JP2842552B2 - Thixotropic polyurethane composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a polyurethane resin composition used as a coating material, an adhesive or a sealing material, and more particularly to a thixotropic polyurethane resin composition. [Prior Art] When a polyurethane resin is used as a coating material, an adhesive or a sealing material, it is necessary to impart thixotropic properties to the resin because the resin is applied on a vertical surface or an inclined surface. As a method of imparting thixotropic properties to the polyurethane resin,
Many proposals have already been made. Japanese Patent Publication No. 45-11110 discloses a thixotropic polyurethane resin comprising a combination of colloidal silica and a polyoxyethylene glycol derivative. Modified polyurethane resin, furthermore, JP-B-51-11656, 5
2-1747, 53-5899, JP-A-50-80354, 51-47046, 60
-108479, 60-120750 propose thixotropic polyurethane resin compositions. [Problems to be Solved by the Invention] However, all of these thixotropic polyurethane resins use hydrophilic colloidal silica as the main agent of the thixotropic agent, and their storage stability is not always sufficient. Polyurethane resin and storage stability in closed containers are important properties in such coatings, adhesives or sealants, and their quality determines the commercial value in the market. Relatively higher than normal temperature, e.g. 50
Needless to say, a composition having a high storage stability in a closed container at a temperature of ° C and a small change in workability and the like is preferable. It is known that the use of hydrophobic colloidal silica results in better storage stability compared to hydrophilicity. However, although the use of this type of silica has an effect of increasing the viscosity of the resin composition, thixotropic properties are insufficient. [Means for Solving the Problem] The present inventors have studied compositions to be combined with hydrophobic colloidal silica in order to impart thixotropic properties. As a result, conventional polyoxyethylene derivatives, dimethyl sulfoxide, tetramethyl It has been found that thixotropic cannot be imparted with a conventionally known combination such as a polar solvent such as urea, and as a result of further intensive studies, the addition of an aliphatic or alicyclic polyisocyanate with a monoamine and / or a diamine has been found. Is found to be extremely effective in imparting thixotropic properties,
The present invention has been reached. That is, the present invention provides: (a) a latent active hydrogen compound in which active hydrogen is regenerated by a polyisocyanate and / or isocyanate-terminated prepolymer and moisture; (b) a hydrophobic colloidal silica; Alternatively, an adduct of an alicyclic polyisocyanate and a monoamine and / or diamine (provided that the following general formula, (Where R is C ₃ H ₆ or C ₂ H ₄ NHC ₃ H ₆ , R ′ is CH ₃ , C
_{2 H 5, C m H 2m} + 1 OC 2 H 4 or _{C m H 2m + 1 OC 2} H 4 OC 2 H 4, m and m '
Is an integer of 1 to 4 and may be the same or different, and n is 2
Or 3, n 'represents 1 or 2. The reaction product of the aminosilane compound and polyisocyanate represented by) is excluded. A thixotropic polyurethane resin composition comprising: The first component of the present invention, (a) the polyisocyanate and / or the isocyanate-terminated prepolymer and the latent active hydrogen compound from which active hydrogen is regenerated by moisture, are polyisocyanate and / or polyisocyanate and two per molecule. An isocyanate-terminated pre-polymer obtained by reacting a known compound having at least two active hydrogens with an excess of isocyanate, and a latent active hydrogen compound whose active hydrogen is regenerated by moisture are isocyanate groups and active hydrogen groups in equivalent amounts. It is a compounding component for obtaining a resin obtained by reacting nearby. Examples of the polyisocyanate which is a component of the latent active hydrogen compound (a) of the present invention in which the active hydrogen is regenerated by (a) the polyisocyanate and / or the isocyanate-terminated premolymer and moisture are as follows. 1) Tolylene diisocyanate (including various mixtures of isomers), diphenylmethane diisocyanate (including various mixtures of isomers), 3,3'-dimethyl-4.4'-
Biphenylene diisocyanate, 1,4-phenylene diisocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, 1.4 -Cyclohexyl diisocyanate, 1
Diisocyanates such as -methyl-2,4-diisocyanate-cyclohexane, 2,4,4-trimethyl-1,6-diisocyanate-hexane, 2) 4.4'4'-triphenylmethane triisocyanate, tris (4- Phenyl isocyanate) triisocyanate such as thiophosphate; 3) urethanized modified product, isocyanurated modified product, carbodiimidated modified product, buret modified product, crude triresin diisocyanate, polymethylene polyphenylisocyanate, etc. Multifunctional isocyanate The isocyanate group-terminated prepolymer used in the present invention refers to the above-mentioned various organic polyisocyanate compounds and known polyols, known polyamines and the like having two or more active hydrogens in one molecule. Known A compound in a known manner is obtained by reacting so as to leave free isocyanate groups. That is prepared by reacting for several hours at 100 ° C. and known compounds having an isocyanate and an active hydrogen.
