JP3464972B2 - Curable resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition, and more particularly, to a curable resin composition having good storage stability and excellent internal curability, which is suitable for a sealing material, an adhesive, a coating agent and the like. Resin composition.

[0002]

2. Description of the Related Art A modified silicone resin, which is a polyoxyalkylene polymer having a silicone reactive group at the end, which is also called a modified silicone resin, is a liquid polymer and its cured product is flexible even at a relatively low temperature. Since it retains its properties, it is widely used as a sealing material, an adhesive, a coating, and the like.

The silicone-reactive group at the end of the modified silicone resin has one alkoxy group per silicon atom.
A modified silicone resin having an alkoxysilyl group having one, two or three is typical, and a modified silicone resin having an alkoxysilyl group having two alkoxy groups as a silicone-reactive group is, for example, JP-A-3-725.
No. 27, No. 3-47825 and the like, for example, as a modified silicone resin composed of an alkoxysilyl group having three alkoxy groups, for example, Japanese Patent Publication Nos. 58-10418 and 58-10430, and further International Patent Publications. They are described in WO98 / 47939 and the like.

The modified silicone resin composed of an alkoxysilyl group having two alkoxy groups and the modified silicone resin composed of an alkoxysilyl group having three alkoxy groups have respective merits and demerits, and in order to eliminate these disadvantages, an alkoxy group is required. It has also been attempted to use a modified silicone resin having two alkoxy silyl groups and a modified silicone resin having three alkoxy silyl groups. For example, in the above-mentioned International Patent Publication WO98 / 47939, a modified silicone resin composed of an alkoxysilyl group having three alkoxy groups is mixed with a modified silicone resin composed of an alkoxysilyl group having one or two alkoxy groups. Although it is described that it is possible, the effect of mixing a modified silicone resin composed of an alkoxysilyl group having one or two alkoxy groups is not shown.

On the other hand, it is obtained by polymerizing a polymerizable unsaturated group-containing monomer with a modified silicone resin having an alkoxysilyl group having two alkoxy groups or a modified silicone resin having an alkoxysilyl group having three alkoxy groups. It is also known to blend a polymer, and the above-mentioned International Patent Publication WO98 / 47939 discloses that
It is described that the adhesive strength is improved by blending the polymer with a modified silicone resin composed of an alkoxysilyl group having three alkoxy groups. Further, as a method of blending the polymer with a modified silicone resin having an alkoxysilyl group having three alkoxy groups described in the above specification, a method of polymerizing in a modified silicone resin having an alkoxysilyl group having three alkoxy groups can be used. A method of polymerizing an unsaturated group-containing monomer is mentioned.

Further, according to the invention of the present applicant, (a) a silicone resin whose silicone-reactive group is a trimethoxy group and / or triethoxy group and whose main chain is a polyoxypropylene structure, (b) a silicone-reactive group is methyl A silicone reactive group obtained by polymerizing a silicone resin having a polyoxypropylene structure in the main chain and a (meth) acrylic acid ester containing a polyalkoxysilyl group, which is a dimethoxy group and / or a methyldiethoxy group. A composition (Japanese Patent Laid-Open No. 10-251552) composed of an acrylic resin has been proposed, which has excellent storage stability, fast curing property, and excellent adhesive property in internal curing property. .

However, the modified silicone resins obtained by the above-mentioned proposals and the compositions containing them are as follows:
It cannot be said that the storage stability and the internal curability are sufficient, and there is a demand for an adhesive resin composition having a lower viscosity, good storage stability, and excellent internal curability.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a modified silicone type curable resin composition having good storage stability and excellent internal curability.

[0009]

[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, have found that a polymerizable unsaturated group in a modified silicone resin composed of an alkoxysilyl group having three alkoxy groups. It was found that a composition obtained by combining a polymerization product obtained by polymerizing a contained monomer and a modified silicone resin having an alkoxysilyl group having two alkoxy groups can achieve the object of the present invention. Arrived

That is, according to the present invention, (a) the main chain is polyoxyalkylene, and a hydrolyzable silicon group (a) -Si (OR ¹ ) ₂ (R ² ) (R ¹ is a carbon number 1 to 8 alkyl groups, R ² is an alkyl group having 1 to 8 carbon atoms), and (b) the main chain is polyoxyalkylene, and the main chain of the resin is Decomposable silicon group (b) -Si (OR ¹ ) ₃ (R
¹ is an alkyl group having 1 to 8 carbon atoms. And a polymerization product (D) obtained by polymerizing a polymerizable vinyl group-containing monomer (C) in a silicone resin (B) composed of an alkoxysilyl group represented by The content ratio of the resin (A) and the polymerization product (D) is 30 to 30 for the silicone resin (A).
The curable resin composition is characterized by being 99% by mass and 70 to 1% by mass of the polymerization product (D) (however, in the above (B), the silicone resin (B) and the silicone). When the resin (A) is used in combination, the content of the silicone resin (A) is 50% by mass or less.).

