JPH1067865A - Photocurable prepreg composition and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable prepreg compsn. in which the state of B stage of a thermosetting resin (e.g. an unsatd. polyester resin or a vinyl ester resin) contained can be easily controlled and which has a good storage stabiliy and gives a molded item with a good curability and to provide a process for producing the same. SOLUTION: This compsn. contains an unsatd. polyester resin and/or a vinyl ester resin, at least two photopolymn. initiators different from each other in wavelengths to which they are sensitive, and an inorg. or org. fibrous reinforcement and/or a filler and has been treated with light having such wavelengths that a part of the free-radical polymerizable unsatd. groups of the resin are prepolymerized and that at least one photopolymn. initator and a part of the unsatd. groups remain unchanged.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable prepreg composition having various shapes such as a sheet, roll, tube, or tube formed from a resin and a fiber reinforcing material and / or a filler, and a method for producing the same. About.

[0002]

2. Description of the Related Art Fiber-reinforced plastics (hereinafter referred to as FRP) used for molded articles requiring structural strength, structural materials of buildings, etc. are made of inorganic or organic reinforcing materials such as glass fiber and carbon fiber, and epoxy resin. A combination of a so-called thermosetting resin such as an unsaturated polyester resin and a vinyl ester resin (also referred to as an epoxy acrylate resin) is used.

Conventionally, a prepreg using a thermosetting resin is prepared by impregnating a fibrous base material such as glass fiber or carbon fiber with a thermosetting resin containing a non-reactive solvent as a diluent and heating the resin to a non-reactive state. Simultaneous drying and removal of the conductive solvent and B-stage (thickening) of the thermosetting resin, or impregnation of a fibrous base material such as glass fiber and carbon fiber with a non-solvent thermosetting resin, It is manufactured by performing a B stage by heating or the like. Among these prepregs, large-sized ones that cannot be heated or uniform heating is difficult, and those that are light-cured for outdoor installations have been adopted. It has attracted attention from the viewpoint that it can be easily and simply constructed on buildings and the like.

[0004] As a method of B-stage of a thermosetting resin for the production of a prepreg, there is a method in which a part of the curing reaction of a thermosetting resin as a raw material is advanced and a polymerization reaction is stopped at an appropriate B-stage state. However, it is difficult to always achieve a constant B-stage state in a normal manufacturing process. In particular, in the case of a resin containing a compound having a radically polymerizable unsaturated group such as an unsaturated polyester resin or a vinyl ester resin, upon prepolymerizing the radically polymerizable unsaturated group in the resin to form a B-stage, It is difficult to always achieve a constant B-stage state.

[0005] Therefore, as a known thickening method of the vinyl ester resin, for example, hydroxyl group in the vinyl ester resin skeleton,
Alternatively, a method of reacting a diisocyanate with a carboxyl group pendant to a hydroxyl group to form a B-stage is also known. However, since this B-stage reaction is greatly affected by a small amount of water, active groups, and the like in a resin, this method is used. However, it is difficult to always achieve a constant B-stage state.

As a general method for thickening the unsaturated polyester resin, Japanese Patent Application Laid-Open Nos. Sho 62-73914, 62-73915, 62-73916 and 62-73917 are known. For example, there is a method of adding magnesium oxide as disclosed in Japanese Unexamined Patent Publication (Kokai) No. H10-15095.

However, in the above-mentioned thickening method using diisocyanate and adding magnesium oxide, the prepreg is not used because 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 was a problem that these reactive diluents separated during storage and dripped.

In addition, JP-A-6-287524 discloses a method in which a gelling agent is added to a prepreg raw material to form a collapsible jelly, but the B-stage state is further advanced from the jelly state. It is difficult to adjust the B stage, and the problems of the B-stage conversion method for unsaturated polyester resin, vinyl ester resin and the like have not been solved.

[0009]

According to the present invention, the B-stage state of a thermosetting resin such as an unsaturated polyester resin or a vinyl ester resin can be easily adjusted, and a constant B-stage state can be always realized. Yes, the prepared prepreg composition has good storage stability, and has good curability after shaping, and has various shapes such as sheet, roll, tube, and tube, and structural materials for building. Another object of the present invention is to provide a photocurable prepreg composition which can be used for a wide range of uses such as repair and reinforcement thereof, and a method for producing the same.

[0010]

According to the present invention, there are provided (1) an unsaturated polyester resin and / or a vinyl ester resin, at least two photopolymerization initiators each having a different photosensitive wavelength, and an inorganic or organic fiber reinforced resin. A composition comprising a material and / or a filler, wherein the composition preliminarily polymerizes a part of the radically polymerizable unsaturated groups in the resin, and comprises at least one kind of a photopolymerization initiator and a radical. A photocurable prepreg composition that has been treated with light of a specific wavelength such that a part of the polymerizable unsaturated group remains,

(2) The photopolymerization initiator is a combination of a photopolymerization initiator having photosensitivity in a near-infrared light region and a photopolymerization initiator having photosensitivity in a visible light and / or ultraviolet region. (1) The photocurable prepreg composition according to (1),

(3) The photopolymerization initiator has a wavelength of 500 nm
A photopolymerization initiator having photosensitivity in the visible light region,
The photocurable prepreg composition according to the above (1), which is a combination of a photopolymerization initiator having photosensitivity in a visible light region and / or an ultraviolet light region of less than 00 nm.

[0013] (4) wavelength photopolymerization initiator having photosensitivity in a visible light or near infrared light region above 500 nm, cationic dye represented by the general formula ^{(1), D + · A} - ( wherein , D ⁺ is at least methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, or one of pyrylium-based dye cations having a wavelength of at least 500 nm that is sensitive to visible light or near infrared light. a ^- represents various anions).

And a sensitizer represented by the general formula (2):

Embedded image (Wherein, Z ⁺ represents any 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 photocurable prepreg composition according to the above (2) or (3), which is a combination with

(5) The cationic portion (D ⁺ ) of the photopolymerization initiator represented by the general formula (1) having a photosensitive wavelength in the visible light or near-infrared light region having a wavelength of 500 nm or more is a cyanine-based or The photocurable prepreg composition according to the above (4), which is a triarylmethane-based cationic dye,

(6) One of the photopolymerization initiators having photosensitivity in the visible light region and / or the ultraviolet region is a combination of a hexaarylbiimidazole compound and a hydrogen donating compound or an acylphosphine oxide compound. 1) to the photocurable prepreg composition according to (5),

(7) A composition containing an unsaturated polyester resin and / or a vinyl ester resin, at least two photopolymerization initiators each having a different photosensitive wavelength, an inorganic or organic fiber reinforcing material and / or a filler. The product is prepolymerized by irradiating the product with light having a wavelength of at least one photosensitive wavelength region of the photopolymerization initiator in the composition and not including the wavelength of the photosensitive wavelength region of at least one other photopolymerization initiator. A method for producing a photocurable prepreg composition, comprising:

(8) A composition containing an unsaturated polyester resin and / or a vinyl ester resin, each containing at least two photopolymerization initiators having different photosensitive wavelengths, an inorganic or organic fiber reinforcing material, and / or a filler. Object, 5
The method for producing a photocurable prepreg composition according to (7), wherein the composition is prepolymerized by irradiation with visible light or near infrared light having a wavelength of 00 nm or more,

(9) The prepreg composition is prepared by applying or molding the photocurable prepreg composition described in (1) and irradiating the prepreg composition with light containing the photosensitive wavelength of the photopolymerization initiator contained in the prepreg composition. Curing method of photocurable prepreg composition, characterized by curing

(10) A molded product cured by applying or molding the photocurable prepreg composition according to (1), and irradiating light containing the photosensitive wavelength of the photopolymerization initiator contained in the prepreg composition. The above objectives were achieved by developing.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Among the resins and the like used in the present invention, unsaturated polyesters may be those produced by a known method, and specific examples of the raw materials include phthalic anhydride, isophthalic acid and terephthalic acid. , Tetrahydrophthalic acid, a saturated polybasic acid having no active unsaturated bond such as adipic acid or an anhydride thereof, and fumaric acid, maleic anhydride, maleic acid, having an active unsaturated bond such as itaconic acid Unsaturated polybasic acid or its anhydride as an acid component, ethylene glycol, propylene glycol,
Diethylene glycol, dipropylene glycol, 1,
2-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 2-
Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4
A polyhydric alcohol such as dimethanol, bisphenol A ethylene oxide adduct or bisphenol A propylene oxide adduct is used as an alcohol component, and the acid component and the alcohol component are obtained by dehydration polycondensation.

The vinyl ester may also be produced by a known method, and may be an epoxy (meth) acrylate or an epoxy (meth) acrylate obtained by subjecting one of them to an addition reaction with an epoxy resin and acrylic acid or methacrylic acid as components. Epoxy compounds containing a saturated polyester or unsaturated polyester having a terminal carboxyl group and an α, β-unsaturated carboxylic acid ester group obtained by using a saturated dicarboxylic acid and an unsaturated dicarboxylic acid or one of the dicarboxylic acids and a polyhydric alcohol as components. And unsaturated polyester (meth) acrylates obtained by reacting as a component.

Examples of the epoxy resin as a raw material used for producing the vinyl ester include bisphenol A diglycidyl ether and its high molecular weight homologues, novolak type polyglycidyl ethers and the like.

The saturated dicarboxylic acid used as a raw material for the saturated or unsaturated polyester having a terminal carboxyl group used for producing a vinyl ester includes dicarboxylic acids having no active unsaturated group, for example, phthalic acid and isophthalic acid. Acids, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid and the like.Unsaturated dicarboxylic acids include dicarboxylic acids having an active unsaturated group, such as fumaric acid, maleic acid, maleic anhydride, itacone Examples of the polyhydric alcohol component include, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol, 6-hexanediol, 2-methyl-1 3-propane diol, 2,2
And polyhydric alcohols such as -dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, and propylene oxide adduct of bisphenol A.

As an epoxy compound containing an α, β-unsaturated carboxylic acid ester group, glycidyl methacrylate can be exemplified.

The unsaturated polyester or vinyl ester used for the resin or the like preferably has a high degree of unsaturation, and has an unsaturated group equivalent (molecular weight per unsaturated group) of 100 to 100.
About 800 are used. Unsaturated group equivalent is 100
If the amount is less than 80, the synthesis is impossible, and the unsaturated group equivalent is less than 80.
If the value is 0 or more, the density of the reactive group is too low, and the curing reaction is slow, or a cured product having high hardness cannot be obtained.

The unsaturated polyester resin or vinyl ester resin used in the present invention is a mixture of the unsaturated polyester or vinyl ester with a monomer having a radically polymerizable unsaturated group such as a styrene monomer or methyl methacrylate.

The monomer having a radically polymerizable unsaturated group incorporated in the resin or the like of the present invention can be kneaded or impregnated with a fiber reinforcing material such as a resin or a filler when producing a photocurable prepreg composition. Is important for improving the hardness, strength, chemical resistance, water resistance, etc. of the cured product of the composition.
10 to 250 parts by weight, preferably 2 to 100 parts by weight
0 to 100 parts by weight are blended. If the amount is less than 10 parts by weight, the resin or the like has a high viscosity and is difficult to be impregnated with the fiber reinforcing material or filler, and is not suitable for molding. If the amount exceeds 250 parts by weight, a hardened product with high hardness cannot be obtained, Runs short and F
This is not desirable as an RP material.

As the monomer having a radical polymerizable unsaturated group, a styrene monomer is preferably used.
A part or all of the styrene monomer is substituted with another monomer having a radical polymerizable unsaturated group, for example, chlorostyrene, methyl methacrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, ethylene glycol dimethacrylate, etc. It is also possible.

The fiber reinforcing material used in the present invention is an organic or inorganic fiber such as glass fiber, carbon fiber, aramid fiber, polyethylene terephthalate fiber, and the like.
Known fibers such as vinylon fibers can be used. Of course, it is also possible to use these fibers in combination.
The amount used is 5 to 30 parts by weight per 100 parts by weight of resin or the like.
0 parts by weight, preferably 10 to 100 parts by weight.

The filler used in the present invention can be used alone with or without fiber reinforcement. The filler is an inorganic filler, an organic filler or a polymer. Examples of the inorganic filler include known calcium carbonate, talc, clay, glass powder, glass beads, silica, aluminum hydroxide, barium sulfate, and titanium oxide. Can be used. Of course, these inorganic fillers can be used in combination. The amount of the inorganic filler to be used is 0 to 300 parts by weight, preferably 0 to 200 parts by weight, per 100 parts by weight of the resin or the like. If the compounding amount of the inorganic filler is more than 300 parts by weight, the viscosity of the resin or the like becomes high, impairing the impregnating property, easily leaving bubbles in the resin, the fluidity of the prepreg during molding becomes poor,
Problems such as difficulty in bringing the mold into close contact with the mold occur, and the quality also deteriorates.

Other organic fillers or polymers that can be incorporated into the composition of the present invention include, for example, known polystyrene and polyvinyl acetate, which are effective as a low-shrink material.
Polymethyl methacrylate, polyethylene, polyvinylidene chloride microballoons, polyacrylonitrile microballoons and the like can be used. When used as a low shrinkage material, the amount used is 0 to 100 parts by weight of resin and the like.
It is 40 parts by weight, preferably 0 to 30 parts by weight. If the amount of the low-shrinkage material exceeds 40 parts by weight, the viscosity becomes too high and the moldability decreases, and the surface smoothness and heat resistance of the cured product decrease.

Further, pigments can be used in the present invention. There is no particular limitation on the type, and organic pigments or inorganic pigments can be used. At that time, the amount is at most 20 parts by weight, preferably up to 10 parts by weight, based on 100 parts by weight of the resin or the like.

The photopolymerization initiator having a photosensitive wavelength in the visible light or near-infrared light region having a wavelength of 500 nm or more used in the present invention is represented by the general formula (1):

[0035] D ⁺ · A ^- (wherein, D ⁺ is methine having a wavelength sensitive to a visible light or near infrared light region above 500 nm, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, pyrylium a dye cation, a ^-. is a cationic dye represented by showing a variety of anions), the general formula (2)

[0036]

Embedded image (Wherein, Z ⁺ represents any 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. )

A photopolymerization initiator combining a boron compound represented by the formula (1) is preferred. Examples of the cation Z ⁺ of the organoboron compound in the general formula (2) include a quaternary ammonium cation, a quaternary pyridinium cation, and a quaternary quinolinium cation having no photosensitivity in the visible light or near infrared light region. Organic cations such as diazonium cations, tetrazolium cations, sulfonium cations, oxosulfonium cations, metal cations such as sodium, potassium, lithium, magnesium and calcium, and cation charges on oxygen atoms such as flavinium and pyranium (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 organoboron compound with a cationic dye having a photosensitive wavelength in the visible or near infrared region, the dye irradiated with light having a wavelength in the photosensitive region is excited to exchange electrons with the organoboron compound. By performing the above, the dye is decolorized and radicals are generated, thereby causing a polymerization reaction of the coexisting polymerizable unsaturated compound. Unlike the conventionally known dye-sensitized photopolymerization reaction, in the photopolymerization reaction of the present invention, the irreversible decolorization reaction of the dye occurs because the light absorption of the dye itself does not hinder the transmittance of the irradiation light, There is an advantage that the prepreg or the main cured product is not colored with a dye.

Accordingly, as will be described later, the counter ion of the cationic dye having sensitivity in the usable light or near infrared light region used in the present invention may be a boron anion.
The cation portion, which is a counter ion of the organic boron compound, needs to be a colorless cation that does not absorb visible light.

Examples of combinations of the above cationic dyes and organic boron compounds are described in JP-A-3-111402,
JP-A-3-119003, JP-A-4-80204
JP, JP-A-4-146905, JP-A-4-4-2
JP-A-61405, JP-A-4-261406, JP-A-5-194619, JP-A-5-59110 and the like have detailed descriptions. Tables 1 and 2 show specific examples of the cationic dye [D ⁺ ]. Among these cationic dyes, a cyanine-based cationic dye and a triarylmethane-based dye are preferably used. In general, cyanine-based cationic dyes easily transfer electrons with an organic boron-based compound, so that the reaction of the present invention is easily caused.Triarylmethane-based cationic dyes have very little coloring of prepreg after aging. It is preferred in terms of.

[0041]

[Table 1]

[0042]

[Table 1]

[0043]

[Table 2]

[0044]

[Table 2]

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)

[0046]

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,
Represents an alkenyl group, alkynyl group, silyl group, heterocyclic group, halogen atom, substituted alkyl group, substituted aryl group, substituted acyl group, substituted aralkyl group, substituted alkenyl group, substituted alkynyl group, substituted silyl group or substituted heterocyclic group . )

The four-coordinate boron anion represented by the following formula is particularly preferred.

The composition ratio of the organic boron compound of the present invention to the near-infrared light or visible light absorbing cationic dye compound is 1/5 to 1 / 0.01, preferably 1/1 to 1/1 by weight.
0.1. In general, it is preferable to use an organic boron compound rather than a cationic dye from the viewpoint of the decoloring reaction of the dye and the efficiency of radical generation.

Examples of the visible light polymerization initiator having photosensitivity in the visible light region include a combination of a hexaarylbiimidazole compound and a hydrogen-donating compound or, for example, Yamaoka et al., “Surface” 27 (7) 548 (1989), Sato's third
Of the 10th Polymer Material Forum 1BP18 (199
Visible light polymerization initiator used alone such as camphorquinone, benzyl, trimethylbenzoyldiphenylphosphine oxide, methylthioxanthone, biscyclopentadienyltitanium-di (pentafluorophenyl) described in 4), and organic peroxides And pigment system, diphenyliodonium salt / dye system, biimidazole / keto compound, thiopyrylium salt / mercaptobenzothiazole,
In addition to metal arenes / cyanine dyes,
No. 377, hexaarylbiimidazole /
Known composite initiator systems such as radical generators can be used.

As the ultraviolet light polymerization initiator having photosensitivity in the ultraviolet region, known polymerization initiators such as acetophenone, benzyl ketal, and (bis) acyl phosphine oxides can be used. The feature of the present invention is that it is difficult to use conventional light curing by using light of a long wavelength.Because it is in the light curing of a material having a low transmittance of short-wavelength ultraviolet light, a relatively long wavelength, preferably 300
It is preferable to use an ultraviolet light polymerization initiator such as a (bis) acyl phosphine oxide type having photosensitivity in a wavelength region of nm or more.

The amount of these photopolymerization initiators, ie, near-infrared light polymerization initiator, visible light polymerization initiator, and ultraviolet light polymerization initiator, is 0.01 to 20 parts by weight per 100 parts by weight of the resin and the like. Preferably it is 0.05 to 15 parts by weight. When the amount of the photopolymerization initiator is less than 0.01 part by weight, the polymerization tends to be insufficient, and when the amount exceeds 20 parts by weight, the strength and durability of the cured product are insufficient.

The visible light polymerization initiator having photosensitivity in the near-infrared light or a wavelength region of 500 nm or more used in the production of the prepreg of the present invention and the visible light and / or ultraviolet light polymerization initiator used for photocuring of the prepreg. Is in a weight ratio of 0.1 / 5 to 5 / 0.1, preferably 0.5 / 5 to 5/5.
/0.5. When this ratio is less than 0.1 / 5, the precuring does not proceed to the B-stage state when the photocurable composition of the present invention is irradiated with light having a wavelength of 500 nm or more, and the B-stage state is not irradiated with light having a wavelength less than 500 nm. Go too far. On the other hand, if the ratio of the initiator exceeds 5 / 0.1, the opposite is true, and neither is preferable.

In the present invention, near-infrared light is 780 to 1
Light in the wavelength region of 200 nm, visible light is 380 to 78
The light in the wavelength region of 0 nm and the ultraviolet light refer to the light in the wavelength region of less than 380 nm.

The light source used in the production of the B-staged prepreg such as the resin of the present invention may be any light source having a spectral distribution in the photosensitive wavelength region of the photopolymerization initiator to be used. , A sodium lamp, a xenon lamp, a halogen lamp, a fluorescent lamp, an incandescent lamp, a sunlight lamp, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, and the like. Further, it is also possible to use a wavelength cut filter as a lamp or a light source that emits light of a wavelength in a long wavelength region to select and irradiate light having a wavelength necessary for the B-stage.

When the photocurable prepreg composition of the present invention is cured using natural light, sunlight, or the like, at the time of prepreg production, use a wavelength cut filter and use near-infrared light or visible light of 500 nm or more. B-staging is advantageous. The irradiation time of the lamp for forming the B stage of the resin or the like cannot be specified unconditionally because the effective wavelength region of the light source, the output, the irradiation distance, the thickness of the molding material, and the like are different. Is 0.0
Conditions that irradiate for 5 hours or more may be selected.

The method for producing a photocurable prepreg composition in the present invention can be easily applied to a conventional method for producing a prepreg composition based on an unsaturated polyester resin or a vinyl ester resin, and the shape can be adjusted according to the application. It can be used in any shape such as a shape, a roll, a tube, a tube, etc., and is particularly suitably used for repairing the inner surface of various sheet-like molded articles or tubular molded articles such as sewer pipes.

The photocurable prepreg composition thus produced can be rapidly cured by irradiating light having a photosensitive wavelength of the remaining photopolymerization initiator.

[0058]

The present invention will now be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. Further, “part” in each example indicates a weight basis.

