JP2001294687A - Curable prepreg composition, method for producing the same and method for curing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable prepreg composition capable of stabilized thickening reaction in a short time, causing no running out of a resin from a fibrous base during storage in the form of a prepreg sheet, and high in weatherability as well. SOLUTION: This curable prepreg composition which comprises (A) 100 pts.wt. of an unsaturated polyester resin and/or vinyl ester resin, (B1) 0.01-20 pt(s).wt. of at least two photopolymerization initiators each having photosensitivity in the region ranging from ultraviolet region to near-infrared region, (C) 0.01-5 pt(s).wt. of an ultraviolet light absorber and (D) 1-400 pt(s).wt. of an inorganic or organic fibrous reinforcing material and/or filler, is obtained by prepolymerization of a part of radical-polymerizable groups in the above resin along with treatment with rays of such a specific wavelength as to leave at least one of the photopolymerization initiators and the radical-polymerizable unsaturated groups.

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 structures in the fields of FRP molding, construction and civil engineering, and the like. The present invention relates to curable prepreg compositions having various shapes such as a roll shape, a tubular shape, and a tubular shape, a method for producing the same, and a curing method.

[0002]

2. Description of the Related Art Reinforced fiber plastics (hereinafter referred to as FRP) used for molded articles requiring structural strength, structural materials for buildings, and the like.
That. ) Is a combination of inorganic or organic reinforcing material such as glass fiber and carbon fiber and so-called thermosetting resin such as epoxy resin, unsaturated polyester resin and vinyl ester resin (also called epoxy acrylate resin). Have been. Taking the waterproofing material used as a waterproof covering on concrete or mortar of civil engineering buildings such as rooftops, verandas, parking lots, corridors, pools, etc., the required characteristics include vibration and falling of civil engineering buildings. It can withstand the impact of an object, sufficiently follow cracks in the underlying concrete or mortar, has alkali resistance, and has high adhesiveness to the foundation. Conventionally, asphalt or urethane resin has been used as a lining material for concrete or mortar, but this is not sufficient.In recent years, the FRP method combining an unsaturated polyester resin or vinyl ester resin having flexibility with a fiber reinforced material is often used. ing. However, when lining is performed using an unsaturated polyester resin or a vinyl ester resin, normal temperature curing with a peroxide catalyst is usually performed, and it takes a long time to completely cure. If the curing takes too much time, not only does the workability deteriorate, but also a volatile reactive monomer (such as styrene monomer) volatilizes, causing air pollution at the work site and a change in the mixing ratio of the resin composition. As a result, there is a danger of performance deterioration, loss of resin amount and ignition.
In addition, there is always a danger such as an explosion because the peroxide catalyst is directly handled, and such an accident has actually occurred. Furthermore, complicated operations such as weighing a peroxide catalyst with a dropper at the site and mixing it with the resin are involved, and the gelling time varies greatly depending on the temperature, making it difficult to adjust the amount of catalyst and failing to adjust the pot life. There are many.

As means for solving these drawbacks, air pollution and curability have been improved in the field by replacing volatile monomers in the resin with other high-boiling compounds. The problem that it takes a long time to completely cure the room-temperature curing system with the vinyl ester resin-based peroxide catalyst, 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 Application Laid-Open No. H10-716
As disclosed in JP-A-61-61, there is a photo-curable prepreg sheet obtained by metal-thickening an unsaturated polyester resin impregnated in glass fiber or the like. In the technology of thickening metals such as magnesium oxide of unsaturated polyester resin and isocyanate of vinyl ester resin, it takes a long time to thicken, and it is difficult to stabilize the thickened state. And other reactive diluents do not participate in the thickening reaction of the vinyl ester resin or unsaturated polyester resin, causing problems such as the resin flowing out of the fibrous base material during storage of the prepreg sheet, and furthermore, photocuring. The type of sex has insufficient weather resistance, and the problem remains that the problem of weather resistance must be solved. Also, thermosetting prepregs have similar problems with the conventional thickening method, and none of them has solved these problems.

