JP2002018991A - Curable prepreg, method for manufacturing the same and curing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable prepreg capable of being stably thickened for a short time, preventing the outflow of a resin from a fibrous base material during the preservation of the prepreg, not peeled during a period from bonding to curing even when an adherend has a complicated shape and capable of developing high adhesive strength without using a primer, a method for manufacturing the same and a curing method. SOLUTION: The curable prepreg having a pressure-sensitive adhesive layer provided to the single surface or both surfaces thereof is disclosed. The curable prepreg is manufactured by applying a pressure-sensitive adhesive to a film to form the pressure-sensitive adhesive layer and laminating a curable prepreg composition on the pressure-sensitive adhesive layer and irradiating the curable prepreg composition with visible light and/or near infrared rays to preparatorily polymerizing the same up to a B-stage to integrate the polymerized composition layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding sheet made of a resin and a fiber reinforcing material and / or a filler used for repairing, reinforcing, and waterproofing a structure in the field of FRP molding, construction and civil engineering, and the like. The present invention relates to curable prepregs having various shapes such as a roll shape, a tubular shape, and a tubular shape, a method for producing the same, and a method for curing the same.

[0002]

2. Description of the Related Art Fiber-reinforced plastics (hereinafter referred to as FRP) used for molded articles requiring structural strength and structural materials of buildings.
That. ) Is a combination of an inorganic or organic reinforcing material such as glass fiber and carbon fiber and a so-called thermosetting resin such as an epoxy resin, an unsaturated polyester resin, and a vinyl ester resin (also referred to as an epoxy acrylate resin). ing. For example, when repairing a molded article, a building, or the like using an unsaturated polyester resin or a vinyl ester resin, normal temperature curing with a peroxide catalyst is usually performed, but it takes a long time to completely cure.
If curing takes too long, not only does workability deteriorate, but also volatile reactive monomers (such as styrene monomer) volatilize, causing air pollution at the work site, and changing the mixing ratio of the resin composition. This leads to the risk of loss of resin, loss of resin and ignition. In addition, the danger of handling the peroxide catalyst directly, complicated operations such as weighing the peroxide catalyst with a dropper on site and mixing it with the resin, and the gelation time varies greatly depending on the temperature. Is difficult, and there are many troubles that fail to adjust the pot life.

In order to solve these drawbacks, air pollution and curability have been improved on site by replacing volatile monomers in the resin with other high-boiling compounds. The problem that it takes a long time for the room temperature curing system with the vinyl ester resin-based peroxide catalyst to completely cure, the danger of handling the peroxide catalyst directly, the complexity of the peroxide catalyst addition operation, The problem of difficulty in adjusting the pot life has not been solved. To solve such a problem, Japanese Patent Laid-Open No.
As disclosed in Japanese Patent No. 71661, a photocurable prepreg sheet in which an unsaturated polyester resin impregnated in glass fiber or the like is metal-thickened has been proposed, but a conventional thermosetting resin thickening method has been proposed. For example, in the case of a known technique of thickening a metal with an unsaturated polyester resin such as magnesium oxide or isocyanate thickening of a vinyl ester resin,
It takes a long time to thicken, and it is difficult to stabilize the thickened state, and the reactive diluent such as styrene monomer in the resin does not participate in the thickening reaction of vinyl ester resin or unsaturated polyester resin. There are problems such as resin flowing out of the fibrous base material during storage of the prepreg sheet,
Furthermore, when the shape of the adherend to which the prepreg sheet is to be attached is complicated, there is a problem that the prepreg sheet is peeled off before the prepreg sheet is attached and photocured, or the adhesive strength is insufficient unless a primer is used. Was. In addition, there is a similar problem with thermosetting prepregs, which solves the problem that the prepreg sheet is peeled off before being attached and thermally cured, or the adhesive strength is insufficient unless a primer is used. There was no.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present invention provides a stabilized thickening reaction in a short period of time, and prevents a resin from flowing out of a fibrous base material during storage of a prepreg sheet. A curable prepreg that does not peel off before the prepreg sheet is applied and cured even when the shape of the adherend is complicated, and that can sufficiently exhibit adhesive strength without using a primer, and a method for producing the same. And a curing method.

[0005]

SUMMARY OF THE INVENTION The present invention provides a curable prepreg characterized by having a pressure-sensitive adhesive layer on one or both sides of the curable prepreg layer. The present invention also has a pressure-sensitive adhesive layer on one or both sides of a curable prepreg layer, and the curable prepreg layer is composed of (H) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin, and (I1) two or more kinds. 0.01-20 parts by weight of a photopolymerization initiator having photosensitivity from the ultraviolet region to the near infrared region
(J) 0 to 5 parts by weight of an ultraviolet absorber and (K) inorganic or organic fiber reinforcing material and / or filler 1 to 400
Parts by weight of the composition, wherein the composition preliminarily polymerizes some of the radically polymerizable unsaturated groups in the resin, and at least one kind of a photopolymerization initiator and a radically polymerizable unsaturated group. A curable prepreg characterized by being treated with light of a specific wavelength such that a part of the curable prepreg is provided, and an adhesive layer or a curable adhesive on one or both surfaces of the curable prepreg layer. A curable prepreg layer comprising (H) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin,
(I1) 0.01 to 10 parts by weight of a photopolymerization initiator having photosensitivity from an ultraviolet light region to a near infrared light region, (I2) 0.01 to 10 parts by weight of a thermal polymerization initiator, (J) an ultraviolet absorber : 0
A composition containing 5 parts by weight and (K) an inorganic or organic fiber reinforcing material and / or a filler: 1 to 400 parts by weight, and the composition comprises a radical polymerizable unsaturated group in the resin. A curable prepreg characterized by being partially prepolymerized and treated with light having a specific wavelength such that a thermal polymerization initiator and a part of a radical polymerizable unsaturated group remain. Is what you do.

Further, the present invention relates to a method for applying a visible light after laminating the above-mentioned curable prepreg composition on a pressure-sensitive adhesive layer formed by applying the pressure-sensitive adhesive on a film before the prepolymerization. And / or a method for producing a curable prepreg, which comprises prepolymerizing and integrating the curable prepreg composition by irradiation with near-infrared light, and two or more photopolymerization initiators or photopolymerization initiators. After laminating the curable prepreg composition in a state before the pre-polymerization on the curable pressure-sensitive adhesive layer formed by applying the curable pressure-sensitive adhesive composition containing a thermal polymerization initiator, visible light as well as/
Or by irradiation with near-infrared light, while providing a method for producing a curable prepreg, characterized in that the curable pressure-sensitive adhesive and the curable prepreg are pre-polymerized and integrated, and the curable prepreg is exposed to visible light and Another object of the present invention is to provide a method of curing a curable prepreg, which comprises curing or heating by irradiation with near-infrared light.

[0007]

Next, the present invention will be described in detail.
The curable prepreg of the present invention has a pressure-sensitive adhesive layer on one side or both sides of a curable prepreg layer. As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer, any of a non-curable pressure-sensitive adhesive and a curable pressure-sensitive adhesive can be used.

The non-curable pressure-sensitive adhesive used in the present invention comprises:
The polymer is a polymer of two or more kinds of radically polymerizable unsaturated compounds. As the radically polymerizable unsaturated compound, known compounds can be used and are not particularly limited. Specific examples thereof include styrene, α-, o-, m-, p of styrene.
-Alkyl, nitro, cyano, amide, ester derivatives, butenes such as butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, methyl (meth) acrylate, ethyl (meth) acrylate, n- (meth) acrylate Propyl, i-propyl (meth) acrylate,
N-butyl (meth) acrylate, s (meth) acrylate
ec-butyl, tert-butyl (meth) acrylate,
Pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate , Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid 2
-Methylcyclohexyl, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth)
Adamantyl acrylate, allyl (meth) acrylate,
Propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate, anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate , Furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, pyranyl (meth) acrylate, benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate , (Meth) acrylic acid 1,1,
1-trifluoroethyl, perfluoroethyl (meth) acrylate, perfluoro-n-propyl (meth) acrylate, perfluoro-i-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, ( Meta)
Cumyl acrylate, (meth) acrylic acid 3- (N, N-
Dimethylamino) propyl, (meth) acrylic acid-2-
(Meth) acrylic esters such as hydroxyethyl and 2-hydroxypropyl (meth) acrylate, (meth) acrylamide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N -Diethylamide, (meth) acrylic acid N, N-dipropylamide,
(Meth) acrylic acid N, N-di-i-propylamide,
(Meth) acrylic acid amides such as (meth) acrylic acid anthracenylamide, (meth) acrylic anilide,
(Meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl compounds such as vinyl acetate, diethyl citrate, diethyl maleate, diethyl fumarate, itacone Unsaturated dicarboxylic acid diesters such as diethyl acid, monomaleimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide, and N- (meth) acryloylphthalimide. Can be

Further, a vinyl ester resin, a vinyl ester resin,
A mixture of a known radically polymerizable resin such as an unsaturated polyester resin and a urethane (meth) acrylate resin can also be mentioned as the non-curable pressure-sensitive adhesive. The mixing amount is 5 to 200 parts by weight, preferably 10 to 100 parts by weight, per 100 parts by weight of the polymer of one or more radically polymerizable unsaturated compounds. If the mixing amount is less than 5 parts by weight, the curability is insufficient, and if it exceeds 200 parts by weight, the tackiness is insufficient.

The curable pressure-sensitive adhesive used in the present invention includes (A) 100 parts by weight of a polymer of one or more radically polymerizable unsaturated compounds, and (B) 5 to 300 parts by weight of a radically polymerizable unsaturated compound. And (C) a polymerization initiator of 0.1 to 10
Parts by weight (hereinafter referred to as "curable pressure-sensitive adhesive composition-
1 ". ), (D) one or more radically polymerizable unsaturated compounds and one or more radically polymerizable unsaturated compounds having an epoxy group are copolymerized to form an unsaturated compound capable of reacting with the epoxy group in the obtained copolymer. 100 parts by weight of a polymer obtained by adding a radically polymerizable unsaturated compound having a saturated monobasic acid and / or an amino group to 5 to 100 mol% of the epoxy group, and (B) 5 to 300 parts by weight of the radically polymerizable unsaturated compound And (C) a composition comprising 0.1 to 10 parts by weight of a polymerization initiator (hereinafter referred to as “curable pressure-sensitive adhesive composition-2”),
(E) one or more radically polymerizable unsaturated compounds and 1
A radical having an epoxy group capable of reacting with a carboxyl group and / or an amino group in the obtained copolymer by copolymerizing at least one kind of unsaturated monobasic acid and / or a radical polymerizable unsaturated compound having an amino group. 100 parts by weight of a polymer obtained by adding a polymerizable unsaturated compound to the carboxyl group and / or amino group capable of reacting at 5 to 100 mol%, (B) 5 to 300 parts by weight of a radical polymerizable unsaturated compound, and ( C) a composition comprising 0.1 to 10 parts by weight of a polymerization initiator (hereinafter referred to as “curable pressure-sensitive adhesive composition-3”),
(F) one or more radically polymerizable unsaturated compounds and 1
A radical polymerizable unsaturated compound having at least one kind of hydroxyl group and / or a radical polymerizable unsaturated compound having an amino group is copolymerized, and the hydroxyl group and / or
Or 100 parts by weight of a polymer in which a radically polymerizable unsaturated compound having an isocyanate group capable of reacting with an amino group is added in an amount of 5 to 100 mol% with respect to a portion capable of reacting with a hydroxyl group and / or an amino group, (B) radical polymerization 5 to 300 parts by weight of the unsaturated compound and 0.1 to 1 of the polymerization initiator (C)
0 parts by weight (hereinafter referred to as "curable pressure-sensitive adhesive composition-
4 ". ) And (G) one or more radically polymerizable unsaturated compounds and one or more radically polymerizable unsaturated compounds having an isocyanate group, and a hydroxyl group capable of reacting with the isocyanate group in the obtained copolymer. 100 parts by weight of a polymer obtained by adding a radical polymerizable unsaturated compound having an amino group to 5 to 100 mol% of the isocyanate group, (B) 5 to 300 parts by weight of the radical polymerizable unsaturated compound, and (C) Polymerization initiator 0.1 to 10
Parts by weight (hereinafter referred to as "curable pressure-sensitive adhesive composition-
5 ". ) Can be used.

As the radically polymerizable unsaturated compound used in the polymer of the above components (A), (D), (E), (F) and (G), known compounds can be used, and those which are particularly limited is not. Specific examples thereof include styrene, α-, o-, mp-alkyl, nitro, cyano, amide, and ester derivatives of styrene, butenes such as butadiene, 2,3-dimethylbutadiene, isoprene, and chloroprene; ) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, sec- (meth) acrylate Butyl, (meth)
Tert-butyl acrylate, pentyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate , Dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, isobornyl (meth) acrylate, (meth) acryl Adamantyl acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracenyl (meth) acrylate,
Anthraninonyl (meth) acrylate, piperonyl (meth) acrylate, salicyl (meth) acrylate, furyl (meth) acrylate, furfuryl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth)
Pyranyl acrylate, benzyl (meth) acrylate,
Phenethyl (meth) acrylate, cresyl (meth) acrylate, 1,1,1-trifluoroethyl (meth) acrylate, perfluoroethyl (meth) acrylate,
Perfluoro-n-propyl (meth) acrylate, Perfluoro-i-propyl (meth) acrylate, (meth)
Triphenylmethyl acrylate, cumyl (meth) acrylate, 3- (N, N-dimethylamino) propyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate (Meth) acrylic acid esters such as propyl, (meth) acrylic acid amide, (meth) acrylic acid N, N-dimethylamide, (meth) acrylic acid N, N-diethylamide, (meth) acrylic acid N, N- (Meth) acrylic acid amides such as dipropylamide, (meth) acrylic acid N, N-di-i-propylamide, (meth) acrylic acid anthracenylamide, (meth) acrylic anilide, (meth) acryloylnitrile , Acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinyl Pyridine, vinyl compounds such as vinyl acetate, diethyl citraconic acid, diethyl maleate, diethyl fumarate, unsaturated dicarboxylic acid diester of itaconic acid diethyl, N- phenylmaleimide,
Mono-maleimide compounds such as N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide, and N- (meth) acryloylphthalimide.

In the polymers of the above components (D), (E), (F) and (G), the radical polymerizable unsaturated compound having a functional group, that is, the radical polymerizable unsaturated compound having an epoxy group, A saturated monobasic acid, a radical polymerizable unsaturated compound having a hydroxyl group, a radical polymerizable unsaturated compound having an amino group, or a radical polymerizable unsaturated compound having an isocyanate group is used. Glycidyl (meth) is a radical polymerizable unsaturated compound having an epoxy group.
Acrylate, allyl glycidyl ether, styrene
Examples of the unsaturated monobasic acid include acrylic acid, methacrylic acid, crotonic acid, and o, m, p-vinylbenzoic acid, which are unsaturated carboxylic acids having an ethylenically unsaturated double bond. And monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro and cyano substituted products of (meth) acrylic acid.

As the radical polymerizable unsaturated compound having a hydroxyl group, known compounds can be used, and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerin di (meth) acrylate
Acrylate, glycerol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth)
Mono (meth) acrylates such as acrylates are mentioned, and radical polymerizable unsaturated compounds having an amino group include (meth) acrylamide, diethylaminoethyl methacrylate and the like. Examples of the radical polymerizable unsaturated compound having an isocyanate group include methacryloyl isocyanate (manufactured by Nippon Paint Co., Ltd.) and isocyanate ethyl methacrylate (manufactured by Showa Denko KK) (for details, see JP-A-11-228688, It is described in JP-A-11-228689.) As the radical polymerizable unsaturated compound having such a functional group, one having one radical polymerizable unsaturated group is preferable.

In addition, a radical polymerizable unsaturated group is introduced by an addition reaction between a functional group in the copolymer and a functional group in a radical polymerizable unsaturated compound having a functional group capable of reacting with the functional group. In doing so, a compound having two or more radically polymerizable unsaturated bonds can be included in addition to the above-mentioned radically polymerizable unsaturated compound having a functional group. The amount of the radically polymerizable unsaturated compound having a functional group in the copolymer in the components (D), (E), (F) and (G) is 5 out of the monomers constituting the copolymer. Desirably, the content is less than 5 mol%, and sufficient curability cannot be obtained. Use of a radically polymerizable unsaturated compound having a functional group capable of reacting with a functional group in the copolymer in the components (D), (E), (F) and (G) to cause an addition reaction. The amount is 5 to 1 with respect to the functional group in the copolymer.
Desirably, it is 00 mol%. If it is less than 5 mol%, the curability cannot be sufficiently exhibited.

As the (co) polymerization reaction for obtaining the polymers of the above-mentioned components (A), (D), (E), (F) and (G), a known solution polymerization method is applied. The polymerization reaction may be carried out by dissolving the initiator in a solvent and raising the temperature while stirring, or the monomer to which the polymerization initiator has been added may be dropped into the heated and stirred solvent. Further, the monomer may be dropped while the polymerization initiator is added to the solvent and the temperature is raised.
Reaction conditions can be freely changed according to the target molecular weight.

The solvent to be used is not particularly limited as long as it is inert to radical polymerization, and a commonly used organic solvent can be used. Specific examples thereof include ethylene glycol monoalkyl ether acetates such as ethyl acetate, isopropyl acetate, cellosolve acetate and butyl cellosolve acetate, diethylene glycol monoalkyl ether acetates such as diethylene glycol monomethyl ether acetate, carbitol acetate, butyl carbitol acetate, and propylene. Acetates such as glycol monoalkyl ether acetates and dipropylene glycol monoalkyl ether acetates; ethylene glycol dialkyl ethers; diethylene glycol dialkyl ethers such as methyl carbitol, ethyl carbitol and butyl carbitol; triethylene glycol dialkyl ether , Propylene glycol dialkyl ether , Dipropylene glycol dialkyl ethers, ethers such as 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and hydrocarbons such as benzene, toluene, xylene, octane and decane; Examples include petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha, lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate, dimethylformamide, N-methylpyrrolidone and the like. These solvents may be used alone or in combination of two or more. The amount of the solvent used is 30 to 100 parts by weight per 100 parts by weight of the resin component.
0 parts by weight, preferably 50 to 800 parts by weight. Outside this range, it becomes difficult to control the molecular weight.

The radical polymerization initiator used in the (co) polymerization is not particularly limited as long as it can initiate radical polymerization, and a commonly used organic peroxide catalyst or azo compound can be used. Can be used. Specific examples include well-known ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters and peroxydicarbonates, and azo compounds are also effective. is there. More specifically,
For example, benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate,
t-hexylperoxybenzoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxy-2-ethylhexanoate, 1,1-bis (t
-Butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl Peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl Peroxide, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) 3,3
5-trimethylcyclohexane, azobisisobutyronitrile, azobiscarbonamide and the like. An appropriate half-life radical initiator is selected according to the polymerization temperature. The amount of the polymerization initiator to be used is 0.5 to 20 parts by weight, preferably 1 to 10 parts by weight, based on 100 parts by weight of the radical polymerizable unsaturated compound in total.

The reaction for introducing a radically polymerizable unsaturated group by adding a radically polymerizable unsaturated compound having a functional group capable of reacting with a functional group in the copolymer can be carried out by a known method. After the completion of the copolymerization reaction, the addition reaction is performed by heating in the presence of each reaction catalyst. For example, the reaction of adding an unsaturated monobasic acid to the epoxy group in the copolymer, the reaction of adding a radically polymerizable unsaturated compound having an epoxy group to the carboxyl group of the copolymer, in the presence of a catalyst,
The stirring is performed at a temperature of about 80 to 130 ° C. Reaction for adding a radical polymerizable unsaturated compound having an amino group to an epoxy group in a copolymer, reaction for adding a radical polymerizable unsaturated compound having an epoxy to an amino group in a copolymer, The reaction of adding a radical polymerizable unsaturated compound having an amino group to an isocyanate group, and the reaction of adding a radical polymerizable unsaturated compound having an isocyanate group to an amino group in a copolymer are performed at a temperature of about 60 to 130 ° C. Perform with stirring. The reaction of adding a radically polymerizable unsaturated compound having a hydroxyl group to the isocyanate group in the copolymer, and the reaction of adding the radically polymerizable unsaturated compound having an isocyanate group to the hydroxyl group in the copolymer are carried out in the presence of a catalyst in the presence of a catalyst. The stirring is performed at a temperature of about 130 ° C.

The radically polymerizable unsaturated compound used as the component (B) in the present invention includes (A), (D),
The radically polymerizable unsaturated compound used in the production of the polymer of the components (E), (F) and (G) includes the above-mentioned compounds, and further includes bisphenol A diethoxydi (meth)
Acrylate, bisphenol A dipropoxydi (meth) acrylate, bisphenol A polyethoxydi (meth) acrylate, bisphenol A polypropoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, diethylene glycol di (meth) acrylate, ethylene glycol di (meth)
Acrylate, propylene glycol di (meth) acrylate, 1,6 hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neohydroxypivalate Polyfunctional monomers such as (meth) acrylates such as di (meth) acrylate of ε-caprolactone adduct of pentyl glycol, and further vinyl ester resins, unsaturated polyester resins, and urethane (meth)
Known radically polymerizable resins such as acrylate resins can also be mentioned.

When one or more radically polymerizable unsaturated compounds of component (B) are used in combination with component (A) (the curable pressure-sensitive adhesive composition-1), the amount of component (A) is 100
5 to 300 parts by weight, preferably 10 to 2 parts by weight per part by weight
00 parts by weight. If the amount is less than 5 parts by weight, the curability is insufficient, and if it exceeds 300 parts by weight, the tackiness is insufficient. On the other hand, one or more radically polymerizable unsaturated components of the component (B) are also added to the polymer having the radically polymerizable unsaturated group introduced therein, ie, the components (D), (E), (F) and (G). Compounds can be mixed (the curable pressure-sensitive adhesive compositions -2 to 5), but the amounts used are (D), (E),
The amount is up to 300 parts by weight per 100 parts by weight of the component (F) or (G), and if this amount exceeds 300 parts by weight, the tackiness becomes insufficient.

The polymerization initiator of the component (C) in the curable pressure-sensitive adhesive used in the present invention may be one or two or more of photopolymerization initiators having photosensitivity from the ultraviolet region to the near infrared region. It is preferable to use a combination of a polymerization initiator, or a photopolymerization initiator having photosensitivity from the ultraviolet light region to the near infrared light region and a thermal polymerization initiator. Therefore, the curable pressure-sensitive adhesive in the curable prepreg of the present invention is a photocurable pressure-sensitive adhesive whose polymerization initiator is one kind of photopolymerization initiator having photosensitivity from the ultraviolet region to the near-infrared region. The agent is at least two types of photopolymerization initiators having photosensitivity from the ultraviolet region to the near infrared region, and prepolymerizes a part of the radical polymerizable unsaturated groups in the pressure-sensitive adhesive composition, A photocurable pressure-sensitive adhesive which is treated with light having a specific wavelength such that at least one kind of photopolymerization initiator and a part of the radical polymerizable unsaturated group remains, and a heat treatment wherein the polymerization initiator is a thermal polymerization initiator. A curable pressure-sensitive adhesive or a photo-polymerization initiator and a heat-polymerization initiator having photosensitivity from the ultraviolet region to the near-infrared region, and a radical polymerizable unsaturated group in the pressure-sensitive adhesive composition Prepolymerization and thermal polymerization Thermosetting adhesive portion of the initiator and a radical polymerizable unsaturated group is treated with light of a specific wavelength such as to leave, at either.

When two or more types of photopolymerization initiators are used for the curable pressure-sensitive adhesive, a photopolymerization initiator having photosensitivity in the visible light or near-infrared light region having a wavelength of 500 nm or more,
It is preferable to use in combination with a photopolymerization initiator having photosensitivity in the visible light region and / or ultraviolet region of less than 00 nm. When a photopolymerization initiator and a thermal polymerization initiator are used in combination for the curable pressure-sensitive adhesive, the photopolymerization initiator may be a light having a wavelength of 500 nm or more and having sensitivity to visible light or near-infrared light. It is preferred to use a polymerization initiator. Since the photopolymerization initiator and the thermal polymerization initiator are the same as the polymerization initiator contained in the curable prepreg layer described below,
The details are omitted here, and will be described later in the description of the polymerization initiator in the curable prepreg layer composition.

In the case of the photocurable pressure-sensitive adhesive composition, the amount of the photopolymerization initiator having photosensitivity from the ultraviolet region to the near infrared region is 0.01 to 20 parts by weight based on 100 parts by weight of the resin or the like. Parts, preferably 0.05 to 15 parts by weight. If the amount of the photopolymerization initiator is less than 0.01 part by weight, the thickening reaction or polymerization after the thickening tends to be insufficient, and if the amount exceeds 20 parts by weight, the strength of the cured product is insufficient. In the case of a thermosetting pressure-sensitive adhesive composition, the amount of the thermal polymerization initiator used (however, when a photopolymerization initiator having photosensitivity from the ultraviolet light region to the near infrared light region is used in combination with the thermal polymerization initiator) Is the total usage)
Is 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, based on 100 parts by weight of the resin or the like. If the amount of the polymerization initiator is less than 0.01 part by weight, the thickening reaction or polymerization after the thickening tends to be insufficient, and if the amount exceeds 20 parts by weight, the strength of the cured product is insufficient.

When a photopolymerization initiator for the B-stage (preliminary polymerization) reaction and a photopolymerization initiator for fully curing the B-staged product are used in combination, the composition ratio is 0.1 / 5 by weight. ５5 / 0.1, preferably 0.5 / 5-5 /
0.5. If the ratio of the B-stage photopolymerization initiator to the main curing photopolymerization initiator is less than 0.1 / 5, the photocurable pressure-sensitive adhesive composition is irradiated with light having the photosensitive wavelength of the B-stage photopolymerization initiator. In some cases, however, the thickening reaction does not proceed. On the other hand, if the ratio exceeds 5 / 0.1, the thickening reaction may proceed too much. When a photopolymerization initiator for the B-stage reaction and a thermal polymerization initiator for fully curing the B-staged product are used in combination, the composition ratio is 0.1 / wt.
5/5 / 0.1, preferably 0.5 / 5-5 / 0.5. If the ratio of the B-stage photopolymerization initiator to the main curing thermopolymerization initiator is less than 0.1 / 5, the thermosetting adhesive composition is irradiated with light having the photosensitive wavelength of the B-stage photopolymerization initiator. In some cases, the thickening reaction does not proceed even when the ratio is 5 /
If the amount exceeds 0.1, the thickening reaction may proceed too much.

The curable prepreg of the present invention has a pressure-sensitive adhesive layer as described above on one or both sides of the curable prepreg layer. In addition, as the pressure-sensitive adhesive to be used, in addition to the above, a hydroxyl group, a carboxyl group, an epoxy group is introduced into a conventional copolymer composition, and an isocyanate, an epoxy compound or the like is used as a cross-linking agent, or a rubber-based Publicly known pressure-sensitive adhesives such as agents can also be used. The curable prepreg layer comprises (H) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin, and (I1) a photopolymerization initiator having photosensitivity from two or more kinds of ultraviolet light regions to near infrared light regions. 01 to 20 parts by weight, (J) UV absorber 0
5 parts by weight and (K) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler, and the composition comprises one of the radically polymerizable unsaturated groups in the resin. Part is pre-polymerized and treated with light having a specific wavelength such that at least one kind of photopolymerization initiator and a part of radically polymerizable unsaturated groups remain, or (H) 100 parts by weight of a saturated polyester resin and / or vinyl ester resin, (I1) 0.01 to 10 parts by weight of a photopolymerization initiator having photosensitivity from an ultraviolet region to a near infrared region, and (I2) a thermal polymerization initiator 0 .0
A composition comprising 1 to 10 parts by weight, (J) 0 to 5 parts by weight of an ultraviolet absorber, and (K) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or filler, and the composition. However, while prepolymerizing a part of the radically polymerizable unsaturated groups in the resin, it is treated with light having a specific wavelength such that a thermal polymerization initiator and a part of the radically polymerizable unsaturated groups remain. Things. In addition to the above prepreg, it is also possible to use a prepreg obtained by thickening a conventional metal such as magnesium oxide or isocyanate.

Among the unsaturated polyester resin or vinyl ester resin (H), the unsaturated polyester used as a raw material thereof may be a known method. It may be produced, and specifically, a saturated polybasic acid having no polymerizable unsaturated bond such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid or an anhydride thereof. And an unsaturated polybasic acid or an anhydride thereof having an active unsaturated bond such as fumaric acid, maleic anhydride, maleic acid, itaconic acid, and the like,
This and ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2
-Butanediol, 1,3-butanediol, 1,5-
Pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-
1,3-propanediol, cyclohexane-1,4-
It is produced by reacting polyhydric alcohols such as dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A as alcohol components.

The vinyl ester resin may be one produced by a known method, and may be a resin obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid, or a saturated dicarboxylic acid or And / or resins obtained by reacting a saturated polyester having a terminal carboxyl group or an unsaturated polyester obtained from an unsaturated dicarboxylic acid and a polyhydric alcohol with an epoxy compound containing an α, β-unsaturated carboxylic acid ester group. Can be As an epoxy resin as a raw material,
Bisphenol A diglycidyl ether and its high molecular weight homologues, novolak-type polyglycidyl ethers and the like can be mentioned.

Examples of the saturated dicarboxylic acid used for the terminal carboxyl polyester include dicarboxylic acids having no active unsaturated group, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and the like. As the unsaturated dicarboxylic acid, a dicarboxylic acid having an active unsaturated group, for example, fumaric acid,
Maleic acid, maleic anhydride, itaconic acid and the like can be mentioned. Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol,
Polyhydric alcohols such as an ethylene oxide adduct of bisphenol A and a propylene oxide adduct of bisphenol A are exemplified.

Glycidyl methacrylate is a typical example of an epoxy compound containing an α, β-unsaturated carboxylic acid ester group used for producing a vinyl ester.

Unsaturated polyester used for resins, etc.
The vinyl ester and urethane acrylate are preferably those having a relatively high degree of unsaturation, and have an unsaturated group equivalent (unsaturated group 1).
Those having a molecular weight of about 100 to 800 are used. Those having an unsaturated group equivalent of less than 100 cannot be synthesized.
However, if the unsaturated group equivalent exceeds 800, a cured product having high hardness cannot be obtained.

The unsaturated polyester resin and vinyl ester resin used in the present invention are obtained by blending the above unsaturated polyester and vinyl ester with a monomer having an unsaturated group represented by styrene monomer. The monomer having an unsaturated group, which is blended with the resin of the above, increases the kneading property and impregnation property of the fiber reinforcing material and the filler when producing a composite material, and also improves the hardness, strength,
It is important for improving chemical resistance, water resistance and the like, and is 10 to 250 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of the unsaturated polyester or vinyl ester.
Used by weight. If the amount used is less than 10 parts by weight, molding becomes difficult due to high viscosity. If the amount exceeds 250 parts by weight, a product with high hardness cannot be obtained, heat resistance is insufficient, and FRP is insufficient.
It is not preferable as a material. Examples of the monomer having an unsaturated group other than the styrene monomer include styrene monomers such as chlorostyrene, vinyltoluene, and divinylbenzene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and the like. There are polymerizable monomers having a (meth) acryloyl group such as ethylene glycol di (meth) acrylate and the like, and they can be substituted for and used without impairing the gist of the present invention.

Next, a photopolymerization initiator and a thermal polymerization initiator which are polymerization initiators used in the curable pressure-sensitive adhesive and the curable prepreg composition of the present invention will be described. As the photopolymerization initiator having photosensitivity in a visible light region or infrared light region of wavelengths longer than 500 nm, the general formula ^{(1) D + · A -} ··· (1) wherein, D ⁺ visible At least one of methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, and pyrylium dye cations having a sensitivity in the light region or near-infrared light region;
^- represents various anions. A cationic dye represented by the general formula (2):

[0033]

Embedded image

[Wherein, Z ⁺ represents an arbitrary cation;
¹ , R ² , R ³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group , A substituted acyl group,
It represents a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. )) Are preferred.

Examples of the cation “Z ⁺ ” in the general formula (2) include a quaternary ammonium cation, a quaternary pyridinium cation, and a quaternary pyridinium cation having no photosensitivity in the visible light region or the near infrared light region. Cation charge on oxygen atoms such as quinolinium cations, diazonium cations, tetrazolium cations, sulfonium cations, oxosulfonium cations, metal cations such as sodium, potassium, lithium, magnesium and calcium, and flavylium and pyranium salts (Organic) compounds, carbon cations such as tropylium and cyclopropylium, halogenium cations such as iodonium, and cations of metal compounds such as arsenic, cobalt, palladium, chromium, titanium, tin and antimony. By combining this organic boron compound with a cationic dye having a photosensitive wavelength in the visible light region or near infrared light region, the dye irradiated with light having a wavelength in the photosensitive region is excited and exchanges electrons with the organic boron compound. As a result, the dye is discolored and radicals are generated, thereby causing a polymerization reaction of the coexisting polymerizable unsaturated compound. In this polymerization reaction, unlike the conventional ultraviolet polymerization reaction, it is easy to control the generated radical,
When some of the unsaturated groups in the resin are radically polymerized, they can be easily stopped. Further, since a long wavelength in a visible light region or a near infrared light region is used, the reaction is easily performed even in a system to which a filler, a pigment, and the like are added.

Examples of combinations of the above cationic dyes and boron compounds are described in JP-A-3-111402, JP-A-3-179003, and JP-A-4-146.
905, JP-A-4-261405, JP-A-4-261406, JP-A-5-194609, and the like have detailed descriptions. Specific examples of the cationic dye “D ⁺ ” are shown in Tables 1 and 2. Among these cationic dyes, cyanine-based, styryl-based cationic dyes and triarylmethane-based dyes are preferably used. Cyanine-based and styryl-based cationic dyes are preferred in that the electron transfer with the organic boron-based compound generally occurs easily and the reaction of the present invention is easily caused.

[0037]

[Table 1]

[0038]

[Table 2]

[0039]

[Table 3]

[0040]

[Table 4]

A ^{− as} the counter anion of the cationic dye represented by the general formula (1) is any anion such as p-toluenesulfonate ion, organic carboxylate ion, perchlorate ion and halide ion. , General formula (3)

[0042]

Embedded image

Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent an alkyl group, an aryl group, an acyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group,
A heterocyclic group, a halogen atom, a substituted alkyl group, a substituted aryl group, a substituted acyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. ] Is particularly preferable. The composition ratio of the organic boron compound of the present invention to the near infrared or visible light absorbing cationic dye compound is 1/5 to 1 / 0.05, preferably 1/1 to 1/0.
It is one. In general, it is preferable to use a larger amount of the organic boron compound than the cationic dye from the viewpoint of the decoloring reaction of the dye and the radical generation efficiency.

As the visible light polymerization initiator having photosensitivity in the visible light region, for example, Yamaoka et al., “Surface”, 27 (7),
548 (1989), Sato et al., "Summary of the 3rd Polymer Material Forum", IBP 18 (1994),
Independent visible light polymerization initiators such as camphorquinone, benzyltrimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, and dicyclopentadienyltitanium-di (pentafluorophenyl); organic peroxides / dyes; and diphenyliodonium salts / Dyes, imidazoles / keto compounds, hexaarylbiimidazole compounds / hydrogen-donating compounds, mercaptobenzothiazole / thiopyrylium salts, metal arenes / cyanine dyes, etc. And other known composite initiator systems.

As an initiator having photosensitivity from the ultraviolet region to the visible region, an acylphosphine oxide compound is effective. A specific example is a screw (2,
6-dichlorobenzoyl) -phenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,5-
Dimethylphenylphosphine oxide, bis (2,6
-Dichlorobenzoyl) -4-ethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl)
-4-biphenylphosphine oxide, bis (2,6
-Dichlorobenzoyl) -4-propylphenylphosphine oxide, bis (2,6-dichlorobenzoyl)
-2-naphthylphosphine oxide, bis (2,6-
Dichlorobenzoyl) -1-naphthylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-chlorophenylphosphine oxide, bis (2,6-dichlorobenzoyl) -2,2-dimethoxyphenylphosphine oxide, bis (2,6-dichlorobenzoyl)
-Dodecylphosphine oxide, bis (2,6-dichlorobenzoyl) -4-octylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)
-2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4,5-trimethoxybenzoyl) -2,5-dimethylphenylphosphine oxide, bis (2,6-dichloro-3,4, 5-trimethoxybenzoyl) -4-ethoxyphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,
5-phenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-biphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-ethoxybiphenylphosphine oxide, bis (2-methyl-1-naphthoyl) ) -2-Naphthylphosphine oxide, bis (2-methyl-1-naphthoyl) -4-propylphenylphosphine oxide, bis (2-methyl-1-naphthoyl) -2,5-dimethylphenylphosphine oxide, bis (2- Methyl-1-naphthoyl)
-4-methoxyphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6-diphenylbenzoyl-diphenyl Phosphine oxide, 2,6-dimethoxybenzoyl-diphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyl-diphenylphosphine oxide,
2,6-dichlorobenzoyl-diphenylphosphine oxide, 2,3,6-trimethylbenzoyl-diphenylphosphine oxide, 2-phenyl-6-methylbenzoyl-diphenylphosphine oxide, 2,6
-Dibromobenzoyl-diphenylphosphine oxide, 2,8-dimethylnaphthalene-1-carbonyl-diphenylphosphine oxide, 1,3-dimethoxynaphthalene-2-carbonyl-diphenylphosphine oxide, 2,4,6-trimethylbenzoyl-phenylphosphine Acid methyl ester, 2,6-dimethylbenzoyl-phenylphosphinic acid methyl ester, 2,6-
Examples include dichlorobenzoyl-phenylphosphinic acid methyl ester.

Specifically, for example, 2-hydroxy-2-
Methyl-1-phenylpropan-1-one (trade name: D
arocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl)
75% of 2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.)
Trade name Irgacure-1 mixed at a ratio of% / 25%
700 (manufactured by Ciba Specialty Chemicals Co., Ltd.)
1-hydroxy-cyclohexyl-phenyl-ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Special) Tea Chemicals Co., Ltd.
(Trade name) Irgacure 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75% / 25%, and Irgacure 1850 (ciba specialty) mixed at a ratio of 50% / 50% Chemicals Co., Ltd.), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819, Ciba Specialty Chemicals Co., Ltd.), 2,4,6-trimethylbenzoyl-diphenyl Phosphine oxide (trade name: Lucirin)
TPO, manufactured by BASF Corporation), 2-hydroxy-2-
Methyl-1-phenylpropan-1-one (trade name: D
arocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Luciri)
nTPO, manufactured by BASF Corp.) in a ratio of 50% / 50%, such as Darocur4265. The visible light initiator may be any photopolymerization initiator having photosensitivity in the wavelength range of 380 nm to 780 nm, and may be used in combination. As the ultraviolet polymerization initiator, in addition to the (bis) acylphosphine oxide-based polymerization initiator, known polymerization initiators such as acetophenone-based and benzyl ketal-based polymerization initiators can be used. Ultraviolet light has a relatively long wavelength, preferably 30
It is preferable to use an ultraviolet polymerization initiator such as a (bis) acyl phosphine oxide type having photosensitivity in a wavelength region of 0 nm or more.

The thermal polymerization initiator used in the present invention is, for example, an organic peroxide catalyst or an azo compound which generates a radical upon heating, such as benzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, or the like.
Ditertiary butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,
5-dimethyl-2,5-bis (t-butylperoxy)
Hexin-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl)
Peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3
5-trimethylhexanoyl peroxide, lauryl peroxide, azobisisobutyronitrile, azobiscarbonamide and the like can be used. Dicumyl peroxide, ditertiary butyl peroxide, t-butyl hydroperoxide and the like are particularly effective because of good storage stability.

In the case of a photocurable prepreg composition, the amount of at least two photopolymerization initiators having photosensitivity from the ultraviolet light region to the near infrared light region is 0.01 to 100 parts by weight of the resin or the like. To 20 parts by weight, preferably 0.05 to 15 parts by weight. If the amount of the photopolymerization initiator is less than 0.01 part by weight, the thickening reaction or polymerization after the thickening tends to be insufficient, and if the amount exceeds 20 parts by weight, the strength of the cured product is insufficient.
When the photopolymerization initiator for the B-stage (preliminary polymerization) reaction and the photopolymerization initiator for fully curing the B-staged product are used in combination, the composition ratio is 0.1 / 5 to 5/0. 1,
Preferably it is 0.5 / 5 to 5 / 0.5. The ratio of the photopolymerization initiator for B-stage to the photopolymerization initiator for main curing is 0.1
If the ratio is less than / 5, the photocurable prepreg composition may not be subjected to the thickening reaction even when irradiated with light having the photosensitive wavelength of the photopolymerization initiator for B-stage formation. If the amount exceeds the above, the thickening reaction may proceed too much.

In the case of the thermosetting prepreg composition, the photopolymerization initiator and the photopolymerization initiator having photosensitivity from the ultraviolet region to the near-infrared region are all used with respect to 100 parts by weight of the resin and the like. 0.01 to 10 parts by weight, preferably 0.05 to
7 parts by weight. If the amount is less than 0.01 part by weight, the thickening reaction or polymerization after the thickening tends to be insufficient, and if the amount exceeds 10 parts by weight, the strength of the cured product is insufficient. B
When a photopolymerization initiator for the staging reaction and a thermal polymerization initiator for fully curing the B-staged product are used in combination, the composition ratio is 0.1 / 5 to 5 / 0.1, preferably 0 to 5 by weight. .
5/5 to 5 / 0.5. If the ratio of the photopolymerization initiator for B-stage and the thermal polymerization initiator for main curing is less than 0.1 / 5,
Even if the thermosetting prepreg composition is irradiated with light having a photosensitive wavelength of the photopolymerization initiator for B-stage formation, the thickening reaction may not proceed, whereas if the ratio exceeds 5 / 0.1, the viscosity may increase. The reaction may proceed too much.

The curable prepreg composition of the present invention may contain (K)
The fiber reinforcement used as a component is an organic and / or inorganic fiber, such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, and ceramic fiber. Is used, and may be in the form of a mat, cloth, nonwoven fabric, or the like. of course,
These fibers may be used in combination of two or more kinds.
Among these reinforcing materials, glass fibers and organic fibers are particularly desirable in the present invention, and mat-like ones are preferred in view of workability and the like. The amount of fiber reinforcement used is
It is 1 to 400 parts by weight, preferably 10 to 200 parts by weight, based on 100 parts by weight of the resin (H). If this amount exceeds 400 parts by weight, resin impregnation becomes insufficient.

The filler used as the component (K) is an inorganic filler, an organic filler or a polymer. Examples of the inorganic filler include aluminum hydroxide, calcium carbonate, talc, clay, glass powder and silica. Known materials such as barium sulfate, titanium oxide, and cement are used, but aluminum hydroxide is effective for imparting flame retardancy to the curable prepreg composition.
Of course, these inorganic fillers can be used in combination. The amount of the inorganic filler used is 100
5 to 300 parts by weight, preferably 100 to 100 parts by weight
200 parts by weight. When the amount of the inorganic filler is more than 300 parts by weight, the viscosity is too high, and the workability is reduced, and the foam tends to remain, and the strength is reduced. The amount of the fiber reinforcing material and / or the filler is 1 to 4 parts by weight based on 100 parts by weight of the resin (H).
00 parts by weight, preferably 10 to 200 parts by weight. If this amount exceeds 400 parts by weight, resin impregnation becomes insufficient. Further, in the present invention, thixotropic may be imparted by a known method. Examples of the thixotropic agent include silica powder (aerosil type), mica powder, casium carbonate powder and the like, 100 parts by weight of a polymerizable unsaturated compound. 0.1 to 50 parts by weight based on the weight of the mixture.

As the organic filler or polymer, for example, known polystyrene, which is also effective as a low shrinkage agent,
Polyvinyl acetate, polymethyl methacrylate, polyethylene, polyvinylidene chloride microballoons, polyacrylonitrile microballoons and the like can be used. When used as a low shrinkage agent, the amount used is 0 to 40 parts by weight, preferably 0 to 30 parts by weight, based on 100 parts by weight of the resin. When the amount of the low shrinkage agent exceeds 40 parts by weight,
Viscosity becomes too high and moldability decreases, and the smoothness and heat resistance of the cured product surface decrease. Pigments can be used in the present invention. There are no particular restrictions on that type,
Organic and inorganic pigments can be used. At that time, the compounding amount is at most 20 parts by weight with respect to 100 parts by weight of the resin.
Preferably the amount is up to 10 parts by weight.

The curable prepreg composition of the present invention includes:
An ultraviolet absorber can be used as the component (J),
Known UV absorbers such as benzophenone, salicylate, benzotriazole, benzoate and cyanoacrylate can be used. Specifically, benzophenones such as 2,4-di-hydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, 2-hydroxy-4-methoxybenzophenone, and 2,2′-di-
Hydroxy-4-methoxybenzophenone, 2,2'-
Di-hydroxy-4,4′-methoxybenzophenone,
2-hydroxy-4-o-octoxybenzophenone,
2-hydroxy-4-i-octoxybenzophenone,
2-hydroxy-4-octadecyloxybenzophenone, 2,2'-di-hydroxy-4,4'-dimethoxy-5,5'-disulfobenzophenone-di-sodium,
2-hydroxy-4 (2-hydroxy-3-methacryloxy) propoxybenzophenone, phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate as salicylate esters,
2 (2′-hydroxy-)
5′-methylphenyl) benzotriazole, 2 (2 ′
-Hydroxy-3 ', 5'-di-t-butylphenyl)
Benzotriazole, 2 (2'-hydroxy-3'-t
-Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotriazole, 2 (2'-hydroxy- 3 ', 5'-di-t-amylphenyl) benzotriazole, 2 (2'-hydroxy-5'-t-butylphenyl) benzotriazole,
2 (2'-hydroxy-5'-t-octylphenyl)
Benzotriazole, 2 ', 4' as benzoate
-Di-t-butylphenyl-3,5-di-t-butyl-
Examples of 4-hydroxybenzoate and cyanoacrylate include ethyl-2-cyano-3,5-diphenylacrylate. The amount of the ultraviolet absorber used is within 5 parts by weight based on 100 parts by weight of the resin or the like. If the amount of the ultraviolet absorber exceeds 5 parts by weight, physical properties are reduced. In addition, a known hindered amine-based stabilizer that captures and stabilizes a radical such as an alkyl radical or a peroxide radical can be used in combination with these ultraviolet absorbers. As a known compound, a compound having a hindered piperidine ring is generally used.

In the present invention, other than aluminum hydroxide, known flame retardants such as halogen-based and phosphorus-based flame retardants can be used.

The curable prepreg with the pressure-sensitive adhesive layer of the present invention can be coated into a film on the upper and lower sides to form a sheet-like curable prepreg. Examples of the film used for producing such a sheet-like curable prepreg include vinylon film, PET film, polyethylene film, polypropylene film, aluminum foil, and release paper.
Known ones can be used. For these films, a transparent type or a colored type can be used. In order to prevent the film from shifting, an embossed film is also effective. A release paper is effective as a film used for the pressure-sensitive adhesive layer. In the case of photocurable prepreg,
It is desirable to use a film for light shielding in addition to using a transparent film. A film that completely blocks light may be used, but a film that transmits as little light as possible in the photosensitive wavelength range of the photopolymerization initiator present in the prepreg, such as cellophane or a colored film whose base is visible to the naked eye during operation, is desirable.

In the case of producing the curable prepreg of the present invention, after forming the pressure-sensitive adhesive layer, a curable prepreg layer may be formed thereon and integrated therewith, or after forming the curable prepreg layer, Alternatively, a pressure-sensitive adhesive layer may be formed and integrated. Specifically, for example, when the pressure-sensitive adhesive composition is diluted with a solvent, after coating on a film to volatilize the solvent to form a pressure-sensitive adhesive layer, a curable prepreg composition is laminated thereon and visible. The curable prepreg composition is irradiated with light and / or near-infrared light to form a B-stage. As a method of forming the pressure-sensitive adhesive layer, there is a method of volatilizing a solvent or irradiating visible light and / or near-infrared light to make the pressure-sensitive adhesive layer B-stage. B
The staging may be performed separately or simultaneously.
The pressure-sensitive adhesive layer may be formed on the entire surface of the prepreg, or may be partially formed. It may be a prepreg partially attached to the adhesive.

In the present invention, ultraviolet light means 280-38.
0 nm, visible light refers to light rays in a wavelength range of 380 to 780 nm, and near infrared light refers to light rays in a wavelength range of 780 to 1200 nm. In the present invention, the light source used for producing the prepreg for the B-stage reaction of the resin or the like may be a light source having a spectral distribution in the photosensitive wavelength region of the photopolymerization initiator, such as a near-infrared lamp, a sodium lamp, and the like. Halogen lamps, fluorescent lamps, metal halide lamps and the like can be used. Further, it is also possible to select and irradiate a wavelength necessary for the B-stage by combining these lamps or light in a wide wavelength range with a light source and a wavelength cut filter. The wavelength used for the B-stage reaction is desirably long-wavelength light having a low energy level. In particular, when near-infrared light is used, the B-stage reaction is easily controlled.

The irradiation time of the lamp for converting the photocurable prepreg composition to the B-stage cannot be specified unconditionally because the effective wavelength range, output, irradiation distance, thickness of the composition and the like of the light source are different. 0.01 hours or more, preferably 0.1 hours or more.
Irradiation may be performed for at least 05 hours. The curable prepreg thus produced sufficiently adheres to the adherend, and can be fully cured quickly by light irradiation with the remaining photopolymerization initiator in the case of the photocurable prepreg, and the remaining heat in the case of the thermosetting prepreg. It can be quickly cured by heating with a polymerization initiator. In addition, it is also possible to allow the adhesive to adhere to the adherend and then leave the adhesive to cure by natural light or the peroxide, and then adhere. In addition, it can be completely adhered to the adherend by being cured, and on the contrary, the adhesiveness can be reduced to facilitate peeling. The light source that can be used for the main curing of the photocurable prepreg composition may be any light source having a spectral distribution in the photosensitive wavelength region of the remaining photopolymerization initiator, such as sunlight, natural light, metal halide lamp, halogen lamp, ultraviolet lamp, and the like. There is.

[0059]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited by these.

Synthesis Example 1 146 g of ethyl acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube.
The mixture was stirred and refluxed while replacing with nitrogen. Next, azobisisobutyronitrile was added to a monomer mixture composed of 0.5 mol (92 g) of 2-ethylhexyl acrylate, 0.1 mol (10 g) of methyl methacrylate, and 0.4 mol (51.3 g) of n-butyl acrylate. Monomer mixture 10
A mixture obtained by adding 1.5 parts (2.3 g) to 0 parts was dropped from the dropping funnel into the flask kept refluxing over 2 hours, and further stirred for 4 hours to carry out aging. A polymer for agent 1 was obtained. Further, 100 parts of Polymer-1 for pressure sensitive adhesive, vinyl ester resin [Showa Kogaku (
Co., Ltd., trade name: VR-60] 15 parts and t-butyl peroxybenzoate (manufactured by NOF CORPORATION, hereinafter abbreviated as perbutyl Z) 0.2 part, were mixed to prepare a thermosetting pressure-sensitive adhesive composition. 1 was obtained.

Synthesis Example 2 149 g of ethyl acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube.
The mixture was stirred and refluxed while replacing with nitrogen. Next, 0.3 mol (55.3 g) of 2-ethylhexyl acrylate, 0.3 mol (42.6 g) of glycidyl methacrylate, and n-
A mixture obtained by adding 2 parts (3.0 g) of azobisisobutyronitrile to 100 parts of the monomer mixture to a monomer mixture consisting of 0.4 mol (51.3 g) of butyl acrylate is maintained under reflux from the dropping funnel. Was dropped into the flask over 2 hours, and aging was performed by continuing stirring for 4 hours. Next, the inside of the flask was replaced with air, and 0.21 mol (15.1 g) of acrylic acid to which 0.6 g of trisdimethylaminomethylphenol (DMP-30) and 0.03 g of hydroquinone were added was aged. The reaction was continued for 10 hours while refluxing, and the reaction was terminated when the solid content acid value reached 0.8. After cooling, 100 parts of the solid content was exposed from the ultraviolet region to the visible region. Bisacylphosphine oxide-based polymerization initiator [Ciba Specialty Chemicals Co., Ltd., trade name: Irgacure 1800:
-1800. ]: 0.5 part and 0.15 part of a benzotriazole-based ultraviolet absorber (trade name: Seesorb 705, manufactured by Cipro Kasei Co., Ltd.) to obtain a photocurable pressure-sensitive adhesive composition-1.

Synthesis Example 3 110 g of ethyl acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer and gas inlet tube.
The mixture was stirred and refluxed while replacing with nitrogen. Next, azobisisobutyronitrile was added to a monomer mixture consisting of 0.3 mol (55.3 g) of 2-ethylhexyl acrylate, 0.2 mol (17 g) of methacrylamide, and 0.5 mol (64 g) of n-butyl acrylate. A mixture obtained by adding 2 parts (2.9 g) to 100 parts of the monomer mixture was added dropwise to the flask in a state where reflux was continued from the dropping funnel over 2 hours, and stirring was continued for 4 hours to perform aging. Next, the inside of the flask was replaced with air, and a mixture obtained by adding 0.03 g of hydroquinone to 0.16 mol (22.7 g) of glycidyl methacrylate was charged into the above-mentioned aging. The reaction was terminated when methacrylate was no longer detected by GPC measurement, and after cooling, 5 parts of aminoethyl methacrylate and vinyl ester resin [manufactured by Showa Polymer Co., Ltd., trade name: VR-77] per 100 parts of solids. 10 parts, 1,1,5,5-tetrakis (p-diethylaminophenyl) -2,4-pentadienyltriphenyl-n-butyl borate [No. 3 in Table 1] (manufactured by Showa Denko KK: Abbreviated as IRB. Near infrared light absorbing cationic dye]
03 parts and tetra-n-butylammonium triphenyl-n-butyl borate (manufactured by Showa Denko KK, hereinafter referred to as P
Abbreviated as 3B. B-1 stage near-infrared photopolymerization initiator in combination with 0.15 part of boron compound), I-1800:
1.2 parts and 0.2 parts of Seesorb 705 were added to obtain a photocurable pressure-sensitive adhesive composition-2.

Synthesis Example 4 110 g of ethyl acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer and a gas inlet tube.
The mixture was stirred and refluxed while replacing with nitrogen. Next, 0.2 mol (36.8 g) of 2-ethylhexyl acrylate,
0.5 mol (58 g) of hydroxymethyl acrylate,
Azobisisobutyronitrile was added to a monomer mixture consisting of 0.1 mol (10 g) of methyl methacrylate and 0.2 mol (25.6 g) of n-butyl acrylate in an amount of 2 parts (2.6 g) based on 100 parts by weight of the monomer mixture. The resulting mixture was dropped from the dropping funnel into the flask kept refluxing over 2 hours, and further stirred for 4 hours to perform aging. Next, the inside of the flask was replaced with air, and 0.42 g (62 g) of isocyanateethyl methacrylate (trade name: Karenz MOI, manufactured by Showa Denko KK) was added to 0.62 g of dibutyltin dilaurate and 0.062 g of hydroquinone.
g is added to the above-mentioned aging,
The reaction was continued for 1.5 hours under reflux, and the reaction was terminated when isocyanate ethyl methacrylate was no longer detected by GPC measurement. After cooling, 5 parts of aminoethyl methacrylate per 100 parts of solids, vinyl ester resin [Showa Kogaku Kogyo Co., Ltd. (Trade name: VR-77), 5 parts, I
0.02 parts of RB, 0.01 parts of P3B and Perbutyl Z
0.5 part was mixed to obtain a thermosetting pressure-sensitive adhesive composition-2.

Example 1 (1) Preparation of Photocurable Resin Composition for Prepreg Layer Vinyl ester resin [manufactured by Showa Polymer Co., Ltd., trade name: Lipoxy R-802]: 0.03 parts of IRB and 100 parts of PB
Near-infrared light polymerization initiator for B-stage combining in combination with 0.15 parts of 3B, bisacylphosphine oxide-based polymerization initiator I-1800 having a photosensitivity from ultraviolet light to visible light region for fully curing the B-staged product: 1.0 part, Seesorb 705 which is a benzotriazole ultraviolet absorber:
0.2 part was added to obtain a photocurable resin composition.

(2) Preparation of Photocurable Prepreg with Photocurable Adhesive Next, the photocurable pressure-sensitive adhesive composition-1 was put on a release paper at 50 μm
m, and left in an oven at 80 ° C. for 3 minutes to evaporate the solvent.
# 450 chopped strand glass mat (made by Asahi Fiberglass Co., Ltd.) was impregnated with the above photocurable resin composition so as to have a glass content of 25% by weight, laminated, and covered with a transparent PET film. 380-12
AL-Spotlight (ALF-10) 1KW which is a light source including a wavelength range of 00 nm (manufactured by RDS)
SC-50 which is a cut filter of 500 nm or less
(Fuji Film Co., Ltd.) was used in combination, and irradiation was performed at a distance of 20 cm. The B-stage was formed in 2 minutes, and the B-stage state was not changed even after one spectral irradiation. Thus, a light-curable prepreg with a light-curable adhesive was prepared by attaching yellow cellophane to a transparent PET film in a B-stage state after light irradiation for 3 minutes, and the storage stability in a dark place at 30 ° C. was examined. However, the hardness of the prepreg did not change for more than 6 months.

(3) Curing of a photocurable prepreg with a photocurable adhesive A release sheet of a photocurable prepreg with a photocurable adhesive was taken and attached to an iron plate placed in direct sunlight, and the yellow cellophane was applied from above. The bubbles were expelled while being handled with a roll. In this state, the photocurable prepreg did not cure even if it was left in direct sunlight for 30 minutes or more. Next, when only the yellow cellophane was peeled off and allowed to stand, the photocurable prepreg was cured in 10 minutes. After curing, the upper PET film was peeled off and exposed outdoors for half a year, but no change in color or appearance was observed.
When a tensile strength test was conducted by the Kenken formula,
Kgf / cm ² adhesive strength and fracture mode FR
Good results were obtained with P cohesion failure.

Comparative Example 1 The same operation as in Example 1 was carried out except that the photocurable pressure-sensitive adhesive layer was not provided, but the adhesion to an iron plate was insufficient, and a tensile strength test was conducted by the Kenken formula. However, 6Kgf / c
At an adhesive strength of m ² , the failure mode was also interface failure.

Example 2 (1) Preparation of Photocurable Resin Composition 100 parts of unsaturated polyester resin (trade name: Rigolac FK-2000, manufactured by Showa Polymer Co., Ltd.), 2.0 parts of triethylamine, Seesorb 705 : Near-infrared photopolymerization initiator for B-stage formation obtained by combining 0.03 part of IRB and 0.15 part of P3B with 0.2 part added, and I-1800 for fully curing the B-staged product: 3.0 The parts were mixed to obtain a photocurable resin composition.

(2) Preparation of Photocurable Prepreg with Photocurable Adhesive Next, 50 μm of photocurable adhesive composition-2 was placed on release paper.
m, and left in a dryer at 80 ° C. for 3 minutes to evaporate the solvent.
# 450 chopped strand glass mat (made by Asahi Fiberglass Co., Ltd.) was impregnated with the above photocurable resin composition so as to have a glass content of 25% by weight, laminated, and covered with a transparent PET film. 380-12
AL-Spotlight (ALF-10) 1KW which is a light source including a wavelength range of 00 nm (manufactured by RDS)
SC-50 which is a cut filter of 500 nm or less
(Manufactured by Fuji Film Co., Ltd.) and irradiated at a distance of 20 cm, the photocurable pressure-sensitive adhesive layer and the photocurable prepreg layer became B-stage in 3 minutes. The situation did not change. Therefore, a light-curable prepreg with a photo-curable adhesive was prepared by attaching yellow cellophane to a transparent PET film in a B-stage state after light irradiation for 4 minutes, and the storage stability in a dark place at 30 ° C. was examined. However, the hardness of the prepreg did not change for more than 6 months.

(3) Curing of a photocurable prepreg with a photocurable adhesive A release paper of a photocurable prepreg with a photocurable adhesive was taken and attached to a concrete sidewalk board placed in direct sunlight.
The bubbles were expelled while handling with a roll from above the yellow cellophane. In this state, the photocurable prepreg did not cure even if it was left in direct sunlight for 30 minutes or more. Next, when only the yellow cellophane was peeled off and allowed to stand, the photocurable prepreg was cured in 10 minutes. After curing, the upper PET film was peeled off and exposed outdoors for half a year, but no change in color or appearance was observed. In addition, when a tensile strength test was conducted according to the Kenken formula, an adhesive strength of 30 kgf / cm ² was obtained, and a favorable result was obtained in the fracture mode of concrete base material fracture.

Comparative Example 2 The same operation as in Example 2 was performed except that the photocurable pressure-sensitive adhesive layer was not provided. However, 14
With an adhesive strength of Kgf / cm ² , the failure mode was 30% for the concrete base material and 70% for the interface failure.

Example 3 (1) Preparation of thermosetting resin composition for prepreg layer: 100 parts of vinyl ester resin (manufactured by Showa Polymer Co., Ltd., trade name: Lipoxy H-630), 0.03 part of IRB and 100 parts of P3
B-staged near-infrared light polymerization initiator combined with 0.15 parts of B and 1.0 part of perbutyl Z were mixed to obtain a thermosetting resin composition.

(2) Preparation of thermosetting prepreg with thermosetting pressure-sensitive adhesive Next, thermosetting pressure-sensitive adhesive composition-1 was placed on release paper at 50 μm.
m, and left in a dryer at 80 ° C. for 3 minutes to evaporate the solvent.
m # 450 chopped strand glass mat (manufactured by Asahi Fiber Glass Co., Ltd.) is impregnated with 3 plies of the above-mentioned photocurable resin composition so that the glass content becomes 25% by weight, and the resultant is covered with a transparent PET film. 380-1
AL-Spotlight (ALF-10) 1KW which is a light source including a wavelength range of 200 nm (RDS Co., Ltd.)
SC-5 which is a cut filter of 500 nm or less.
0 (manufactured by Fuji Film Co., Ltd.), irradiation was performed at a distance of 20 cm, and the B-stage was formed in 2 minutes, and the B-stage state did not change even after one-spectral irradiation was continued. Thus, a thermosetting prepreg with a thermosetting adhesive was obtained in the B-stage state after light irradiation for 3 minutes.

(3) Curing of a thermosetting prepreg with a thermosetting adhesive A release paper of a thermosetting prepreg with a thermosetting adhesive was taken and attached to stainless steel, and bubbles were expelled while squeezing with a roll. When left in a dryer at 100 ° C. for 1 hour in this state, the thermosetting prepreg with the thermosetting adhesive was cured. Further, when a tensile strength test was conducted by the Kenken formula, an adhesive strength of 23 Kgf / cm ² was obtained, and the failure mode was also a good result in FRP cohesive failure.

Comparative Example 3 The same operation as in Example 3 was performed except that the thermosetting pressure-sensitive adhesive layer was not provided. 4kg
At an adhesive strength of f / cm ² , the failure mode was interface failure.

Example 4 (1) Preparation of thermosetting resin composition for prepreg layer: 100 parts of vinyl ester resin (trade name: Lipoxy H-630, manufactured by Showa Polymer Co., Ltd.), 0.03 part of IRB and 100 parts of P3
B-staged near-infrared photopolymerization initiator in combination with 0.15 part of B, perbutyl Z 1.0 part, and aluminum hydroxide powder [manufactured by Showa Denko KK, trade name: Hygirant HBT-320] Forty parts were mixed to obtain a thermosetting resin composition.

(2) Preparation of thermosetting prepreg with thermosetting pressure-sensitive adhesive Next, thermosetting pressure-sensitive adhesive composition-2 was placed on release paper at 50 μm.
m, and left in a dryer at 80 ° C. for 3 minutes to evaporate the solvent.
m # 450 chopped strand glass mat (manufactured by Asahi Fiber Glass Co., Ltd.) is impregnated with 3 plies of the above-mentioned photocurable resin composition so that the glass content becomes 25% by weight, and the resultant is covered with a transparent PET film. 380-1
AL-Spotlight (ALF-10) 1KW which is a light source including a wavelength range of 200 nm (RDS Co., Ltd.)
SC-5 which is a cut filter of 500 nm or less.
0 (manufactured by Fuji Film Co., Ltd.) was used, and irradiation was performed at a distance of 20 cm. The B-stage was formed in 2 minutes, and the B-stage state was not changed even after one spectral irradiation. Thus, a thermosetting prepreg with a thermosetting adhesive was obtained in the B-stage state after light irradiation for 3 minutes.

(3) Curing of Thermosetting Prepreg with Thermosetting Adhesive A thermosetting prepreg release paper and a PET film were taken and wound around a crack in a steam pipe. When heated in this state with a dryer for 10 minutes, the thermosetting prepreg with the thermosetting adhesive was cured, and no steam leakage was observed even when steam was passed.

Example 5 (1) Preparation of photocurable resin composition for prepreg layer: 100 parts of a bilester resin (manufactured by Showa Polymer Co., Ltd., trade name: Lipoxy R-804), 0.03 part of IRB and 100 parts of P3B
A near-infrared photopolymerization initiator for B-stage formation, combined with 0.15 part, I-1800: 1.0 part was added to obtain a photocurable resin composition.

(2) Preparation of photocurable prepreg with photocurable pressure-sensitive adhesive Next, polymer-1 for pressure-sensitive adhesive was applied to a release paper to a thickness of 50 μm, and dried in an oven at 80 ° C. The mixture was allowed to evaporate, the solvent was evaporated, and cooled, and then the above photocurable resin composition was added to 3 plies of 30 cm × 30 cm # 450 chopped strand glass mat (manufactured by Asahi Fiberglass Co., Ltd.) at a glass content of 25 plies. % By weight and laminated, covered with a transparent PET film and
AL-Spotlight (ALF-10) 1KW (manufactured by RDS), which is a light source including a wavelength range of 0 nm, is used in combination with SC-50 (manufactured by Fuji Film Co., Ltd.) which is a cut filter of 500 nm or less. Irradiation at a distance of 20 cm resulted in a B-stage in 2 minutes, and the B-stage state did not change even after one-spectral irradiation. Then, a yellow PET was adhered on a transparent PET film in the B-stage state after light irradiation for 3 minutes to obtain a photocurable prepreg with an adhesive, and the storage stability in a dark place at 30 ° C. was examined. The hardness of the prepreg did not change.

(3) Curing of Photocurable Prepreg with Adhesive A release paper of the photocurable prepreg with an adhesive was taken and adhered to a concrete pillar inside the room, and bubbles were expelled while handling with a roll from above the yellow cellophane. Next, only the yellow cellophane was peeled off and left for one week to cure. Also,
25kgf
/ Cm ² was obtained, and the failure mode was good with concrete base material failure. Table 3 summarizes the test results of the adhesive strength and the failure mode obtained in each of the above Examples and Comparative Examples.

[0082]

[Table 5]

[0083]

According to the present invention, a stabilized thickening reaction can be carried out in a short time, the resin does not flow out of the fibrous base material during storage of the prepreg sheet, and the shape of the adherend can be further improved. Even in the case of a complicated case, a curable prepreg that does not peel off before the prepreg sheet is attached and cured, and that can sufficiently exhibit adhesive strength without using a primer can be efficiently provided.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 2/50 C08F 299/02 4J040 299/02 C08J 5/24 CEZ C08J 5/24 CEZ C09J 4/06 / / C09J 4/06 5/00 5/00 201/00 201/00 B29K 67:00 B29K 67:00 105: 06 105: 06 C08L 87:00 C08L 87:00 B29C 67/14 WF term (reference) 4F072 AA02 AA07 AB04 AB05 AB06 AB09 AB10 AB28 AB29 AD34 AD38 AK01 AL17 4F100 AA01A AA01H AD11A AG00A AH02A AH02B AH02C AH02H AH03H AH08A AH08B AH08C AK01D AK01E AK01H AK02B AK02C AK02J AK04E AK23D AK23E AK42D AK42E AK44A AK47A AL01B AL01C AL06B AL06C AR00B AR00C BA02 BA03 BA05 BA06 BA10B BA10C BA10D BA10E BA13 CA07A CA23A CA30A CA30B CA30C DA11 DG03A DG06A DG10D DG10E DG12A DG15A DH01A EC183 EH461 EJ082 EJ083 EJ422 EJ423 EJ5 42 EJ911 EJ913 GB08 HB00E JA05E JB12A JB12B JB12C JB13A JB13B JB13C JB13H JB14A JB14B JB14C JB14H JD09E JK06 JL05 JL10E JL13B JL13C JN17A JN17B JN17C JN17H YY00A YY00B YY00C YY00H 4F205 AA41 AB04 AB11 AB14 AD16 HA19 HA33 HA35 HA39 HA45 HB01 HB02 HC12 HC14 HC16 HC17 HF02 4J011 QA03 QA09 QA19 QB13 QB19 SA77 SA83 SA85 SA86 SA87 TA02 TA09 UA01 UA06 VA04 WA07 XA02 4J027 AB04 AE01 CB10 CD02 CD09 4J040 CA031 CA032 DB011 DB012 DB091 DC011 DC012 DC091 DC092 DD061 DF12 DF2 DF022 DF021 022 FA012 FA021 FA022 FA041 FA042 FA051 FA052 FA061 FA062 FA081 FA082 FA101 FA102 FA111 FA112 FA131 FA132 FA181 FA191 FA192 FA231 FA271 FA291

Claims (29)

