JPS63243171A - Curable resin composition - Google Patents

Abstract

PURPOSE:To provide the titled composition capable of giving cured products which is outstanding in initial dryability and stain resistance, comprising a specific hydrolyzable silyl group-contg. fluorolefin copolymer, solvent and catalyst for hydrolysis-condensation. CONSTITUTION:The objective composition comprising (A) a fluorolefin copolymer prepared by copolymerization between (i) a fluorolefin, (ii) a hydrolyzable silyl group-contg. vinyl monomer and (iii) a vinyl carboxylic acid of formula (R<1>, R<2> and R<3> are each 1-4C alkyl or chloromethyl, the number of the carbon atoms. in R<1>, R<2> and R<3> totaling 3-6) as the three chief components, and furthermore, if needed, (iv) another vinyl monomer copolymerizable with the components (i), (ii) and (iii), (B) a solvent and (C) a hydrolysis-condensation catalyst for the hydrolyzable silyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel and useful room-temperature curable resin composition, and more particularly, it relates to a specific fluoroolefin copolymer, a curing catalyst and a solvent. The present invention relates to a resin composition which is moisture curable at room temperature and which contains the following as an essential component.

The composition of the present invention having such a structure can be used as a paint for home appliances, or as an exterior paint for buildings, roof tiles or coil coatings such as Grecote and Tometal (PCM), or as an enamel paint for automobiles.

It can be used as various automotive paints such as cream paints or clear paints, as a surface protective film for glass, ceramic, or plastic products, and as a sealing resin composition, but is not particularly limited to these.

[Prior art and problems to be solved by the invention] The present inventors have previously developed a fluoroolefin copolymer containing a hydrolyzable silyl group as shown in Japanese Patent Application No. 60-223479, We have already filed a patent application for a resin composition containing a solvent and a curing catalyst that provides a cured product with excellent weather resistance.

Furthermore, JP-A-61-141713 discloses a fluoroolefin copolymer obtained by copolymerizing a fluoroolefin, a vinyl ether, and an organosilicon compound having an olefinic unsaturated bond and a hydrolyzable group in a specific ratio. A resin composition containing a polymer is disclosed.

However, since the initial drying properties of the coating film obtained from such a composition are poor, foreign matter easily adheres to the coating film, which in turn impairs the appearance, and the stain resistance is insufficient even after long drying. For this reason, there were limits to its use.

[Means for resolving the gap]

However, as a result of intensive research in view of the above points, the present inventors have found that a fluorocarbon containing a hydrolyzable silyl group obtained by using vinyl carboxylate having a specific structure as a monomer to be copolymerized. It has been discovered that a composition comprising an olefin copolymer and a curing catalyst has good initial drying properties and can yield a cured product with excellent stain resistance.
The present invention has now been completed.

That is, the present invention relates to a fluoroolefin, a vinyl monomer having a hydrolyzable silyl group, and the following general formula (I).
Cal represented by ? A fluoroolefin copolymer (A) component obtained by copolymerizing vinyl monomers as an essential monomer component and, if necessary, other vinyl monomers that can be copolymerized with these; comprising an agent (B) component and a catalyst (C) for hydrolysis-condensation of a hydrolyzable silyl group;
A curable resin composition is provided.

Hereinafter, the configuration of the present invention will be explained in detail.

The fluoroolefins constituting the entire vinyl polymer (A) component used in the present invention include hinyl fluoride, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, promotrifluoroethylene, Pentafluoropropylene, hexafluoropropylene, or trifluoromethyl trifluorovinylether, pentafluoroethyl trifluorovinylether, heptafluoropropyl trifluorovinylether, heptafluoropropyl trifluorovinylether, trifluoroethyl trifluorovinylether, tetra Examples include (per)fluoroalkyl perfluorovinyl ethers such as fluoropropyl trifluorovinyl ether and hahentafluoroptyl trifluorovinyl ether, among others, tetrafluoroethylene, vinylidene fluoride, chloro Preference is given to using trifluoroethylene or hexafluoropropylene. These fluoroolefin monomers may be used alone or in combination of two or more.

Next, the vinyl monomer having a hydrolyzable silyl group used in the present invention includes a halosilyl group, an alkoxysilyl group, an acyloxysilyl group represented by the following general formula (II),
It refers to monomeric gold containing easily hydrolyzed functional groups such as phenoxysilyl, mercatosilyl, lyl, aminosilyl, iminooxysilyl, or alkenyloxysilyl groups.

Among such monomers, alkoxysilyl groups, iminooxysilyl groups, and alkenyloxysilyl groups are particularly preferred from the viewpoint of not generating undesirable volatile components during curing.

Specific examples of such hydrolyzable silyl group-containing vinyl monomers include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinylmethyljethoxysilane, Vinyl tris (β-
methoxyethoxy) silane, trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylethyl vinyl ether, methyldimethoxysilylethyl vinyl ether, trimethoxysilylglobin vinyl ether, triethoxysilylglobin vinyl ether, vinyltriisopropenyloxysilane, Vinylmethylnoisoproynyloxysilane, triimbroinyloxysilylethyl vinyl ether, triisopropenyloxysilylglobin vinyl ether, triisoproynyloxy7lylbutylvinyl ether, vinyltris(dimethyliminooxy)silane, vinyltris(methylethylimino) oxy)silane, vinylmethylbis(somethyliminooxy)silane, vinyldimethyl(dimethyliminooxy)silane, tris(dimethyliminooxy)silylethyl vinyl ether, methylbis(dimethyliminooxy)silylethyl vinyl ether, tris(dimethyliminooxy) Silylbutyl vinyl ether, r-(meth)acryloyloxyglobyltrimethoxysilane, r-(meth)acryloyloxyglobyltriethoxysilane, r-(meth)acryloyloxypropylmethyldimethoxysilane, γ-(meth)acryloyloxy! Examples include lopyltriisoglopenyloxysilane or γ-(meth)acryloyloxyglobiltris(dimethyliminooxysilane).

Among these, it is easy to copolymerize in a polymerization system in which fluoroolefins and carboxylic acid vinyl esters coexist, and therefore, hydrolyzable silyl groups can be efficiently introduced into the fluoroolefin polymer (A). Particularly preferred are vinyl silanes having a hydrolyzable silyl group and male nyl ethers having both a hydrolyzable silyl group.

These monomers having a hydrolyzable silyl group may be used alone or in combination of two or more.

As a specific example of the cargenic acid vinyl ester represented by the general formula (1), vinyl-2,2-dimethy #7'
OA/ate, vinyl-2,2-dimethylbutanoate, vinyl-2,2-dimethylpentanoate, vinyl-2,2-tmethylhexanoate, vinyl-2,2
-diethylbutanoate, vinyl-2-ethyl-2-methylbutanoate, vinyl/l/ -2-ethyl-2-methyl(ntanoate, or vinyl-3-chloro-2
, 2-dimethylzolonoate.

In the present invention, as constituent monomers of the vinyl copolymer (A) component, in addition to the above-mentioned essential monomer components, other vinyl monomers copolymerizable with these may be used as necessary. Can be done. Other vinyl monomers that can be copolymerized include methyl vinyl ether, ethyl vinyl ether, n-7'' propyl vinyl ether, inglobil vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, tart-butyl vinyl ether, n-
Alkyl vinyl ethers or substituted alkyl vinyl ethers such as pentyl vinyl ether, n-hexyl vinyl ether, h-octyl vinyl ether, 2-ethylhexyl vinyl ether, chloromethyl vinyl ether, chloroethyl vinyl ether, pentyl vinyl ether, phenylethyl vinyl ether; cyclointhyruvinyl ether, cyclohexyl vinyl ether Cycloalkyl vinyl ethers such as Mataha methyl cyclohexyl vinyl ether; (per)fluoroalkyl vinyl ethers such as trifluoromethyl vinyl ether, pentafluoroethyl vinyl ether, tetrafluoroethyl V vinyl ether, tetrafluoroglobin vinyl ether, and hegtafluoroglobin vinyl ether ; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, and 4-hydroxybutyl vinyl ether f
/' Class: Vinyl acetate, vinyl zolopionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, C,
The above general formula (1) which is an essential monomer of the present invention, such as branched aliphatic vinyl caprate, C1° branched aliphatic vinyl cardate, C4 branched aliphatic vinyl cardate, or vinyl stearate. Aliphatic vinyl carboxylates other than vinyl caprate represented by: Vinyl cyclohexane caldenate, vinyl methylcyclohexane caldenate, vinyl benzoate, and vinyl p-tart-butylbenzoate having a cyclic structure. α-vinyl esters such as ethylene, propane or butene-1
Olefins; Various non-logonated olefins other than fluoroolefins, such as vinyl chloride or vinylidene chloride; Aromatic vinyl compounds such as styrene, α-methylstyrene modi or vinyltoluene; Methyl methacrylate, ethyl methacrylate, butyl methacrylate or methacrylic acid esters such as cyclohexyl methacrylate; acrylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate; allyl alcohol or allyl glycidyl ether; unsaturated bond-containing such as fumaric acid or maleic acid. Di- or monoesters of polybasic acids; (meth)acrylonitrile,
Nitrogen-containing monomers such as (meth)acrylamide, N-methylol (meth)acrylamide or N-butoxymethyl (meth)acrylamide; or unsaturated bond-containing compounds such as (anhydrous) maleic acid or (anhydrous) itaconic acid; ) polybasic acids; and (meth)acrylic/l/acid esters.