Example 1 100 parts of a vinyl ester resin (Lipoxy R-802: manufactured by Showa Polymer Co., Ltd.)
1,5,5-tetrakis (p-diethylaminophenyl) -2,4-pentadienyl triphenyl-n-butyl borate (manufactured by Showa Denko KK, hereinafter abbreviated as IRB.): NIR light absorbing cyanine-based cation Ion dye) 0.0
3 parts, tetra-n-butylammonium triphenyl-n-butylborate (manufactured by Showa Denko KK, hereinafter P3B
Abbreviated. Boron compound) 0.15 parts, 2,2'-bis-
0.3 parts of (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-bisimidazole (manufactured by Wako Pure Chemical Industries, Ltd .; hereinafter abbreviated as BIm), 2-mercapto Benzothiazole (Wako Pure Chemical Industries, Ltd .; MB
Abbreviated as T. ) 1.0 part [BIm / MBT combination =
A photopolymerization initiator having photosensitivity in the visible light region] is mixed with a # 450 chopped strand mat (manufactured by Asahi Fiberglass Co., Ltd.) 10 cm × 10 cm, 1 ply
To make the glass content 30 wt%.

Next, this composite material composition was coated with a mylar film, and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm.
(RDS Co., Ltd.) and SC60 (Fuji Film Co., Ltd.), which is a cut filter of 600 nm or less, were used in combination, and irradiation was performed at a distance of 50 cm. However, the B stage state did not change. Then, the thing of the B stage state after light irradiation for 10 minutes was made into a photocurable prepreg, and 3
The storage stability in a dark place at 0 ° C. was examined. 30 ° C,
The photocurable prepreg after storage for 2 months in a dark place was laminated by 3 ply, and the curability in the sunlight and shade outdoors was examined. The curability was 10 minutes in sunlight and 1 hour in shade.

The measurement of Barcol hardness according to JIS K-6911 of the cured product left standing for 1 hour under sunlight and the cured product left for 6 hours in the shade was performed using a Barcol hardness meter 934-1, and the bending strength was also measured. Are shown in Table 3.

[0062]

[Table 3]

[0063]

[Table 3]

[0064]

[Table 3]

[0065]

[Table 3]

(Example 2) 100 parts of a vinyl ester resin (Lipoxy H-630: manufactured by Showa Polymer Co., Ltd.)
A mixture of 0.03 part, 0.15 part of P3B, and 1.0 part of Irgacure 1700 (manufactured by Ciba Geigy Co., Ltd.), which is an ultraviolet-visible light initiator, was mixed with # 45 as in Example 1.
0 chopped strand mat 10cm x 10cm
One ply was impregnated so that the glass content was 30 wt%.

Next, this composite material composition was coated with a Mylar film, and AL-Spotlight (ALF-10) 1 KW, a light source having a wavelength range of 390 to 1200 nm, was coated.
Irradiated at a distance of 50 cm together with SC60, which is a cut filter of 600 nm or less, turned into the B-stage state in 5 minutes, and the B-stage state did not change even if light irradiation was continued for 10 minutes thereafter. Therefore, B after 10 spectral irradiation
The photocurable prepreg in the stage state is 30
The storage stability in the dark at ℃ was examined. When 3 ply of photocurable prepregs after storage for 2 months at 30 ° C. in a dark place were laminated, and the curability under sunlight and shade outdoors was examined, it was 7 minutes under sunlight and 40 minutes under shade. Cured.

The Barcoal hardness of the cured product left for 1 hour in the sunlight and the cured product left for 6 hours in the shade was measured according to JIS K-6911 using a Barcol hardness meter 934-1, and the bending strength was also measured. Are shown in Table 3.

Example 3 100 parts of a vinyl ester resin (Lipoxy R-802: manufactured by Showa Polymer Co., Ltd.)
Visible light absorbing dye shown in 4 (counter ion is chloride anion)
0.02 parts, 0.15 parts of P3B, Irgacure 1800 which is an ultraviolet-visible light initiator (manufactured by Ciba Geigy Co., Ltd.)
A mixture of 1.0 part was mixed with # 450 as in Example 1.
Chopped strand mat (manufactured by Asahi Fiberglass Co., Ltd.) 10 cm × 10 cm, impregnated in 1 ply,
The glass content was adjusted to 30 wt%.

Next, this composite material composition was coated with a Mylar film, and AL-Spotlight (ALF-10) 1 KW as a light source including a wavelength range of 390 to 1200 nm.
(RDS Co., Ltd.) and SC50 (Fuji Film Co., Ltd.), which is a cut filter of 500 nm or less, were used at a distance of 50 cm. However, the B stage state did not change. Then, the thing of the B stage state after light irradiation for 10 minutes was made into a photocurable prepreg, and 3
The storage stability in a dark place at 0 ° C. was examined. 30 ° C,
When the photocurable prepreg after storage for 2 months in the dark was laminated 3 ply, and the curability under sunlight and shade outdoors was examined, it was cured in 7 minutes under sunlight and 40 minutes in shade.

Further, Barco hardness of the cured product left for 1 hour in the sunlight and the cured product left for 6 hours in the shade was measured with a Barcol hardness meter 934-1 according to JIS K-6911, and the bending strength was also measured. Are shown in Table 3.

Example 4 Table 2 was added to 100 parts of a vinyl ester resin (Lipoxy H-630: manufactured by Showa Polymer Co., Ltd.).
6, 0.02 parts of a triarylmethane-based visible light absorbing dye (counter ion is tetraphenylborate anion), tetra-n-butylammonium tri (pt-butylphenyl) -n-butylborate (Showa Denko KK (Hereinafter referred to as BP3B). A mixture of 0.20 part of a boron compound and 1.0 part of Irgacure 1800 (manufactured by Ciba Geigy Co., Ltd.) was mixed with # 450 chopped strand mat 10 cm × 10 cm 1 ply as in Example 1. To make the glass content 30 wt%.

