JP2003313421A - Curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyoxyalkylene-type curable resin composition that is excellent in transparency by blending a filler such as a silica fine powder or the like and that has a reactive silicon group imparting good adhesion. <P>SOLUTION: The curable resin composition comprises, as the components, (A) a silylated urethane-based resin the main chain of which is a polyoxyalkylene polymer having a reactive silicon group at the molecular end and having a substituted urea bond in the molecule and (B) a fine powder selected from a silica fine powder and an organic polymer fine powder. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition having excellent transparency and good adhesiveness.

[0002]

2. Description of the Related Art A technique for obtaining a curable resin composition having excellent transparency by blending a filler such as silica fine powder with a polyoxyalkylene type modified silicone resin whose main chain skeleton is polyoxypolypropylene is known. Has been. However, this curable resin composition has the disadvantage of poor adhesion,
Further, if a large amount of filler is added for the purpose of improving the reinforcing effect and the adhesiveness, the viscosity will remarkably increase, which causes difficulty in workability.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a polyoxyalkylene type curable resin composition containing a filler such as silica fine powder, which has excellent transparency and good adhesiveness and which has a reactive silicon group. The purpose is to do.

[0004]

[Means for Solving the Problems] In order to achieve the above object, the inventors of the present invention have conducted extensive studies, and as a result, by adding silica fine powder or organic polymer fine powder to silylated urethane resin It was found that a curable resin composition having excellent properties and transparency can be obtained. Further, by adding an acrylic polymer having a special reactive silicon group, the adhesiveness is further improved, and a curable resin composition having excellent adhesive strength after application time (open time) can be obtained. The present invention was started and the present invention was completed.

That is, according to the present invention, the main chain is a polyoxyalkylene polymer, has a reactive silicon group at its molecular end, and has a substituted urea bond in the molecule, a silylated urethane resin (A) and silica. A gist of a curable resin composition is characterized by containing one or more kinds of fine powder (B) selected from fine powder and organic polymer fine powder as a component.

Further, in the present invention, the main chain is a polyoxyalkylene polymer, has a reactive silicon group at its molecular end, and has a substituted urea bond in the molecule, a silylated urethane resin (A), a polymerized polymer. Vinyl polymer (C) obtained by polymerizing a vinyl group-containing monomer, and one or more fine powders (B) selected from silica fine powder and organic polymer fine powder
A curable resin composition characterized by containing as a component. Further, the curable resin composition of the present invention is characterized in that the vinyl polymer (C) is a polymer obtained by polymerizing a polymerizable vinyl group-containing monomer in the silylated urethane resin (A). To do. Further, the curable resin composition of the present invention, the polymerizable vinyl group-containing monomer has a reactive silicon group in the molecule, a thiourethane bond, a urea bond, a substituted urea bond, a nitrogen atom derived from the Michael addition reaction and The curable resin composition of the present invention, which has one or more selected from sulfur atoms derived from the Michael addition reaction, further comprises a polymerizable vinyl group in the silylated urethane resin (A). It is characterized in that it contains a vinyl polymer (C) obtained by polymerizing a contained monomer as a component.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The urethane resin (A), which is a component of the curable resin composition of the present invention, has a polyoxyalkylene polymer as the main chain and has a reactive silicon group at its molecular end, A silylated urethane resin having a substituted urea bond in the molecule, more specifically, a urethane resin having a group represented by the following general formula (1) and the following general formula (2) in the molecule. is there.

[0008]

[Chemical 1]

[Chemical 2]

However, R ¹ is a group represented by the following general formula (3), the following general formula (4), the following general formula (5) or the following general formula (6), a phenyl group or 1 to 20 carbon atoms. R ² represents a substituted or unsubstituted organic group, R ² represents a substituted or unsubstituted organic group having 1 to 20 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and n represents 0, 1 or 2. when R ² there are a plurality may be different and those R ² the same, X their X may be the same or different when there are multiple.

[0010]

[Chemical 3]

[Chemical 4]

[Chemical 5]

[Chemical 6]

However, R³Is a hydrogen atom or -COOR
¹¹To R^FourIs a hydrogen atom or a methyl group, R^FiveIs -COO
R¹²Or a nitrile group, R⁶Is a substitution of 1 to 20 carbon atoms
Alternatively, an unsubstituted divalent organic group is replaced with R⁷Has a molecular weight of 500
The following organic groups which may contain a silicon atom are represented by R⁸And R⁹
Is the above general formula (3) or the following general formula (7) (where R is⁷
Has the same meaning as above. ) Is a group represented by R^TenIs fe
Nyl group, cyclohexyl group or substituted with 1 to 20 carbon atoms
Or, each represents an unsubstituted monovalent organic group, R ⁸Over
And R⁹May be the same or different. R¹¹And R¹²Is the molecule
An organic group having an amount of 500 or less is shown.

[0012]

[Chemical 7]

Examples of the hydrolyzable group represented by X in the general formula (2) include an alkoxy group, an acetoxy group, an oxime group and the like, and an alkoxy group is particularly preferable. The urethane-based resin (A) has a main chain of a polyoxyalkylene polymer, and has a compound having at least one group selected from a hydroxyl group, a primary amino group and a secondary amino group in its molecule (compound (a )) With a polyisocyanate compound (compound (b)) to produce a urethane prepolymer,
Further, it can be produced by reacting a urethane prepolymer with a compound represented by the following general formula (8) (compound (c)).

The polyoxyalkylene polymer used as a raw material for the compound (a) is preferably a hydroxyl group-terminated polymer produced by reacting an initiator with a monoepoxide or the like in the presence of a catalyst. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used.

As the monoepoxide, ethylene oxide, propylene oxide, butylene oxide, hexylene oxide, tetrahydrofuran or the like can be used. The urethane resin (A) in the present invention is preferably a polyoxyalkylene polymer having a main chain containing at least polyoxyethylene. Therefore, as a monoepoxide, ethylene oxide is an essential component, and propylene oxide and butylene oxide. , Hexylene oxide and tetrahydrofuran are preferably used together. Examples of the catalyst include alkali metal catalysts such as potassium compounds and cesium compounds, complex metal cyanide compound complex catalysts, and metal porphyrin catalysts. The complex metal cyanide compound complex catalyst is preferably a complex containing zinc hexacyanocobaltate as a main component, an ether and / or alcohol complex. As the composition of the ether and / or alcohol complex, the composition essentially described in JP-B-46-27250 can be used. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme) and the like are preferable, and glyme is particularly preferable from the viewpoint of handling during production of the complex. Examples of alcohol include, for example, JP-A-4-14512.
Although those described in Japanese Patent No. 3 can be used, especially t
ert-butanol is preferred.