[0004]

SUMMARY OF THE INVENTION In view of the above situation, the present invention enables a stabilized thickening reaction in a short time, and prevents a resin from flowing out of a fibrous base material during storage of a prepreg sheet. It is another object of the present invention to provide a curable prepreg composition having excellent weather resistance, a method for producing the same, and a method for curing the composition.

[0005]

The present invention relates to (A) an unsaturated polyester resin and / or a vinyl ester resin.
0 parts by weight, (B1) at least two types of photopolymerization initiators having photosensitivity from the ultraviolet region to the near infrared region of 0.01 to 2
A composition comprising 0 parts by weight, (C) 0.01 to 5 parts by weight of an ultraviolet absorber, and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler. A substance having a specific wavelength such that a part of the radically polymerizable unsaturated groups in the resin is preliminarily polymerized, and at least one kind of a photopolymerization initiator and a part of the radically polymerizable unsaturated groups remain. Curable prepreg composition, and (A) 100 parts by weight of an unsaturated polyester resin and / or vinyl ester resin, and (B1) photopolymerization having photosensitivity from the ultraviolet region to the near infrared region. 0.01 to 10 parts by weight, (B2) thermal polymerization initiator 0.01
A composition comprising (C) 0.01 to 5 parts by weight of an ultraviolet absorber and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler. To provide a curable prepreg composition obtained by pre-polymerizing a part of the radically polymerizable unsaturated group in the photopolymerization so as to leave a thermal polymerization initiator and a part of the radically polymerizable unsaturated group. Things.

The present invention further relates to (A) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin, and (B1) at least two kinds of photopolymerization initiators having photosensitivity from the ultraviolet region to the near infrared region. A composition comprising 0.01 to 10 parts by weight of an agent, (C) 0.01 to 5 parts by weight of an ultraviolet absorber, and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler. ,
(A) 100 parts by weight of an unsaturated polyester resin and / or vinyl ester resin, (B1) 0.01 to 10 parts by weight of a photopolymerization initiator having photosensitivity from an ultraviolet light region to a near infrared light region, (B2) heat 0.01 to 10 parts by weight of a polymerization initiator,
(C) 0.01 to 5 parts by weight of an ultraviolet absorber and (D) inorganic or organic fiber reinforcing material and / or filler 1 to 1
A method for producing a curable prepreg composition, comprising prepolymerizing a composition containing 400 parts by weight to a B stage by irradiation of visible light and / or near-infrared light. An object of the present invention is to provide a method for curing a curable prepreg composition, which comprises irradiating the prepreg composition with visible light or heating a curable prepreg composition containing a thermal polymerization initiator.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Among the unsaturated polyester resins or vinyl ester resins used in the present invention (hereinafter, both resins may be collectively referred to as resins, etc.), the unsaturated polyester used as a raw material is as follows. May be produced by a known method, and specifically, a saturated polybase having no polymerizable unsaturated bond such as phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid and sebacic acid. Acid or anhydride and fumaric acid,
An unsaturated polybasic acid having an active unsaturated bond such as maleic anhydride, maleic acid, itaconic acid or the like or an anhydride thereof is used as an acid component, and ethylene glycol, propylene glycol, diethylene glycol, Dipropylene glycol, 1,2-butanediol, 1,3-butanediol
1,5-pentaneddiol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2
Polyhydric alcohols such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, an ethylene oxide adduct of bisphenol A, and a propylene oxide adduct of bisphenol A; -It is produced by reacting as a metal component.

The vinyl ester resin may be one produced by a known method, such as a resin obtained by reacting an epoxy resin with an unsaturated monobasic acid such as acrylic acid or methacrylic acid, or a resin obtained by reacting a saturated dicarboxylic acid and And / or a resin obtained by reacting a saturated polyester or unsaturated polyester having a terminal carboxyl group 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, and diethylene glycol.
, Dipropylene glycol, 1,2-butanediol
1,3-butanediol, 1,5-pentanedio-
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 epoxy compound containing an α, β-unsaturated carboxylic acid ester group used in the production of vinyl esters.