The isocyanate group content is preferably from 0.5 to 10.0% by weight. As used herein, a known compound having two or more active hydrogens in one molecule refers to two or more hydroxyl groups, one or more amino groups, two or more mercapto groups, or two or more hydroxyl groups. A compound having an amino group or a compound having a hydroxyl group and a mercapto group, for example, polyhydric alcohols such as water, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, and sucrose, or aniline , Tolylenediamine, p, p'-diamino-
Aromatic amines such as diphenylmethane, aliphatic amines such as ethylenediamine, ethanolamine and diethanolamine, or alkanolamines and compounds having two or more active hydrogens in one molecule thereof, or propylene oxide or propylene oxide And polyether polyols obtained by addition polymerization of ethylene oxide, polyether polyols obtained by converting hydroxyl groups of the polyether polyols into amino groups, polytetraethylene ether polyols, polycarbonate polyols ,
Polycaprolactone polyols, polyester polyols such as polyethylene adipate, polybutadiene polyols, esters of higher fatty acids such as castor oil, polymer polyols obtained by grafting vinyl monomers to polyether polyols or polyester polyols, one molecule A compound obtained by copolymerizing a known ethylenically unsaturated monomer having one or more active hydrogens therein,
Ethers having a mercapto group. The (a) polyisocyanate and / or isocyanate-terminated prepolymer, which is the first component of the present invention, and the latent active hydrogen compound whose active hydrogen is regenerated by moisture are the aforementioned polyisocyanate and / or the isocyanate-terminated prepolymer. It is a compounding component for converting a latent active hydrogen compound from which active hydrogen is regenerated by moisture into a resin obtained by reacting isocyanate groups and active hydrogen groups in almost equal amounts. The latent active hydrogen compound in which active hydrogen is regenerated by moisture is polyketimine shown in British Patent No. 1064841 or polyenamine shown in Japanese Patent Publication No. 57-16126, and Japanese Patent Application No. 62-11233. Β-amino-β shown
-Lactams and also compounds such as oxazolidine. The production of β-amino-β-lactam is performed by the following method. That is, a secondary amine and an aldehyde are subjected to an azeotropic dehydration reaction using a solvent such as toluene or xylene, and the obtained condensate is dissolved in a solvent to perform an addition reaction with an organic isocyanate compound. The ratio of the polyisocyanate and / or the isocyanate-terminated prepolymer to the active hydrogen compound is determined by the ratio of the number of isocyanate groups to the number of active hydrogen groups or, in the case of latent active hydrogen, the number of active hydrogen generated by hydrolysis. (Equivalent ratio) is preferably 0.7 to 1.3. The first component of the present invention, (a) a polyisocyanate and / or an isocyanate-terminated prepolymer and a latent active hydrogen compound whose active hydrogen is regenerated by moisture, are used for controlling viscosity, resin properties and weather resistance. , A filler, a plasticizer, a solvent, an adhesion-imparting agent, a coloring agent, and a stabilizer can be mixed. Fillers include, for example, calcium carbonate, talc, kaolin, zeolite, diatomaceous earth, vinyl chloride paste resin,
There are glass balloons, vinylidene chloride resin balloons, etc., which are used in the resin in a range of up to 60% by weight. Examples of the plasticizer include dioctyl phthalate, dibutyl phthalate, dilauryl phthalate, butyl benzyl phthalate, dioctyl phthalate, diisodecyl adipate, trioctyl phosphate, and the like. Examples of the solvent include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, heptane and octane, petroleum solvents ranging from gasoline to kerosene fractions, esters such as ethyl acetate and butyl acetate, and acetone. , Methyl ethyl ketone, ketones such as methyl isobutyl ketone,
There are ether esters such as cellosolve acetate and butyl cellosolve acetate, which are used in the resin in a range of up to 50% by weight. A silane coupler or the like is used as an adhesion-imparting agent, a carbon black or titanium white is used as a coloring agent, and a hindered phenol compound, a triazole-based compound or the like is used as a stabilizer. The hydrophobic colloidal silica as the second component of the present invention has a carbon content of 0.5 to 5% by weight and usually has a BET specific surface area of 10%.
It is finely divided silica of 0 to 300 m ² / g. Usually, hydrophilic colloidal silica obtained by a combustion hydrolysis method is reacted with an organosilane such as dimethyldichlorosilane or trimethylchlorosilane to obtain a hydrophobic surface.
