detail. The composition of the present invention contains 100 parts by mass of a urethane prepolymer having two or more isocyanate groups in one molecule and 0.1 to 30 parts by mass of a malonate compound having a molecular weight of 200 or more.

First, the urethane prepolymer used in the composition of the present invention will be described. The urethane prepolymer used in the composition of the present invention is a reaction product obtained by reacting a polyol compound with an excess of a polyisocyanate compound (that is, an excess of NCO groups with respect to OH groups). 0.5 to 10 mass% of isocyanate groups are contained at the molecular ends.

Specific examples of the polyisocyanate compound which produces such a urethane prepolymer include:
2,4-Tolylene diisocyanate (2,4-TD
I), 2,6-tolylene diisocyanate (2,6-T
DI), 4,4'-diphenylmethane diisocyanate (4,4'-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), p-phenylene diisocyanate, polymethylene polyphenylene polyisocyanate, xylylene diisocyanate ( XD
I), tetramethylxylylene diisocyanate (TM)
XDI), 1,5-naphthalene diisocyanate (ND
I), aromatic-containing polyisocyanates such as tolidine diisocyanate (TODI); aliphatic polyisocyanates such as hexamethylene diisocyanate (HDI); isophorone diisocyanate, H ₆ XDI (hydrogenated XDI),
Preferred examples include alicyclic polyisocyanates such as H ₁₂ MDI (hydrogenated MDI); carbodiimide-modified polyisocyanates of the above polyisocyanates, and isocyanurate-modified polyisocyanates thereof. These are used alone or in combination of two or more.

As the polyol used for the urethane prepolymer, for example, polyether polyol, polyester polyol, other polyols, and mixed polyols thereof can be used. Specifically, as the polyether polyol, ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, 1,3-butanediol,
Dihydric alcohols such as 1,4-butanediol, 4,4'-dihydroxyphenylpropane and 4,4'-dihydroxyphenylmethane; glycerin, 1,1,1-trimethylolpropane, 1,2,5-hexanetriol ,
Polyhydric alcohols such as pentaerythritol; Diamines such as ethylenediamine and aromatic diamines; One or more kinds of sugars such as sorbitol, and one kind of alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide. Or a polyol obtained by adding two or more kinds thereof; polyoxytetramethylene oxide and the like can be mentioned.

Polyester polyols are roughly classified into condensation type polyester polyols, lactone type polyols and polycarbonate diols. Specifically, one or more of ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, cyclohexanedimethanol, glycerin, 1,1,1-trimethylolpropane, or other low molecular weight polyols and , Glutaric acid, adipic acid, pimelic acid,
Condensation polymers with suberic acid, sebacic acid, terephthalic acid, isophthalic acid, dimer acid, and one or more kinds of other low-molecular-weight carboxylic acids and oligomer acids; ring-opening polymers such as propionlactone and valerolactone Is mentioned.

Other polyols include acrylic polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, etc., whose main chain is a carbon-carbon bond; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentane. Preferable examples are low molecular weight polyols such as diol and hexanediol.

The mixing ratio of the polyol compound and the polyisocyanate compound at the time of obtaining the urethane isocyanate prepolymer having a terminal isocyanate group from the above-mentioned polyisocyanate compound and the polyol compound is usually such that the polyisocyanate is equivalent to 1 equivalent (OH equivalent) of the polyol compound. Compound 1.2 to 10 equivalents (NCO equivalent), preferably 1.5
~ 5 equivalents. Further, such a urethane prepolymer, like a normal urethane prepolymer, for example,
The above two compounds are mixed in a predetermined quantitative ratio, and 30 to 12
It is synthesized by heating and stirring at 0 ° C, preferably 50 to 100 ° C.