Unsaturated polyesters 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 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 in the resin or the like, enhances the kneadability and impregnation with the fiber reinforcing material and the filler when producing a composite material, and 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 monomers having an unsaturated group other than styrene monomer include styrene monomers such as chlorostyrene, vinyltoluene and divinylbenzene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, There is a polymerizable monomer having a (meth) acryloyl group such as ethylene glycol di (meth) acrylate, and the polymerizable monomer can be used in place of the gist of the present invention as long as the gist of the present invention is not impaired.

[0013] As the photopolymerization initiator having photosensitivity in a visible light region or infrared light region of 500nm or more wavelength used in the present invention have the general formula ^{(1) D + · A -} ··· (1 Wherein D ⁺ is at least one of methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane and pyrylium dye cations having sensitivity to visible light or near infrared light. a ^- represents various anions. A cationic dye having absorption in the near infrared region represented by the general formula (2):

[0014]

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 , Substituted acyl,
Indicates a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group, a substituted silyl group or a substituted heterocyclic group. The photopolymerization initiator which combined the organic boron compound (sensitizer) represented by these] is preferable.

The cation “Z” in the general formula (2)
Examples of " ⁺ " include quaternary ammonium cations, quaternary pyridinium cations, quaternary quinolinium cations, diazonium cations, tetrazolium cations, and sulfonium cations that are insensitive to visible light or near infrared light. Ions, oxosulfonium cations, metal cations such as sodium, potassium, lithium, magnesium, calcium, etc., (organic) compounds having a cation charge on oxygen atoms such as flavylium and pyranium salts, and carbons such as tropylium and cyclopropylium Examples include cations, 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. This discolors the dye and generates radicals, causing a polymerization reaction of the coexisting polymerizable unsaturated compound. In this polymerization reaction, unlike a conventional ultraviolet polymerization reaction or the like, generated radicals can be easily controlled, and a part of unsaturated groups in the resin can be easily stopped at the time of radical polymerization. In addition, since a long wavelength in the visible light region or near infrared light region is used, the reaction can be easily promoted even in a system in which a filler, a pigment, or the like is 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. Of these cationic dyes, cyanine-based, styryl-based cationic dyes and triarylmethane-based dyes are preferably used. Cyanine-based and styryl-based cationic dyes are preferable in that the electron transfer with an organic boron-based compound generally occurs easily and the reaction of the present invention is easily caused.

[0018]

[Table 1]

[0019]

[Table 2]

[0020]

[Table 3]

[0021]

[Table 4]

A ⁻ , which is a 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)

[0023]

Embedded image

[Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently 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 viewpoints of the decoloring reaction of the dye and the efficiency of radical generation.

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, 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.

An acylphosphine oxide compound is effective as an initiator having photosensitivity from the ultraviolet region to the visible region. 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 thereof include methyl dichlorobenzoyl-phenylphosphinate.

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 (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)
(trade name: Darocur4265) in which n TPO (manufactured by BASF Corporation) is mixed at a ratio of 50% / 50%. 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. UV light has a relatively long wavelength, preferably 3
It is preferable to use a (bis) acylphosphine oxide-based polymerization initiator having photosensitivity in a wavelength region of 00 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 by 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 the photocurable prepreg composition, the amount of the at least two photopolymerization initiators having photosensitivity from the ultraviolet region to the near infrared 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 and polymerization after the thickening tend 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 reaction and a photopolymerization initiator for fully curing the B-staged product are used in combination, the composition ratio is 0.1 / 5 to 5 / 0.1 by weight ratio, preferably 0.5 / 5 to 5 / 0.5. If the ratio of the B-staged photopolymerization initiator to the main curing photopolymerization initiator is less than 0.1 / 5, the photocurable prepreg composition is irradiated with light having the photosensitive wavelength of the B-staged photopolymerization initiator. Even when the ratio exceeds 5 / 0.1, the thickening reaction may progress too much.