AEROSIL R972 (DEGUSSA), WACKER HDK H-2000
(WACKER) is a typical hydrophobic colloidal silica. Adduct of (c) aliphatic or alicyclic polyisocyanate which is the third component of the present invention with monoamine and / or diamine (provided that the following general formula: (Where R is C ₃ H ₆ or C ₂ H ₄ NHC ₃ H ₆ , R ′ is CH ₃ , C
_{2 H 5, C m H 2m} + 1 OC 2 H 4 or _{C m H 2m + 1 OC 2} H 4 OC 2 H 4, m and m '
Is an integer of 1 to 4 and may be the same or different, and n is 2
Or 3, n 'represents 1 or 2. The reaction product of the aminosilane compound represented by and a polyisocyanate is excluded. ) Has a ratio between the number of isocyanate groups and the number of total nitrogen in the monoamine and / or diamine of from 0.8 to 3.0, preferably from 0.95 to 3.0.
It is a compound obtained under normal temperature mixing at 2.05. The aliphatic or alicyclic polyisocyanate which is a component of the third component of the present invention includes xylylene diisocyanate, tetramethyl xylylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, hydrogen Xylylene diisocyanate, 1,4-cyclohexyl diisocyanate, 1-methyl-2,4-diisocyanate-cyclohexane, 2,4,4-trimethyl-1,6-
Diisocyanates such as diisocyanate-hexane; and polyfunctional isocyanates such as urethane-modified, isocyanurate-modified, carbodiimidated-modified and buret-modified modified diisocyanates. Monoamine is another component of the third component of the present invention _{H m N (R 1) 3} -n ( where, n is 1 or 2, R ₁ is an alkyl group, a vinyl group an aryl group such as, an ether group, May contain an ester group or the like.) (However, n and m are 1 or 2 and may be the same or different, and R ₂ and R ₄ may be an alkyl group, an aryl group or the like, and may contain a vinyl group, an ether group, an ester group, or the like. R ₃
Is an alkylene group, an arylene group or the like, and may contain a vinyl group, an ether group, an ester group, or the like. ). Monoamines include, for example, methylamine, dimethylamine, butylamine, dibutylamine, aniline, o-
Methylaniline, o-chloroaniline, N-methylaniline, N-butylaniline and the like can be exemplified, and as the diamine, for example, ethylenediamine, 1.6-hexanediamine, 1.4-butanediamine, polyetheramine having a molecular weight of 200 to 6000, N, N '-Dimethylethylenediamine, N, N'
-Dibutyl butylenediamine, tolylenediamine, 2,
4'-diamino-diphenylmethane and the like can be exemplified. The mixing ratio of the composition of the present invention is as follows: (a) 0.5 parts by weight of the hydrophobic colloidal silica to 100 parts by weight of the polyisocyanate and / or the isocyanate-terminated prepolymer and the latent active hydrogen compound whose active hydrogen is regenerated by moisture. The adduct of the aliphatic or alicyclic polyisocyanate with the monoamine and / or diamine is particularly preferably 0.1 to 50 parts by weight based on 100 parts by weight of the hydrophobic colloidal silica. [Effects of the Invention] In the present invention, hydrophobic colloidal silica, aliphatic or alicyclic polyisocyanate and monoamine and / or
Alternatively, a polyurethane resin composition containing an adduct with a diamine has high storage stability, and a resin having a small change in workability even at a relatively high temperature can be obtained. Examples Examples of the present invention will be described below. In the examples, “parts” indicates “parts by weight”. The following materials were used in the examples. Isocyanate-terminated prepolymer: Prepolymer A Using 598 parts of 2,4-tolylene diisocyanate as a diisocyanate, 2600 parts of polyoxypropylene glycol (molecular weight 2000), 1802 parts of polyoxypropylene triol (molecular weight 3000) and 10 hours at 100 ° C. The reaction was performed to obtain prepolymer A. 1.89% terminal NCO group, viscosity 41,000c
ps / 25 ° C. Prepolymer B Isophorone diisocyanate as diisocyanate
Using 973 parts, 5081 parts of polyoxypropylene glycol (molecular weight 3000), 3946 parts of polyoxypropylene triol (molecular weight 5000), catalyst dibutyltin dilaurate
0.5 part was reacted at 100 ° C. for 3 hours to obtain a prepolymer B.