In the curable resin composition of the present invention, the content ratio of the silicone resin (A) is 40 to 97% by mass,
The content ratio of the polymerization product (D) is 60 to 3% by mass. Further, the curable resin composition of the present invention is characterized in that the above-mentioned polymerizable vinyl group-containing monomer (C) is a compound which gives a polymer having a glass transition temperature of 0 to 200 ° C. by its own polymerization. . Further, the curable resin composition of the present invention is characterized in that the compound is one or more compounds selected from acrylonitrile, styrene, glycidyl methacrylate and methyl methacrylate.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The curable resin composition of the present invention comprises
(A) The main chain is polyoxyalkylene, and a hydrolyzable silicon group (a) -Si (OR ¹ ) ₂ (R
² ) A silicone resin (A) having (R ¹ is an alkyl group having 1 to 8 carbon atoms and R ² is an alkyl group having 1 to 8 carbon atoms) and (b) a main chain of polyoxyalkylene. And a hydrolyzable silicon group (b) -S at its molecular end.
Polymerization in silicone resin (B) having i (OR ¹ ) ₃ (R ¹ is an alkyl group having 1 to 8 carbon atoms), or in silicone resin (B) and silicone resin (A) The polymerization product (D) obtained by polymerizing the polymerizable vinyl group-containing monomer (C) is contained as an active ingredient, and the content ratio of the silicone resin (A) and the polymerization product (D) is the silicone resin. It is characterized in that (A) is 30 to 99 mass% and the polymerization product (D) is 70 to 1 mass%.
However, in the above (b), when the silicone resin (B) is used alone, the silicone resin (B) has 5
It may have 0 mol% or less of a hydrolyzable silicon group (a) at the same time. When the silicone resin (B) and the silicone resin (A) are used in combination, the content of the silicone resin (A) is 50. It is not more than mass%.

The additives present in the above-mentioned silicone resin (A)
R of water-decomposable silicon group (a)¹And R ²Carbon number
1-8 alkyl groups include methyl, ethyl, n-
Propyl, isopropyl, n-butyl, isobutyl, s
ec-butyl, tert-butyl, n-hexyl, n-
Examples include octyl and 2-ethyl-hexyl, but
Methyl and ethyl are preferred, and methyl is particularly preferred.
It The two alkyl groups may be the same or different.
Yes. Hydrolyzability present in the silicone resin (B)
R of silicon group (b)¹Alky having 1 to 8 carbon atoms represented by
Group, methyl, ethyl, n-propyl, isoprene
Ropyr, n-butyl, isobutyl, sec-butyl, t
ert-butyl, n-hexyl, n-octyl, 2-eth
Tyl-hexyl and the like, but preferably methyl and
And ethyl, particularly preferably methyl. In addition, three
The alkyl groups may be the same or different.

The silicone-based resin (A) and the silicone-based resin (B) are described in, for example, JP-A-3-47825 and JP-A-3-47825.
-72527, 3-79627, etc. are described. As described below, the silicone resin (A) is preferably produced by using a polyoxyalkylene polymer having a functional group as a raw material and introducing a hydrolyzable silicon group (a) at an end through an organic group. . Further, since the silicone resin (A) can have the hydrolyzable silicon group (b) in an amount of 50% or less of the total of the hydrolyzable silicon group (a) and the hydrolyzable silicon group (b), In this case, it is preferable to introduce the hydrolyzable silicon group (a) and the hydrolyzable silicon group (b) at the terminal via an organic group optionally for production. Furthermore,
As described below, the silicone-based resin (B) is preferably produced by using a polyoxyalkylene polymer having a functional group as a raw material and introducing a hydrolyzable silicon group (b) at an end through an organic group. . Hereinafter, the introduction of the hydrolyzable silicon group (a) or the hydrolyzable silicon group (b) is generically referred to and the hydrolyzable silicon group (a) and / or the hydrolyzable silicon group (b) is introduced. Say.

The raw material polyoxyalkylene polymer is preferably a hydroxyl group-terminated polymer produced by reacting an initiator with a monoepoxide in the presence of a catalyst. As the initiator, a hydroxy compound having one or more hydroxyl groups can be used. Examples of the monoepoxide include ethylene oxide, propylene oxide, butylene oxide and hexylene oxide. Tetrahydrofuran and the like can also be used. 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.

In the present invention, the starting polyoxyalkylene polymer has a number average molecular weight of 500 to 30,000.
It is preferable to use 0, particularly 2,000 to 20,000. In order to make a relatively low molecular weight one produced by using an alkali metal catalyst into a high molecular weight one, it is possible to increase the amount by reacting a polyhalogen compound such as methylene chloride. The polyoxyalkylene polymer produced using the complex metal cyanide complex catalyst is usually of high molecular weight. 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. As the alcohol, for example, those described in JP-A-4-145123 can be used, but tert-butanol is particularly preferable.

The raw material polyoxyalkylene polymer preferably has two or more functional groups, specifically, polyoxyethylene, polyoxypropylene, polyoxybutylene,
Examples thereof include copolymers of polyoxyhexylene, polyoxytetramethylene, and two or more kinds of monoepoxides. The preferred raw material polyoxyalkylene polymer is a polyoxypropylene polyol having 2 to 6 valences, particularly polyoxypropylene diol and polyoxypropylene triol. However, when used in the following methods (I) and (IV), allyl-terminated polyoxyalkylene polymers are used. An olefin-terminated polyoxyalkylene polymer such as oxypropylene polyol can also be used.

The silicone resin (A) and the silicone resin (B) can be produced by introducing the hydrolyzable silicon group (a) and / or the hydrolyzable silicon group (b). Usually, these groups are introduced via an organic group (R ⁰ ). That is, silicone resins (A) and silicone resin (B) has the formula -R ⁰ -Si (OR ¹⁾
₂ (R ² ) or a group represented by the formula —R ⁰ —Si (OR ¹ ) ₃ is preferable. The organic group (R ⁰ ) is a divalent group, and has 1 to 10 carbon atoms such as methylene, ethylene, propylene, tetramethylene and hexamethylene, phenylene, diphenylmethane, diphenylethane, diphenylene and naphthalene. Examples thereof include an arylene group having 6 to 20 carbon atoms.

The method of introducing the hydrolyzable silicon group (a) and / or the hydrolyzable silicon group (b) into the raw material polyoxyalkylene polymer is not particularly limited, but for example, the following (I) to (IV) ) Method.