In the case of the thermosetting prepreg composition, the total amount of the photopolymerization initiator and the heat polymerization initiator having photosensitivity from the ultraviolet light region to the near infrared light region is based on 100 parts by weight of the resin or the like. 0.01-20 parts by weight, preferably 0.05-1
5 parts by weight. If the amount of the photopolymerization initiator composition 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 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 0.5 / 5 to 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 prepreg 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 / 0.1.
If the amount exceeds the above, the thickening reaction may proceed too much.

The fiber reinforcement used in the curable prepreg composition of the present invention is an organic and / or inorganic fiber,
For example, known materials such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, vinylon fiber, polyester fiber, amide fiber, metal fiber, and ceramic fiber are used. Good. Of course, two or more of these fibers may be used in combination. Among these reinforcements,
In the present invention, glass fibers and organic fibers are particularly desirable, and mat-like ones are preferable in view of workability and the like. The amount of the fiber reinforcement used is 1 to 400 parts by weight, preferably 10 to 2 parts by weight, per 100 parts by weight of the resin (A).
00 parts by weight. If this amount exceeds 400 parts by weight, resin impregnation becomes insufficient.

A filler may be added to the curable prepreg composition of the present invention, and the filler used is an inorganic filler, an organic filler or a polymer. Examples of the inorganic filler include aluminum hydroxide and carbonate. Known materials such as calcium, talc, clay, glass powder, silica, barium sulfate, titanium oxide, and cement are used. However, when imparting flame retardancy to the curable prepreg composition, aluminum hydroxide is effective. is there. Of course, these inorganic fillers can also be used in combination, and the amount used is 1 to 30 parts by weight based on 100 parts by weight of the resin.
0 parts by weight, preferably 100 to 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. Further, in the present invention, thixotropic may be imparted by a known method,
As the thixotropic agent, for example, silica powder (aerosil type), mica powder, calcium carbonate powder or the like is used in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the polymerizable unsaturated compound.
There is a method of adding 0 parts by weight.

Other organic fillers or polymers that can be incorporated into the composition of the present invention include polystyrene, polyvinyl acetate, polymethyl methacrylate, polyethylene, and polychloride, which are also known to be effective as low-shrinkage agents. Vinylidene microballoons, polyacrylonitrile microballoons and the like can be used. When used as a low shrinkage agent, the amount used is 0 to 100 parts by weight of resin
It is 40 parts by weight, preferably 0 to 30 parts by weight. If the amount of the low-shrinkage agent is more than 40 parts by weight, the viscosity becomes too high and the moldability is reduced, and the smoothness and heat resistance of the cured product surface are reduced. Pigments can be used in the present invention. There is no particular limitation on the type, and organic pigments and inorganic pigments can be used. The compounding amount at that time is at most 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the resin.

In addition, as the ultraviolet absorber which can be blended in the composition of the present invention, known ones such as benzophenone type, salicylic acid ester type, benzotriazole type, benzoate type and cyanoacrylate type can be used. Specifically, benzophenones such as 2,4-di-hydroxybenzophenone, 2-hydroxy-4-acetoxyethoxybenzophenone, and 2-hydroxy-4
-Methoxybenzophenone, 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 a salicylic acid ester type, and 2 (2′-hydroxy-5′-methylphenyl) benzotriazole, 2 (2′-hydroxyl as a benzotriazole type -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′-benzoate
Di-t-butylphenyl-3,5-di-t-butyl-4
-Hydroxybenzoate and cyanoacrylates include ethyl-2-cyano-3,5-diphenylacrylate. The amount of UV absorber used is resin 10
0.01 to 5 parts by weight, preferably 0.1 to 5 parts by weight, per 0 parts by weight.
03 to 2 parts by weight. If the amount of the ultraviolet absorber exceeds 5 parts by weight, physical properties are reduced. If the amount is less than 0.01 part by weight, the effect as the ultraviolet absorber is not exhibited. 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 composition of the present invention may be covered with a film on the upper and lower sides to form a sheet-like curable prepreg composition. Films used for producing such a sheet-like curable prepreg composition include vinylon films, polyethylene terephthalate films,
Known materials such as polyethylene film, polypropylene film, nylon film, aluminum foil, and release paper can be used. These films may be of the transparent type or of the colored type. In order to prevent the film from shifting, an embossed film is also effective. In the case of a photocurable prepreg composition, it is preferable to use a transparent film and also use a film for shielding light. 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 work, is desirable.

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 of a wide wavelength range with a light source and a wavelength cut filter. The wavelength used in the B-stage reaction is desirably long-wavelength light having a low energy level.
Easy to control staging reaction.

The irradiation time of the lamp for converting the photocurable prepreg composition into 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 composition thus produced can be fully cured quickly by light irradiation with the remaining photopolymerization initiator in the photocurable prepreg composition, and remains in the thermosetting prepreg composition in the thermosetting prepreg composition. Can be quickly cured by heating. 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, a metal halide lamp, a halogen lamp, and an ultraviolet lamp. .

[0039]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the present invention is not limited by these, and "parts" in each example is based on weight.

Example 1 1,1,5,5-Tetrakis (p-diethylamino) shown in No. 3 of Table 1 was added to 100 parts of a vinyl ester resin (trade name: Lipoxy R-802, manufactured by Showa Polymer Co., Ltd.). Phenyl) -2,4-pentadienyl triphenyl-n-
0.03 parts of butyl borate (manufactured by Showa Denko; hereinafter abbreviated as IRB; near-infrared light absorbing cationic dye) and tetra-n-
Butyl ammonium triphenyl-n-butyl borate (manufactured by Showa Denko, hereinafter abbreviated as P3B; boron compound)
0.15 parts of a near-infrared light polymerization initiator for B-stage formation, a bisacylphosphine oxide-based polymerization initiator having a photosensitivity from ultraviolet light to visible light region for fully curing the B-staged product (trade name, Irgacure 1800: manufactured by Ciba Specialty Chemicals Co., Ltd., hereinafter I-1
1.0 part, benzotriazole-based ultraviolet absorber (Cipro Kasei Co., Ltd., trade name: Seesorb 70)
5) 0.2 parts was added to obtain a photocurable resin composition. Next, three plies of 30 cm × 30 cm # 450 chopped strand glass mat (manufactured by Asahi Fiberglass Co., Ltd.) were impregnated with a glass content of 25% by weight and covered with a transparent PET film. ~ 120
AL-Spotlight (ALF-10) which is a light source including a wavelength range of 0 nm, 1 KW (manufactured by RDS) 500
Irradiation at a distance of 20 cm using SC-50 (manufactured by Fuji Film Co., Ltd.) which is a cut filter of nm or less, B-stage is formed in 2 minutes, and then B-stage state does not change even if one spectral irradiation is continued. Was. Then, the thing of the B stage state after light irradiation for 3 minutes was made into a photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined.
The hardness of the prepreg did not change for more than a month. Also, 30
2 hours after curing for 6 months in a dark place
It was placed at a distance of 1 m below a KW metal halide lamp and irradiated with light for 10 minutes to cure. When the mechanical strength of the cured product was measured in accordance with JIS K 6911, it was found that the cured product reached the level of room temperature curing by peroxide. The results are shown in Table 3.
For the weather resistance of the cured product, refer to Dew Cycle Sunshine Super Long Life Weather Meter: WE
Exposure test for 240 hours by L-SUN-DC-B type (manufactured by Suga Test Instruments Co., Ltd.) [irradiation 60 minutes (room temperature 40 ° C, black panel 63 ° C, humidity 50%), darkness 60 minutes (room temperature 30 ° C, Humidity 100%)], observe the appearance and observe JIS K
When the mechanical strength at 6911 was measured, there was no change in both appearance and strength. The results are shown in Table 3.

Comparative Example 1 The same operation as in Example 1 was performed except that no ultraviolet absorber (Seesorb 705) was added, and the measurement of mechanical strength and the weather resistance test were performed. The results are shown in Table 3.