The terminal NCO group was 1.12%, and the viscosity was 48,000 cps / 25 ° C. Prepolymer C Using 218 parts of p, p'-diphenylmethane diisocyanate as a diisocyanate, 1185 parts of polyoxypropylene glycol (molecular weight 3000), 397 parts of polyoxypropylene triol (molecular weight 4000), and 0.02 part of catalyst dibutyltin dilaurate at 100 ° C. The reaction was allowed to proceed for 5 hours, and then 200 parts of xylene was charged while air cooling to obtain a prepolymer C. The terminal NCO group was 1.31%, and the viscosity was 17,000 cps / 25 ° C. Hydrophobic colloidal silica: WACKER HDK H-20 Latent active hydrogen compound: enamine When producing an enamine (ENA) obtained by condensing a secondary amine with an aldehyde or ketone, a suitable combination for the present invention is: Table 1 shows the results. That is, ENA-1 is obtained by condensing 1 mol of dimer tall oil fatty acid with 2 mol of anhydrous piperazine, and further condensing 1 mol of the obtained secondary diamine with 2 mol of 3,3,5-trimethylcyclohexanone. ENA-2 is piperazine 1
It is an enamine obtained by condensing 2 moles and 2 moles of isobutyraldehyde. β-Amino-β-lactam When producing an β-amino-β-lactam (LAC) by adding an organic isocyanate to a condensate of a secondary amine and an aldehyde, combinations suitable for the present invention are shown in Table-2. It is as follows. That is, LAC-1 is obtained by condensing 2 mol of isobutyraldehyde with 1 mol of 4,4'-dipiperidylpropane,
LAC-2 is a lactam obtained by adding 2 mol of o-tolyl isocyanate. LAC-2 is obtained by condensing 2 mol of isobutyraldehyde with 1 mol of piperazine, and then adding an equimolar reaction product of TDI and isopropyl alcohol. Lactam. Thixotropic properties were evaluated by the slump test specified in 6.2 of JIS-A5758 (1986). Changes in storage stability and workability were evaluated as a one-pack moisture-curable polyurethane resin composition, and after tightly storing for a certain period of time, JIS-K2808 (1961), 2 seconds value and 5 seconds value of penetration [10 ^-1] mm] was measured. The physical properties of the cured urethane resin composition were measured according to JIS-K6301. The curing conditions were as follows: 23 ° C, 50% relative humidity for 7 days,
The condition of leaving for days was adopted. Example 1 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Next, dibutylamine 3.9
Part, polyetheramine Jeffamine D-400
Charge and mix 6 parts. Furthermore, a dioctyl phthalate solution of hexamethylene diisocyanate (NCO weight% = 5.62)
Was added and reacted at room temperature. After stirring for 20 minutes, prepolymer A445 parts, β-amino-β-
98 parts of a 60% cellosolve acetate solution of lactam LAC-1 was charged and kneaded at room temperature for 15 minutes. Further, 85 parts of colloidal silica WACKER HDK H-20 and 175 parts of xylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin of the present invention. As shown in Table 3, the storage stability of this urethane resin composition after sealed storage at 50 ° C. for 14 days was remarkably improved as compared with the composition using hydrophilic silica. Furthermore, as shown in Table 3, the physical properties of the resin cured product were excellent. Example 2 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Next, 15 parts of butylamine are charged. Further, 73 parts of a dioctyl phthalate solution of hydrogenated xylylene diisocyanate (NCO weight% = 12.39) was added and reacted at room temperature. After stirring for 20 minutes, prepolymer B451 parts, enamine ENA-1
77 parts were charged and kneaded at room temperature for 15 minutes. Further, 85 parts of colloidal silica WACKER HDK H-20 and 175 parts of xylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin of the present invention. As shown in Table 3, the storage stability of this urethane resin composition after sealed storage at 50 ° C. for 14 days was remarkably improved as compared with the composition using hydrophilic silica. Furthermore, as shown in Table 3, the physical properties of the resin cured product were excellent. Example 3 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Next, 13.4 parts of butylamine are charged and mixed. Further, 75 parts of a dioctyl phthalate solution (NCO wt% = 6.14) of trimer-modified hexamethylene polyisocyanate (Coronate EH) was added and reacted at room temperature. After stirring for 20 minutes, prepolymer B511 parts, enamine ENA-2
17 parts were charged and kneaded at room temperature for 15 minutes. Further, 85 parts of colloidal silica WACKER HDK H-20 and 175 parts of Kirylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin of the present invention. As shown in Table 3, the storage stability of this urethane resin composition after sealed storage at 50 ° C. for 14 days was remarkably improved as compared with the composition using hydrophilic silica. Furthermore, as shown in Table 3, the physical properties of the resin cured product were excellent. Example 4 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Next, dibutylamine 13.4
Part, Jeffamine D-3000 which is a polyetheramine
Charge and mix 30 parts. Further, a dioctyl phthalate solution of isophorone diisocyanate (NCO weight% = 5.62) was added to 48
Was added and reacted at room temperature. After stirring for 20 minutes, 455 parts of prepolymer A, β-amino-β-
142 parts of a 60% cellosolve acetate solution of lactam LAC-2 was charged and kneaded at room temperature for 15 minutes. Further, 85 parts of colloidal silica WACKER HDK H-20 and 175 parts of xylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin of the present invention. As shown in Table 3, the storage stability of this urethane resin composition after sealed storage at 50 ° C. for 14 days was remarkably improved as compared with the composition using hydrophilic silica. Furthermore, as shown in Table 3, the physical properties of the resin cured product were excellent. Comparative Example 1 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Next, dibutylamine 3.9
Part, polyetheramine Jeffamine D-400
Charge and mix 6 parts. Furthermore, a dioctyl phthalate solution of hexamethylene diisocyanate (NCO weight% = 5.62)
Was added and reacted at room temperature. After stirring for 20 minutes, prepolymer A445 parts, β-amino-β-
98 parts of a 60% cellosolve acetate solution of lactam LAC-1 was charged and kneaded at room temperature for 15 minutes. Further, 85 parts of AEROSIL # 200 hydrophilic colloidal silica and 175 parts of xylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin. As shown in Table 3, this urethane resin composition has a thickness of 50%.