The above raw material polyoxyalkylene polymer has a number average molecular weight of 500 to 30,000, particularly 2,
It is preferable to use those of 000 to 20,000.

The raw material polyoxyalkylene polymer preferably has two or more functional groups, specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene,
Examples thereof include polyoxyhexylene and polyoxytetramethylene. In particular, polyoxyethylene, or polyoxypropylene containing 1 mass% or more of polyoxyethylene,
Polyoxybutylene, polyoxyhexylene, polyoxytetramethylene and the like are preferable. A preferable raw material polyoxyalkylene polymer is a polyoxyethylene polyol having a valence of 2 to 6, or a mixture of polyoxyethylene polyol and polyoxypropylene polyol. Particularly, the polyoxyethylene polyol is polyoxyethylene diol, and the polyoxypropylene polyol is polyoxypropylene diol and polyoxypropylene triol.

The compound (a) is commercially available, and they can be used in the present invention. Examples of commercially available products include Asahi Denka Kogyo KK, trade names: P-2000, P-30.
00, manufactured by Asahi Glass Co., Ltd., product name: PML-3005, PML
-3010, PML-3012, PML-4002, P
ML-4010, PML-5005, Sumitomo Bayer Eretan Co., Ltd., trade name: Sumiphen 3700, SBU
-Polyol 0319 etc. are mentioned. In addition, polyoxypropylene having a primary amino group at the terminal (for example, manufactured by San Techno Japan, trade name: Jeffamine D-2
30, D-400, D-2000) or a polyoxypropylene having a secondary amino group at the terminal (for example, manufactured by San Techno Japan, trade name: Jeffamine D-230,
D-400, D-2000) and one or two or more selected from α, β-unsaturated carbonyl compounds, maleic acid diesters and acrylonitrile can be used.

Examples of the compound (b) include diisocyanate compounds, polyisocyanate compounds excluding diisocyanate compounds, and the like. As the diisocyanate compound, for example, aliphatic, alicyclic, araliphatic,
Examples thereof include aromatic diisocyanate compounds. Less than,
Specific examples thereof will be given.

Aliphatic diisocyanate compound: trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene Diisocyanate, 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanate methylcaproate and the like. Alicyclic diisocyanate compound: 1,3-cyclopentene diisocyanate, 1,4
-Cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, 3-isocyanate methyl-
3,5,5-trimethylcyclohexyl isocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and the like. Aroaliphatic diisocyanate compound: 1,3- or 1,4-xylylene diisocyanate or a mixture thereof, ω,
ω'-diisocyanate-1,4-diethylbenzene,
1,3- or 1,4-bis (1-isocyanate-
1-methylethyl) benzene or a mixture thereof. Aromatic diisocyanate compound: m-phenylene diisocyanate, p-phenylene diisocyanate, 4,4 ′
-Diphenyl diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-toluidine diisocyanate, 4,
4'-diphenyl ether diisocyanate and the like.

Examples of the polyisocyanate compound excluding the diisocyanate compound include aliphatic, alicyclic, araliphatic and aromatic polyisocyanate compounds. Specific examples thereof will be given below.

Aliphatic polyisocyanate compound: lysine ester triisocyanate, 1,4,8-triisocyanate octane, 1,6,11-triisocyanate undecane, 1,8-diisocyanate-4-isocyanatomethyl octane, 1,3,3. 6-triisocyanate hexane, 2,5,7-trimethyl-1,8-diisocyanate-5-isocyanate methyloctane and the like. Alicyclic polyisocyanate compound: 1,3,5-triisocyanate cyclohexane, 1,3,5-trimethylisocyanate cyclohexane, 3-isocyanate-
3,3,5-Trimethylcyclohexyl isocyanate, 2- (3-isocyanatopropyl) -2,5-di (isocyanatomethyl) -bicyclo [2,2,1] heptane, 2- (3-isocyanatopropyl) -2, 6
-Di (isocyanatomethyl) -bicyclo [2,2,2
1] Heptane, 5- (2-isocyanatoethyl) -2
-Isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 6- (2
-Isocyanatoethyl) -2-isocyanatomethyl-3- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane, 5- (2-isocyanatoethyl) -2-isocyanatomethyl-2- (3-isocyanatopropyl) ) -Bicyclo [2,2,1] heptane, 6- (2-isocyanatoethyl) -2- (3-isocyanatopropyl) -bicyclo [2,2,1] heptane and the like. Aroaliphatic polyisocyanate compound: 1,
3,5-triisocyanate methylbenzene and the like. Aromatic polyisocyanate compound: triphenylmethane-4,
4 ', 4 "-triisocyanate, 1,3,5-triisocyanate benzene, 2,4,6-triisocyanate toluene, 4,4'-diphenylmethane-2,2',
5,5'-tetraisocyanate and the like. Other polyisocyanate compounds: Diisocyanates containing a sulfur atom such as phenyldiisothiocyanate.

The compound (c) is a compound represented by the following general formula (8).

[0024]

[Chemical 8]

However, R ¹ , R ² , X and n have the same meanings as defined above, and Y is a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, represented by the following general formula (9) Alternatively, the following general formula (10) is shown respectively.

[0026]

[Chemical 9]

[Chemical 10]

However, R ³ , R ⁴ , R ⁵ , R ⁶ R and R ⁷
Is as defined above, and R ¹³ and R ^{14 each} have 1 carbon atom.
It shows 10 substituted or unsubstituted divalent organic groups.

Specific examples of the compound (c) include N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane,
N- (n-butyl) -γ-aminopropyltrimethoxysilane, N- (n-butyl) -γ-aminopropylmethyldimethoxysilane, N-ethylaminoisobutyltrimethoxysilane, N-methylaminopropylmethyldimethoxysilane, Examples thereof include N-methylaminopropyltrimethoxysilane and bis (trimethoxysilylpropyl) amine, but they can also be produced by the following method.