Next, this composite material composition was coated with a Mylar film, and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm was used.
Irradiated at a distance of 50 cm together with SC50, which is a cut filter of 500 nm or less, turned into the B-stage state in 5 minutes, and the B-stage state did not change even if light irradiation was continued for 10 minutes thereafter. Then, the thing of the B stage state after 5 spectral irradiation was made into a photocurable prepreg,
The storage stability in the dark was examined. 30 ° C, dark place 2
3 months of photocurable prepreg after storage for 3 months,
When the curability under sunlight and shade outdoors was examined, it was cured in 7 minutes under sunlight and 40 minutes in shade.

The measurement of Barcol hardness according to JIS K-6911 of the cured product left standing for 1 hour in sunlight and the cured product left for 6 hours in the shade was performed using a Barcol hardness meter 934-1, and the bending strength was also measured. Are shown in Table 3.

Example 5 100 parts of a vinyl ester resin (Lipoxy R-802: manufactured by Showa Polymer Co., Ltd.)
0.02 parts of a triarylmethane-based visible light-absorbing dye No. 7 (counter ion is tetraphenylborate anion), BP3
A mixture of 0.20 part of B, 0.3 part of BIm and 1.0 part of MBT was impregnated into the same # 450 chopped strand mat, 10 cm × 10 cm, 1 ply as in Example 1, so that the glass content became 30 wt%. .

Next, this composite material composition was coated with a Mylar film, and AL-Spotlight (ALF-10) 1 KW which was a light source including a wavelength range of 390 to 1200 nm.
Irradiated at a distance of 50 cm together with SC50, which is a cut filter of 500 nm or less, turned into the B-stage state in 5 minutes, and the B-stage state did not change even if light irradiation was continued for 10 minutes thereafter. Then, the thing of the B stage state after 5 spectral irradiation was made into a photocurable prepreg,
The storage stability in the dark was examined. 30 ° C, dark place 2
3 months of photocurable prepreg after storage for 3 months,
When the curability under sunlight and shade outdoors was examined, it was cured in 10 minutes under sunlight and 40 minutes in shade.

The Barco hardness of the cured product left for 1 hour in the sunlight and the cured product left for 6 hours in the shade was measured using a Barcol hardness meter 934-1 type according to JIS K-6911, and the bending strength was also measured. Are shown in Table 3.

(Comparative Example 1) Vinyl ester resin R-80
2 100 parts of diphenylmethane diisocyanate (M
DI) ISONATE 143L (Mitsubishi Dow)
4 parts, 1.0 part of Irgacure 1700, # 450 chopped strand mat 10 cm x 1
0 cm 1 ply impregnated, glass content 30
wt%.

Next, the composite material composition was covered with a mylar film and left at 40 ° C. in a dark place to be in the B-stage state in 24 hours. Then, the B-stage state was used as a photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. As a result, the resin flowed out of the photocurable prepreg in one week. Therefore, a curing experiment could not be performed.

(Example 6) 100 parts of an unsaturated polyester resin (Rigolac 1557, manufactured by Showa Polymer Co., Ltd.)
RB 0.1 parts, P3B 0.5 parts, BIm 0.1
Part, MBT 0.1 part, and # 450 chopped strand mat 10 cm × 10 cm 1 pl
y was impregnated so that the glass content was 30 wt%.

Next, this composite material composition was coated with a mylar film to form a gallium lamp UNIREC URM-30.
0, 3 KW (USHIO Inc.) 650 nm long wavelength cut series which is a cut filter of 650 nm or more
(Asahi Spectroscopy Co., Ltd.) was used in combination, and irradiation was performed at a distance of 100 cm. So 3
The thing of the B stage state after spectral irradiation was made into a photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. In addition, 3 ply of the photocurable prepreg after storage at 30 ° C. in a dark place for 2 months was laminated by AL-spotlight (ALF-1).
0) When the curability under 1 KW irradiation (irradiation distance 50 cm) was examined, it was cured in 10 minutes.

Further, Barco hardness of the cured product irradiated with AL-spotlight for 20 minutes was measured according to JIS K-6911 using a Barcol hardness meter 934-1, and bending strength was also measured. The results are shown in Table 3. .

Example 7 100 parts of an unsaturated polyester resin (Rigolac 2141: manufactured by Showa Polymer Co., Ltd.)
0.03 parts of RB, 0.15 parts of P3B, BIm 0.
A mixture of 3 parts and 0.6 parts of MBT is mixed with # 450 chopped strand mat 10 cm × 10 cm 1 p
ly was impregnated so that the glass content was 30 wt%.

Next, this composite material composition was coated with a mylar film, and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm.
Was irradiated with a distance of 50 cm using a cut filter of 600 nm or less at a distance of 50 cm. Then, the thing of the B stage state after 5 spectrum irradiation was made into the photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. Further, 3 ply of photocurable prepregs stored at 30 ° C. for 2 months in a dark place were laminated, and a gallium lamp Unirec URM-300, 3 KW (irradiation distance 10
0 cm), it was cured in 3 minutes.

Further, a gallium lamp UNIREC URM-3
The cured product irradiated with 00, 3 KW (irradiation distance 100 cm) for 6 minutes was measured for Barcol hardness according to JIS K-6911 using a Barcol hardness meter 934-1, and the bending strength was also measured. The results are shown in Table 3. Indicated.