(I) After introducing an olefin group at the terminal of a polyoxyalkylene polymer having a hydroxyl group, the compound of formula HS
i (OR ¹ ) ₂ (R ² ) and / or the formula HSi (O
A method of reacting a hydrosilyl compound represented by R ¹ ) ₃ (wherein R ¹ and R ² are as defined above). As a method of introducing an olefin group, a compound having an unsaturated group and a functional group is reacted with a terminal hydroxyl group of a polyoxyalkylene polymer having a hydroxyl group, and then bonded by an ether bond, an ester bond, a urethane bond or a carbonate bond. There is a method of making it. A method of introducing an olefin group into the side chain of the raw material polyoxyalkylene polymer by adding an olefin group-containing epoxy compound such as allyl glycidyl ether and copolymerizing the same when polymerizing the alkylene oxide can also be adopted. Further, when the hydrosilyl compound is reacted, a catalyst such as a platinum-based catalyst, a rhodium-based catalyst, a cobalt-based catalyst, a palladium-based catalyst or a nickel-based catalyst can be used. Chloroplatinic acid, platinum metal, platinum chloride,
Platinum based catalysts such as platinum olefin complexes are preferred. The reaction for reacting the hydrosilyl compound is 30 to 150.
It is preferable to carry out at a temperature of 60 ° C., especially 60 to 120 ° C. for several hours.

(II) At the end of the polyoxyalkylene polymer having a hydroxyl group, the formula (R ² ) Si (OR ¹ ) ₂ (R
³ NCO) and / or formula Si (OR ¹ ) ₃ (R ³ NC
A method of reacting an isocyanate silyl compound represented by O) (wherein R ¹ and R ² have the same meanings as described above, and R ³ is a divalent hydrocarbon group having 1 to 17 carbon atoms). A known urethanization catalyst may be used in the above reaction. or,
The above reaction is preferably carried out at a temperature of 20 to 200 ° C., particularly 50 to 150 ° C. for several hours.

(III) Polyoxyalkyl having hydroxyl group
At the end of the polymer,
Isocyanate compound reacts with isocyanate group
After the end, the formula (R²) Si (OR¹)₂(R³W)
And / or the formula Si (OR¹) ₃(R³W)
Method of reacting silicon compound (wherein R¹, R²And R
³Is as defined above, W is hydroxyl group, carboxy group, merca
Activity selected from a puto group and an amino group (primary or secondary)
There is a hydrogen group).

(IV) A method of introducing an olefin group into a terminal of a polyoxyalkylene polymer having a hydroxyl group and then reacting the olefin group with the mercapto group of the silicon compound of the above method (III) wherein W is a mercapto group. Examples of the silicon compound include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane,
Examples include 3-mercaptopropyltriethoxysilane and the like. At the time of the reaction, a polymerization initiator such as a radical generator may be used, and in some cases, the reaction may be performed by radiation or heat without using the polymerization initiator. As the polymerization initiator, a peroxide-based, azo-based or redox-based polymerization initiator, a metal compound catalyst or the like can be used, and a polymerization initiator having a reactive silicon functional group as the peroxide-based or azo-based polymerization initiator. Can also be used. Specifically, 2,2'-azobis (2-isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), benzoyl peroxide, tert-alkylperoxy ester, acetyl peroxide, Diisopropyl peroxycarbonate, 2,2'-azobis (2-methyl-4-trimethoxysilylpentonitrile), 2,2'-azobis (2-
Methyl-4-methyldimethoxysilylpentonitrile)
Etc. Further, the above reaction is preferably carried out at a temperature of 20 to 200 ° C., particularly 50 to 150 ° C. for several hours to several tens hours.

The silicone resin (A) and the silicone resin (B) can be synthesized as described above, but the silicone resin (B) and the silicone resin used in combination with the silicone resin (B) can be synthesized. The system resin (A) includes, among the methods (I) to (IV), in which the hydrolyzable silicon group (a) and / or the hydrolyzable silicon group (b) is introduced.
Particularly, those produced by introducing the hydrolyzable silicon group (a) and / or the hydrolyzable silicon group (b) by the above methods (I) and (IV) are preferable.

The silicone-based resin (A) and the silicone-based resin (B) each have a number average molecular weight of 500 to 3
It is preferable to use one having a molecular weight of 10,000, particularly 2,000 to 20,000. As the silicone resin (A), a commercially available product called a modified silicone resin is preferably used. As the commercially available product, for example, trade name: MS Polymer S203, S303, S manufactured by Kaneka Corporation
810, Cyril SAT030, SAT200, SAX
400, SAX710, Asahi Glass Co., Ltd. product name: Excester S2410, S2420, S3430, etc. can be mentioned.

As the polymerizable vinyl group-containing monomer (C), acrylic acid, methacrylic acid, acrylic acid ester or methacrylic acid ester (hereinafter referred to as (meth)
Write as acrylate. ), Styrene compounds, acrylonitrile, α-methylacrylonitrile, 2,4-dicyanobutene-1, vinylpyrrolidone, vinylcarbazole, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-methacryloyloxyethyl phthalate. , Hexahydrophthalic acid 2-
Methacryloyloxyethyl, acrylamide, methacrylamide, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, vinyl chloride, vinyl acetate, vinyl propionate, butadiene,
Isoprene, chloroprene; olefins other than these,
Examples thereof include unsaturated esters, halogenated olefins and vinyl ethers.

As the (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate,
n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate,
Isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, tetradecyl (meth) acrylate, Hexadecyl (meth) acrylate, octadecyl (meth) acrylate, etc. Alkyl ester of acrylic acid or methacrylic acid whose alkyl group has 1 to 20 carbon atoms; cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate,
Phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate,
Dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl acrylate, tert-butylaminoethyl methacrylate, cyclohexylaminoethyl acrylate, cyclohexylaminoethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, allyl acrylate, allyl Methacrylate, 2-
Hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, 2-hydroxy-3
-Phenoxypropyl acrylate, 2-hydroxy-
3-phenoxypropyl methacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, trade name: M-110 manufactured by Toagosei Co., Ltd.
And M-111, Shell Chemical Company trade name: Veova 9 and Veova 10, trifluoroethyl methacrylate, and the like.

Examples of styrene compounds include styrene, vinyltoluene, divinylbenzene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene and p-methoxystyrene. . These polymerizable vinyl group-containing monomers (C) are not limited to one type, and two or more types can be used, but it is preferable to use two or more types. When two or more are used, at least one of them is preferably a compound which gives a polymer having a glass transition temperature of 0 to 200 ° C. by polymerization of the following monomer (C) itself.

The polymerizable vinyl group-containing monomer (C) is preferably a compound which gives a polymer having a glass transition temperature of 0 to 200 ° C. by polymerization of the monomer (C) itself. Examples of these compounds include methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, n-tetradecyl methacrylate, n-hexadecyl methacrylate,
n-octadecyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, benzyl acrylate, benzyl methacrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, dimethylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, cyclohexylaminoethyl acrylate, Glycidyl methacrylate, tetrahydrofuran acrylate, tetrahydrofuran methacrylate, allyl methacrylate, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, trade name: M-110 and M-111, manufactured by Toagosei Co., Ltd. Product name: Veova And VeoVa 10, trifluoroethyl methacrylate, styrene, alpha-methyl styrene, o
-Methylstyrene, m-methylstyrene, p-methylstyrene, p-ethylstyrene, p-methoxystyrene,
Acrylonitrile, vinylpyrrolidone, vinylcarbazole, 2-methacryloyloxyethyl succinate, 2-methacryloyloxyethyl maleate, 2-phthalic acid
Methacryloyloxyethyl, hexahydrophthalic acid 2
-Methacryloyloxyethyl, vinyl chloride and the like, but among these, one or more compounds selected from acrylonitrile, styrene, glycidyl methacrylate and methyl methacrylate are preferable,
It is particularly preferable to use two kinds of compounds selected from those preferable compounds in combination.

As the polymerizable vinyl group-containing monomer (C), a vinyl group-containing monomer having the hydrolyzable silicon group (a) and / or the hydrolyzable silicon group (b) can also be used. Examples of the vinyl group-containing monomer include vinylmethyldimethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, and tris (2
-Methoxyethoxy) vinylsilane, 3-acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, and the like. 3-Acryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-acryloyloxypropyltrimethoxysilane and 3-methacryloyloxypropyltrimethoxysilane are particularly preferred.
When using these vinyl group-containing monomers, it is preferable to use 0.01 to 10 parts by mass of the vinyl group-containing monomer per 100 parts by mass of the polymerizable vinyl group-containing monomer (C) excluding the vinyl group-containing monomer.

The polymerization product (D), which is an essential component of the composition of the present invention, contains a polymerizable vinyl group in the silicone resin (B) or in the silicone resin (B) and the silicone resin (A). The polymerizable vinyl group-containing monomer (C) can be obtained by polymerizing the monomer (C) by a known method such as radical polymerization, anionic polymerization, cationic polymerization or the like which is usually carried out for the polymerization of these monomers. Either of these can be adopted. 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), product name: VA manufactured by Wako Pure Chemical Industries, Ltd.
-046B, VA-057, VA-061, VA-08
5, VA-086, VA-096, V-601, V-6
5 and VAm-110 and the like, radical polymerization method carried out in the presence of a peroxide polymerization initiator such as benzoyl peroxide, t-alkyl peroxy ester, acetyl peroxide, diisopropyl peroxy carbonate and the like is preferable. At this time, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, thio-β-naphthol, thiophenol, n-butylmercaptan, ethylthioglycolate, isopropylmercaptan, t-butylmercaptan, γ The polymerization can be carried out in the presence of a chain transfer agent such as trimethoxysilylpropyl disulfide. 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. These solvents may be removed by a method such as vacuum distillation after the completion of polymerization, if necessary,
The curable resin composition of the present invention may be prepared by mixing with the silicone resin (A) without removing these solvents.

When the polymerizable vinyl group-containing monomer (C) is polymerized in the silicone resin (B), the silicone resin (B) has a total of 50 with the hydrolyzable silicon group (b) at its molecular end. It may have a hydrolyzable silicon group (a) of not more than% mol. Further, the silicone resin (B) and the polymerizable vinyl group-containing monomer (C) in the silicone resin (A)
When polymerizing, the content of the silicone-based resin (A) must be 50% by mass or less of the total of the silicone-based resin (B). If it exceeds 50% by mass, the effect of the present invention is not sufficiently exhibited.

When the polymerizable vinyl group-containing monomer (C) is polymerized in the silicone resin (B), the proportions of the silicone resin (B) and the polymerizable vinyl group-containing monomer (C) used, and the silicone resin ( Use of the silicone resin (B) and the silicone resin (A) and the polymerizable vinyl group-containing monomer (C) when polymerizing the polymerizable vinyl group-containing monomer (C) in the B) and the silicone resin (A) In each case, the ratio of the polymer of the polymerizable vinyl group-containing monomer (C) in the polymerization product (D) is 3 to 200% by mass,
In particular, it is preferable that the amount is 5 to 100% by mass.
If the proportion of the polymer of the monomer (C) is less than 3% by mass, sufficient rapid curability cannot be obtained, and if it exceeds 200% by mass, the viscosity is high and the internal curability deteriorates, which is not preferable.

The curable resin composition of the present invention contains the silicone resin (A) and the polymerization product (D) as active ingredients, and the content ratio of the silicone resin (A) and the polymerization product (D). Is silicone resin (A) 30-9
It is 9% by mass, preferably 40 to 97% by mass, and the polymerization product (D) is 70 to 1% by mass, preferably 60 to 3% by mass. In the content ratio of the silicone resin (A) and the polymerization product (D), if the silicone resin (A) is less than 30% by mass, the storage stability is poor, and if it exceeds 99% by mass, sufficient rapid curing property is obtained. I will not be able to.

The curable resin composition of the present invention contains the silicone resin (A) and the polymerization product (D) as the active ingredients. In addition to the above active ingredients, a curing catalyst and a filler may be added if necessary. Agents, various additives may be included.

As the above-mentioned curing catalyst which can be contained as necessary, an organic tin compound, a metal complex, a basic compound, an organic phosphorus compound and water (humidity in the air) can be used. Specifically, as the organic tin compound, dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin diacetylacetate, dibutyltin diversate, dibutyltin oxide, dibutyltin oxide and Examples include reaction products with phthalic acid diesters. 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, cobalt naphthenate, bismuth octylate and bismuth versatate, and metal acetylacetonate complexes such as aluminum acetylacetonate complex and vanadium acetylacetonate complex. As the basic compound, γ-
Aminosilanes such as aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, quaternary ammonium salts such as tetramethylammonium chloride and benzalkonium chloride, DABCO (registered trademark) series manufactured by Sankyo Air Products, DABCO B
L 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 phosphorus compound include monomethylphosphoric acid and di-n-
Examples include butyl phosphoric acid and triphenyl phosphate. The mixing ratio of the curing catalyst is 100% of the active ingredient of the curable resin composition.
It is 0.01 to 10 parts by mass per part by mass.

Examples of the filler include fumed silica, calcium carbonate, magnesium carbonate, clay, talc, silica and various balloons.

Examples of various additives include plasticizers, additives, solvents and dehydrating agents. As the plasticizer, phthalic acid esters such as dioctyl phthalate and dibutyl phthalate, and aliphatic carboxylic acid esters such as dioctyl adipate and dibutyl sebacate can be used.

The above-mentioned additives include antiaging agents, thixotropic agents, ultraviolet absorbers, pigments, various tackifiers, silane coupling agents, titanate coupling agents, aluminum coupling agents, bisphenol A type and bisphenol F type. And other epoxy resins. As the silane coupling agent, aminosilane is particularly preferable.

Any solvent may be used as the solvent as long as it has good compatibility with the curable resin composition and the like and has a water content of 500 ppm or less.

Examples of the dehydrating agent include quicklime, orthosilicate, anhydrous sodium sulfate, zeolite, methyl silicate, ethyl silicate, various alkylalkoxysilanes and various vinylalkoxysilanes.

[0042]

EXAMPLES The present invention will be specifically described below with reference to examples. The polymerizable vinyl group-containing monomer, chain transfer agent, silicone resin (A) and silicone resin (B) used in the following synthesis examples, and the silicone resin used when preparing the adhesive resin composition (D), a tin catalyst, and a silane coupling agent are as follows. Other than these, reagents were used.

Polymerizable vinyl group-containing monomer Acrylic ester SL (mixed alkyl methacrylate of C ₁₂ and C ₁₃ , manufactured by Mitsubishi Rayon Co., Ltd.) KBM502 (γ-methacrylyloxypropylmethyldimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) Silicone resin ( A) SAT200 (Molecular end methyldimethoxysilyl type modified silicone resin, manufactured by Kanegafuchi Chemical Industry Co., Ltd.) ES-S2420 (Molecular end methyldimethoxysilyl type modified silicone resin, manufactured by Asahi Glass Co., Ltd.) SAX710 (Molecular end methyldimethoxysilyl type resin) Modified silicone resin, manufactured by Kanegafuchi Chemical Industry Co., Ltd. Silicone resin (B) ES-X3440-ST (modified silicone resin of molecular terminal trimethoxysilyl type, manufactured by Asahi Glass Co., Ltd.) Chain transfer agent KBM802 (γ-mercaptopropylmethyl) Dimethoxysilane, Shin-Etsu Chemical Industry Co., Ltd.) DSPTMS (γ-trimethoxysilylpropyl disulfide, manufactured by Shin-Etsu Chemical Co., Ltd.) Polymerization product (D) ES-GX3406a (vinyl group-containing monomer (mixture of acrylonitrile and styrene) Polymerization terminal trimethoxysilyl type Modified silicone resin, vinyl group-containing monomer polymerized molecule content of about 23% by mass, Asahi Glass Co., Ltd. calcium carbonate NS2300 (surface untreated calcium carbonate, manufactured by Nitto Koka Kogyo Co., Ltd.) White Gloss Flower CC-R (surface treated calcium carbonate, Shiroishi Industry) Silane coupling agent KBM903 (γ-aminopropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) KBM403 (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.) Shin-Etsu Chemical Co., Ltd.) KBM603 (N beta (aminoethyl)-.gamma.-aminopropyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd.) Epoxy resin Epikote E828 (bisphenol A type epoxy resin, produced by Yuka Shell Epoxy Co., Ltd.) Catalyst No. 918 (Tin catalyst: reaction product of dibutyltin oxide and dioctyl phthalate, manufactured by Sansha Kisei Co., Ltd.) Ancamine K54 (tertiary amine catalyst, manufactured by Air Products Co., Ltd.)