(1) R ¹ is represented by the above general formula (3),
Compound in which Y is a divalent organic group Primary amino group and hydrolyzable group-containing silicon group or hydroxyl group-containing silicon group (preferably hydrolyzable group-containing silicon group)
A compound having one each of (compound (d)) and one or more selected from the chemical equivalent to the α, β-unsaturated carbonyl compound (compound (e)), maleic acid diester (compound (f)) and acrylonitrile. Method of reacting two or more kinds (2) R ¹ is a compound represented by the above general formula (3) and Y is a compound represented by the above general formula (9). Primary amino group, secondary amino group and hydrolysis Compound (compound (g)) each having one functional group-containing silicon group or hydroxyl group-containing silicon group (preferably a hydrolyzable group-containing silicon group), and a primary amino group and a secondary compound in the compound (g) Method (3) of reacting an amino group with one or more compounds selected from chemical equivalents of compound (e), compound (f) and acrylonitrile, R ¹ is represented by the above general formula (3), and Y is Formula represented by general formula (10) Object compound (g), the compound (g) the primary amino group and a chemical equivalent of the compound in (e), after reaction of the compound (f) and one or more selected from acrylonitrile,
The chemical equivalent formula R ⁷ with the secondary amino group in the compound (g)
Method (4) in which a monoisocyanate compound (compound (h)) represented by NCO (R ⁷ has the same meaning as above) is reacted, R ¹ is represented by the above general formula (4), and Y is a divalent organic group. A method of reacting a compound (g) which is a compound (g) with a primary amino group in the compound (g) and a chemical equivalent of the compound (h), R ¹ is represented by the above general formula (5), and R ⁸ and R ⁹ in the general formula (5) are represented by the above general formula (3),
A compound compound (g) in which Y is a divalent organic group, and a primary amino group in the compound (g) and 2
Method (6) of reacting one or more selected from chemical equivalents of compound (e), compound (g) and acrylonitrile, R ¹ is represented by the above general formula (5), and general formula (5) Wherein R ⁸ is represented by the above general formula (3), R ⁹ is represented by the above general formula (7), and Y is a divalent organic group, and a compound (g) After reacting the primary amino group with one or more compounds selected from the chemical equivalents of compound (e), compound (f) and acrylonitrile,
Method (7) of reacting a secondary amino group produced by this reaction with a chemical equivalent of the compound (h) R ¹ is represented by the above general formula (6), and Y is a divalent organic group Compound compound ( A method of reacting d) with a primary amino group in compound (d) and a chemical equivalent of a maleimide compound (i).

Examples of the compound (d) include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane and aminophenyltrimethoxysilane. Can be mentioned.

Examples of the compound (e) include (meth) acrylic compounds, vinyl ketone compounds, vinyl aldehyde compounds and other compounds. As the (meth) acrylic compound, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate,
t-butyl (meth) acrylate, pentyl (meth) acrylate, amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth)
Acrylate, 2-ethylhexyl acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (Meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol (meth ) Acrylate, polypropylene glycol (meth) acrylate, methoxyethylene glycol (meth) acrylate, Carboxymethyl ethylene glycol (meth) acrylate, methoxy polyethylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, dicyclopentadienyl
(Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, bornyl (meth) acrylate, isobornyl (meth) acrylate, diacetone (meth) acrylate, iso Butoxymethyl (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformaldehyde, N, N-dimethylacrylamide, t-octylacrylamide, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, 7 -Amino-3,7-dimethyloctyl (meth) acrylate, N, N-dimethyl (meth) acrylamide, N, N'-dimethylaminopropyl (meth) acrylamide, acryloylmo Other such Hollin, Toagosei Chemical Industry Co., Ltd. under the trade name: Aronix M-102, M-1
11, M-114, M-117, trade name manufactured by Nippon Kayaku Co., Ltd .: Kayahard TC110S, R629, R644,
Trade name: Viscoat 3700 manufactured by Osaka Organic Chemical Co., Ltd., and the like.

Further, trimethylolpropane tri (meth) acrylate, pentaerythritol (meth) acrylate, pentaerythritol tetra (meth) acrylate, ethylene glycol di (meth) acrylate,
Tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4
-Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane trioxyethyl (meth) acrylate, tris (2-hydroxyethyl) isocyanurate Tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, epoxy obtained by adding (meth) acrylate to glycidyl ether of bisphenol A (meth). ) A polyfunctional compound such as acrylate and a commercial product of the polyfunctional compound manufactured by Mitsubishi Chemical Co., Ltd .: trade name: UPIMER UV, SA1002, SA2
007, product name of Osaka Organic Chemical Company: Viscote 70
0, product name of Nippon Kayaku Co., Ltd .: Kayahard R604, D
PCA-20, DPCA-30, DPCA-60, DP
CA-120, HX-620, D-310, D-33
0, product name of Toagosei Chemical Industry Co., Ltd .: Aronix M-
210, M-215, M-315, M-325 and the like.

In addition to the above compounds, γ-methacryloxypropyltrimethoxysilane having an alkoxysilyl group, γ-methacryloxypropyltriethoxysilane,
γ-methacryloxymethyldimethoxysilane, γ-methacryloxymethyldiethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxymethyldimethoxysilane and the like can be mentioned.

Examples of vinyl ketone compounds include vinyl acetone, vinyl ethyl ketone, vinyl butyl ketone, and the like.
Examples of vinyl aldehyde compounds include acrolein, methacrolein, and crotonaldehyde, and examples of other compounds include maleic anhydride, itaconic anhydride, itaconic acid, crotonic acid, N-methylol acrylamide, diacetone acrylamide, N- [3- (Dimethylamino) propyl] methacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-
Examples thereof include t-octyl acrylamide and N-isopropyl acrylamide.

In addition to the above compounds, compounds containing a fluorine atom, a sulfur atom or a phosphorus atom therein are also included. Examples of the compound containing a fluorine atom include perfluorooctylethyl (meth) acrylate and trifluoroethyl (meth) acrylate, and examples of the compound containing a phosphorus atom include (meth) acryloxyethylphenyl acid phosphate.

Among the above-mentioned compounds (e), methyl acrylate, ethyl acrylate, propyl acrylate, from the viewpoints of easy reaction and wide commercial availability.
Butyl acrylate, t-butyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate and the like are preferable. Of these, methyl acrylate and ethyl acrylate are particularly preferable for imparting fast curing property, and 2-ethylhexyl acrylate and lauryl acrylate are particularly preferable for imparting flexibility. The compound (e) can be used alone or in combination of two or more.

As the compound (f) (maleic acid diester), dimethyl maleate, diethyl maleate, dibutyl maleate, di2-ethylhexyl maleate,
Examples thereof include dioctyl maleate, and these can be used alone or in combination of two or more. Among these, the ease of reaction,
Dimethyl maleate, diethyl maleate, dibutyl maleate, and di2-ethylhexyl maleate are preferred because they are widely marketed and easily available. The compound (f) may be used alone or in combination of two or more.

As the compound (g), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-
β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) -γ
-Aminopropylmethyldiethoxysilane, N-3-
[Amino (dipropyleneoxy)] aminopropyltrimethoxysilane, (aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl)
Aminopropyltrimethoxysilane, N- (2-aminoethyl) -11-aminoundecyltrimethoxysilane, other special aminosilane manufactured by Shin-Etsu Chemical Co., Ltd.,
Product name: KBM6063, X-12-896, KBM5
76, X-12-565, X-12-580, X-12
-5263, KBM6123, X-12-575, X-
12-562, X-12-5202, X-12-520
4, KBE9703 and the like.