The storage stability after closed storage at 14 ° C for 14 days was markedly poor. Comparative Example 2 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Next, 15 parts of butylamine are charged. Further, 73 parts of a dioctyl phthalate solution of hydrogenated xylylene diisocyanate (NCO weight% = 12.39) was added and reacted at room temperature. After stirring for 20 minutes, prepolymer B451 parts, enamine ENA-1
77 parts were charged and kneaded at room temperature for 15 minutes. Further, 85 parts of AEROSIL # 200 hydrophilic colloidal silica and 175 parts of xylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin. As shown in Table 3, this urethane resin composition has a thickness of 50%.
The storage stability after closed storage at 14 ° C for 14 days was markedly poor. Comparative Example 3 In a 3 liter planetary mixer, 380 parts of dioctyl phthalate, 475 parts of calcium carbonate, 99 parts of titanium oxide,
8 parts of a weathering stabilizer (Irganox 1010) was charged and kneaded at room temperature for 15 minutes, followed by dehydration operation under vacuum at 100 ° C. for 1 hour. Then, aniline 3.5 parts, polyetheramine Jeffamine D-400 7.4 parts,
Charge and mix. Further, a solution of hexamethylene diisocyanate in dioctyl phthalate (NCO wt% = 5.62) was added to 60
Was added and reacted at room temperature. After stirring for 20 minutes, charge the prepolymer C616 parts at room temperature
Kneaded for 15 minutes. AEROSIL hydrophilic colloidal silica
70 parts of # 200 and 175 parts of xylene were charged and kneaded in a vacuum at room temperature for 10 minutes to obtain a one-part curable polyurethane resin. As shown in Table 3, this urethane resin composition has a thickness of 50%.
The storage stability after closed storage at 14 ° C for 14 days was markedly poor. Comparative Example 4 A one-part curable polyurethane resin was obtained in the same manner as in Example 1 except that dibutylamine, jeffamine and hexamethylene diisocyanate were not used. As a result of the slump test, this urethane resin flowed down and did not show thixotropic.

Continuation of the front page (51) Int.Cl. ⁶ Identification code FI C09J 175/00 C09J 175/00 Joint panel Referee Chief Shizuyoshi Referee Masato Ikeda Referee Akiko Ishii (56) References JP-A-60-120750 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08L 75/00-75/16 C08K 3 / 36,5 / 16 C09D 175/00-175/16 C09J 175/00- 175/16

Claims (1)

(57) [Claims] (A) a latent active hydrogen compound whose active hydrogen is regenerated by polyisocyanate and / or isocyanate-terminated prepolymer and moisture; (b) hydrophobic colloidal silica; and (c) aliphatic or alicyclic. Adduct of polyisocyanate with monoamine and / or diamine (provided that the following general formula, (Where R is C ₃ H ₆ or C ₂ H ₄ NHC ₃ H ₆ , R ′ is CH ₃ , C
_{2 H 5, C m H 2m} + 1 OC 2 H 4 or _{C m H 2m + 1 OC 2} H 4 OC 2 H 4, m and m '
Is an integer of 1 to 4 and may be the same or different, and n is 2
Or 3, n 'represents 1 or 2. The reaction product of the aminosilane compound and polyisocyanate represented by) is excluded. A thixotropic polyurethane resin composition comprising: