JP2003048929A - Curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable resin composition capable of overcoming problems of a (meth)acryloyl group-containing curable resin composition, an epoxy group- containing curable resin composition and a curable resin composition containing both a (meth)acryloyl group and an epoxy group. SOLUTION: This curable resin composition comprises (A) a vinyl ether group-containing curable resin having a structural unit represented by represented by general formula (1) (R<1> is a hydrogen atom or a methyl group; R<2> is a 2-20C organic residue; R<3> is a hydrogen atom or a 1-11C organic residue) and (B) a reactive diluent.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a curable resin composition, a resin composition for curing active energy rays containing the curable resin composition, its use, and an article obtained by curing the composition. Specifically, the present invention relates to a curable resin composition curable by heat or irradiation with active energy rays, an active energy ray curable resin composition, a curable adhesive / adhesive sheet composition, and an article obtained by curing them. ..

[0002]

2. Description of the Related Art In a curing technique utilizing active energy rays such as heat, ultraviolet rays or electron rays, a curable composition using a curable resin and a reactive diluent is drawing attention. In particular, active energy ray curing has advantages such as energy saving, space saving, and short-time curing, and its range of use is expanding.

Curable resin compositions that have been developed so far include (meth) acryloyl groups such as polyester (meth) acrylate, urethane poly (meth) acrylate, polysiloxane poly (meth) acrylate, and polyamide poly (meth) acrylate. Curable resin composition containing curable resin containing; curable resin composition containing epoxy group-containing curable resin such as novolac type epoxy resin, aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin A curable resin composition containing a curable resin containing both (meth) acryloyl group-epoxy group such as epoxy poly (meth) acrylate and carboxylic acid modified epoxy (meth) acrylate.

[0004]

However, generally, a curable resin composition containing a (meth) acryloyl group-containing curable resin is 1) subjected to polymerization inhibition by oxygen, and 2) has a large volume shrinkage upon curing. ) There are problems such as poor adhesion to metal. Further, the curable resin composition containing the epoxy group-containing curable resin has the problems that 1) the polymerization rate is slow, and 2) the hydroxyl group generated by curing may affect the physical properties.

[0005]

The present invention has been made in view of the above circumstances, and overcomes the problems of the (meth) acryloyl group-containing curable resin composition and the epoxy group-containing curable resin composition. It can be applied to various applications such as paints, inks, adhesives, pressure sensitive adhesives, surface modification materials, curable tacky adhesive sheets, laminated glass binders, paper treatment agents, fiber surface modification agents, molding materials, etc. It is an object of the present invention to provide a curable resin composition capable of being processed, an active energy ray-curing resin composition containing the same, a curable tacky-adhesive sheet composition, and an article obtained by curing them.

The present inventors have made various studies on the curable resin composition and found that a curable resin composition containing a vinyl ether group-containing curable resin containing a vinyl ether group as a pendant and a reactive diluent is used. According to the above, it was found that the above problems of the (meth) acryloyl group-containing curable resin composition and the epoxy group-containing curable resin composition can be overcome, and the present invention has been accomplished. Also,
It has been found that a curable resin composition containing the curable resin composition and a polymerization initiator has excellent curability and improved adhesiveness, and thus can be suitably applied to various applications. It was Moreover, it has been found that such a curable resin composition is suitable as a resin composition for curing active energy rays. Further, they have found that such a curable resin composition is suitable as a component of a curable tacky adhesive sheet. Furthermore, the inventors have arrived at the present invention by thinking that an article obtained by curing such a curable resin composition can be used for various purposes.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below.

The curable resin composition of the present invention has the following (A)
General formula (1):

[0009]

[Chemical 2] (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ²
Represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. ) A vinyl ether group-containing curable resin having a structural unit represented by) and (B) a reactive diluent.

The vinyl ether group-containing curable resin which is the component (A) of the present invention is a compound having a structural unit represented by the general formula (1), and the substituent represented by R ¹ in the formula is hydrogen. An atom or a methyl group, the substituent represented by R ² is an organic residue having 2 to 20 carbon atoms, and the substituent represented by R ³ is a hydrogen atom or an organic residue having 1 to 11 carbon atoms.

The organic residue having 2 to 20 carbon atoms represented by R ² in the general formula (1) is, for example, a linear, branched or cyclic alkylene group having 2 to 20 carbon atoms, in the structure. An alkylene group having 2 to 20 carbon atoms having an oxygen atom by an ether bond and / or an ester bond, and 6 to 11 carbon atoms
And optionally substituted aromatic groups and the like. Of these, an alkylene group having 2 to 10 carbon atoms and an alkylene group having 2 to 10 carbon atoms having an oxygen atom through an ether bond are preferably used.

The organic residue having 1 to 11 carbon atoms represented by R ³ in the general formula (1) is, for example, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or the carbon number. 6-11
And optionally substituted aromatic groups and the like. Of these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 8 carbon atoms are preferably used.

Among the compounds having the structural unit represented by the general formula (1), the substituent represented by R ¹ in the formula is a hydrogen atom or a methyl group, and the substituent represented by R ² has a carbon number. A compound having 4 to 10 alkylene groups and an alkylene group having 4 to 10 carbon atoms having an oxygen atom through an ether bond, wherein the substituent represented by R ³ is a hydrogen atom,
Since the vinyl ether group is located away from the main chain, it is preferable in terms of easiness of curing. In particular, a compound in which the substituent represented by R ² is an alkylene group having 4 to 10 carbon atoms and having an oxygen atom through an ether bond has compatibility with a reactive diluent, a polymerization initiator, and other additives described later. It is particularly preferable in terms of good points.

The method for producing a vinyl ether group-containing curable resin having the structural unit represented by the general formula (1) is, for example, a reaction of a poly (meth) acrylic acid ester structure-containing polymer with a hydroxyl group-containing vinyl ether. Method (Production method 1); Method by reaction of poly (meth) acrylic acid metal salt structure-containing polymer with halogen-containing vinyl ethers (Production method 2); Poly (meth) acrylic acid structure-containing polymer and hydroxyl group-containing vinyl ethers Method (Production method 3); Reaction of poly (meth) acrylic acid halide structure-containing polymer with hydroxyl group-containing vinyl ether (Production method 4); Poly (meth) acrylic acid structure-containing polymer and halogen-containing vinyl ether Method by reaction with compounds (Production method 5); vinyl ether group-containing (meth) acrylic acid esters alone If and / or copolymerization process according to (Process 6); and the like. Among them, the production method 6 is preferable because the molecular design of the curable resin and the control of its physical properties are easy.
Is preferred.

As typical examples of the vinyl ether group-containing (meth) acrylic acid esters used in the production method 6, specifically, 2-vinyloxyethyl (meth) acrylate,
3- (vinyloxypropyl) (meth) acrylate, (meth)
1-methyl-2-vinyloxyethyl acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1- (meth) acrylic acid
Methyl-3-vinyloxypropyl, 1-vinyloxymethylpropyl (meth) acrylate, (meth) acrylic acid 2
-Methyl-3-vinyloxypropyl, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, (meth)
3-vinyloxybutyl acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxy (meth) acrylate Hexyl, 4-vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexylmethyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxy (meth) acrylate Methylphenylmethyl,
M-Vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxy) (meth) acrylate Isopropoxy) ethyl, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, (meth )
2- (vinyloxyisopropoxy) isopropyl acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, (meth) acrylic acid 2- (Vinyloxyisopropoxyethoxy) ethyl,
2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, (meth ) 2- (vinyloxyisopropoxyethoxy) propyl acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, (meth) acrylic Acid 2- (vinyloxyethoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyethoxy) isopropyl, (meth) acrylic acid 2- (vinyloxyisopropoxyisopropoxy) isopropyl, (meth) acrylic acid 2- (vinyloxy Butoxy ethoxy) ethyl, (meth) acrylic acid 2- (vinyloxy ethoxy ethoxy ethoxy ethoxy) ethyl, (meth) acrylic acid 2
-(Isopropoxyethoxy) ethyl, 2- (isopropoxyethoxyethoxy) ethyl (meth) acrylate,
2- (Isopropoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (Isopropoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, polyethylene glycol monovinyl ether (meth) acrylate, polypropylene glycol (meth) acrylate Examples include monovinyl ether.

Among these, 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate,
4-vinyloxycyclohexyl (meth) acrylate,
6-vinyloxyhexyl (meth) acrylic acid, (meth)
4-vinyloxymethylcyclohexylmethyl acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyiso) (meth) acrylate Propoxy) propyl is preferred, 4-vinyloxybutyl (meth) acrylate, 2- (meth) acrylate
(Vinyloxyethoxy) ethyl, (meth) acrylic acid 2
Especially preferred is-(vinyloxyethoxyethoxy) ethyl. Such vinyl ether group-containing (meth) acrylic acid esters may be used alone or in combination of two or more.

The vinyl ether group-containing (meth) acrylic acid ester is curable by homopolymerization or copolymerization with another copolymerizable polymerizable compound, and is curable by the vinyl ether group-containing curable compound represented by the general formula (1). A resin can be manufactured.

Specific examples of the above-mentioned copolymerizable polymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, amyl (meth) acrylate, 2-ethylhexyl (meth) acrylate,
Octyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentanyl (meth) acrylate, n-stearyl (meth) acrylate, isobornyl (meth) )
(Meth) acrylates such as acrylate, 2- (acetoacetoxy) ethyl (meth) acrylate, phenoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (Meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (α-hydroxymethyl) acrylate, ethyl (α
-Hydroxymethyl) acrylate, caprolactone-modified hydroxy (meth) acrylate (trade name Praxel; manufactured by Daicel Chemical Industries, Ltd.), 4-hydroxymethylcyclohexylmethyl (meth) acrylate and other hydroxyl group-containing (meth) acrylates; acrylic acid, Methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, maleic anhydride, carboxyl group-terminated caprolactone-modified (meth) acrylate (trade name Praxel; manufactured by Daicel Chemical Industries, Ltd.), sulfoethyl (meth) acrylate, 2- Containing an acidic functional group such as (meth) acryloyloxyethyl acid phosphate, 2- (meth) acryloyloxypropyl acid phosphate (meth)
Acrylates; vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, divinylbenzene, vinyl acetate, vinyl chloride, vinylidene chloride; vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltriethoxysilane, vinyltri Silicon-containing polymerizable monomers such as methoxysilane, γ-methacryloxypropyltrimethoxysilane, and trimethylsiloxyethyl methacrylate; trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Halogen-containing polymerizable monomers such as heptadodecafluorodecyl acrylate, β- (perfluorooctyl) ethyl (meth) acrylate, and perfluorooctylethyl (meth) acrylate; Meth) acrylamide, N- isopropyl (meth) acrylamide, t- butyl (meth)
Acrylamide, methylenebis (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-
Ethoxymethyl (meth) acrylamide, N-methylol (meth) acrylamide, N, N'-dimethylaminoethyl (meth) acrylate, N, N'-diethylaminoethyl (meth) acrylate, N-methyl-N-
Vinylformamide, dimethylaminoethyl (meth) acrylate sulfate, N-vinylpyridine, N-vinylimidazole, N-vinylpyrrole, N-vinylpyrrolidone, diacetone acrylamide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-iso Nitrogen atom-containing polymerizable monomers such as propenyl-2-oxazoline; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, polypropylene glycol di (meth) acrylate EO-modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, glycerin di (meth) ) Polyfunctional polymerizable monomers such as acrylate; glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate (trade name CYCLOMER; Daicel Chemical Industries, Ltd. )) And other epoxy group-containing polymerizable monomers; 2- (meth) acryloyloxyethyl isocyanate (trade name Karenz; Showa Denko KK), (meth) acryloyl isocyanate (trade name MAI; Isocyanate group-containing polymerizable monomers such as Nippon Paint Co., Ltd .;
2- [2'-hydroxy-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole,
2- [2'-hydroxy-5 '-(meth) acryloyloxypropylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-5'-(meth) acryloyloxyhexylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5 '-(meth) acryloyloxyethylphenyl] -2H-benzotriazole, 2- [2'-hydroxy-3'-tert-butyl-5'- Isocyanate group-containing polymerizable monomers such as (meth) acryloyloxyethylphenyl] -5-chloro-2H-benzotriazole; 4- (meth) acryloyloxy-2,2,6,
6-Tetramethylpiperidine, 4- (meth) acryloyloxy-1,2,2,6,6-pentamethylpiperidine, 4-cyano-4- (meth) acryloylamino-
2,2,6,6-tetramethylpiperidine, 4-crotonoyloxy-2,2,6,6-tetramethylpiperidine, 1- (meth) acryloyl-4- (meth) acryloylamino-2,2,6 , 6-Tetramethylpiperidine, 1- (meth) acryloyl-4-cyano-4- (meth) acryloylamino-2,2,6,6-tetramethylpiperidine and other UV stable polymerizable monomers. To be Such copolymerizable polymerizable compounds may be used alone or in combination of two or more kinds.

In the present invention, the ratio of the vinyl ether group-containing (meth) acrylic acid ester to the above-mentioned copolymerizable polymerizable compound is arbitrary, but the curability of the resin composition, the storage stability, and the toughness of the cured product. And from the economical point of view,
The proportion of vinyl ether group-containing (meth) acrylic acid ester units in the vinyl ether group-containing curable resin is
The lower limit is preferably 1% by mass or more, and the upper limit is 100.
It is preferably not more than mass%. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and the upper limit is more preferably 80% by mass or less, further preferably 50% by mass or less. Also, when it is used as a mixture of FRP or non-FRP lining materials, coating materials such as paints and coating materials, or various organic / inorganic reinforcing materials and fillers, it adheres to the base material, reinforcing materials and fillers. From a sex perspective
The proportion of vinyl ether group-containing (meth) acrylic acid ester units in the vinyl ether group-containing curable resin is
The lower limit is preferably 3% by mass or more, and the upper limit is preferably 30% by mass or less. The lower limit is more preferably 5% by mass or more, further preferably 7% by mass or more, and the upper limit is more preferably 25% by mass or less, further preferably 20% by mass or less.

The method for producing a vinyl ether group-containing curable resin using the above vinyl ether group-containing (meth) acrylic acid ester and a copolymerizable polymerizable compound includes heat, ultraviolet ray, radiation, electron beam, radical polymerization initiator and anionic polymerization initiation. Various known methods utilizing agents and the like can be adopted.

The reactive diluent which is the component (B) in the present invention is preferably a liquid substance having a viscosity at 25 ° C. of 1 Pa · s or less, and is a monofunctional or polyfunctional radically polymerizable and / or ionic polymerizable. The compound can be selected appropriately.

Specific examples of the above-mentioned reactive diluent include:
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth)
Acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, cyclohexylmethyl (meth)
Acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, methoxyethoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth ) Acrylate, methoxy polyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 4-hydroxymethyl Cyclohexylmethyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylic acid, (meth) acryloylmorpholine, N, - dimethylaminoethyl (meth) acrylate, phenylethyl (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, alpha-hydroxymethyl acrylate methyl,
Single α-hydroxymethyl acrylate, α-hydroxymethyl butyl acrylate, α-bromomethyl acrylate, α-bromomethyl acrylate, α-bromomethyl acrylate, α-acetoxymethyl acrylate, etc. Functional (meth) acrylates;
Monofunctional (meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether,
Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4
-Hydroxymethylcyclohexylmethyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, and other monofunctional vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyl-N-methylformamide, N
-Vinylimidazole, N-vinylformamide, N
-Monofunctional N-vinyl compounds such as vinylacetamide;
Monofunctional vinyl compounds such as styrene, α-methylstyrene, allyl acetate, vinyl acetate, vinyl propionate, vinyl benzoate; maleic anhydride, maleic acid, dimethyl maleate, monomethyl maleate, dimethyl fumarate, monomethyl fumarate. , Itaconic anhydride, itaconic acid, dimethyl itaconic acid, monomethyl itaconic acid, methylenemalonic acid, dimethylmethylenemalonate, monomethylmethylenemalonate, cinnamic acid, methylcinnamate, crotonic acid, monofunctional α, β -Unsaturated compounds; methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, cyclohexyl glycidyl ether, cyclohexyl Chill glycidyl ether,
Benzyl glycidyl ether, dicyclopentenyl glycidyl ether, methoxyethyl glycidyl ether,
Ethoxyethyl glycidyl ether, butoxyethyl glycidyl ether, methoxyethoxyethyl glycidyl ether, ethoxyethoxyethyl glycidyl ether, methoxypolyethylene glycol glycidyl ether, tetrahydrofurfuryl glycidyl ether, 2-
Monofunctional epoxy compounds such as hydroxyethyl glycidyl ether, 2-hydroxypropyl glycidyl ether, 4-hydroxybutyl glycidyl ether, 4-hydroxymethylcyclohexylmethyl glycidyl ether, polyethylene glycol glycidyl ether; 3-
Methyl-3-hydroxymethyl oxetane, 3-ethyl-3-hydroxymethyl oxetane, 3-methyl-3-
Phenoxymethyl oxetane, 3-ethyl-3-phenoxymethyl oxetane, 3-methyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-
Monofunctional alicyclic ether compounds such as (2-ethylhexyloxymethyl) oxetane; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate ,
Hexanediol di (meth) acrylate, cyclohexanedimethanol di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate,
Polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate; ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, tri Polyfunctional vinyl ethers such as methylolpropane trivinyl ether; polyfunctional vinyl compounds such as divinylbenzene; ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexanediol diglycidyl ether, Bisphenol A alkylene oxide Diglycidyl ether, polyfunctional epoxy compounds such as trimethylolpropane triglycidyl ether; di [1-methyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)]
Methyl ether, 1,4-bis {[(3-methyl-3-
Oxetanyl) methoxy] methyl} benzene, 1,4-
Bis {[(3-ethyl-3-oxetanyl) methoxy]
Polyfunctional fats such as methyl} benzene, bis {4-[(3-methyl-3-oxetanyl) methoxy] methyl} benzyl ether, bis {4-[(3-ethyl-3-oxetanyl) methoxy] methyl} benzyl ether Cyclic ether compounds; 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate,
2-Vinyloxypropyl (meth) acrylate, (meth)
4-vinyloxybutyl acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethylpropyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, (meth ) 1,1-Dimethyl-2-vinyloxyethyl acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, (meth) acrylic Acid 4
-Vinyloxycyclohexyl, (meth) acrylic acid 6-
Vinyloxyhexyl, (meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid 3
-Vinyloxymethylcyclohexylmethyl, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate,
P-vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenylmethyl (meth) acrylate, 2- (vinyloxyethoxy) (meth) acrylate ) Ethyl, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid
(Vinyloxyethoxy) isopropyl, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) (meth) acrylate Ethyl, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylate , (Meth) acrylic acid 2-
(Vinyloxyethoxyethoxy) propyl, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl (meth) acrylate, 2- (meth) acrylic acid
(Vinyloxyisopropoxyisopropoxy) propyl, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) isopropyl (meth) acrylate, (meth)
Acrylic acid 2- (vinyloxyisopropoxyethoxy)
Isopropyl, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate, (meth)
2- (vinyloxyethoxyethoxyethoxy) ethyl acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxy) ethyl (meth) acrylate, (meth) acrylic acid 2- (isopropenoxyethoxyethoxy) ethyl, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, (meth) acrylic Acid ether glycol monovinyl ether, vinyl ether group-containing (meth) acrylic acid esters such as (meth) acrylic acid polypropylene glycol monovinyl ether; and the like. Among them, monofunctional acrylates, monofunctional acrylamides, monofunctional vinyl ethers, monofunctional epoxy compounds, monofunctional alicyclic ether compounds, polyfunctional acrylates, polyfunctional acrylamides, polyfunctional vinyl ethers, polyfunctional vinyl ethers, Functional epoxy compounds, polyfunctional alicyclic ether compounds, fumaric acid esters, maleic acid esters, and vinyl ether group-containing (meth) acrylic acid esters are preferably used. Such reactive diluents may be used alone or in combination of two or more kinds.

The mixing ratio of the vinyl ether group-containing curable resin as the component (A) and the reactive diluent as the component (B) is arbitrary, but the vinyl ether group-containing curable resin 100 may be used.
The lower limit of the mixing ratio of the reactive diluent to the mass is 1
The amount is preferably 0 parts by mass or more, and the upper limit is preferably 100 parts by mass or less. If it is less than 10 parts by mass, the viscosity of the composition may be high and it may be difficult to apply it. If it exceeds 100 parts by mass, the physical properties of the cured product obtained by curing the resin composition are dominated by the polymer of the reactive diluent. Is not preferred. The lower limit is more preferably 15 parts by mass or more, further preferably 20 parts by mass or more, and the upper limit is more preferably 95 parts by mass or less, further preferably 90 parts by mass or less.

In the present invention, a curable resin other than the vinyl ether group-containing curable resin may be used together with the vinyl ether group-containing curable resin.

As the curable resin other than the vinyl ether group-containing curable resin used at that time, specifically, polyester (meth) acrylate, urethane poly (meth) acrylate, polysiloxane poly (meth) acrylate,
(Meth) acryloyl group-containing curable resin such as polyamide poly (meth) acrylate; epoxy group-containing curable resin such as novolac type epoxy resin, aromatic epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin; epoxy poly (Meth) acryloyl group-epoxy group-containing curable resin such as (meth) acrylate and carboxylic acid-modified epoxy (meth) acrylate; and the like. Such curable resins may be used alone or in combination of two or more.

In the present invention, when a curable resin other than the vinyl ether group-containing curable resin is used, the ratio of the addition amount of the curable resin other than the vinyl ether group-containing curable resin to the vinyl ether group-containing curable resin is arbitrary. As for the ratio of the addition amount of the curable resin other than the vinyl ether group-containing curable resin to 100 parts by mass of the vinyl ether group-containing curable resin, the lower limit is preferably 1 part by mass or more, and the upper limit is 100 parts by mass. The following are preferred. If the ratio of the added amount is less than 1 part by mass, the effect of adding the curable resin other than the vinyl ether group-containing curable resin may not substantially appear, and the ratio of the added amount may be 10% or less.
If it exceeds 0 parts by mass, the excellent effect of the curable resin composition of the present invention, that is, the good curability and adhesiveness may be sacrificed. The lower limit is more preferably 5 parts by mass or more, and 1
The amount is preferably 0 parts by mass or more, more preferably 90 parts by mass or less, and further preferably 80 parts by mass or less.

When a curable resin other than the vinyl ether group-containing curable resin is contained, the total amount of the vinyl ether group-containing curable resin and the other curable resin and the compounding ratio of the reactive diluent are arbitrary, but vinyl ether With respect to the total amount of the group-containing curable resin and other curable resins, 100 parts by mass, the lower limit of the compounding ratio of the reactive diluent is preferably 10 parts by mass or more, and the upper limit thereof is preferably 100 parts by mass or less. If it is less than 10 parts by mass, the viscosity of the composition may be high and it may be difficult to apply it. If it exceeds 100 parts by mass, the physical properties of the cured product obtained by curing the resin composition are dominated by the polymer of the reactive diluent. Is not preferred. The lower limit is 1
It is more preferably 5 parts by mass or more, further preferably 20 parts by mass or more, and the upper limit is more preferably 95 parts by mass or less, 90
It is more preferable that the amount is less than or equal to parts by mass.

The ratio of the total amount of the vinyl ether group-containing curable resin and the reactive diluent to the entire curable resin composition of the present invention is arbitrary, and varies greatly depending on the application and use of the curable resin composition. Generally, the lower limit of the total amount of the curable resin containing a vinyl ether group and the reactive diluent is preferably 5% by mass or more and the upper limit thereof is preferably 100% by mass or less with respect to the entire curable resin composition. If the ratio of the total amount is less than 5% by mass, the excellent effect brought about by the vinyl ether group-containing curable resin may not be substantially exhibited. The lower limit is more preferably 10 mass% or more, further preferably 20 mass% or more, particularly preferably 30 mass% or more, and the upper limit is more preferably 95 mass% or less, further preferably 90 mass% or less, and 80 mass% or less. Is particularly preferable.

The curable resin composition of the present invention and further (C)
A curable resin composition containing a polymerization initiator as a component is one of the preferred embodiments of the present invention. As the polymerization initiator, one kind or two or more kinds can be used. Also,
It is also preferable to further add a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator and the like.

As the above-mentioned polymerization initiator, a thermal polymerization initiator exhibiting a polymerization initiation effect by heat and / or a photopolymerization initiator exhibiting a polymerization initiation effect by light can be used.

Examples of the thermal polymerization initiator include a thermal radical polymerization initiator that generates a polymerization initiation radical by heating and a thermal cationic polymerization initiator that generates a polymerization initiation cation by heating.

Specific examples of the thermal radical polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl cyclohexanone peroxide, methyl acetoacetate peroxide, acetyl acetate peroxide, and 1,1-bis (t-hexyl peroxide). Oxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) -cyclohexane, 1,1-bis (t-butylperoxy)
-3,3,5-Trimethylcyclohexane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, 1,1-bis (t-butylperoxy) -cyclohexane, 1,1-bis (t -Butylperoxy) cyclododecane, 1,1-bis (t-butylperoxy) butane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, p-menthane hydroperoxide, Diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-
Hexyl hydroperoxide, t-butyl hydroperoxide, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) ) Hexane, t-butyl cumyl peroxide,
Di-t-butyl peroxide, 2,5-dimethyl-
2,5-bis (t-butylperoxy) hexyne-3,
Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, stearoyl peroxide, succinic acid peroxide, m-toluoyl benzoyl peroxide, benzoyl peroxide, di-n -Propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-t-
Butylcyclohexyl) peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate, di-
2-ethoxyhexyl peroxydicarbonate, di-
3-methoxybutyl peroxydicarbonate, di-s
-Butyl peroxydicarbonate, di (3-methyl-
3-methoxybutyl) peroxydicarbonate, α,
α'-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxy neodecanoate, 1,
1,3,3-Tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, t-hexyl peroxy neodecanoate, t-butyl peroxy neodecanoate ,
t-hexyl peroxypivalate, t-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-bis (2 -Ethylhexano-peroxy) hexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexa Noate, t-hexyl peroxyisopropyl monocarbonate, t-butyl peroxyisobutyrate, t-butyl peroxymalate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butyl peroxy Oxylaurate, t-butyl peroxy isopropyl monocarbonate, t-butyl per Xy-2-ethylhexylmonicarbonate, t-butylperoxyacetate, t-butylperoxy-m-toluylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, 2,5-dimethyl- 2,5-bis (m-toluylperoxy) hexane, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyallyl monocarbonate, t- Butyltrimethylsilyl peroxide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone,
Organic peroxide initiators such as 2,3-dimethyl-2,3-diphenylbutane; 2-phenylazo-4-methoxy-
2,4-dimethylvaleronitrile, 1-[(1-cyano-1-methylethyl) azo] formamide, 1,1′-
Azobis (cyclohexane-1-carbonitrile),
2,2'-azobis (2-methylbutyronitrile),
2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2 '
-Azobis (2,4-dimethyl-4-methoxyvaleronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2
-Methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine)] dihydrochloride, 2,2'-azobis [N- (4-hydro Phenyl) -2-methylpropionamidine)] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride,
2,2'-azobis [2-methyl-N- (2-propenyl) propionamidine] dihydrochloride, 2,2 '
-Azobis [N- (2-hydroxyethyl) -2-methylpropionamidine)] dihydrochloride, 2,2 '
-Azobis [2- (5-methyl-2-imidazoline-2
-Yl) propane) dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane)
Dihydrochloride, 2,2'-azobis [2- (4,
5,6,7-Tetrahydro-1H-1,3-diazepin-2-yl) propane) dihydrochloride, 2,2′-
Azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane) dihydrochloride, 2,
2'-azobis [2- (5-hydroxy-3,4,5,5
6-Tetrahydropyrimidin-2-yl) propane) dihydrochloride, 2,2′-azobis {2- [1- (2
-Hydroxyethyl) -2-imidazolin-2-yl]
Propane} dihydrochloride, 2,2′-azobis [2
-(2-Imidazolin-2-yl) propane], 2,
2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N-
[1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2′-azobis [2-methyl-N-
(2-Hydroxyethyl) propionamide], 2,
2'-azobis (2-methylpropionamide), 2,
2'-azobis (2,4,4-trimethylpentane),
2,2'-azobis (2-methylpropane), dimethyl 2,2-azobis (2-methylpropionate), 4,
4'-azobis (4-cyanopentanoic acid), 2,2'-
Azo-based initiators such as azobis [2- (hydroxymethyl) propionitrile]; and the like.

Among these, metal soaps such as methyl ethyl ketone peroxide, cyclohexanone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate and benzoyl peroxide, and /
Alternatively, a compound capable of efficiently generating a radical by a catalytic action of an amine compound, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile) is preferable. is there.

Specific examples of the thermal cationic polymerization initiator include Lewis acids (for example, boron trifluoride, ferrous titanium chloride, salts or ferric titanium, ferrous chloride, ferric chloride, zinc chloride, Zinc bromide, stannous chloride, stannic chloride, stannous bromide, stannic bromide, dibutyl stannic dichloride, dibutyl stannic dibromide, tetraethyltin, tetrabutyltin, triethylaluminum, Diethylaluminum chloride, ethylaluminum dichloride, etc. and an electron-donating compound (for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphoric triamide, dimethylsulfoxide, trimethyl phosphate, Complexes with triethyl phosphate, etc .; protonic acids (eg halogenocarboxylic acids, sulfonic acids, sulfuric acid monoesters) Phosphoric acid monoesters, phosphoric acid diesters, polyphosphoric acid esters, boric monoesters, boric acid diesters, etc.) base (e.g., ammonia, monoethylamine, diethylamine, triethylamine, pyridine, piperidine, aniline, morpholine,
A compound neutralized with cyclohexylamine, monoethanolamine, diethanolamine, triethanolamine, butylamine and the like).

Of these, amine complexes of various protonic acids are preferable because they can ensure a good pot life.

Examples of the photopolymerization initiator include a photoradical polymerization initiator which generates a polymerization initiation radical upon irradiation with a light beam, and a photocationic polymerization initiator which generates a polymerization initiation cation upon irradiation with a light beam.

Specific examples of the radical photopolymerization initiator include diethoxyacetophenone and 2-hydroxy-2-.
Methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-
Hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-2-dimethylamino-1-
Acetophenones such as (4-morpholinophenyl) butanone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] poropanone oligomer; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoins such as benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butyl) Peroxylcarbonyl) benzophenone, 2,
4,6-Trimethylbenzophenone, 4-benzoyl-
Benzophenones such as N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethanaminium bromide and (4-benzoylbenzyl) trimethylammonium chloride; 2-isopropylthioxanthone, 4- Isopropyl thioxanthone, 2,
4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2- (3-dimethylamino-2-hydroxy)-
Thioxanthones such as 3,4-dimethyl-9H-thioxanthone-9-one mesochloride; and the like.

Of these, acetophenones, benzophenones and acylphosphine oxides are preferable. Especially 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino (4
-Thiomethylphenyl) propan-1one is preferred.

Specific examples of the photocationic polymerization initiator include arylsulfonium salts such as triphenylsulfonium hexafluorophosphate and triphenylsulfonium hexafluoroantimonate; diphenyliodonium hexafluoroantimonate and diphenyliodonium hexafluorophosphate. , (Trilycumyl) iodonium tetrakis (pentafluorophenyl) borate and other aryl iodonium salts; phenyldiazonium tetrafluoroborate and other aryldiazonium salts; and the like. Among these, arylsulfonium salts and diazonium salts are preferable. Particularly, (trilycumyl) iodonium tetrakis (pentafluorophenyl) borate is preferable.

These polymerization initiators may be used alone or in combination of two or more kinds. However, in order to fully exert the effects of the vinyl ether group-containing curable resin of the present invention, it is preferable to use at least one cationic polymerization initiator.

The lower limit of the total amount of the above-mentioned polymerization initiator added to the entire curable resin composition is preferably 0.05% by mass or more, and the upper limit thereof is preferably 20% by mass or less. If the amount of the polymerization initiator is less than 0.05% by mass, sufficient curing may not be obtained, and if it is more than 20% by mass, no further improvement in the physical properties of the cured product is observed, and rather adverse effects may occur. However, it may impair economic efficiency. The lower limit is
0.1 mass% or more is more preferable, 0.2 mass% or more is still more preferable, and the upper limit is more preferably 15 mass% or less, still more preferably 10 mass% or less.

In order to lower the decomposition temperature of the thermal radical polymerization initiator, a thermal polymerization accelerator capable of promoting the decomposition of the thermal radical polymerization initiator and effectively generating radicals can be used. As the thermal polymerization accelerator, metal soaps such as cobalt, copper, tin, zinc, manganese, iron, zirconium, chromium, vanadium, calcium, potassium, primary, secondary, tertiary amine compounds, quaternary ammonium salts, Thiourea compounds and ketone compounds are preferred. Among these, cobalt octylate, cobalt naphthenate, copper octylate, copper naphthenate, manganese octylate, manganese naphthenate, dimethylaniline, trietalamine, triethylbenzylammonium chloride, di (2-hydroxyethyl) p-toluidine, Ethylene thiourea, acetylacetone, methyl acetoacetate are preferred. Such thermal polymerization accelerators may be used alone or in combination of two or more kinds.

The lower limit of the total amount of the thermal polymerization accelerator added to the entire curable resin composition is preferably 0.001% by mass, and the upper limit thereof is preferably 20% by mass. The lower limit is more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and the upper limit is more preferably 10% by mass or less and further preferably 5% by mass or less. The range of the thermal polymerization accelerator is preferable from the viewpoint of curing, physical properties of the cured product, and economy.

Specific examples of the photosensitizer include 2-chlorothioxanthone, 2,4-diethylthioxanthone,
2,4-diisopropylthioxanthone and the like can be mentioned. Such photosensitizers may be used alone or in combination of two or more kinds.

The lower limit of the total amount of the photosensitizer added to the entire curable composition is preferably 0.05% by mass or more, and the upper limit thereof is preferably 20% by mass or less. The lower limit is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and the upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less. The range of the photosensitizer is preferable from the viewpoint of curing, physical properties of the cured product, and economy.

Specific examples of the photopolymerization accelerator include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl p-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,
4'-Dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone and the like can be mentioned. Among these, triethanolamine, methyldiethanolamine, and triisopropanolamine are preferable. Such a photopolymerization accelerator may be used alone,
You may use 2 or more types together.

The lower limit of the total amount of the photopolymerization accelerator added to the entire curable resin composition is preferably 0.05% by mass or more, and the upper limit thereof is preferably 20% by mass or less.
The lower limit is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and the upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less. The range of the photopolymerization accelerator is preferable in terms of curing, physical properties of the cured product, and economy.

When a thermal polymerization initiator, a photopolymerization initiator, a thermal polymerization accelerator, a photosensitizer, a photopolymerization accelerator, etc. are added in combination, the addition amount thereof with respect to the entire curable resin composition. The lower limit of the total amount is preferably 0.05% by mass or more, and the upper limit is preferably 20% by mass or less. The lower limit is more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and the upper limit is more preferably 15% by mass or less, and further preferably 10% by mass or less. The range of the total amount of addition is preferable from the viewpoint of curing, physical properties of the cured product, and economy.

The curable resin composition of the present invention further comprises, if necessary, an inorganic filler, a non-reactive resin (eg, acrylic polymer, polyester, polyurethane, polystyrene, polyvinyl chloride, etc.), an organic solvent as an additive. , Color pigments, plasticizers, polymerization inhibitors, UV absorbers, antioxidants, matting agents, dyes, defoamers, leveling agents, antistatic agents, dispersants, slip agents, surface modifiers, thixotropic agents. It is also possible to add a thixotropic agent or the like. The presence or absence of these additives does not particularly affect the effects of the present invention. These additives may be used alone or in combination of two or more.

The addition amount of the above-mentioned additive to the whole curable resin composition of the present invention is the kind of additive, purpose of use of the additive, use of the curable resin composition, method of using the curable resin composition, etc. Will be set accordingly.

For example, the inorganic filler has an addition amount lower limit of preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, based on the entire curable resin composition. The upper limit of the amount added is preferably 800% by mass or less, more preferably 600% by mass or less, and 50
0 mass% or less is more preferable.

The above non-reactive resin, organic solvent, color pigment,
As the plasticizer and the auxiliary change agent, the addition amount lower limit is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and the addition amount upper limit, based on the entire curable resin composition. However, 40 mass% or less is preferable, 30 mass% or less is more preferable, and 25 mass% or less is still more preferable.

As the above-mentioned polymerization inhibitor, ultraviolet absorber, antioxidant, matting agent, dye, defoaming agent, leveling agent, antistatic agent, dispersant, slip agent, surface modifier, auxiliary auxiliary agent, , With respect to the entire curable resin composition, the lower limit of the addition amount,
0.0001 mass% or more is preferable and 0.001 mass%
The above is more preferable, 0.01% by mass or more is further preferable, the upper limit of the added amount is preferably 5% by mass or less, and 3% by mass is preferable.
The following is more preferable, and 1% by mass or less is further preferable.

The curable resin composition of the present invention is obtained by mixing a curable resin containing a vinyl ether group-containing curable resin, a reactive diluent, and other components such as additives, and heating, dissolving, and mixing. be able to. The resulting curable resin composition of the present invention is hand-coated such as brush coating depending on the purpose of use, roll coating, gravure coating, gravure offset coating, curtain flow coating, reverse coating, screen printing, spray coating and dipping. It is applied to the substrate by a known method such as a method. The coating amount is usually preferably 0.2 g / m ² or more, more preferably 0.5 g / m ² or more, and preferably 100 g / m ² or less, 70
It is more preferably g / m ² or less.

Examples of the base material include metals such as iron, aluminum, steel plates, tin-free steel plates, tin plates, and polyethylene terephthalate film laminated steel plates; concrete; polyethylene, polypropylene, polyacryl, polyethylene terephthalate, polycarbonate, polyamide. Preferred are resin moldings and films of polyimide, nylon, polyvinyl chloride, polyvinylidene chloride, etc .; coated paper such as polyethylene-coated paper and polyethylene terephthalate-coated paper; paper such as uncoated paper; wood; and the like.

Curing of the curable resin composition of the present invention can be performed by heating, irradiation with active energy rays, etc. It is preferable to use active energy rays such as electron rays and gamma rays. In particular, ultraviolet rays and electron beams are preferable because they can improve the flexibility of the cured product and the processing adhesion. That is, a preferred form of the curable resin composition of the present invention is an active energy ray-curable resin composition that is cured by irradiation with active energy rays. Such a curable resin composition containing the above-mentioned (A) vinyl ether group-containing curable resin and (B) reactive diluent or a curable resin composition further containing (C) a polymerization initiator. The active energy ray-curing resin composition containing is also one aspect of the present invention.

In the case of curing by the above ultraviolet rays, a wavelength of 150
It is preferable to use a light source containing light in the range of ~ 450 nm. As such a light source, specifically, a sun ray, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a gallium lamp, a xenon lamp, a carbon arc lamp and the like are suitable. With these light sources, it is also possible to use heat by infrared rays, far infrared rays, hot air, high frequency heating, and the like.

The lower limit of the accelerating voltage for the curing by the electron beam is preferably 10 kV or more, more preferably 20 kV.
As described above, an electron beam having an upper limit of 30 kV or higher and an upper limit of preferably 500 kV or lower, more preferably 300 kV or lower, and further preferably 200 kV or lower may be used. The lower limit of the irradiation amount is preferably 2 kGy or more, more preferably 3 kGy or more, and 5 kGy.
The above is more preferable, and the lower limit thereof is preferably 500 kGy or less, more preferably 300 kGy or less, and 200
It is more preferably kGy or less. Infrared rays along with electron beams
The combined use of heat from far infrared rays, hot air, high frequency heating, etc. is also possible.

The curable resin composition of the present invention comprises an adhesive, an adhesive, a biomaterial, a dental material, an optical member, an information recording material,
Optical fiber materials, resist materials, plasma display panel partition walls, insulators, encapsulants, inks, inkjet inks, printing inks, screen printing inks, paints, curable adhesive sheets, laminated glass binders, paper treatment agents, fibers Surface modifier, casting material, decorative board, WPC, coating material, photosensitive resin plate, dry film, lining material,
Civil engineering building material, putty, repair material, flooring material, paving material gel coat, overcoat, hand lay-up, spray-up, pultrusion molding, filament winding, SMC,
It can be used for a wide range of applications such as molding materials such as BMC and sheets.

Among these, inks, printing inks, screen printing inks, paints, adhesives, curable tacky adhesive sheets, laminated glass binders, paper treating agents, fiber surface modifiers, encapsulants, photosensitive resins It is preferably used in application fields such as plates, plasma display panel partition walls, dry films, molding materials, civil engineering and construction materials, and vehicles such as automobiles.

When the curable resin composition of the present invention is used for coatings, various fillers such as talc, mica, alumina, silica, aluminum hydroxide can be added, if necessary. In the case of a colored paint, pigments, dyes, dispersants and the like can be added in addition to the above fillers. The paint thus obtained is one of the preferred embodiments of the present invention.
Is one. Such a coating is applied to the above-mentioned various base materials and the like, and if necessary, heating, electromagnetic waves, ultraviolet rays, visible light,
It can be cured by irradiation with active energy rays such as infrared rays, electron rays and gamma rays.

When the curable resin composition of the present invention is used for ink, a binder such as a resin, various fillers, pigments, dyes, dispersants and the like can be added if necessary. The ink thus obtained is one of the preferred embodiments of the present invention. Such an ink is applied on a metal, paper, resin, or other substrate, and if necessary, heating, active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, gamma rays, and the like. It can be cured by irradiation with rays. In particular, it is preferable to cure with light such as ultraviolet rays, visible rays, and near infrared rays.

When the curable resin composition of the present invention is used as an adhesive or a pressure-sensitive adhesive (hereinafter referred to as "adhesive adhesive"), it may have tackiness such as tackifier as required. Additives, various fillers, pigments, dyes, dispersants and the like can be added. The adhesive thus obtained is
It is one of the preferred embodiments of the present invention. Such an adhesive is applied on metal, paper, resin, or other base material, and if necessary, heating, active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron rays, gamma rays, etc. It can be cured by irradiation with active energy rays. In particular, it is preferable to cure with light such as ultraviolet rays, visible rays, and near infrared rays.

Incidentally, in recent years, a curable pressure-sensitive adhesive sheet obtained by processing various polymerizable resin compositions into a sheet or film /
The film is drawing attention. Unlike conventional non-curable tacky adhesive sheets / films, it has excellent tackiness and heat resistance, and unlike liquid adhesives, it is easy and easy to work with. Used for. Specifically, an uncured curable resin composition (prepreg) processed into a sheet shape or a film shape is attached to a base material and heated,
The adhesive layer is formed by curing by irradiation with active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, and gamma rays. This curable tacky adhesive sheet / film is one of the preferred embodiments of the curable resin composition of the present invention.

When the curable resin composition of the present invention is used for a curable molding material, various fillers, pigments, dyes, dispersants and the like can be added as required. The curable molding material thus obtained is one of the preferred embodiments of the present invention. Such a curable molding material can be used as it is or by impregnating reinforcing fibers such as glass fibers, carbon fibers, and aramid fibers, and if necessary, heating, electromagnetic waves, ultraviolet rays, visible rays, infrared rays, Electron beam,
It can be cured and shaped by irradiation with active energy rays such as gamma rays. In particular, it is preferable to cure and shape with heat, a highly transparent electron beam, a visible ray, a near infrared ray or the like.

An article obtained by curing the curable resin composition of the present invention is also one of the preferred embodiments of the present invention. In the present invention, the “article” includes a curable resin composition containing the above-mentioned (A) vinyl ether group-containing curable resin of the present invention and (B) a reactive diluent, or further (C) a polymerization initiator. An adhesive, a pressure-sensitive adhesive, a biomaterial, a dental material, an optical member, an information recording material, an optical fiber material, a resist material, a plasma display panel partition wall, an insulator, a sealing material, an ink, which comprises a curable resin composition comprising Inkjet ink, printing ink, screen printing ink, paint, curable adhesive sheet, laminated glass binder, paper treatment agent, fiber surface modifier, casting material, decorative board, WPC, coating material, photosensitive resin plate , Dry film, lining material,
Civil engineering building material, putty, repair material, flooring material, paving material gel coat, overcoat, hand lay-up, spray-up, pultrusion molding, filament winding, SMC,
A cured adhesive, a cured adhesive, which is obtained by curing a molding material such as BMC or a sheet by heating or irradiation with active energy rays such as electromagnetic waves, ultraviolet rays, visible rays, infrared rays, electron beams, gamma rays and the like. Biomaterial cured product, dental material cured product, optical member cured product, information recording material cured product, optical fiber material cured product, resist material cured product, plasma display panel partition cured product, insulator cured product, encapsulant cured product, Ink cured product, inkjet ink cured product, printing ink cured product, screen printing ink cured product,
Cured paint, curable adhesive / bonded sheet cured product, laminated glass binder cured product, paper treatment agent cured product, fiber surface modifier cured product, casting material cured product, decorative board cured product, WPC cured product, coating material Cured product, Photosensitive resin plate cured product, Dry film cured product, Lining material cured product, Civil engineering building material cured product, Putty cured product, Repair material cured product, Floor material cured product, Paving material gel coat cured product, Overcoat cured product , Hand layup, spray up, pultrusion, filament winding,
It is a cured product of a molding material such as SMC / BMC or a cured product of a sheet. Here, the "cured product" means a substance having no fluidity.

[0067]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. [Synthesis Example 1; Synthesis of vinyl ether group-containing curable resin (1)] In a 10-liter four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 6500 parts of toluene and 2-acrylic acid After adding 650 parts of (vinyloxyethoxy) ethyl and 20 parts of 2,2′-azobisisobutyronitrile, the temperature was gradually raised to 60 ° C. under a nitrogen stream and further reacted at the same temperature for 8 hours, and then under reduced pressure. Toluene (4500 parts) was distilled off, and hexane (5000 parts) was used for reprecipitation to obtain a vinyl ether group-containing curable resin (1).

[Synthesis Example 2; Synthesis of vinyl ether group-containing curable resin (2)] To a 5 liter four-necked flask equipped with a stirrer, a thermometer, a cooling pipe and a nitrogen gas introduction pipe, 3500 parts of toluene and acrylic 2- (vinyloxyethoxy) ethyl acid 325 parts, butyl acrylate 325 parts and 2,2′-azobisisobutyronitrile 20 parts were added, and the temperature was gradually raised to 60 ° C. under a nitrogen stream and further at the same temperature. After reacting for 8 hours, 2500 parts of toluene was distilled off under reduced pressure, and 5000 parts of hexane was used for reprecipitation to obtain a vinyl ether group-containing curable resin (2).

[Synthesis Example 3; Synthesis of vinyl ether group-containing curable resin (3)] 2- (vinyloxyethoxy) ethyl acrylate (450 parts) and butyl acrylate (200 parts) were 585 parts, respectively. By performing the same operation as in Synthesis Example 2, a vinyl ether group-containing curable resin (3) was obtained.

[Synthesis Example 4; Synthesis of vinyl ether group-containing curable resin (4)] 2- (vinyloxyethoxy) ethyl acrylate is converted to 2- (vinyloxyethoxy) methacrylate.
A vinyl ether group-containing curable resin (4) was obtained by performing the same operations as in Synthesis Example 2 except that ethyl was used.

[Synthesis Example 5: Synthesis of vinyl ether group-containing curable resin (5)] The same operation as in Synthesis Example 2 was performed except that 2- (vinyloxyethoxy) ethyl acrylate was changed to 4-vinyloxybutyl acrylate. Thus, a vinyl ether group-containing curable resin (5) was obtained.

[Synthesis Example 6; Synthesis of vinyl ether group-containing curable resin (6)] 2- (vinyloxyethoxy) ethyl acrylate was replaced with 4-vinyloxybutyl methacrylate.
By performing the same operation as in Synthesis Example 2 except that
A vinyl ether group-containing curable resin (6) was obtained.

[Synthesis Example 7: Synthesis of vinyl ether group-containing curable resin (7)] A vinyl ether group-containing curable resin (7) was prepared in the same manner as in Synthesis Example 2 except that butyl acrylate was used as the styrene monomer. ) Got.

[Synthesis Example 8: Synthesis of vinyl ether group-containing curable resin (8)] A vinyl ether group also containing an epoxy group was obtained by performing the same operation as in Synthesis Example 2 except that butyl acrylate was changed to glycidyl methacrylate. Curable resin (8) was obtained.

[Comparative Synthesis Example 1; Synthesis of Urethane Acrylate Resin (a)] To a one-liter four-necked flask equipped with a stirrer, a thermometer, a cooling tube and a gas introduction tube, 348 parts of tolylene diisocyanate and dibutyltin were added. 0.3 part of dilaurate was added and maintained at 40 ° C. under a nitrogen stream, 260 parts of hydroxypropyl acrylate was added dropwise at the same temperature over 2 hours, and then 141 parts of dipropylene glycol was added dropwise over 2 hours at the same temperature. 5 at the same temperature
The reaction was carried out for a time to obtain a urethane acrylate resin (a).

Comparative Synthesis Example 2 Synthesis of Epoxy Resin (b) Partially Modified with Acrylic Acid! 144 parts, 690 parts of cresol novolac type epoxy resin (epoxy equivalent 230) and 4.3 parts of triethylamine were added, and 115 ° C. under air flow.
The temperature is gradually raised to 10 hours at the same temperature,
An epoxy resin (b) partially modified with methacrylic acid was obtained.

[Examples 1 to 13 and Comparative Examples 1 to 8]
(Thermosetting of various curable resin compositions) Reactive with curable resins (1) to (8), curable resins (a) and (b) for comparison, and commercially available epoxy resins at the ratios shown in Tables 1 to 3. A diluent, a thermal polymerization initiator, and a polymerization accelerator were added to prepare a curable resin composition, and the room temperature thermosetting property and thermosetting physical property of each composition were measured.

The results are shown in Tables 1 to 3. The methods for measuring various physical properties are shown below.

(Appearance of resin) A resin composition having a diameter of 1 is selected.
It was poured into an 8 mm test tube and the appearance was visually evaluated.

(Dry to touch) Glass plate (size 150 m
m × 100 mm) using a bar coater and wet thickness 4
Each curable resin composition was applied so as to have a thickness of 0 μm and left at room temperature. After 6 hours from the end of coating, the tackiness of the surface of the coating film was confirmed by touching with a finger. When the tackiness disappeared, the mark was ○, when the tackiness was slightly left, Δ, when the tackiness was clearly left, ×. And

(Solvent resistance) A cured coating film obtained by using the same conditions and materials as described above and curing the composition at room temperature for 6 hours was treated 10 times with gauze impregnated with MEK (methyl ethyl ketone). Rub up to 50 times,
The gloss change on the surface of the coating film was visually evaluated (it was counted as one time by reciprocating the gauze once). When the gloss did not change, it was evaluated as ◯, when the gloss was slightly decreased, it was evaluated as Δ, and when the gloss was completely lost, it was evaluated as x. (Strength property of casting plate) Each curable resin composition was cast into a glass casting container (thickness: 3 mm), allowed to stand at room temperature for 1 day after curing at room temperature, and then after-cured at 110 ° C. for 2 hours. Regarding the template, according to JIS K-7113,
Tensile strength and tensile elongation were measured.

(Heat Resistance) Each curable resin composition was cast into a glass casting container (4 mm thick), cured at room temperature, left for one day and night, and then after-cured at 110 ° C. for 2 hours to obtain the obtained casting. The deflection temperature under load (HDT) was measured for the template according to JIS K-7207.

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[Examples 14 to 21 and Comparative Examples 9 to 1]
3] (UV curing of various curable resin compositions) Curable resins (1) to (3), (8) and comparative curable resin in the proportions shown in Tables 4 and 5 are reactive diluents and photopolymerization initiation. A curable resin composition was prepared by blending the agent, and the photocurability and photocurable physical properties of each composition were measured. The results are shown in Tables 4 and 5. The methods for measuring various physical properties are shown below.

(Photocurable) The composition was applied on a degreased oak veneered veneered plywood (size 150 mm × 100 mm) using a bar coater to a wet thickness of 40 μm, and then a high pressure of 80 W / cm. Exposure was carried out using a belt conveyor UV irradiation device equipped with one mercury lamp.
Distance from light source is 10 cm, conveyor speed is 15 m
/ Min, the effective exposure length was set to 60 cm (with respect to the traveling direction of the conveyor), and the number of passes until tackiness disappeared from the coating film surface was measured by touching with a finger. By the way, when this UV irradiation device is used to perform exposure under the above conditions, the amount of UV irradiation energy per pass is 140 mJ / cm2 (3
(65 nm conversion). In each of the measured values in the table, it means that the composition having a smaller number of passes has a better photocurability.

(Pencil Hardness) A cured coating film obtained by exposing the belt conveyor ultraviolet ray irradiating device and other conditions and materials at a pass number of 10 has a pencil hardness according to JIS K-5400. It was measured.

(Adhesion) The number of passes is set to 2 by using the above belt conveyor ultraviolet irradiation device and other conditions and materials.
A cellophane tape (manufactured by Nichiban) having a width of 18 mm was attached to the cured coating film obtained by performing exposure as 0 times with a length of 20 mm, and a tape peeling test was performed. In the table, ∘ indicates that there was no change in the coating film, Δ indicates that it was partially peeled, and × indicates that it was peeled.

[0090]

[Table 4]

[0091]

[Table 5]

[Examples 22-24 and Comparative Examples 14-1
6] (Electron beam curing of various curable resin compositions) Table 6 shows the curable resin (2) and the comparative curable resin (a).
The curable resin composition was prepared by blending the reactive diluent in the proportion shown in, and the electron beam curability and the physical properties of the electron beam cured product of each composition were measured. The results are shown in Table 6. The methods for measuring various physical properties are shown below.

(Electron beam curability) A glass plate was coated with the composition so as to have a wet thickness of 100 μm using a bar coater, and then an electron beam was irradiated using an electron curtain type electron beam irradiation apparatus. Check the coating surface by touching the finger,
The amount of electron beam irradiation until the tackiness disappeared was measured. In each of the measured values in the table, a composition having a smaller electron beam irradiation amount has a higher electron beam curability.

(Appearance of coating film) Using the above electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 KG.
The gloss and color of the cured coating film obtained by irradiation as y were visually evaluated. A sample with excellent gloss was marked with O, a sample with slightly deteriorated gloss was marked with Δ, and a sample with no gloss (matte appearance) was marked with X. The uncolored ones are ○,
The one that was slightly colored was marked with Δ, and the one that was clearly colored was marked with x.

(Solvent resistance) Using the above-mentioned electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 KG.
The cured coating film obtained by irradiation as y was rubbed 10 times with gauze impregnated with MEK (methyl ethyl ketone), and finally up to 50 times, to visually evaluate the change in gloss of the coating surface (1 gauze was used). 1 by going back and forth
Counted as times. ). When the gloss did not change, it was evaluated as ◯, when the gloss was slightly decreased, it was evaluated as Δ, and when the gloss was completely lost, it was evaluated as x.

(Pencil hardness) Using the above electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 KG.
The pencil hardness of the cured coating film obtained by irradiating y was measured according to JIS K-5400.

(Weather Resistance) Using the above-mentioned electron beam irradiation apparatus and other conditions and materials, the irradiation energy amount was 50 KGy.
About the cured coating film obtained by irradiating as
2 in carbon arc type sunshine weatherometer
After accelerated exposure for 000 hours, the color difference between the cured coating film after exposure and the initial (before exposure) cured coating film was visually evaluated. Those having no difference from the initial cured coating film were marked with ◯, slightly colored ones with Δ, and clearly colored ones with x.

[0098]

[Table 6]

[Example 25] (Curable adhesive sheet) 30 parts of 2- (vinyloxyethoxy) ethyl acrylate and epoxy resin were placed in a flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube in a four-necked flask. (Ciba Specialty Chemicals Araldite GY-250) 90 parts, triethylene glycol divinyl ether 10 parts, photoradical polymerization initiator (Ciba Specialty Chemicals Irgacure 1700) 0.2 parts and photocationic polymerization initiator. (Asahi Denka Co., Ltd. Optomer SP-170) 0.5
Parts were added and stirred at room temperature under a nitrogen stream to obtain a photopolymerizable composition.

Then, the resin composition was applied to a PET film with an applicator to a thickness of 300 μm, and further PE was applied.
It was sandwiched between T films. Near-ultraviolet light (maximum wavelength 400 μm obtained by cutting ultraviolet light of 360 nm or less on the obtained film
m) was irradiated at 1 mW / cm2 for 10 minutes. Through this step, radical polymerization proceeded, and a flexible and tacky curable tacky-adhesive sheet having a vinyl ether group was obtained.

The obtained sheet was cut into a size of 25 mm × 25 mm, attached to a stainless (SUS304) plate, and exposed to ultraviolet light (maximum wavelength 360 μm) of 30 mW / cm 2.
For 1 minute. By this step, cationic polymerization proceeded and the resin was completely cured to obtain a cured adhesive / adhesive sheet.

The shear adhesive strength of the cured adhesive / bonding sheet was measured according to JIS Z0237, and found to be 26 kgf.
/ Cm2, which shows a practically sufficient shear adhesive strength.

Example 26 (Curable Adhesive Sheet) Shear adhesion was carried out by the same procedure except that the epoxy resin used in Example 25 was changed to Araldite CY-179 manufactured by Ciba Specialty Chemicals. When the force was measured, the resin composition was then applied to a PET film with an applicator to a thickness of 300 μm, and the PET film was sandwiched between the PET films. 1 near UV light (maximum wavelength 400 μm) obtained by cutting UV light of 360 nm or less was obtained.
Irradiation was performed at mW / cm2 for 10 minutes. Through this step, radical polymerization proceeded, and a flexible and tacky curable tacky-adhesive sheet having a vinyl ether group was obtained.

The obtained sheet was cut into a size of 25 mm × 25 mm, attached to a stainless (SUS304) plate, and exposed to ultraviolet light (maximum wavelength 360 μm) of 30 mW / cm 2.
For 1 minute. By this step, cationic polymerization proceeded and the resin was completely cured to obtain a cured adhesive / adhesive sheet.

The shear adhesive strength of the cured product of the above-mentioned adhesive / bonding sheet was measured according to JIS Z0237 and found to be 22 kgf.
/ Cm2, which shows a practically sufficient shear adhesive strength.

Example 27 (Curable Adhesive Sheet) A flask equipped with a stirrer, a nitrogen gas introducing tube and a cooling tube was placed in a four-necked flask, and 30 parts of vinyloxyethoxyethyl methacrylate and an epoxy resin (Ciba Specialty. Chemicals Co. Araldite GY-250) 90 parts, triethylene glycol divinyl ether 10 parts, thermal radical polymerization initiator (Kayaku Akzo Co., Ltd. Perkadox 16 (bis (4-t-butylcyclohexyl) peroxydicarbonate)) ) 1 part and a photocationic polymerization initiator (Asahi Denka Co., Ltd. Optomer SP-170) 0.5 part were added,
The mixture was stirred at room temperature under a nitrogen stream to obtain a heat / photopolymerizable composition.

Then, the resin composition was applied to a PET film with an applicator so as to have a thickness of 300 μm.
It was sandwiched between T films. The obtained fill was allowed to stand for 10 minutes in an air circulation oven whose temperature was adjusted to 60 ° C. Through this step, radical polymerization proceeded, and a flexible and tacky photocurable pressure-sensitive adhesive sheet having a vinyl ether group was obtained.

The obtained sheet was cut into a size of 25 mm × 25 mm and attached to a stainless (SUS304) plate, and ultraviolet light (maximum wavelength 360 μm) was 30 mW / cm ^2.
For 1 minute. By this step, cationic polymerization proceeded and the resin was completely cured to obtain a cured adhesive / adhesive sheet.

The shear adhesive strength of the cured adhesive / bonding sheet was measured according to JIS Z0237 and found to be 25 kgf.
/ Cm ² and showed a shearing adhesive force practically sufficient.

[0110]

According to the present invention, by using a curable resin composition comprising a vinyl ether group-containing curable resin containing a vinyl ether group as a pendant and a reactive diluent, a (meth) acryloyl group-containing curable resin is obtained. The problems of the composition, the epoxy group-containing curable resin composition and the (meth) acryloyl group-epoxy group-containing curable resin composition can be overcome.

A curable resin composition comprising the above-mentioned vinyl ether group-containing curable resin and a reactive diluent obtained according to the present invention is used in various applications such as paints, inks, adhesives, pressure-sensitive adhesives, surface-modifying materials and molding materials. Can be applied to.

Continued front page    F-term (reference) 4J027 AA02 AA08 AB10 AB36 AC03                       AC06 AC07 AD02 AE07 AE10                       AF05 AG33 AG36 AJ08 AJ09                       BA04 BA05 BA06 BA07 BA08                       BA10 BA11 BA12 BA13 BA14                       BA15 BA17 BA19 BA20 BA23                       BA26 CA02 CA03 CA06 CA10                       CA11 CA29 CA34 CA36 CB03                       CB07 CB09 CB10 CC02 CC04                       CC05 CC06 CD01 CD02 CD07                       CD08 CD09 CD10                 4J100 AL74P BA02P BA08P BC04P                       BC43P CA01 JA01 JA03                       JA05 JA07 JA11 JA13 JA32                       JA35 JA38 JA52 JA57 JA67

Claims (5)

[Claims] 1. (A) General formula (1): (In the formula, R ¹ represents a hydrogen atom or a methyl group. R ²
Represents an organic residue having 2 to 20 carbon atoms. R ³ represents a hydrogen atom or an organic residue having 1 to 11 carbon atoms. A curable resin composition comprising a vinyl ether group-containing curable resin having a structural unit represented by the above) and (B) a reactive diluent. 2. A curable resin composition comprising the curable resin composition according to claim 1 and (C) a polymerization initiator. 3. A resin composition for curing active energy rays, which comprises the curable resin composition according to claim 1. 4. A curable tacky-adhesive sheet comprising the curable resin composition according to claim 1. 5. An article obtained by curing the curable resin composition according to claim 1 or 2.