(Synthesis Example 1) International Patent Publication WO98 /
According to Example 1 of the specification of No. 47939, a silicone resin (B) having a trimethoxy group at the molecular end was obtained. That is, propylene oxide was reacted with glycerin as an initiator in the presence of a zinc hexacyanocobaltate-glyme complex catalyst. Obtained number average molecular weight 17,000
A methanol solution of sodium methoxide was added to polypropylene oxide of 0, Mw / Mn1.3, and methanol was distilled off under reduced pressure with heating to convert the terminal hydroxyl group of polypropylene oxide to sodium methoxide. next,
Allyl chloride was reacted. Unreacted allyl chloride was removed and purified to obtain an allyl group-terminated polypropylene oxide (this is referred to as polymer U-1). The polymer U-1 was reacted with trimethoxysilane, which is a hydrosilyl compound, in the presence of a platinum catalyst to obtain a polymer B-1 having a trimethoxysilyl group.

(Synthesis Example 2) A silyl compound, 3-mercaptopropyltrimethoxysilane, was added to the polymer U-1 obtained in the same manner as in Synthesis Example 1 by using 2,3 as a polymerization initiator.
With 2'-azobis-2-methylbutyronitrile,
A polymer B-2 having a trimethoxysilyl group was obtained.

(Synthesis Example 3) A polymer U-1 obtained in the same manner as in Synthesis Example 1 was treated with a mixture of a hydrosilyl compound, methyldimethoxysilane and trimethoxysilane (molar ratio = 3/7), as a platinum catalyst. To give a polymer B-3 having both a methyldimethoxysilyl group and a trimethoxysilyl group in one molecule.

(Synthesis Example 4) 50 g of ES-X3440-ST was placed in a 300 ml four-necked flask. 100
While maintaining at ℃, ES-X3440-S-T 20g, glycidyl methacrylate 15g, acrylonitrile 15
A mixture of g, 0.6 g of azobisisobutyronitrile and 0.5 g of lauryl mercaptan was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring was continued for 30 minutes at the same temperature to complete the reaction, the mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers to obtain a polymer D-1.
Got

(Synthesis Example 5) 100 g of B-1 obtained in Synthesis Example 1 was placed in a 300 ml four-necked flask. 100 ° C
While maintaining the above condition, a mixture of 50 g of methyl methacrylate, 30 g of acrylic ester SL, 1 g of butyl acereiro, 0.6 g of azobisisobutyronitrile and 1 g of lauryl mercaptan was added dropwise under nitrogen atmosphere over 2 hours while stirring. After stirring was continued at the same temperature for 30 minutes to terminate the reaction, the reaction mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers to obtain a polymer D-2.

(Synthesis Example 6) In a 300 ml four-necked flask, 50 g of B-2 obtained in Synthesis Example 2 was placed. 20g of B-2, acrylonitrile 30 while keeping at 100 ° C
A mixture of g, 0.6 g of azobisisobutyronitrile and 0.5 g of lauryl mercaptan was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring the mixture at the same temperature for 30 minutes to complete the reaction, the mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers to obtain a polymer D-3.
Got

(Synthesis Example 7) 50 g of B-3 obtained in Synthesis Example 3 was placed in a 300 ml four-necked flask. While keeping at 100 ° C., 20 g of B-3, styrene 15 g, acrylonitrile 15 g, azobisisobutyronitrile 0.6
and 0.5 g of lauryl mercaptan were added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring was continued for 30 minutes at the same temperature to complete the reaction, 13.P
a, 110 degreeC was heated for 2 hours, the unreacted monomer was removed, and the polymer D-4 was obtained.

(Synthesis Example 8) 100 g of ES-X3440-ST was placed in a 300 ml four-necked flask. 10
While maintaining the temperature at 0 ° C., a mixture of butyl acrylate 50 g, azobisisobutyronitrile 0.6 g and lauryl mercaptan 0.5 g was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring was continued at the same temperature for 30 minutes to complete the reaction, the reaction mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers to obtain a polymer D-5.

(Synthesis Example 9) 60 g of B-2 obtained in Synthesis Example 2 and 40 g of SAX7 were placed in a 300 ml four-necked flask.
I put 10. While maintaining at 100 ℃, styrene 15
g, 15 g of acrylonitrile, 0.6 g of azobisisobutyronitrile, and 0.5 g of lauryl mercaptan were added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring was continued at the same temperature for 30 minutes to complete the reaction, the reaction mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers to obtain a polymer AB-1.

(Synthesis Example 10) 100 g of B-1 obtained in Synthesis Example 1 was placed in a 300 ml four-necked flask. 100
While maintaining at ℃, 50 g of methyl methacrylate, 12.5 g of acrylic ester SL, 1 g of KBM-802,
2 g of a mixture of 1.5 g of KBM-502 and 0.6 g of azobisisobutyronitrile under a nitrogen atmosphere with stirring 2
It dripped over time. After stirring was continued for 30 minutes at the same temperature to terminate the reaction, the mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers, and thus polymer D-6 was obtained.

(Synthesis Example 11) 100 g of B-1 obtained in Synthesis Example 1 was placed in a 300 ml four-necked flask. 100
While maintaining the temperature at ℃, a mixture of 40 g of methyl methacrylate, 22.5 g of stearyl methacrylate, 2 g of DSPTM and 0.5 g of lauryl mercaptan under a nitrogen atmosphere.
The mixture was added dropwise with stirring for 2 hours. After stirring was continued for 30 minutes at the same temperature to terminate the reaction, 13.3 Pa, 11
It heated at 0 degreeC for 2 hours, the unreacted monomer was removed, and the polymer D-7 was obtained.

(Synthesis Example 12) 100 g of SAT200 was placed in a 300 ml four-necked flask. While maintaining at 100 ° C, 25 g of styrene, 15 g of acrylonitrile,
A mixture of 0.6 g of azobisisobutyronitrile and 0.5 g of lauryl mercaptan was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring was continued at the same temperature for 30 minutes to complete the reaction, the reaction mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers to obtain a polymer E-1.