Next, the malonate compound used in the composition of the present invention will be described. The malonate compound used in the composition of the present invention is a compound having a molecular weight of 200 or more. The composition of the present invention has a low volatile molecular weight of 200.
Since the above malonate compounds are used, problems such as sick house syndrome do not occur even when used for architectural purposes. Such a malonate compound may be a polyester compound obtained by polymerizing a malonate unit.

Such malonate compounds include, for example, one or more dihydric to tetrahydric polyols and the following formula (1):

[0027]

[Chemical 7]

[In the formula, R ¹ and R ² each independently represent a hydrocarbon group having 1 to 18 carbon atoms and optionally having a heteroatom. ] The malonate compound (henceforth "malonate compound (1)") obtained by transesterification with 1 or more types of malonate compounds represented by these. The method for producing the malonate compound (1) is
There is no particular limitation. In the above formula (1), examples of the hydrocarbon group having 1 to 18 carbon atoms represented by R ¹ and R ² include a methyl group, an ethyl group, a phenyl group, a propenyl group, and an isopropyl group. , N-butyl group, isobutyl group, bromopropenyl group, stearyl group and benzyl group are mentioned, but methyl group, ethyl group and propyl group are particularly preferable in production. Examples of the malonate compound represented by the above formula (1) include, for example,
Examples thereof include dimethyl malonate, diethyl malonate, diisopropyl malonate, dibutyl malonate and diphenyl malonate. Examples of the divalent polyol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-
Butanediol, 1,4-butanediol, 4,4'-
Examples thereof include dihydroxyphenyl propane and 4,4'-dihydroxyphenyl methane. Examples of the trivalent polyol include glycerin, 1,1,1-trimethylolpropane and 1,2,5-hexanetriol. Examples of the tetravalent polyol include pentaerythritol.

A preferred example of such a malonate compound is represented by the following formula (2)

[0030]

[Chemical 8]

[In the formula, R ^3's independently of each other have 1 to 1 carbon atoms.
A hydrocarbon group which may have 18 heteroatoms, R ⁴
Represents a divalent polyol residue having 1 to 18 carbon atoms and optionally having a hetero atom, and n represents an integer of 1 to 20. n is 2
When the integers are the above, the n R ^{4 s} may be the same or different. ] The malonate compound represented by these (henceforth "malonate compound (2)" is also mentioned.).

In the above formula (2), R ³ has 1 to 10 carbon atoms.
Examples of the hydrocarbon group which may have 18 hetero atoms include, for example, methyl group, ethyl group, phenyl group, propenyl group, isopropyl group, n-butyl group, isobutyl group, bromopropenyl group, stearyl group, benzyl. Examples of the group include a methyl group, an ethyl group and a propyl group, which are particularly preferable in terms of production. The divalent polyol residue of R ⁴ which may have a hetero atom having 1 to 18 carbon atoms is a residue of methylene group, ethylene group, trimethylene group, tetramethylene group, hexamethylene group, diethylene glycol- _{(CH 2) 2 -O- (CH} 2) 2 -, triethylene glycol residues, dipropylene glycol residues, and the like preferably. n is preferably an integer of 1 to 10, and from the viewpoint of the effect on storage stability, 1, 2,
It is more preferably 3, 4 or 5. Among these malonate compounds (2), poly (tetramethylene malonate) in which R ⁴ is a tetramethylene group is particularly preferable.

Further, as a suitable example of the malonate compound used in the composition of the present invention, the following formula (3)

[0034]

[Chemical 9]

[In the formula, R ⁵ represents a hydrocarbon group having 1 to 18 carbon atoms and optionally having a hetero atom. ] A malonate compound having at least one benzyl ester group represented by the following (also referred to as "malonate compound (3)" hereinafter).
Can also be mentioned. In the above formula (3), R ⁵ has 1 carbon atom.
Specific examples of the hydrocarbon group which may have a hetero atom of to 18 include the same groups as those exemplified for R ³ in the above formula (2).

Among these malonate compounds (3), methylbenzyl malonate or ethylbenzyl malonate in which R ⁵ is a methyl group or an ethyl group, and R ⁵
A dibenzyl malonate represented by the following formula (4) in which is a benzyl group is one of the preferred embodiments.

[0037]

[Chemical 10]

The composition of the present invention containing such a malonate compound can be stably stored for a long period of time and has an excellent curing rate after storage. Further, the above malonate compound has low volatility and does not have a problem such as sick house syndrome. Among them, the malonate compound (2) is particularly excellent in that it has low volatility. Further, the malonate compound (3) is excellent in that the storage stability is improved with a small addition amount. Furthermore, the dibenzyl malonate represented by the above formula (4) is extremely useful in that it is easy to synthesize.

The amount of the malonate compound blended is 0.1 to 30 parts by mass, preferably 0.2 to 10 parts by mass, based on 100 parts by mass of the urethane prepolymer. This is because if the malonate compound is less than 0.1 parts by mass, sufficient storage stability may not be ensured, and if it exceeds 30 parts by mass, curing may be poor.

Molecular weight 200 used in the composition of the present invention
The above malonate compound can be synthesized by a conventional method, and the production method is not particularly limited. That is, monohydric alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 4,4'-dihydroxyphenylpropane, 4,4'- A dihydric alcohol such as dihydroxyphenylmethane; a trihydric alcohol such as glycerin, 1,1,1-trimethylolpropane and 1,2,5-hexanetriol; a polyol such as a tetrahydric alcohol such as pentaerythritol; It can be synthesized by transesterification using a malonate compound represented by 1) (for example, diethyl malonate) as a raw material. For example, the malonate compound (2) is 1,4
It is obtained by dealcoholation reaction at 80 to 130 ° C. using a polyol such as butanediol, a malonate compound such as diethyl malonate and an ester exchange catalyst such as tetraisopropoxy titanium. Further, the malonate compound (3) can be obtained by reacting a malonate compound such as diethyl malonate with benzyl alcohol similarly to the malonate compound (2). A branched malonate compound can be obtained by using a trihydric alcohol such as trimethylolpropane or a tetrahydric alcohol such as pentaerythritol. Such a branched malonate compound corresponds to the malonate compound (1).

The composition of the present invention contains, in addition to the essential components of the urethane prepolymer and the malonate compound described above, a curing catalyst, a plasticizer, a filler, a silane coupling agent, an antioxidant as long as the object of the present invention is not impaired. Additives such as agents, pigments and solvents can be contained.

Examples of the curing catalyst include organic metal compounds, amine catalysts and latent curing agents. Examples of the organometallic compound include titanium acetylacetonate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin marker butide, zirconium acetylacetonate and the like. Especially for improving the adhesiveness,
Various titanium compounds described in JP-A-2002-265868, that is, Ti (OR) ₄ (wherein R represents an organic group. The four Rs are each independently an acetylacetone residue and acetoacetic acid. It is preferably a group selected from the group consisting of an ester residue, a glycol residue, an alcohol residue and a carboxylic acid residue.), And / or a condensate thereof is preferably used. . As such an organic titanium compound, for example,
Titanium tetraacetylacetonate is preferable. These organometallic compounds may be used alone or in combination of two or more.

Examples of amine-based catalysts include monoamines such as triethylamine; diamines such as N, N, N ', N'-tetramethylethylenediamine; triamines such as tetramethylguanidine; cyclic amines such as triethylenediamine. Bis (2-dimethylaminoethyl)
Examples thereof include ether amines such as ether. These amine-based catalysts may be used alone or in combination of two or more. The compounding amount of the curing catalyst is preferably 0.001 to 0.1 equivalent in the case of an organometallic compound, and 0.001 to 1 equivalent in the case of an amine catalyst, with respect to 1 equivalent of the isocyanate group of the urethane prepolymer. It is preferably 0.1 equivalent. Examples of the latent curing agent include enamine compounds, ketimine compounds, aldimine compounds, oxazolidine compounds and the like.

Examples of the plasticizer include dioctyl phthalate (DOP), dibutyl phthalate (DBP), dilauryl phthalate (DLP), dibutyl benzyl phthalate (BBP), dioctyl adipate, diisodecyl adipate, trioctyl phosphate, tris (chloroethyl). ) Phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, propylene glycol adipate polyester, butylene glycol adipate polyester, alkyl epoxystearate, epoxidized soybean oil and the like can be mentioned. In addition to this, the molecular weight is 500 to 10,
000 acrylic oligomers such as butyl acrylate. These plasticizers are used alone or in combination of two or more. The blending amount of the plasticizer is preferably 5 to 100 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass of the urethane prepolymer. However, particularly when the one-part moisture-curable urethane resin composition of the present invention is used as an adhesive or the like for interior materials for construction such as flooring floors, etc., a volatile organic substance (VO) is used.
It is preferable not to use C), the endocrine disrupting chemicals, and phthalate plasticizers as the raw materials thereof.

As the filler, for example, fatty acid, fatty acid ester, surface-treated calcium carbonate (precipitated, heavy) containing a higher alcohol-added polyisocyanate described in JP-A-9-263708, etc. Treated heavy calcium carbonate, carbon black, clay, talc, titanium oxide, slaked lime, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin, glass balloon,
Examples thereof include shirasu balloon, vinylidene chloride resin balloon, and acrylonitrile-methacrylic acid ester copolymer balloon. These fillers are used alone or in combination of two or more. The blending amount of the filler is 10 to 100 parts by mass of the urethane prepolymer.
The amount is preferably 200 parts by mass, more preferably 20 to 150 parts by mass.

As the silane coupling agent, for example,
Chloropropyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, γ
-Ureidopropyltriethoxysilane and the like can be mentioned. The compounding amount of the silane coupling agent is preferably 0.3 to 10 parts by mass, and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the urethane prepolymer.

Antioxidants include, for example, butylhydroxytoluene (BHT) and butylhydroxyanisole (BHT).
HA), diphenylamine, phenylenediamine, triphenyl phosphite and the like. Examples of the pigment include inorganic pigments such as titanium dioxide, zinc oxide, ultramarine blue, red iron oxide, lithopone, lead, cadmium, iron, cobalt, aluminum, hydrochloride and sulfate; organic pigments such as azo pigment and copper phthalocyanine pigment. Can be mentioned. Examples of the solvent include aromatic hydrocarbon solvents such as xylene and toluene. These additives may be used alone or in combination of two or more.

The method for producing the composition of the present invention is not particularly limited, and examples thereof include a method of sufficiently kneading the above-mentioned various components until they are uniformly dispersed under reduced pressure or in an inert atmosphere.

Since the composition of the present invention has an excellent balance between storage stability and curability, it can be used as an adhesive for construction, automobiles, etc.
It is preferably used as a sealing material, a coating agent and the like.
In particular, since it does not cause problems such as sick house syndrome, it is preferably used as an adhesive for construction, a sealing material, and a coating agent. Specifically, plywood, MDF (Med
It is used as an adhesive for wood materials such as secondary wood products such as ium Density Fiberboard), floor materials, furniture, and joinery. Further, it is also used as an adhesive for wall covering materials and the like.

[0050]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. (Examples 1 to 4 and Comparative Examples 1 and 2) Each urethane resin composition was produced with the composition shown in Table 1 and subjected to the following tests. (1) Presence or absence of volatile components 50 g of the urethane resin composition was applied to a sheet having a thickness of 2 mm and cured at 23 ° C. and 65% RH for 2 weeks. A part (1 cm ² ) of the sheet was put into a 100 mL vial bottle. It was put and heated at 100 ° C. for 1 hour. The gas in the vial was measured by GC-MS to measure the malonate compound.
The results are shown in Table 1.