Among such other copolymerizable vinyl monomers, it is possible to increase the polymerization yield of the fluoroolefin copolymer (A) component in the present invention and efficiently introduce hydrolyzed silyl groups into the copolymer (A). From the point of view of introducing and improving the transparency of the cured product, at least one of (substituted) alkyl vinyl ethers or cycloalkyl vinyl ethers should be introduced without impairing properties such as initial drying properties and stain resistance. It is preferable to use it within this range.

When preparing the fluoroolefin copolymer (A) component from each of the monomer components described above, the yield, initial drying properties, weather resistance, stain resistance, and the present invention of the vinyl copolymer (A) component are determined. Of composition? From the viewpoint of trifing, etc., the ratio of each monomer component used is 10 to 70% by weight of fluoroolefin, preferably 20 to 60% by weight, and vinyl monomer having a hydrolyzable silyl group. body 1-4
0 weight'#, ratio 1 preferably 3 to 30% by weight, general formula (I
The amount of vinyl cardenate represented by ) is controlled to be 5 to 70% by weight, preferably 10 to 65% by weight, and the amount of other copolymerizable vinyl monomers is controlled to be 0 to 50% by weight.

Furthermore, the glass transition temperature of the obtained copolymer (A) measured by DSC should be in the range of more than 20°C and less than 70°C in terms of initial drying properties, stain resistance, and removability. It is preferable to determine the ratio of monomers used.

From each monomer listed above, the copolymer (A)
To obtain t, bulk polymerization is performed using a radical polymerization initiator.
fc may be polymerized by making full use of known techniques such as solution polymerization.

Such radical polymerization initiators include acetyl oxide or benzoyl I? - diacyl rubber oxides such as methyl ethyl ketone peroxide or cyclohexanone/IF-oxide; hydro A'-oxides such as hydrogen peroxide, t-butylhydronoxide or cumene hydrono-oxide. ; dialkyl oxides such as di-t-butylno-9-oxide or dicumyl AI-oxide; alkyl peroxy esters such as t-butylperoxyacetate or t-butylnooxypivalate; azobisisobutyronitrile or azo initiators such as azobisisovaleronitrile; or persulfates such as ammonium persulfate or potassium persulfate, and, if necessary, an inorganic reducing agent such as sodium bisulfite or sodium pyrosulfite; Alternatively, organic reducing agents such as cobalt naphthenate or dimethylaniline may also be used.

As a copolymerization reaction method, various known methods such as those described above are possible, but among them, solution pressure polymerization is simple. The solvents used in this process are hydrocarbons such as TE, toluene, xylene, cyclohexane, n-hexane or octane; esters such as methyl acetate, ethyl acetate or butyl acetate; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone or methyl Ketones such as amylketone; amides such as dimethylformamide or dimethylacetamide; alcoholic solvents such as methanol, ethanol, i-glopanol, n-butanol, l-butanol, see-f-tanol or ethylene glycol monoalkyl ether; Mixtures of these can be used, but in order to improve the storage stability of the resulting copolymer, it is preferable to use a solvent containing an alcohol solvent. In addition, such solvents include trialkyl orthoformates such as trimethyl orthoformate, triethyl orthoformate, and tributyl orthoformate; trimethyl orthoacetate, triethyl orthoacetate, etc. or trialkyl orthoacetates such as tributyl orthoacetate; trialkyl orthoborate such as trimethyl orthoborate, triethyl orthoborate or tributyl orthoborate; tetramethylsilicate, tetraethylsilicate, tetrabutylsilicate, tetra(2-methoxyethyl)silicate Or tetra (2
- Simple tetra(substituted) alkyl silicates such as chloroethyl silicate; Equivalent substances of the above tetra(substituted) alkyl silicates such as tetraphenyl silicate or tetrabenzyl silicate; or dimers, trimers, tetramers or hexamers of tetraethyl silicate or [ Ethylsilicate 40 (a product of Nippon Colcoat Co., Ltd., which is a mixture of tetramers, pentamers, and hexamers of tetraethylsilicate) and their condensates (e.g., dimers, trimers, and tetramers). , pentamer or hexamer) or a mixture of two or more hydrolyzable ester compounds, or the polymerization solvent and the monomer used for copolymerization contain activated Kyoyo that is reactive with isocyanate groups. If not, benzenesulfonyl isocyanate, p-)luenesulfonyl incyanate, phenyl isocyanate, p-chlorophenylisocyanate),
2.4-) Luene diisocyanate, m-xylylene diisocyanate or hexamethylene diisocyanate, preferably benzenesulfonyl isocyanate, p
- Monoisocyanates such as toluenesulfonyl isocyanate, phenyl isocyanate or p-chlorophenylinocyanate can be present in the coexistence to carry out the polymerization reaction.

In this polymerization, lauryl mercaptan, octyl mercaptano, 2-mercaptoethanol, α-methylstyrene dimer or r-
Various chain transfer agents such as mercagutoglobil trimethoxysilane can also be used.

The reaction temperature during the copolymerization reaction is -20 to 130°C.
The initial reaction pressure is preferably within the range of 0.
．． A range of 5 to 100 and 151" is appropriate.

The number average molecular weight of the fluoroolefin copolymer (A) thus obtained is 1,000 to 50.00.
0, preferably within the range of 3,000 to 30,000.

Next, the solvents as the component (B) constituting the composition of the present invention include the above-mentioned solvents used in preparing the copolymer (A), as well as the above-mentioned solvents used as stabilizers. Hydrolyzable ester compounds such as r-glycidoxyglobyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane or dimethyljethoxysilane may also be used as reactive diluents. can.

Further, as the catalyst for hydrolysis-condensation of the hydrolyzable silyl group, which is the component (C) constituting the present invention, the above-mentioned hydrolyzable silyl group-containing fluoroolefin copolymer (
Known and commonly used catalysts for the hydrolysis or condensation reaction of A) may be used as they are, and representative examples of such curing catalysts include butylamine, dibutylamine, hexylamine, t-butylamine, ethylenediamine, triethylamine, inphoronediamine, Basic compounds such as imidazole, lithium hydroxide, sodium hydroxide, potassium hydroxide or sodium methylate; tetraisoglobyl titanate, tetrabutyl titanate, tin octylate, lead octylate, cobalt octylate, zinc octylate, octylate Calcium acid, lead nanthenate, cobalt naphthenate, diptyltin diacetate, diptyltin dioctoate, dif-thyltin dilaurate or dibutyltin diacetate, dibutyltin dilaurate or dibutyltin diacetate, dibutyltin diacetate, dibutyltin dilaurate or dibutyltin dilaurate, etc. metal-containing compound; p
-Toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, β-hydroxyethyl (
Examples include acidic compounds such as phosphoric acid esters of meth)acrylates or monoalkyl phosphorous acids or alkyl phosphorous acids. The amount of the curing catalyst to be used is in the range of 0.0 to 10M, preferably 0.01 to 5, based on the solid content of the hydrolyzable silyl group-containing fluoroolefin copolymer (A). Within this range is appropriate.

The composition of the present invention can be obtained using the above three components as essential components, but in addition, additives such as pigments, various resins, fluidity regulators, color separation inhibitors, antioxidants, or ultraviolet absorbers are also added. Ingredients can be added.