(Synthesis Example 13) 100 g of toluene was placed in a 300 ml four-necked flask. While maintaining the temperature at 100 ° C., a mixture of 45 g of styrene, 45 g of acrylonitrile, 1.8 g of azobisisobutyronitrile, and 1.5 g of lauryl mercaptan was added dropwise over 2 hours with stirring under a nitrogen atmosphere. The reaction was terminated by continuing stirring at the same temperature for 30 minutes to obtain a toluene solution containing the polymer CP-1.

(Synthesis Example 14) In a 300 ml four-necked flask, 85 g of SAT200 and 15 g of ES-X344 were used.
0-ST was added. While maintaining the temperature at 100 ° C., a mixture of 15 g of styrene, 15 g of acrylonitrile, 0.6 g of azobisisobutyronitrile and 0.5 g of lauryl mercaptan was added dropwise over 2 hours with stirring under a nitrogen atmosphere. After stirring was continued for 30 minutes at the same temperature to terminate the reaction, the mixture was heated at 13.3 Pa and 110 ° C. for 2 hours to remove unreacted monomers, and thus a polymer AB-2 was obtained.

(Synthesis Example 15) 85 g of ES-S2420 and 15 g of ES-X3 were placed in a 300 ml four-necked flask.
A toluene solution containing 440-ST and 61.1 g of the polymer CP-1 obtained in Synthesis Example 13 was added. After stirring,
It heated at 110 degreeC and 13.3 Pa for 2 hours, the unreacted monomer was removed and the polymer ABC-1 was obtained.

Examples 1 to 9 Commercially available polymerization products (D)
Alternatively, the polymerization products (D) obtained in the above Synthesis Examples 4 to 11,
Silicone resin (A), calcium carbonate, a silane coupling agent, and a tin catalyst were mixed in the proportions (mass proportions) shown in Table 1, and a 1-component moisture-curable adhesive composition was prepared using a planetary mixer.

(Comparative Examples 1 to 6) Commercially available silicone resin (D), the above Synthetic Examples 1, 2, 12, 13, 14 or 15
The polymer, the silicone resin (A), the calcium carbonate, the silane coupling agent, and the tin catalyst obtained in step 1 were mixed in the proportions (mass proportions) shown in Table 2, and a 1-component moisture-curable adhesive was applied using a planetary mixer. An agent composition was prepared.

With respect to the one-pack moisture-curable adhesive compositions obtained in Examples 1 to 9 and Comparative Examples 1 to 6, their viscosity, storage stability, thickening rate, initial adhesive strength and internal curability were evaluated. The results were shown in Tables 3 and 4 in the following manner.
In Table 4, the mark *) indicates that the sample is uncured and cannot be measured.

(1) Viscosity (initial viscosity) Measured in an atmosphere of 23 ° C. and 50% RH. ◯: less than 100 Pa · s, Δ: 100 to 200 Pa · s
Less than, x: 200 Pa · s or more (2) Storage stability (viscosity after storage) Each composition was placed in a mayonnaise bottle containing 100 g, purged with nitrogen gas, and then completely sealed. After storing in an incubator at 50 ° C. for 30 days, the temperature was returned to 23 ° C., the package was opened, and the viscosity was immediately measured in an atmosphere of 23 ° C. and 50% RH. (3) Viscosity increase Viscosity after storage / initial viscosity O: less than 1.5 times, Δ: less than 1.5 to 2.0 times, x:
2.0 times or more (4) Initial adhesive strength 23 ° C., in an atmosphere of 50% RH, each composition described above is applied to the surface of one of the two asada materials (application area:
(25 mm × 25 mm), and immediately fixed to the other Asada material with a bonding clip. 15 minutes after bonding,
Tensile-shear adhesive strength is measured by Shimadzu Autograph (AGS-
It was measured using a G type) (pulling speed: 5 mm / min). ◯: 0.5 N / mm ² or more, Δ: 0.1 to 0.5 N / m
m ^{2 or} less, x: less than 0.1 N / mm ² (5) Internal curability Under an atmosphere of 23 ° C. and 50% RH, a polypropylene pudding cup of 50 cc was piled up with each of the above-mentioned compositions, and the surface thereof was putty with a putty knife. The test piece was scraped so as to be horizontal. After allowing these test pieces to stand for 3 days, the hardened part of the surface layer was peeled off, and the uncured adhered part was well wiped from this hardened part, and its thickness was measured at 5 points with a caliper. The average value was used as a measure of internal curability. ◯: 5.0 mm or more, Δ: 2.5 to less than 5.0 mm,
X: less than 2.5 mm

[0063]

[Table 1]

[Table 2]

[Table 3]

[Table 4]

As is clear from the results of Tables 3 and 4,
The adhesive compositions obtained in Examples 1 to 9 in which the silicone resin (A) and the polymerization product (D) were combined were low in viscosity, excellent in storage stability, and excellent in initial adhesive strength and internal curability. ing. In particular, the adhesive compositions obtained in Examples 1, 2 and 9 showed high performance. On the other hand, as is clear from the results of Comparative Examples 1 and 6,
With the combination of the silicone resin (A) and the silicone resin (B), the initial adhesive strength was weak, and the storage stability deteriorated when the proportion of the silicone resin (B) was increased to accelerate the curing rate. Further, as is clear from the results of Comparative Examples 2 to 5, in the combinations other than the constitution of the present invention, the obtained adhesive compositions had high viscosity, poor internal curability, and poor initial adhesive strength. .

(Examples 10 to 19) Commercially available polymerization products (D) or the polymerization products (D) obtained in the above Synthesis Examples 4 to 11, silicone resin (A), calcium carbonate, silane coupling agent. And an amine catalyst in the proportions (mass proportions) shown in Table 5 and mixed in a planetary mixer for the two-component moisture-curable adhesive agent A, the tin catalyst, the epoxy resin, and the calcium carbonate in the proportions shown in Table 5. (Mass ratio)
Was mixed with a planetary mixer to prepare a B agent for a two-component moisture-curable adhesive.