Among the above compounds (g), N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, in view of easiness of reaction, wide commercial availability and availability.
N-β (aminoethyl) -γ-aminopropyltriethoxysilane and N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane are preferable.

Examples of the compound (h) include ethyl isocyanate, n-hexyl isocyanate, n-dodecyl isocyanate, p-toluenesulfonyl isocyanate, n-hexyl isocyanate, benzyl isocyanate, 2-methoxyphenyl isocyanate and the like. Besides, isocyanate silanes such as Shin-Etsu Chemical Co., Ltd. product name: KBM9007 (γ-isocyanatopropyltrimethoxysilane) and the like can be mentioned.

Examples of the compound (i) include N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmaleimide, N-laurelmaleimide, diethylphenylmaleimide, N- (2-chlorophenyl) maleimide and the like.

The method of reacting the compound (a) with the compound (b) to give a urethane prepolymer is the same as the usual method for producing a urethane prepolymer by reacting a polyol compound with a polyisocyanate compound. Just go. The method of reacting the compound (c) with the urethane prepolymer to obtain the silylated urethane resin (A) may be carried out at 50 to 100 ° C. for 30 minutes to 3 hours.

In the curable composition of the present invention, it is preferable that the polymer (B) obtained by polymerizing a polymerizable vinyl monomer is further used as a component because the cured product has good elongation. As the polymerizable vinyl monomer, any compound can be selected from the above compound (e), and the number of them is not limited to one, and 2
More than one species can be used.

In particular, the polymerizable vinyl monomer has a reactive silicon group in the molecule and has a thiourethane bond, a urea bond, a substituted urea bond, a nitrogen atom derived from the Michael addition reaction and a sulfur atom derived from the Michael addition reaction. It is preferable to use a compound having a bond or atom selected from Examples of such a polymerizable vinyl monomer (hereinafter referred to as compound (j)) include, for example, the following compound (j
-1) and compound (j-2) can be mentioned, and each of these compounds can be produced by the following synthetic method. These compound (j-1) and compound (j-2) are
Although they may be used alone, it is preferable to use them by copolymerizing with the compound (e), particularly a (meth) acrylic compound. For example, the compound (j-1) is copolymerized with the (meth) acrylic compound, the compound (j-2) is copolymerized with the (meth) acrylic compound, the compound (j-1) and the compound (j-).
It is preferable to copolymerize 2) with a (meth) acrylic compound.

(1) Compound (j-1) A monoisocyanate compound having a group represented by the following general formula (11) or (12) and an isocyanate group in the molecule, the following general formulas (13) and (14), (15), (1
6) A hydrolyzable silicon group-containing unsaturated compound obtained by reacting the compound represented by (17), (18), (19) or (20).

[0046]

[Chemical 11]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

R ¹⁵ in the general formula (11) is a hydrogen atom or a methyl group, R ¹⁶ in the general formulas (13) to (20) is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, ¹⁷ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms,
An aryl group or an aralkyl group, p is an integer of 1 to 3,
R ¹⁸ is an alkylene group or an arylene group which may have a side chain having 1 to 10 carbon atoms, and R ¹⁹ is a hydrogen atom or a formula —CO
A group represented by OR ²⁰ (R ²⁰ represents an organic group having a molecular weight of 500 or less), R ²¹ represents a hydrogen atom or a methyl group, R ²² represents a phenyl group, a cyclohexyl group or a substituted group having 1 to 20 carbon atoms, or R ²³ is an unsubstituted monovalent organic group having 1 to 2 carbon atoms.
0 alkyl group, aryl group or aralkyl group is represented by R
²⁴ is a hydrogen atom, a phenyl group or a substituted or unsubstituted divalent organic group having 1 to 20 carbon atoms, and R ²⁵ is a molecular weight of 500.
The following substituted or unsubstituted divalent organic groups are shown respectively.

Z is a hydrogen atom, OR ²⁶ , R ²⁶ or NH
₂ , R ²⁶ represents a hydrogen atom, an organic group having a molecular weight of 500 or less, or a group represented by the following general formula (21),

[Chemical 21] (R ¹⁶ , R ¹⁷ and R ¹⁸ are as defined above, and x is 1 to
An integer of 3 is shown. ) V ¹ , W ¹ and V ² are represented by the following general formulas (22), (23),
A group represented by (24) or (25) is shown,
W ² is a general formula (22) when V ² is a general formula (22),
(23), (24) or (26), V ² is represented by the general formula (2
3) in the general formula (22), (23), (24) or (25), when V ² is the general formula (24), the general formula (2
When 2), (23) or (24) and V ² are the general formula (25), they represent a hydrogen atom, respectively.

[0049]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

However, the above general formulas (22), (23),
R ¹⁹ , R ²¹ , R ²² , and R ^{23 in} (24) and (25)
And Z are as defined above.

In the molecule, the above general formula (11) or (12)
Examples of the monoisocyanate compound having a group represented by and an isocyanate group include m-isopropenyl-α, α-dimethylbenzyl isocyanate and 2-methacryloyloxyethyl isocyanate.
A commercial item can be used for these.

The above general formulas (13), (14) and (1
The compounds represented by 5), (16), (17), (18), (19) and (20) will be described.

The compound represented by the general formula (13) is
The compound represented by the following general formula (26) and the following general formula (2
It can be produced by reacting the compound represented by 7). R ¹⁶ and R ¹⁷ in the following general formula (26),
R ¹⁸ and p, and R ¹⁹ and R in the following general formula (27)
²¹ and Z are as defined above. The reaction between the compound represented by the general formula (26) and the compound represented by the general formula (27) is performed at 20 to 100 ° C. for 1 to 200 hours.

[0054]

[Chemical formula 26]

[Chemical 27]

Examples of the compound represented by the general formula (26) include γ-aminopropylmethyldimethoxysilane and γ-aminopropylmethyldimethoxysilane.
Examples thereof include aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and aminophenyltrimethoxysilane.

The compound represented by the general formula (27) includes a compound (e) which is a (meth) acrylic compound, a vinyl ketone compound, a vinyl aldehyde compound and other compounds, and a compound (f) which is a maleic acid diester. Any compound can be selected from the above, and they are not limited to one type, and two or more types can be used.

The compound represented by the above general formula (14) is
It can be produced by reacting the compound represented by the general formula (26) with acrylonitrile. The reaction of both is carried out at 20 to 100 ° C. for 1 to 200 hours.

The compound represented by the above general formula (15) is
The compound represented by the general formula (26) and the following general formula (2
It can be produced by reacting the compound represented by 8). R ²² in the following general formula (28) has the same meaning as described above. The reaction between the two is 1 to 20 to 100 ° C.
It will be held for 200 hours.

As the compound represented by the general formula (28), N-phenylmaleimide, N-cyclohexylmaleimide, hydroxyphenylmonomaleimide, N-laurelmaleimide, diethylphenylmonomaleimide, N
Examples include-(2-chlorophenyl) maleimide.

[0060]

[Chemical 28]

The compound represented by the general formula (16) is
The compound represented by the general formula (26) and a compound represented by the formula R ²³ NCO
It can be produced by reacting a monoisocyanate compound represented by R ²³ in the above formula has the same meaning as described above. The reaction between the two is 1 at 20 to 100 ° C.
~ 200 hours. Examples of the monoisocyanate compound include ethyl isocyanate, n-hexyl isocyanate, n-decyl isocyanate, p-toluenesulfonyl isocyanate, benzyl isocyanate, and isocyanate 2
-Methoxyphenyl and the like.

Examples of the compound represented by the above general formula (17) include γ-aminopropylmethyldimethoxysilane, γ
-Aminopropylmethyldiethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-naphthyl-γ-aminopropyltrimethoxysilane, N- (N-Butyl) -γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropylmethyldimethoxysilane, N-naphthyl-γ
-Aminopropylmethyldimethoxysilane, N- (n-
Butyl) -γ-aminopropylmethyldimethoxysilane, N-ethyl-γ-aminoisobutyltrimethoxysilane, N-methyl-γ-aminopropylmethyldimethoxysilane, N-methyl-γ-aminopropyltrimethoxysilane and the like. .

The compounds represented by the above general formulas (18) and (19) are the compounds represented by the following general formula (29), the compound represented by the above general formula (27), acrylonitrile and the above general formula (28). It can be produced by reacting the compound shown or the above monoisocyanate compound. The reaction is carried out at 20 to 100 ° C. for 1 to 200 hours.

R ¹⁶ , R ¹⁷ , and R ¹⁸ in the general formula (29)
And R ²⁵ have the same meanings as described above, and as the compound,
N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)
-Γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropylethyldiethoxysilane, γ-aminopropyldimethylmethoxysilane,
(Aminoethylaminomethyl) phenethyltrimethoxysilane, N- (6-aminohexyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl)-
11-amino undecyl trimethoxysilane etc. are mentioned. These are not limited to one type, and two or more types can be used.

[0065]

[Chemical 29]

Examples of the compound represented by the general formula (20) include γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane,
Examples include γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

In the molecule, the above general formula (11) or (12)
A monoisocyanate compound having an isocyanate group and an isocyanate group, and the above general formulas (13), (14),
An example of the reaction (formation of a substituted urea bond) with the compound represented by (15), (16), (17), (18), (19) or (20) is shown below.

[0068]

[Chemical 30]

In the molecule, the above general formula (11) or (12)
A monoisocyanate compound having a group and an isocyanate group represented by the following general formulas (13), (14),
The reaction with the compound represented by (15), (16), (17), (18), (19) or (20) is 20 to 50 ° C.
The reaction time is 1 to 200 hours, but there is no problem even if the reaction is performed for more than 200 hours. At this time, a polymerization inhibitor may be present depending on the case.

(2) Compound (j-2) A polyvalent (meth) acrylate compound or polyvalent allyl compound represented by the following general formula (30) and the above general formula (1)
3), (14), (15), (16), (17), (1
8) A compound having a hydrolyzable silicon group-containing unsaturated double bond, which is obtained by reacting the compound represented by the formula (19) or (20).

[0071]

[Chemical 31]

However, A is the following general formula (31) at the molecular end.
A group represented by the following general formula (3
1) a residue of a (meth) acrylic or allyl compound having a group represented by (b), B is —CO— or —CH ₂
-, R ²⁷ is a hydrogen atom or a methyl group when B is -CO-, a hydrogen atom when B is -CH _2- , and R ²⁸ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group or An aralkyl group and m and n each represent an integer of 1 to 3.

[0073]

[Chemical 32]

However, R ²⁷ and R ²⁸ in the following general formula (31) have the same meanings as described above.

The polyvalent (meth) acrylate compound represented by the above general formula (30) includes butanediol, hexanediol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol,
Polypropylene or polymethacrylate of a polyol compound such as tripropylene glycol, glycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, polyethylene glycol, polypropylene glycol, for example, ethylene glycol di (meth) acrylate, triglyceride. Ethylene glycol di (meth) acrylate,
Examples include neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and 1,6-hexanediol di (meth) acrylate. ,
Commercially available as a (meth) acrylic acid adduct of polyglycidyl ether of the above polyol compound, manufactured by Kyoei Chemical Co., Ltd., trade name: epoxy ester 40EM, 70PA, 2
00PA, 80MF, 3002M, 30002A, etc. can also be used.

The polyvalent allyl compounds are the above-mentioned polyvalent (meth) compounds.
A compound in which at least two terminals such as both ends of the acrylate compound are (meth) acryloyl groups, while one terminal is a (meth) acryloyl group and at least the other terminals are allyl groups. Is. Examples of such compounds include compounds in which the (meth) acryloyl group at one terminal of the above-mentioned specific examples of the polyvalent (meth) acrylate compound is an allyl group.

A polyvalent (meth) acrylate compound or polyvalent allyl compound represented by the above general formula (30),
The above general formulas (13), (14), (15), (16),
The reaction with the compound represented by (17), (18), (19) or (20) is carried out at 20 to 100 ° C. for 1 to 200 hours, but there is no problem even if the reaction is carried out for more than 200 hours. . At this time, a polymerization inhibitor may be present depending on the case. An example of reaction formulas of these reactions (Michael addition reaction and generation of nitrogen atom or sulfur atom derived from Michael addition reaction) is shown below.