Example 2 B stage in which 100 parts of an unsaturated polyester resin (trade name: Rigolac M-543, manufactured by Showa Polymer Co., Ltd.) was combined with 1.0 part of triethylamine, 0.03 part of IRB and 0.15 part of P3B. -Infrared photopolymerization initiator for chemical conversion, t-butyl peroxybenzoate (manufactured by NOF CORPORATION, hereinafter abbreviated as perbutyl Z) for fully curing the B-staged product.
0 parts and 0.2 part of Seesorb 705 (ultraviolet absorber) were mixed to obtain a thermosetting resin composition. Next, the thermosetting resin composition was mixed with a 30 cm × 30 cm # 450 chopped strand glass mat (manufactured by Asahi Fiberglass Co., Ltd.) 3
The ply was impregnated with a glass content of 25% by weight and covered with a transparent PET film.
An AL-spotlight (ALF-10), which is a light source including a wavelength range of 200 nm, is used in combination with SC-50, a cut filter of 500 nm or less, at a distance of 20 cm to 1 KW of a light source having a wavelength of 20 cm. The B-stage state did not change even if the spectral irradiation was continued. Then, the thing of the B stage state after light irradiation for 3 minutes was made into a thermosetting prepreg, and when the storage stability in a dark place at 30 ° C. was examined, the hardness of the prepreg did not change. Also: 3
The thermosetting prepreg that had been stored at 0 ° C. for one month in a dark place was subjected to heat and pressure molding (175 ° C., 10 minutes, 50 kg / cm ² ) to obtain a laminate, and the mechanical strength in JIS K 6911 was measured.
The results are shown in Table 3. In addition, when the weather resistance test of the cured product was performed in the same manner as in Example 1, there was no change in both appearance and strength. The results are shown in Table 3.

[0043]

[Table 5]

Example 3 100 parts of an unsaturated polyester resin (trade name: Rigolac 2141, manufactured by Showa Polymer Co., Ltd.), 1.0 part of triethylamine, and CHIMASSORB 2020FDL (trade name) which is a high molecular weight hindered amine stabilizer 0.1 part of T-Chemicals Co., Ltd., trade name: TINUV which is a benzotriazole-based ultraviolet absorber
IN123: 0.2 part was added, and IRB: 0.
Near-infrared photopolymerization initiator for B-stage formation combining 03 parts and P3B: 0.15 part, t-butyl peroxybenzoate (Nippon Oil & Fats Co., Ltd.) for fully curing the B-staged product
(Hereinafter, abbreviated as Perbutyl Z), and 50 parts of aluminum hydroxide powder (trade name: Heidilite HBT-320, manufactured by Showa Denko K.K.) to obtain a thermosetting resin composition. Obtained. Next, the thermosetting resin composition was added to 30
A 3 × 4 cm # 30 cm chopped strand glass mat (manufactured by Asahi Fiberglass Co., Ltd.) impregnated with 3 ply glass having a glass content of 25% by weight was covered with a transparent PET film. AL-spotlight (ALF) which is a light source including a wavelength range
-10) Irradiation at a distance of 20 cm using 1 KW in combination with SC-50 which is a cut filter of 500 nm or less resulted in a B-stage in 2 minutes, and the B-stage state did not change even after one spectral irradiation. Thus, the B-stage state after irradiation with light for 3 minutes is made into a thermosetting prepreg, and heated and pressed (175 ° C., 10 minutes, 50 kg / cm).
² ) The laminate was obtained and subjected to the same weather resistance test as in Example 1. As a result, no change was observed in appearance. Further, a flame retardancy test based on UL-94 was conducted, and the results are shown in Table 4.

Comparative Example 2 Trade name C which is a high molecular weight type hindered amine stabilizer
HIMASSORB2020FDL, trade name: TINUVIN12, a benzotriazole-based UV absorber
3. Example 3 except that aluminum hydroxide was not added
The same operation as in Example 1 was performed, and an appearance inspection after the weather resistance test and a flame retardancy test based on UL-94 were performed in the same manner as in Example 1. The results are shown in Table 4.