Comparative Examples 7 to 14 Commercially available silicone resin (D), the above Synthesis Examples 1, 2, 12, 13, 14 or 1
Table 6 shows the polymer, silicone resin (A), calcium carbonate, silane coupling agent and amine catalyst obtained in Example 5.
In the proportion (mass proportion) shown in Table 6, the agent A for the two-component moisture-curable adhesive, which was blended in the proportion (mass proportion) shown in Table 1, and the tin catalyst, the epoxy resin, and the calcium carbonate, were blended. Then, a B component for a two-component moisture-curable adhesive mixed with a planetary mixer was prepared.

Viscosity, storage stability and thickening rate of agents A and B obtained in Examples 10 to 19 and Comparative Examples 7 to 14, and initial adhesive strength of adhesives containing agents A and B. Were examined in the following manner, and the results are shown in Tables 7 and 8. In Table 8, the mark *) indicates that the sample is uncured and cannot be measured.

(1) Viscosity (initial viscosity) Measured in an atmosphere of 23 ° C. and 50% RH. ◯: less than 400 Pa · s, Δ: 400 to 500 Pa · s
Less than, x: 500 Pa · s or more (2) Storage stability (viscosity after storage) Each composition was put in a mayonnaise bottle containing 100 g, purged with nitrogen gas, and then completely sealed. After storing in an incubator at 50 ° C. for 30 days, the temperature was returned to 23 ° C., the package was opened, and the viscosity was immediately measured in an atmosphere of 23 ° C. and 50% RH. (3) Viscosity increase Viscosity after storage / initial viscosity O: less than 1.5 times, Δ: less than 1.5 to 2.0 times, x:
2.0 times or more (4) Initial adhesive strength 23 ° C., 50% RH, in an atmosphere of 50% RH, the above respective agents A and B were mixed at the compounding ratios shown in Tables 5 and 6, and then two pieces of Asada material Applied to the surface of one Asada material (application area: 25 m
m × 25 mm) and immediately fixed to the other Asada material with a bonding clip. 15 minutes after lamination, the tensile shear adhesive strength is determined by Shimadzu's autograph (AGS-G type)
Was used (tensile speed: 5 mm / min). ◯: 0.5 N / mm ² or more, Δ: 0.1 to 0.5 N / m
less than m ² , x: less than 0.1 N / mm ^2.

[0069]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

As is clear from the results shown in Tables 7 and 8,
The adhesive compositions obtained in Examples 10 to 19 in which the agent A is combined with the silicone resin (A) and the polymerization product (D) have low viscosity, excellent storage stability, and excellent initial adhesive strength. . In particular, the adhesive compositions obtained in Examples 11, 13 and 19 exhibited high performance. On the other hand, as is clear from the results of Comparative Example 9 and Comparative Example 14, in the case where the agent A is a combination of the silicone-based resin (A) and the silicone-based resin (B), the initial adhesive strength is weak and the curing rate is high. When the proportion of the silicone-based resin (B) was increased in order to accelerate it, the storage stability deteriorated. Further, as is clear from the results of Comparative Example 7, Comparative Example 8 and Comparative Examples 10 to 13,
In combinations other than the constitution of the present invention, the obtained adhesive composition had high viscosity and poor initial adhesive strength.

[0071]

EFFECTS OF THE INVENTION The curable resin composition of the present invention has a low viscosity, excellent storage stability, and excellent initial adhesive strength and internal curability, and is effective in applications such as sealing materials, adhesives and coatings. Is.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-6-316692 (JP, A) JP-A-10-251552 (JP, A) JP-A-11-116939 (JP, A) JP-A-10- 195151 (JP, A) JP 2001-200230 (JP, A) JP 2001-220568 (JP, A) JP 7-90169 (JP, A) International Publication 98/047939 (WO, A1) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08L 71/02-71/03 C08F 283/06-283/08 C08L 51/08

Claims (4)

(57) [Claims] 1. (a) The main chain is polyoxyalkylene, and a hydrolyzable silicon group (a) -Si is attached to the molecular end thereof.
Silicone resin (A) having (OR ¹ ) ₂ (R ² ) (R ¹ is an alkyl group having 1 to 8 carbon atoms, R ² is an alkyl group having 1 to 8 carbon atoms), and (R ) The main chain is polyoxyalkylene, and a hydrolyzable silicon group (b) -Si (OR ¹ ) ₃ (R
¹ is an alkyl group having 1 to 8 carbon atoms. In a silicone-based resin (B) or having a silicone-based resin (B)
And a polymerization product (D) obtained by polymerizing the polymerizable vinyl group-containing monomer (C) in the silicone resin (A) as an active ingredient, the silicone resin (A) and the polymerization product ( The content of D) is 30 to 99% by mass of the silicone resin (A), and the polymerization product (D).
Is 70 to 1% by mass, a curable resin composition. (However, in the above (b), the silicone resin (B)
And when the silicone resin (A) is used in combination, the content of the silicone resin (A) is 50% by mass or less. ) 2. The content ratio of the silicone resin (A) is 40 to 97 mass%, and the content ratio of the polymerization product (D) is 60 to 3 mass%. Curable resin composition. 3. The polymerizable vinyl group-containing monomer (C)
Is a compound which gives a polymer having a glass transition temperature of 0 to 200 ° C. by its own polymerization, The curable resin composition according to claim 1 or 2, wherein 4. The curable resin composition according to claim 3, wherein the compound is one or more compounds selected from acrylonitrile, styrene, glycidyl methacrylate and methyl methacrylate.