[0078]

[Chemical 33]

The curable composition of the present invention preferably contains the vinyl polymer (C) as a component, and the vinyl polymer (C) is the compound (e) of the above-mentioned polymerizable vinyl monomer and the above-mentioned compound (e). It can be produced by (co) polymerizing one or more compounds (j). For the (co) polymerization of the polymerizable vinyl monomer, any known method such as radical polymerization, anionic polymerization, cationic polymerization or the like which is usually performed when (co) polymerizing a polymerizable vinyl monomer such as a (meth) acrylate compound is adopted. can do.
In particular, 2,2'-azobisisobutyronitrile, 2,
2'-azobis (2-methylbutyronitrile), 2,
2'-azobis (2,4-dimethylvaleronitrile),
2,2'-azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-methyl-4-methyldimethoxysilylpentonitrile), Wako Pure Chemical Industries, Ltd., trade name: VA-046B, VA-03
7, VA-061, VA-085, VA-086, VA
Azo compounds such as -096, V-65, VAm-110,
Performed in the presence of a peroxide polymerization initiator such as benzoyl peroxide, t-alkyl peroxy ester, acetyl peroxide, diisopropyl peroxy carbonate,
Radical polymerization methods are preferred. At this time, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane,
In the presence of a chain transfer agent such as γ-mercaptopropylmethyldimethoxysilane, thio-β-naphthol, thiophenol, n-butyl mercaptan, ethyl thioglycolate, isopropyl mercaptan, t-butyl mercaptan, γ-trimethoxysilylpropyl disulfide. Polymerization can be carried out. The polymerization reaction is 20 to 200 ° C,
It is particularly preferable to carry out at a temperature of 50 to 150 ° C. for several hours to several tens of hours. Further, the polymerization can be carried out in the presence of a solvent such as xylene, toluene, acetone, methyl ethyl ketone, ethyl acetate, butyl acetate.

The above-mentioned (co) polymerization of the polymerizable vinyl monomer is preferably carried out especially in the silylated urethane resin (A) because the effect of the present invention is further enhanced.

The curable composition of the present invention is characterized by containing, as a component, one or more kinds of fine powder (B) selected from silica fine powder and organic polymer fine powder. The fine powder (B) preferably has a particle size of 10 nm to 300 μm, preferably 100 nm to 100 μm, particularly preferably 1 to 30 μm.

Any fine silica powder may be used as long as it has a particle size as described above, but hydrophobic fine silica powder is particularly preferable. As the hydrophobic silica fine powder, for example,
Fine silica powder such as fumed silica (fumed silica) and silica aerogel, which are often used as thixotropic agents in adhesives and others, are treated with organic silicon compounds such as dimethyldichlorosilane, hexamethyldisilazane, dimethylsiloxane, and trimethoxy. Those treated with octylsilane or the like to be hydrophobic can be used, but fumed silica treated with hexamethyldisilazane and silica airgel treated with dimethylsiloxane and / or hexamethyldisilazane are particularly preferred.

The hydrophobizing treatment is carried out by stirring the fine silica powder and the organosilicon compound at a high temperature at a temperature of about 100 to 400 ° C. In order to uniformly contact the both, it is desirable to carry out in a medium such as an organic solvent. The contact ratio between the fine silica powder and the organosilicon compound is usually 3 to 40 parts by mass of the organosilicon compound per 100 parts by mass of the fine silica powder.

As the organic polymer fine powder, (meth)
It is possible to use a fine powder of homopolymerization of a general-purpose vinyl monomer such as an acrylate compound, vinyl acetate, ethylene, vinyl chloride or the like, or copolymerization with these vinyl monomers and other vinyl monomers. Among the above-mentioned vinyl monomers, it is preferable to use a (co) polymerized (meth) acrylate compound from the viewpoint of transparency. The vinyl (co) polymer fine powder is preferably used in combination with a silyl group-containing polymer, particularly a silyl group-containing (meth) acrylate polymer.

Further, in the present invention, amorphous high-purity fused silica glass fine powder can be used in the same manner as the fine powder (B). As the high-purity fused silica glass fine powder, one having a SiO ₂ content of 99.8% by mass or more and an extremely small amount of alkali metals and other impurities is preferable, and the particle size is 1 to 100 μm
m, especially 2 to 50 μm is preferable.

Amorphous high-purity fused silica glass fine powder is
It may be used as it is, or may be surface-treated with a coupling agent. Examples of the coupling agent include organic titanate compounds, organic aluminum compounds, organic zirconium compounds, and alkoxysilanes.
Examples of the organic titanate compound include tetrapropoxy titanium, tetrabutoxy titanium, tetrakis (2-ethylhexyloxy) titanium, tetrastearyloxy titanium, dipropoxy bis (acetylacetonato) titanium, titanium propoxyoctylene glycolate, titanium stearate, isopropyl. Triisostearoyl titanate, isopropyl tridodecylbenzene sulfonyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl phosphite) titanate, tetraoctyl bis (ditridodecyl phosphite) titanate, tetra (2,2-diallyloxy) Methyl-1-butyl) bis (ditridodecyl) phosphite titanate, bis (dioctyl pyro) Phosphate) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate and the like. Examples of the organoaluminum compound include acetoalkoxyaluminum diisopropylate, and examples of the organozirconium compound include zirconium butyrate, zirconium acetylacetonate, acetylacetone zirconium butyrate, zirconium lactate, zirconium stearate, and the like. Further, as the alkoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, bistris (β-methoxyethoxy) silane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl ) −γ
-Aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (γ, δ- Epoxycyclohexyl) ethyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ
-Methacryloxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, hexamethyldisilazane and the like can be mentioned.

The curable composition of the present invention contains the silylated urethane resin (A), the fine powder (B), and the vinyl polymer (C) as components. Is 1 to 50 parts by mass of the fine powder (B) and 5 to 500 parts by mass of the vinyl polymer (C) per 100 parts by mass of the silylated urethane resin (A). If the fine powder (B) is less than 1 part by mass with respect to 100 parts by mass of the silylated urethane resin (A), the cohesive force of the cured product will be insufficient, and if it exceeds 50 parts by mass, the viscosity will increase and workability will be difficult. Occurs. If the amount of the vinyl polymer (C) is less than 5 parts by mass, the adhesive strength after application for a long time cannot be sufficiently obtained, and if it exceeds 500 parts by mass, the viscosity will increase. When using amorphous high-purity fused silica glass fine powder, the mixing ratio of the glass fine powder is 1 to 300 parts by mass, preferably 5 to 200 parts by mass, per 100 parts by mass of the silylated urethane resin (A). It is a department.

The curable composition of the present invention obtained as described above is suitable for, for example, adhesives, sealants, paints, etc. A curing catalyst, a filler, a plasticizer, various additives, a solvent, a dehydrating agent, etc. may be added and mixed according to the intended performance.
In particular, it is desirable to add a silane coupling agent, a modified silicone resin and a curing catalyst.

The silane coupling agent is preferably a silane coupling agent having an amino group, and the silane coupling agent has a primary or secondary amino group, preferably a primary amino group. A silane compound having an alkoxy group is suitable, and for example, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyl-methyldiethoxysilane, γ-aminopropyl-methyldimethoxysilane, N- Phenyl-γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltriethoxysilane, N-β (aminoethyl)- γ-aminopropylmethyldimethoxysilane, N
-Β (aminoethyl) -γ-aminopropylmethyldiethoxysilane, a special aminosilane manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM6063, X-12-89
6, KBM576, X-12-565, X-12-58
0, X-12-806, X-12-666, X-12-
5263, KBM6123, X-12-577, X-1
2-575, X-12-563B, X-12-562 and the like. The compounding ratio of the silane coupling agent is 0.1 per 100 parts by mass of the silylated urethane resin (A).
It is desirable to be 10 to 10 parts by mass.

The modified silicone resin is an oxyalkylene polymer having a reactive silicon group represented by the following general formula (32) in the molecule.

[0091]

[Chemical 34]

However, X has the same meaning as described above, R ²⁹ is a monovalent hydrocarbon having 1 to 20 carbon atoms or the formula (R ″) ₃ —
SiO- (wherein R "is a monovalent hydrocarbon having 1 to 20 carbon atoms, and three R" may be the same or different) and a is a. 0, 1, 2 or 3,
b is 0, 1 or 2, m is an integer of 1-19. When X and R ²⁹ are two or more, they may be the same or different.

The main chain skeleton of the oxyalkylene polymer is
-CH₂O-, -CH₂CH₂O-, -CH (CH₃)
CH₂O-, -CH (C₂H_Five) CH₂O-, -CH₂
CH ₂CH₂CH₂O-, -C (CH₃)₂CH₂O-
Formed from repeating units consisting of oxyalkylene groups such as
(Co) polymers that can be mentioned, especially --CH (CH
₃) CH₂(Co) weight formed from repeating units of O-
Coalescence is preferred.

Such modified silicone resins are disclosed, for example, in JP-B-45-36319 and JP-B-46-12154.
Known compounds described in JP-A-3-47825, JP-A-3-72527, JP-A-3-79627, and the like,
It is widely commercially available, and it is preferable to use those commercially available products in the present invention. The blending ratio of the modified silicone resin is 100 parts by mass of the silylated urethane resin (A),
It is desirable that the amount is 5 to 500 parts by mass.

As the curing catalyst, organic tin, a metal complex, a base such as amine, an organic phosphoric acid compound and water (moisture in the air) can be used. Specifically, as the organic tin, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, dibutyltin oxide and phthalic acid diester. Reaction product, Nitto Kasei Co., Ltd., trade name: U-70
0, U-700ES, U-303 and the like. As the metal complex, titanate compounds such as tetrabutyl titanate, tetraisopropyl titanate, triethanolamine titanate, lead octylate, lead naphthenate,
Examples thereof include carboxylic acid metal salts such as nickel naphthenate and cobalt naphthenate, aluminum acetylacetonate complexes, metal acetylacetonate complexes such as vanadium acetylacetonate complexes, and the like. As the base, aminosilanes such as γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride, DABCO (registered by Sankyo Air Products Co., Ltd.) Trademark) series, DABCO BL
Series, linear or cyclic tertiary amines containing a plurality of nitrogens such as 1,8-diazabicyclo [5.4.0] undec-7-ene, and quaternary ammonium salts. Examples of the organic phosphoric acid compound include monomethyl phosphoric acid and di-n
-Butyl phosphoric acid, triphenyl phosphate, etc. may be mentioned. The compounding ratio of the curing catalyst is such that the silylated urethane resin (A) 10
It is preferably 0.05 to 10 parts by mass per 0 parts by mass.

Fillers that can be blended as necessary include calcium carbonate, various treated calcium carbonates,
Examples include fumed silica, clay, talc, and various balloons. As the plasticizer, dioctyl phthalate,
Phthalates such as dibutyl phthalate, aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate, and the like can be used. As an additive,
Antiaging agents, ultraviolet absorbers, pigments, various tackifiers, titanate coupling agents, aluminum coupling agents and the like can be mentioned. Any solvent may be used as long as it has good compatibility with the above silicone-based resin and a water content of 500 ppm or less. Examples of the dehydrating agent include quick lime, magnesium oxide, orthosilicate ester, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various vinylalkoxysilanes, various alkylalkoxysilanes, and the like.

[0097]

EXAMPLES The present invention will be described in detail below with reference to examples.

(Synthesis Example 1) 10 parts of ethyl acrylate
16 g of 0.1 g, γ-aminopropylmethyldimethoxysilane (trade name: KBM902, manufactured by Shin-Etsu Chemical Co., Ltd.)
The reaction product 1-A was obtained by reacting at 23 ° C. for 7 days while mixing in a nitrogen atmosphere at a rate of 3.3 g. Similarly, 200.2 g of ethyl acrylate and N-β (aminoethyl)
-Γ-aminopropyltrimethoxysilane (trade name: K
(BM603, manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed at a ratio of 222.4 g under a nitrogen atmosphere and reacted at 23 ° C. for 7 days to obtain a reaction product 1-B. Reactant 1-A and Reactant 1-B
Is an alkoxysilane having a secondary amino group (NH group) generated by the Michael addition reaction and a hydrolyzable group.

(Synthesis Example 2) 10 parts of ethyl acrylate
Reaction mixture 2 was obtained by reacting 0.1 g and allylsilane at a ratio of 57.1 g in a nitrogen atmosphere while reacting at 23 ° C. for 7 days.
Got This reaction product 2 is a polymerizable vinyl compound having an NH group produced by the Michael addition reaction.

(Synthesis Example 3) Polyoxypropylene diol having a number average molecular weight of 4,000 (trade name: Takelac P-
28, Takeda Yakuhin Kogyo Co., Ltd., 1,400 g, number average molecular weight 3,000 polyether polyol (trade name: ADEKA Polyether PR3007, Asahi Denka Kogyo KK, oxypropylene / oxyethylene (mass ratio = 3/7) )) 6
001.g, tolylene diisocyanate (trade name: Sumijour T-80, manufactured by Sumitomo Bayer Urethane Co., Ltd.)
90g at a rate of 6g while stirring and mixing under a nitrogen atmosphere.
And reacted for 3 hours to obtain a synthetic product. Next, 1,000 g of this compound and 132.2 g of the reaction product 1-A were added,
A liquid silylated urethane resin (A) was synthesized by reacting at 90 ° C. for 1 hour while stirring and mixing under a nitrogen atmosphere.

(Synthesis Example 4) The compounds shown in Table 1 were used in the proportions shown in Table 1 (unit: parts by mass; hereinafter the same in Tables 2 to 5), under a nitrogen atmosphere while mixing at 40 ° C. for 7 hours.
The reaction was carried out for a day to obtain reaction products 4-AC. Reactant 4-A
Each of C to C is a polymerizable vinyl group-containing monomer having an isocyanate group and any one of a substituted urea bond, a thiourethane bond and a urethane bond.