(2) Tack-free time (storage stability) In an atmosphere of 23 ° C. and 65% RH, even if the surface of the urethane resin composition was pressed with a finger, the urethane resin composition did not stick to the finger. Time was measured (initial tack free time). Further, after the composition was left at 60 ° C. for 3 days, the tack free time was measured in the same manner as above. The results are shown in Table 1.

(3) Tensile strength T _b and elongation E _{b A} urethane resin composition was cured under an atmosphere of 20 ° C. and 65% RH for 7 days, and an H-shaped test piece was used.
A tensile test was performed according to K6251-1993, and the tensile strength (T _b ) and elongation (E _b ) were measured. The results are shown in Table 1.

[0053]

[Table 1]

As is clear from Table 1, the one-part moisture-curable urethane resin compositions of the present invention (Examples 1 to 4) have no volatile component and thus do not cause sick house syndrome. In addition, a conventional one-component moisture-curable urethane resin composition containing a low-molecular weight malonate compound instead of the specific malonate compound of the one-component moisture-curable urethane resin composition (Examples 1 and 2) of the present invention (comparative Even when compared with Examples 1 and 2), the storage stability is equal to or higher than that, and the curability is also equal.

Examples 5 to 7 and Comparative Example 3 Each urethane resin composition having the composition shown in Table 2 was produced and subjected to the following tests. (1) Presence or absence of volatile component The same method as in Examples 1 to 4 and Comparative Examples 1 and 2 was used. The results are shown in Table 2. (2) Tack free time (storage stability) The tack free time was the same as in Examples 1 to 4 and Comparative Examples 1 and 2. The results are shown in Table 2. (3) Shear adhesive strength A urethane resin composition was applied between a flooring material and a plywood and cured for 7 days in an atmosphere of 20 ° C. and 65% RH, using a test piece obtained according to JIS K6851- 199
A tensile test was performed according to No. 4, and the shear adhesive strength was measured. The results are shown in Table 2. In addition, Table 2 shows Example 2
The shear adhesive strength of Comparative Example 2 is also shown.

[0056]

[Table 2]

As is clear from Table 2, the one-part moisture-curable urethane resin composition of the present invention (Examples 2 and 5)
In 7), there is no volatile component and there is no possibility of causing sick house syndrome. Further, a conventional one-pack moisture-curable urethane resin composition containing a low-molecular-weight malonate compound instead of the specific malonate compound of the one-pack moisture-curable urethane resin composition (Examples 2 and 5) of the present invention (comparative Even when compared with Examples 2 and 3), the storage stability is equal to or higher than that, and the adhesive strength is also equal.

The various components in Tables 1 and 2 are as follows. -Urethane prepolymer 1: 600 g of polypropylene glycol (Excenol 2020, manufactured by Asahi Glass Co., Ltd.), 1500 g of polypropylene triol (Excenol 5030, manufactured by Asahi Glass Co., Ltd.), and 750 g of diphenylmethane diisocyanate (Cosmonate PH, manufactured by Mitsui Chemicals, Inc.) at 50 ° C. according to a conventional method. 1 hour at 80 ° C. for 24 hours, N
A urethane prepolymer 1 having a CO content of 6.6% was obtained.

Urethane prepolymer 2: 400 g of polypropylene glycol (Exenol 2020), 600 of polypropylene triol (Exenol 5030)
g, diphenylmethane diisocyanate (Cosmonate PH) 161 g, and acrylic oligomer (UP10
0, Toagosei Co., Ltd.) 116 g at 70 ° C. for 1 hour, 80 ° C.
And reacted for 24 hours to obtain urethane prepolymer 2 having an NCO content of 1.7%.