Example 8 100 parts of an unsaturated polyester resin (Rigolac 1557, manufactured by Showa Polymer Co., Ltd.) was mixed with a visible light absorbing dye shown in Table 2-3 (the counter ion was a chloride anion).
0.02 parts, P3B 0.15 parts, Irgacure 1800
A mixture of 1.0 part was impregnated into # 450 chopped strand mat 10 cm × 10 cm 1 ply so that the glass content was 30 wt%.

Next, this composite material composition was coated with a mylar film, and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm was used.
Was irradiated at a distance of 50 cm using a cut filter of 500 nm or less at a distance of 50 cm. Then, the thing of the B stage state after 5 spectrum irradiation was made into the photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. Further, 3 ply of the photocurable prepreg after storage for 2 months at 30 ° C. in a dark place was laminated with AL-spotlight (ALF-10) 1 KW (irradiation distance 50 c
When the curability in m) was examined, it was cured in 10 minutes.

The AL-spotlight (ALF-1)
0) Barco hardness of a cured product irradiated with 1 KW (irradiation distance: 50 cm) for 20 minutes was measured according to JIS K-6911 using a Barcol hardness meter 934-1, and bending strength was also measured. The results are shown in Table 3. Indicated.

(Example 9) 100 parts of an unsaturated polyester resin (Rigolac 2141, manufactured by Showa Polymer Co., Ltd.) was mixed with 100 parts of a triarylmethane-based visible light absorbing dye (the counter ion was a chloride anion) of 0.03 in Table 2-5. Part, BP3B 0.3 part,
Irgacure 1800 1.0 part mixed with #
450 chopped strand mat 10cm × 10c
m 1ply impregnated, glass content 30wt
%.

Next, this composite material composition was coated with a mylar film and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm.
Was irradiated with a distance of 50 cm using a cut filter of 500 nm or less at a distance of 50 cm. Then, the thing of the B-stage state after three-spectrum irradiation was made into a photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. Further, 3 ply of the photocurable prepreg after storage for 2 months at 30 ° C. in a dark place was laminated with AL-spotlight (ALF-10) 1 KW (irradiation distance 50 c
When the curability in m) was examined, it was cured in 10 minutes.

Further, AL-spotlight (ALF-1)
0) Barco hardness of a cured product irradiated with 1 KW (irradiation distance: 50 cm) for 20 minutes was measured according to JIS K-6911 using a Barcol hardness meter 934-1, and bending strength was also measured. The results are shown in Table 3. Indicated.

Example 10 100 parts of an unsaturated polyester resin (Rigolac 1557, manufactured by Showa Polymer Co., Ltd.) were mixed with 100 parts of a triarylmethane-based visible light absorbing dye (the counter ion was tetraphenylborate anion) in Table 2-9. .02
Part, BP3B 0.2 part, BIm 0.3 part, MBT
A mixture of 1.0 part was impregnated into # 450 chopped strand mat 10 cm × 10 cm 1 ply so that the glass content was 30 wt%.

Next, this composite material composition was coated with a mylar film and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm.
Was irradiated with a distance of 50 cm using a cut filter of 500 nm or less at a distance of 50 cm. Then, the thing of the B-stage state after three-spectrum irradiation was made into a photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. Further, 3 ply of the photocurable prepreg after storage for 2 months at 30 ° C. in a dark place was laminated with AL-spotlight (ALF-10) 1 KW (irradiation distance 50 c
When the curability in m) was examined, it was cured in 10 minutes.

AL-Spotlight (ALF-1)
0) Barco hardness of a cured product irradiated with 1 KW (irradiation distance: 50 cm) for 20 minutes was measured according to JIS K-6911 using a Barcol hardness meter 934-1, and bending strength was also measured. The results are shown in Table 3. Indicated.

Comparative Example 2 Magnesium oxide Magmic (manufactured by Kyowa Chemical Industry Co., Ltd.) was added to 100 parts of an unsaturated polyester resin (Rigolac 1557, manufactured by Showa Polymer Co., Ltd.).
1 part, Irgacure 1700 1.0 part mixed, # 450 chopped strand mat 10cm × 1
0 cm 1 ply impregnated, glass content 30
wt%.

Next, when this composite material composition was covered with a mylar film and left at 40 ° C. in a dark place, it became a B-stage state in 48 hours. Then, the B-stage state was used as a photocurable prepreg, and the storage stability in a dark place at 30 ° C. was examined. As a result, the resin flowed out of the photocurable prepreg in 10 days. Therefore, a curing experiment could not be performed.

Example 11 100 parts of a vinyl ester resin (Lipoxy R-808: manufactured by Showa Polymer Co., Ltd.) was added to IR
B 0.03 parts, P3B 0.15 parts, BIm 0.3
A mixture of 1.0 part of MBT and 30 parts of aluminum hydroxide (Heidilite HBT-320: manufactured by Showa Denko KK) is used as a # 450 chopped strand mat.
10 cm × 10 cm 1 ply was impregnated so that the glass content was 30 wt%.

Next, this composite material composition was coated with a Mylar film, and AL-Spotlight (ALF-10) 1 KW as a light source having a wavelength range of 390 to 1200 nm was used.
Irradiated at a distance of 50 cm together with SC60, which is a cut filter of 600 nm or less, turned into the B-stage state in 5 minutes, and the B-stage state did not change even if light irradiation was continued for 10 minutes thereafter. Then, the thing of the B stage state after light irradiation for 10 minutes was made into a photocurable prepreg,
As a result of examining storage stability in a dark place at ℃, there was no abnormality for 2 months. Further, 3 ply of photocurable prepregs after storage for 2 months at 30 ° C. in a dark place were laminated, and a metal halide lamp 250W (HQI-TS2 manufactured by Mitsubishi Electric OSRAM Co., Ltd.)
Irradiation was carried out at 50 W / D with a lighting fixture HQI downlight QX038W manufactured by Mitsubishi Electric Lighting Co., Ltd. at an irradiation distance of 30 cm.