[Claims] 1. A curable prepreg having an adhesive layer on one or both sides of a curable prepreg layer. 2. The curable prepreg according to claim 1, wherein the pressure-sensitive adhesive is a non-curable pressure-sensitive adhesive comprising a polymer of one or more radically polymerizable unsaturated compounds. 3. The curable prepreg according to claim 1, wherein the pressure-sensitive adhesive is a curable pressure-sensitive adhesive. 4. A curable pressure-sensitive adhesive comprising: (A) 100 parts by weight of a polymer of one or more radically polymerizable unsaturated compounds, (B)
The curable prepreg according to claim 3, which is a composition comprising 5 to 300 parts by weight of a radical polymerizable unsaturated compound and 0.1 to 10 parts by weight of a polymerization initiator (C). 5. A copolymer obtained by copolymerizing (D) one or more radically polymerizable unsaturated compounds and one or more radically polymerizable unsaturated compounds having an epoxy group. 100 parts by weight of a polymer obtained by adding an unsaturated monobasic acid and / or an amino group-containing radically polymerizable unsaturated compound capable of reacting with an epoxy group to 5 to 100 mol% of the epoxy group, (B) radical polymerizable The curable prepreg according to claim 3, which is a composition comprising 0 to 300 parts by weight of an unsaturated compound and 0.1 to 10 parts by weight of a polymerization initiator (C). 6. The curable pressure-sensitive adhesive is obtained by copolymerizing (E) at least one kind of radically polymerizable unsaturated compound and at least one kind of unsaturated monobasic acid and / or radically polymerizable unsaturated compound having an amino group. A radical polymerizable unsaturated compound having an epoxy group capable of reacting with a carboxyl group and / or an amino group in the obtained copolymer is added to the carboxyl group and / or the amino-reactable moiety in an amount of 5 to 100
The composition according to claim 3, which is a composition comprising 100 parts by weight of a polymer having mol% added, 0 to 300 parts by weight of (B) a radically polymerizable unsaturated compound, and 0.1 to 10 parts by weight of (C) a polymerization initiator. Prepreg. 7. The curable pressure-sensitive adhesive comprises (F) one or more radically polymerizable unsaturated compounds, one or more hydroxyl group-containing radically polymerizable unsaturated compounds, and / or an amino group-containing radically polymerizable unsaturated compound. And a radically polymerizable unsaturated compound having an isocyanate group capable of reacting with a hydroxyl group and / or an amino group in the obtained copolymer is reacted with a hydroxyl group and / or an amino group capable of reacting 5 to 5 100 parts by weight of a polymer added with 100 mol%,
The curable prepreg according to claim 3, which is a composition comprising (B) 0 to 300 parts by weight of a radical polymerizable unsaturated compound and (C) 0.1 to 10 parts by weight of a polymerization initiator. 8. A curable pressure-sensitive adhesive comprising: (G) one or more radically polymerizable unsaturated compounds and one or more radically polymerizable unsaturated compounds having an isocyanate group, and A radically polymerizable unsaturated compound having a hydroxyl group and / or an amino group capable of reacting with an isocyanate group of 5 to 100 mol% of the isocyanate group
The curable composition according to claim 3, which is a composition comprising 100 parts by weight of a polymer added to the polymer, 0 to 300 parts by weight of (B) a radical polymerizable unsaturated compound, and 0.1 to 10 parts by weight of (C) a polymerization initiator. Prepreg. 9. The curable pressure-sensitive adhesive according to claim 4, wherein the component (C) is at least one photopolymerization initiator having photosensitivity from an ultraviolet light region to a near infrared light region. The curable prepreg according to claim 3, which is a photocurable pressure-sensitive adhesive comprising the composition according to (1). 10. The curable pressure-sensitive adhesive is a composition according to any one of claims 4 to 8, wherein the component (C) has a photosensitivity from an ultraviolet region to a near-infrared region. 2
A part of the radically polymerizable unsaturated group in the composition which is a polymerization initiator obtained by combining two kinds of photopolymerization initiators is preliminarily polymerized, and at least one kind of the photopolymerization initiator and a part of the radically polymerizable unsaturated group are obtained. The curable prepreg according to claim 3, wherein the curable prepreg is a photocurable pressure-sensitive adhesive composed of a composition obtained by treating with a light having a specific wavelength such that the remaining resin remains. 11. A thermosetting pressure-sensitive adhesive comprising the composition according to any one of claims 4 to 8, wherein the component (C) is a thermopolymerization initiator. The curable prepreg as described. 12. The curable pressure-sensitive adhesive is a composition according to any one of claims 4 to 8, wherein the component (C) has a photosensitivity from an ultraviolet light region to a near infrared light region. A part of the radically polymerizable unsaturated group in the composition obtained by combining the polymerization initiator and the thermal polymerization initiator as a polymerization initiator is prepolymerized, and a part of the thermal polymerization initiator and a part of the radically polymerizable unsaturated group remain. The curable prepreg according to claim 3, which is a thermosetting adhesive made of a composition obtained by treating with a specific wavelength of light. 13. The curable prepreg layer comprising (H) an unsaturated polyester resin and / or a vinyl ester resin 100.
Parts by weight, (I1) 0.01 to 20 parts by weight of a photopolymerization initiator having photosensitivity from two or more kinds of ultraviolet light region to near infrared light region, (J) 0 to 5 parts by weight of ultraviolet absorber, and (K) ) Inorganic or organic fiber reinforcement and / or fillers 1-4
A prepolymerized part of the radically polymerizable unsaturated group in the resin, and at least one kind of a photopolymerization initiator and a radically polymerizable unsaturated compound. The curable prepreg according to any one of claims 1 to 10, which is a photocurable prepreg composition which is treated with light having a specific wavelength such that a part of the groups remains. 14. A curable prepreg layer comprising (H) an unsaturated polyester resin and / or a vinyl ester resin 100.
Parts by weight, (I1) 0.01 to 10 parts by weight of a photopolymerization initiator having photosensitivity from the ultraviolet region to the near infrared region, (I2)
From a composition containing 0.01 to 10 parts by weight of a thermal polymerization initiator, 0 to 5 parts by weight of (J) an ultraviolet absorber and 1 to 400 parts by weight of (K) an inorganic or organic fiber reinforcing material and / or a filler. And the composition has a specific wavelength such that a part of the radically polymerizable unsaturated group in the resin is preliminarily polymerized, and a thermal polymerization initiator and a part of the radically polymerizable unsaturated group remain. The curable prepreg according to any one of claims 1 to 8, which is a thermosetting prepreg composition obtained by treating with light. 15. A photopolymerization initiator having photosensitivity in a visible light region or a near-infrared light region having a wavelength of 500 nm or more, and a photopolymerization initiator having a photosensitivity in a visible light region and / or an ultraviolet light region of less than 500 nm. The curable prepreg according to claim 10, which is a combination with a photopolymerization initiator having a property. 16. The curable prepreg according to claim 12, wherein the photopolymerization initiator is a photopolymerization initiator having photosensitivity in a visible light region or a near infrared light region having a wavelength of 500 nm or more. 17. A photopolymerization initiator having photosensitivity in a visible light region or a near infrared light region having a wavelength of 500 nm or more,
Formula ^{(1) D + · A -} ··· (1) wherein, D ⁺ is methine having photosensitivity in a visible light region or infrared light region, polymethine, cyan, xanthene,
At least one of oxazine, thiazine, arylmethane and pyrylium dye cations, and A ⁻ represents various anions. And a cationic dye having absorption in the near infrared region represented by the general formula (2): [Wherein, Z ⁺ represents an arbitrary cation, and R ¹ , R ² , R
³ and R ⁴ are each independently an alkyl group, aryl group, acyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group, substituted acyl group, substituted It represents an aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. 17. The curable prepreg according to claim 15, which is a combination of a sensitizer represented by the formula: 18. The photopolymerization initiator according to claim 10, wherein the photopolymerization initiator is an acylphosphine oxide compound.
The curable prepreg according to any one of the above. 19. An inorganic or organic fiber reinforcing material used for the curable prepreg is preferably glass fiber, carbon fiber, or carbon fiber.
The curable prepreg according to claim 13, wherein the curable prepreg is at least one selected from aramid fibers and organic fibers, and the shape is at least one selected from mats, cloths, and nonwoven fabrics. 20. A curable prepreg, wherein upper and lower portions of the curable prepreg according to claim 1 are covered with films. 21. A curable prepreg, wherein the upper and lower portions of the photocurable prepreg according to claim 13 are covered with films, and the film on the curable prepreg layer side is further covered with a light-shielding film. 22. The film for coating the curable prepreg is at least one selected from polyethylene terephthalate, vinylon, and release paper.
The curable prepreg according to the above. 23. The curable prepreg according to claim 21, wherein the light-shielding film is colored cellophane or polyethylene. 24. The non-curable pressure-sensitive adhesive or the curable pressure-sensitive adhesive formed on the film by applying the non-curable pressure-sensitive adhesive or the curable pressure-sensitive adhesive on the film.
After laminating the curable prepreg composition according to 4 in a state before the pre-polymerization, the curable prepreg composition is pre-polymerized by irradiation with visible light and / or near-infrared light to be integrated. A method for producing a curable prepreg. 25. A curable pressure-sensitive adhesive layer according to claim 13 or 14, which is formed by applying the curable pressure-sensitive adhesive composition according to claim 10 or 12 on a film before pre-polymerization. After laminating the curable prepreg composition described in 1 above in a state before the prepolymerization, the curable pressure-sensitive adhesive and the curable prepreg are prepolymerized and integrated by irradiation with visible light and / or near-infrared light. A method for producing a curable prepreg, comprising: 26. The method according to claim 24, wherein the formation of the non-curable pressure-sensitive adhesive layer or the curable pressure-sensitive adhesive layer is carried out by pre-polymerization by volatilization of a solvent and / or irradiation of visible light and / or near-infrared light. 3. The method for producing a curable prepreg according to item 2. 27. A method for curing a curable prepreg, comprising irradiating the curable prepreg according to claim 13 with visible light and / or near-infrared light. 28. The lower film of the curable prepreg according to claim 21, which is peeled off and adhered to an adherend while covering the upper film and the light-shielding film. A method for curing a curable prepreg, characterized in that the curable prepreg is bonded by bonding. 29. A method for curing a curable prepreg, comprising heating the curable prepreg according to claim 14.