Poly (tetramethylene malonate): diethyl malonate and 1,4-butanediol were used in a ratio of 2: 1 (molar ratio), respectively, and condensed by the above-mentioned method,
A compound (poly (tetramethylene malonate)) having a number average molecular weight of about 400 was obtained. -Plasticizer: UP-1000, Toagosei Co., Ltd.-Calcium carbonate 1: Sealets 200, Maruo Calcium Co.-Calcium carbonate 2: Super S, Maruo Calcium Co.-Carbon black: Asahi Thermal FT Class, Asahi Carbon Co.- vinyltrimethoxysilane: A-171, Nippon Unicar Co., Ltd., titanium tetraacetyl acetonate: Orgatix TC-401, by Matsumoto Chemical industry Co., Ltd., amine catalyst: bis (2-dimethylaminoethyl) ether [(CH _{3) 2} NCH ₂ CH ₂ OCH ₂ CH ₂ N (C
H _{3) 2]}

[0061]

INDUSTRIAL APPLICABILITY The one-pack moisture-curable urethane resin composition of the present invention is excellent in storage stability because the specific malonate compound effectively contributes to the stabilization of the urethane prepolymer, and the volatility of the malonate compound is low. So there is no problem with sick house syndrome. Further, the malonate compound used in the present invention has not only an effect as a stabilizer, but also a small increase in tack free time after storage as compared with the case where a low molecular weight malonate compound such as diethyl malonate is added (storage It has excellent stability) and also has the effect of maintaining excellent curability over a long period of time. Therefore,
The composition of the present invention is very suitably used as an adhesive for construction, automobiles, etc., a sealing material, a coating agent and the like.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09J 175/04 C09J 175/04 C09K 3/10 C09K 3/10 D (72) Inventor Hiroyuki Hosoda Hiratsuka, Kanagawa City Oiwake No.2-1 Yokohama Rubber Co., Ltd. Hiratsuka Factory (72) Inventor Hideki Ichihara 344-1 Nase-cho, Totsuka-ku, Yokohama-shi, Kanagawa Taisei Corporation (72) Inventor Keiei Wakayama Yokohama-shi, Kanagawa 34-1, Nase-cho, Totsuka-ku Taisei Construction Co., Ltd. F-term (reference) 4H017 AA04 AB03 AC05 AC17 AD02 AE03 AE05 4J002 CK021 EH096 GH00 GJ01 GJ02 4J034 JA42 MA12 QB12 RA08 4J040 ED052 EF311 HB32 JA12 JB04

Claims (5)

[Claims] 1. A 100 parts by weight of a urethane prepolymer having two or more isocyanate groups in one molecule and a molecular weight of 2
A one-pack moisture-curable urethane resin composition containing 0.1 to 30 parts by mass of 00 or more malonate compound. 2. The malonate compound comprises one or more dihydric to tetrahydric polyols and a compound represented by the following formula (1): [In the formula, R ¹ and R ² each independently have 1 carbon atom;
Represents a hydrocarbon group optionally having 18 to 18 hetero atoms. ] The one-part moisture-curable urethane resin composition according to claim 1, which is a malonate compound obtained by transesterification with one or more malonate compounds represented by the formula [1]. 3. The malonate compound is represented by the following formula (2): [In the formula, R ³ is independently a hydrocarbon group having 1 to 18 carbon atoms and optionally having a hetero atom, and R ⁴ is 1 to 1 carbon atoms.
A divalent polyol residue which may have 18 heteroatoms, n represents an integer of 1 to 20. When n is an integer of 2 or more, n R ^{4 s} may be the same or different. ] The one-component moisture-curable urethane resin composition according to claim 1, which is a malonate compound represented by the formula [1]. 4. The malonate compound is represented by the following formula (3): [In the formula, R ⁵ represents a hydrocarbon group having 1 to 18 carbon atoms and optionally having a hetero atom. ] The one-pack moisture-curable urethane resin composition according to claim 1, which is a malonate compound having at least one benzyl ester group represented by the formula [1]. 5. A wood adhesive comprising the one-part moisture-curable urethane resin composition according to any one of claims 1 to 4.