Further, the cured product irradiated with light for 6 minutes under the same conditions was measured for Barcol hardness according to JIS K-6911 using a Barcol hardness meter 934-1.
It reached a practical level of 40/39.

[0100]

Industrial Applicability The present invention relates to a stable photocurable prepreg composition which has excellent preservability and does not undergo polymerization of radically polymerizable unsaturated groups contained in a resin or the like even during long-term storage, and a method for producing the same. , Constantly B-stage a part of radically polymerizable unsaturated groups to achieve stable thickening,
When heating is impossible or difficult, such as large molded products, outdoor buildings, etc., there is no need to prepare a heat source by light curing,
The present invention has succeeded in providing a photocurable prepreg composition which can be easily applied, has a high curing speed, and can reliably obtain a molded product having a high hardness.

The B-stage of the resin or the like is carried out by polymerization using only a part of a plurality of photopolymerization initiators containing radical polymerizable unsaturated groups and having different absorption wavelengths. Therefore, the polymerization was carried out stably, and as a result, a prepreg composition having excellent storage stability and without sagging due to separation of the monomer in the prepreg could be provided.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Shuichi Sugita, Inventor 1-1-1, Onodai, Midori-ku, Chiba-shi, Chiba Prefecture Showa Denko KK Research Institute (72) Inventor Hirotoshi Kamada 1-chome, Onodai, Midori-ku, Chiba-shi, Chiba 1-1 Showa Denko KK Research Institute (72) Inventor Takeo Watanabe 1-1-1 Ohnodai Midori-ku, Chiba City, Chiba Prefecture Showa Denko KK Research Institute

Claims (10)

[Claims] 1. A composition comprising an unsaturated polyester resin and / or a vinyl ester resin, at least two photopolymerization initiators each having a different photosensitive wavelength, an inorganic or organic fiber reinforcement and / or a filler. And
In addition, the composition preliminarily polymerizes a part of the radically polymerizable unsaturated groups in the resin, and at least one photopolymerization initiator and a specific polymer such that a part of the radically polymerizable unsaturated groups remain. A photocurable prepreg composition treated with light of a wavelength. 2. The photopolymerization initiator is a combination of a photopolymerization initiator having photosensitivity in a near-infrared light region and a photopolymerization initiator having photosensitivity in a visible light and / or ultraviolet light region. 2. The photocurable prepreg composition according to 1. 3. A photopolymerization initiator having photosensitivity in a visible light region having a wavelength of 500 nm or more,
The photocurable prepreg composition according to claim 1, which is a combination of a photopolymerization initiator having photosensitivity in a visible light region and / or an ultraviolet light region of less than nm. 4. A photopolymerization initiator having a wavelength of 500 nm or more and having sensitivity to visible light or near-infrared light, is a cationic dye represented by the general formula (1): D ⁺ · A ⁻ (wherein D ⁺ is at least one of methine, polymethine, cyanine, xanthene, oxazine, thiazine, arylmethane, or pyrylium-based dye cations having a sensitivity to visible light or near-infrared light having a wavelength of 500 nm or more; ^- represent the different anions) and sensitizer general formula represented by the general formula (2) (2);. ## STR1 ## (Wherein, Z ⁺ represents any 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 photocurable prepreg composition according to claim 2 or 3, which is a combination with (1). 5. The cation moiety (D ⁺ ) of the photopolymerization initiator represented by the general formula (1) having a photosensitive wavelength in a visible light or near-infrared light region having a wavelength of 500 nm or more is a cyanine or triamine. Reel methane-based cationic dye,
The photocurable prepreg composition according to claim 4. 6. A photopolymerization initiator having photosensitivity in a visible light region and / or an ultraviolet light region is a combination of a hexaarylbiimidazole compound and a hydrogen-donating compound or an acylphosphine oxide compound. ~
6. The photocurable prepreg composition according to item 5. 7. A composition comprising an unsaturated polyester resin and / or a vinyl ester resin, at least two photopolymerization initiators each having a different photosensitive wavelength, an inorganic or organic fiber reinforcing material and / or a filler. Is prepolymerized by irradiating light at a wavelength of at least one photosensitive wavelength range of the photopolymerization initiator in the composition and not including a wavelength of the photosensitive wavelength range of at least one other photopolymerization initiator. A method for producing a photocurable prepreg composition, comprising: 8. A composition comprising an unsaturated polyester resin and / or a vinyl ester resin, at least two photopolymerization initiators each having a different photosensitive wavelength, an inorganic or organic fiber reinforcement, and / or a filler. To 500
The method for producing a curable prepreg composition according to claim 7, wherein the prepolymerization is performed by irradiation with visible light or near-infrared light having a wavelength of at least nm. 9. The photocurable prepreg composition according to claim 1 is applied or molded, and the prepreg composition is cured by irradiating light containing the photosensitive wavelength of a photopolymerization initiator contained in the prepreg composition. A method for curing a photocurable prepreg composition, comprising: 10. A molded product cured by applying or molding the photocurable prepreg composition according to claim 1, and irradiating light containing a photosensitive wavelength of a photopolymerization initiator contained in the prepreg composition.