[0046]

[Table 6]

Example 4 (Preparation of Photothermosetting Resin Composition) Unsaturated polyester resin (trade name: Rigolac FK-2, manufactured by Showa Polymer Co., Ltd.)
000) 100 parts, to which 2.0 parts of triethylamine and 0.2 part of Seesorb 705 were added, IRB:
A near-infrared photopolymerization initiator for B-stage formation, which is a combination of 0.03 part and P3B: 0.15 part, and I-1800, which fully cures the B-staged product, 3.0 parts, are mixed to form a photocurable resin composition I got something. (Preparation of Photocurable Prepreg) Next, 30 cm × 30 c
m # 450 chopped strand glass mat (manufactured by Asahi Fiberglass Co., Ltd.) is impregnated with 3 plies so that the glass content is 25% by weight, and is covered with a release paper and a transparent PET film. AL-Spotlight (ALF-1) which is a light source including a wavelength range of
0) SC-50 (Fuji Film Co., Ltd.) which is a cut filter of 500 nm or less in 1 KW (manufactured by RDS)
Irradiate at a distance of 20 cm from the top of the transparent PET film.
The B-stage state did not change even if the spectral irradiation was continued.
Therefore, the transparent P of the B stage state after light irradiation for 3 minutes
A photocurable prepreg was prepared by attaching yellow cellophane to an ET film. (Curing of light-curable prepreg) A release paper of the light-curable prepreg was taken and attached to a sidewalk board placed in direct sunlight, and bubbles were expelled from the yellow cellophane 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. 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 favorable results were obtained in the fracture mode of the concrete base material. The results are shown in Table 5.

COMPARATIVE EXAMPLE 3 Except that no seesorb was added, the same operation as in Example 4 was carried out. When exposed outdoors outdoors for half a year, it turned yellow. In a tensile strength test according to the Kenken formula, it was 5 kgf / cm.
Only the adhesive strength of ² was obtained, and the fracture mode also showed interfacial fracture and a decrease in adhesive strength. The results are shown in Table 5.

[0049]

[Table 7]

[0050]

The curable prepreg composition of the present invention can stabilize the viscosity in a short time, and the resin does not flow out of the fibrous base material during storage of the prepreg sheet. The state can be stably maintained, and a cured product having excellent adhesive strength and excellent weather resistance can be produced.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/00 C08K 5/00 5/07 5/07 5/101 5/101 5/3475 5/3475 C08L 63/10 C08L 63/10 67/06 67/06 F term (Reference) 4F072 AB02 AB08 AD38 AE02 AG03 AL17 4J002 BD05X CD20W CF00X CF21W CF22W CL00X CL06X DA019 DA069 DE139 DE149 DE239 DG049 DJ019 DJ039 DJ049 DL009 EE0128 EH0E E038 EH0E EU178 EV306 EV316 EY017 FA04X FA049 FA06X FA089 GL00 4J011 SA78 SA85 SA88 4J027 AB36 AE01 CA06 CA07 CA10 CA14 CA18 CA19 CB10 CD02

Claims (16)