Typical examples of pigments include inorganic pigments such as titanium oxide, calcium carbonate, or carbon black, and organic pigments such as phthalocyanine, quinacridone, or azo pigments. 60-51
Examples include dispersed pigments in which pigments are treated with resins in advance, as disclosed in Japanese Patent No. 753.

As for the various resins, 11 resins that are commonly used as coating resins can be used without particular limitation, but among them, (meth)acrylic resins that may contain styrene are particularly representative. Resin, polyester resin, alkyd resin, melamine-formaldehyde resin, polyisocyanate resin, epoxy resin, vinyl chloride resin such as vinyl chloride/vinyl acetate copolymer, or cellulose such as nitrocellulose, cellulose acetate butyrate, etc. resins, ketone resins, petroleum resins, chlorinated products of polyolefins such as polyethylene or polypropylene, and alkoxysilane-modified products as previously invented by the present inventors and disclosed in JP-A No. 168,625/1982. The above-mentioned (A) obtained by copolymerizing resin, tetrafluoroethylene, chlorotrifluoroethylene, or monomers copolymerizable with these.
Examples include various fluororesins excluding components.

The room-temperature curable resin composition thus obtained is applied to the object to be coated by a conventional method and dried at room temperature for several days.
Alternatively, by baking at 60 to 150°C for 1 minute to 30 minutes, a cured film with extremely excellent weather resistance can be obtained.

〔Example〕

Next, the present invention will be explained in more detail with reference to Reference Examples, Examples, and Comparative Examples. Unless otherwise specified, all parts and units are based on weight.

Reference Example 1 [Example of preparation of hydrolyzable silyl group-containing fluoroolefin copolymer (A)] 550 ml of vinyl-2,2-methylglobin) was placed in a stainless steel autoclave with an internal volume of 2 ml and substituted with nitrogen.
g, vinyltrimethoxysilane 50g1 methyl isobutyl ketone 2001! , Methanol 2011 Orthomethyl 30 & St-Butyl Peroxypivalate 7f! After charging 400.9% of chlorotrifluoroethylene, it was kept at the same temperature for 16 hours until the nonvolatile content was 76.1%.
% and a number average molecular weight of 18,000 was obtained. Hereinafter, this will be abbreviated as '1A-1. The polymerization rate calculated from non-volatile components was 95.1%. The glass transition temperature of the solid resin obtained by heating this copolymer solution under reduced pressure to remove volatile components was 56°C (DSC at a heating rate of 10°C/min). ).

Reference Examples 2 to 8 [Same as above] A fluoroolefin polymer containing a hydrolyzable silyl group was produced by polymerizing in the same manner as in Reference Example 1, except that monomers shown in Table 1 were used. A-2~A
-8 solution was obtained. The polymerization rate and property data calculated from non-volatile components are shown in the same table.

Reference Example 9 [Fluoroolefin copolymer having a hydrolyzable silyl group without using vinyl carboxylate represented by general formula (1) as a copolymerization monomer (preparation example of A)] As a monomer to be copolymerized The non-volatile content was 72.51, the number average molecular weight was 17,
000 hydrolyzable silyl group, and has the general formula (
A solution of a fluoroolefin copolymer containing no vinyl ester unit represented by 1) was obtained. Hereinafter, this will be abbreviated as A'-1. The polymerization rate calculated from non-volatile matter is 9
It was 0.6chi. This copolymer solution was heated under reduced pressure to remove volatile components, and the solid component obtained had a glass transition temperature of -5°C.

/'' 2, ''/'', / Examples 1 to 8 and Comparative Example 1 Fluoroolefin copolymers obtained in Reference Examples 1 to 8 (
A-1) to (A-8) or copolymer A'-1 for comparison obtained in Reference Example 9 was added with a compound for hydrolysis-condensation of hydrolyzable silyl groups as specified in Table 2. Catalyst and xylene/methyl isobutyl ketone/butyl acetate/methanol = 50
A mixed solvent of /20/20/10 (weight ratio) was added to obtain a clear paint with a nonvolatile content of 60%.

Next, a dry film thickness of about 40 μm was applied to a 0.5 mm thick tin plate.
After applying the coating using a doctor blade so that the coating was applied, the coating was left in an atmosphere of 25° C. and relative humidity of 60° C. for 7 days to obtain a cured film. Thereafter, the stain resistance of each coating film was measured.