[0102]

[Table 1]

(Synthesis Example 5) The compounds shown in Table 2 were used in the proportions shown in Table 2, and mixed at 50 ° C. under a nitrogen atmosphere for 7 hours.
Reactants 5-A and B, which are hydrolyzable silicon group-containing compounds, are reacted for a day (corresponding to the compound (j-2)).
Were reacted for 1 day at 40 ° C. to obtain Reactants 5-C to F (corresponding to the compound (j-1)) which are hydrolyzable silicon group-containing compounds.

The light ester G-201 in Table 2
P, KBM 803 and KBM 903 are as follows. Light ester G-201P: trade name manufactured by Kyoeisha Chemical Co., Ltd.,
2-Hydroxy-3-acryloyloxypropyl methacrylate KBM803: Shin-Etsu Chemical Co., Ltd. trade name, γ-aminopropyltrimethoxysilane KBM903: Shin-Etsu Chemical Co., Ltd. trade name, γ-mercaptopropyltrimethoxysilane

[0105]

[Table 2]

(Synthesis Example 6) The silylated urethane resin (A) synthesized in Synthesis Example 3 (Compound 3 in Tables 2 and 4)
Enter. ) As the reaction solvent, the polymerizable vinyl group-containing monomer shown in Table 3, lauryl mercaptan as the chain transfer agent, and 2,2-azobisisobutyronitrile (AIBN) as the polymerization initiator in the proportions shown in Table 3. And heated to 100 ° C. under a nitrogen atmosphere. At that time, the mixed solution of the polymerizable vinyl group-containing monomer, lauryl mercaptan and AIBN was added dropwise over 5 hours, and the reaction was performed for 2 hours to synthesize the vinyl polymer (C). The modified silicone resin (S-203: trade name manufactured by Kanebuchi Chemical Industry Co., Ltd.) was mixed to obtain Compounds 6-AM. The viscosity of the obtained synthetic products 6-A to 6-M was measured by a BH type rotational viscometer (23
C., 10 rpm) and the values are shown in Table 3.

[0107]

[Table 3]

Examples 1 to 14 Compound 3, Compound 6-
A to M and the fine powder (B) shown in Table 4 or Table 5 were put into a planetary mixer at a mixing ratio shown in Table 4 or Table 5, heated and dehydrated at 100 ° C. under reduced pressure, kneaded, and cooled. The silane coupling agent and curing catalyst shown in 4 are
A curable resin composition was obtained by adding and kneading at the compounding ratio shown in Table 4 or Table 5.

(Comparative Examples 1 to 3) The modified silicone resins shown in Table 5 were used in place of the compounds used in Examples, and Comparative Example 3
In, a curable resin composition was obtained in the same manner as in Example except that a large amount of the fine powder (B) was used.

The fine powder (B), silane coupling agent, curing catalyst and modified silicone resin used in this example and comparative example are as follows. MR-10G: trade name manufactured by Soken Kagaku Co., Ltd., (methacrylic acid ester polymer) powder (average particle size: about 9 μm) Silophobic 200: trade name manufactured by Fuji Silysia Chemical Co., silica aerogel R hydrophobically treated with dimethylsiloxane -812: trade name of Nippon Aerosil Co., Ltd., fumed silica hydrophobically treated with hexamethyldisilazane KBM603: KBM403 mentioned above: trade name of Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane No. 918: Sansha Machinery Synthetic Co., Ltd. product name, reaction product of dibutyltin oxide and phthalic acid diester, Cyryl MA-440: Kanebuchi Chemical Co., Ltd. product name, modified silicone containing an acrylic polymer having a silicon atom-containing functional group. Physical properties of the curable resin compositions obtained in Resin Examples and Comparative Examples were measured in the following manner, and the results are shown in Tables 4 and 5.

Viscosity Same as above. Transparency The obtained curable resin composition was stretched to a thickness of 2 mm on a transparent acrylic resin plate, and it was dried at 23 ° C. and 60% relative humidity for 7 minutes.
After curing for a day, the transparency was visually evaluated. ◎: colorless and transparent ○: colorless and slightly cloudy Adhesive strength Asada material (25 mm × 100 mm) coated surface (25 mm
X 25 mm), 0.2 g of the obtained curable resin composition was evenly applied, and immediately an ABS plate (25 mm x 25 m)
m) are attached (however, for the curable resin compositions obtained in Examples 13 and 14, the curable resin composition is applied to both sides of the Asada material and the ABS plate, and after standing for 30 minutes, Was aged for 7 days at 23 ° C. and a relative humidity of 60% to obtain a tensile shear adhesive strength (N /
cm ² ) was measured according to JIS K 6850.

[0112]

[Table 4]

[0113]

[Table 5]

As is clear from Tables 4 and 5, the curable resin compositions according to the examples have excellent transparency, high adhesive strength and low viscosity even when the amount of fine powder used is small. It turns out that the workability is excellent.

[0115]

The curable resin composition of the present invention has excellent transparency and good adhesiveness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 101/00 C08L 101/00 (72) Inventor Shinichi Sato 5-3-35 Nishihori, Saitama City Saitama Prefecture Konishi Stock Company Urawa Institute F term (reference) 4J002 BB043 BD053 BF023 BG032 BG053 BG072 CK041 DJ016 FD013 FD016 GP00 4J011 HA03 HB02 HB22 NA25 PA95 4J026 AB02 AB44 BA17 BA27 BB01 BB02 BB03 DA02 DA12 DA13 DA06 GA06

Claims (4)

[Claims] 1. A silylated urethane resin (A) having a main chain of a polyoxyalkylene polymer, having a reactive silicon group at the molecular end thereof, and having a substituted urea bond in the molecule, silica fine powder and an organic compound. A curable resin composition comprising, as a component, one or more fine powders (B) selected from polymer fine powders. 2. A siloxy urethane-based resin (A) having a polyoxyalkylene polymer as a main chain, having a reactive silicon group at its molecular end and having a substituted urea bond in the molecule, and containing a polymerizable vinyl group. A curable resin containing, as a component, a vinyl polymer (C) obtained by polymerizing a monomer and one or more kinds of fine powder (B) selected from silica fine powder and organic polymer fine powder. Composition. 3. The vinyl polymer (C) is a polymer obtained by polymerizing a polymerizable vinyl group-containing monomer in the silylated urethane resin (A). Curable resin composition. 4. The polymerizable vinyl group-containing monomer has a reactive silicon group in the molecule, a thiourethane bond, a urea bond,
One or two selected from a substituted urea bond, a nitrogen atom derived from the Michael addition reaction and a sulfur atom derived from the Michael addition reaction
It has 1 or more types, The curable resin composition of Claim 2 or 3 characterized by the above-mentioned.