[Claims] (A1) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin, and (B1) at least two photopolymerization initiators 0.01 having photosensitivity from an ultraviolet light region to a near infrared light region. A composition comprising (C) 0.01 to 5 parts by weight of an ultraviolet absorber and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler; The composition, while pre-polymerizing a part of the radically polymerizable unsaturated group in the resin, at a specific wavelength such that at least one kind of photopolymerization initiator and a part of the radically polymerizable unsaturated group remain. A curable prepreg composition obtained by treating with light. 2. (A) 100 parts by weight of an unsaturated polyester resin and / or vinyl ester resin, and (B1) 0.01 to 10 parts by weight of a photopolymerization initiator having photosensitivity from an ultraviolet light region to a near infrared light region. , (B2) thermal polymerization initiator 0.01
A composition comprising (C) 0.01 to 5 parts by weight of an ultraviolet absorber and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler. A curable prepreg composition obtained by preliminarily polymerizing a part of the radically polymerizable unsaturated group in the resin and treating the thermal polymerization initiator and a part of the radically polymerizable unsaturated group in the resin. . 3. The photopolymerization initiator of component (B1) is 500 n
m, a photopolymerization initiator having photosensitivity in a visible light region or a near infrared light region having a wavelength of at least m, an ultraviolet light region and / or 500 n
The curable prepreg composition according to any one of claims 1 and 2, which is a photopolymerization initiator having photosensitivity in a visible light region of less than m or a combination of those photopolymerization initiators. 4. A photopolymerization initiator having a sensitivity in a visible light region or a near infrared light region having a wavelength of 500 nm or more of the component (B1) is represented by the following general formula (1): D ⁺ · A ^−. Wherein D ⁺ is at least one of methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane and pyrylium dye cations having sensitivity to visible light or near infrared light. 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. The curable prepreg composition according to claim 3, which is a combination of sensitizers represented by the formula: 5. The photopolymerization initiator of component (B1),
The curable prepreg composition according to any one of claims 1 to 3, which is a combination of a hexaarylbiimidazole compound and a hydrogen-donating compound or an acylphosphine oxide-based compound. 6. The curable prepreg composition according to claim 1, wherein the ultraviolet absorbent as the component (C) is at least one selected from benzophenone, benzotriazole, and salicylate esters. object. 7. The inorganic or organic fiber reinforcing material of component (D) is at least one selected from glass fiber, carbon fiber, aramid fiber, and organic fiber, and its shape is selected from mat, cloth, and nonwoven fabric. The curable prepreg composition according to any one of claims 1 and 2, which is at least one kind to be performed. 8. The curable prepreg composition according to claim 1, wherein the filler of the component (D) is aluminum hydroxide. 9. A curable prepreg composition, wherein the curable prepreg composition according to claim 1 is covered with films on upper and lower sides. 10. A curable prepreg composition, wherein the photocurable prepreg composition according to claim 1 is covered with upper and lower films, and a light-shielding film is further coated on the upper film. 11. The curable prepreg according to claim 9, wherein the film for coating the photocurable prepreg composition is at least one selected from polyethylene terephthalate, vinylon, and release paper. Composition. 12. The curable prepreg composition according to claim 10, wherein the light-shielding film is colored cellophane or polyethylene. 13. (A) an unsaturated polyester resin and / or
Or 100 parts by weight of a vinyl ester resin, (B1) at least 2 parts having photosensitivity from an ultraviolet light region to a near infrared light region.
0.01 to 20 parts by weight of a photopolymerization initiator, (C) 0.01 to 5 parts by weight of an ultraviolet absorber, and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or a filler. (A) 100 parts by weight of an unsaturated polyester resin and / or a vinyl ester resin,
1) 0.01 to 10 parts by weight of a photopolymerization initiator having photosensitivity from an ultraviolet region to a near infrared region, (B2) 0.01 to 10 parts by weight of a thermal polymerization initiator, and (C) an ultraviolet absorber 0 .01-
A composition containing 5 parts by weight and (D) 1 to 400 parts by weight of an inorganic or organic fiber reinforcing material and / or filler is prepolymerized to the B stage by irradiation with visible light and / or near infrared light. A method for producing a curable prepreg composition, comprising: 14. A method for curing a curable prepreg sheet composition, comprising irradiating the curable prepreg sheet composition according to claim 1 with visible light. 15. A method for curing a curable prepreg sheet composition, comprising heating the curable prepreg sheet composition according to claim 2. 16. A film on the lower side of the curable prepreg sheet composition according to claim 10, which is peeled off, adhered to an adherend while covering the upper film and the light-shielding film, and only the light-shielding film is peeled off and irradiated with light. A method for curing a curable prepreg sheet composition, comprising releasing the upper film after curing.