In addition, each of the above paints was applied to a glass plate with a dry film thickness of approximately 40 μm.
The coating film was coated using a doctor blade so as to have the following properties, and then left in an atmosphere of 25° C. and 60% relative humidity for 24 hours. The drying properties of the resulting coating film were measured. These results are summarized in the same table.

Notes to Table 2: Note 1) A mixed solvent of xylene/methyl inbutyl ketone/butyl acetate/methanol=50/20/20/10 (weight ratio) was used.

Note 2) Draw a line on the coating film with red marker ink and heat it at 25℃ for 1
After leaving it for a day, petroleum benzine/ethanol = 501
The degree to which the marker ink marks remained after wiping with a mixed solvent of 50 (weight ratio) was visually determined.

Judgment criteria ◎・・・・・・No traces remain.

○...A very slight trace remains.

×......Noticeable traces remain.

Note 3) A piece of gauze folded in four was placed on the coating film, and a 160I piece of steel was placed on top of the gauze and left for 1 minute. After removing the piece of steel, the appearance of the coating film was visually judged.

<Judgment Criteria> ◎... No gauze marks are observed on the coating film 6
0: Slight traces of gauze remain on the coating film.

×: There are significant traces of paint left on the paint film.

〔Effect of the invention〕

The composition of the present invention has excellent drying properties and also provides a cured product with excellent stain resistance.

Therefore, the curable resin composition of the present invention is extremely useful for paints, sealants, surface protection, and the like.

Claims (1)

[Claims] 1. (A) A fluoroolefin, a vinyl monomer having a hydrolyzable silyl group, and a vinyl carboxylate represented by the following general formula (I) as essential monomer components; A fluoroolefin copolymer obtained by copolymerizing other vinyl monomers that can be copolymerized with each of the above monomer components, and a general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (I) In the formula R^1, R^2 and R^3 are each independently a C_1 to C_4 alkyl group or chloromethyl group, and the total number of carbon atoms in R^1, R^2 and R^3 is 3.
6 to 6 pieces. A curable resin composition comprising (B) a solvent and (C) a catalyst for hydrolysis-condensation of a hydrolyzable silyl group. 2. The fluoroolefin is at least one compound selected from the group consisting of tetrafluoroethylene, vinylidene fluoride, chlorotrifluoroethylene, and hexafluoropropylene.
The curable resin composition described in . 3. The curable resin composition according to item 1, wherein the vinyl carboxylate is vinyl 2,2-dimethylpropanoate. 4. The curable resin composition according to item 1, wherein the vinyl carboxylate is vinyl 2,2-dimethylbutanoate. 5. The curable resin composition according to item 1, wherein the vinyl carboxylate is vinyl 2,2-dimethylpentanoate. 6. The curable resin composition according to item 1, wherein the vinyl carboxylate is vinyl 2,2-dimethylhexanoate. 7. The vinyl carboxylate is vinyl 2-ethyl-2-
2. The curable resin composition according to item 1, which is methyl butanoate. 8. The curable resin composition according to item 1, wherein the vinyl carboxylate is vinyl 2,2-diethylbutanoate. 9. The vinyl carboxylate is vinyl 2-ethyl-2-
2. The curable resin composition according to item 1, which is methylpentanoate. 10, the vinyl carboxylate is vinyl 3-chloro-2
, 2-dimethylpropanoate, the curable resin composition according to item 1. 11. The composition according to item 1, wherein the other copolymerizable vinyl monomer is an alkyl vinyl ether. 12. The composition according to item 1, wherein the other copolymerizable vinyl monomer is a cycloalkyl vinyl ether. 13. The composition according to item 1, wherein the other copolymerizable vinyl monomer is used in combination with an alkyl vinyl ether and a cycloalkyl vinyl ether. 14. The composition according to item 1, wherein the vinyl monomer having a hydrolyzable silyl group is a vinyl silane having a hydrolyzable silyl group. 15. The composition according to item 1, wherein the vinyl monomer having a hydrolyzable silyl group is a vinyl ether having a hydrolyzable silyl group. 16. The vinylsilane having a hydrolyzable silyl group is vinyltrimethoxysilane,
The composition according to item 12.