JP2002265635A - Sheet-formed reinforcing material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a sheet-formed reinforcing material having excellent applicability, sufficiently suppressing the defective bonding to various substrates to improve the adhesivity, durability, etc., sufficiently curable by photosetting, capable of coloring a photosetting molding material layer and usable for various uses. SOLUTION: The sheet-formed reinforcing material has a photosetting molding material layer containing a photosetting resin, a filler and a reinforcing fiber as essential components. The filler contains a transparent filler giving a melt-formed article having an average light transmittance of 15-90% at 400-500 nm wavelength.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a sheet-like reinforcing material.

[0002]

2. Description of the Related Art A sheet-like reinforcing material containing a photocurable molding material layer has flexibility before curing, so that it can be processed into an arbitrary size or shape. And has the same basic properties as cured fiber-reinforced plastic, such as mechanical, chemical and electrical properties, after curing.

In a sheet-like reinforcing material containing such a photocurable molding material layer, when colored with a toner or a pigment,
Since the penetration of light into the photocurable molding material layer is blocked and the photocuring cannot be performed sufficiently, the photocurable molding material layer is made transparent and colored by being applied after photocuring. Was. However, if the sheet-like reinforcing material itself can be colored, it has an advantage that post-coating can be omitted, so that it can sufficiently perform photocuring and includes a colored photocurable molding material layer. The material was longing. In addition, processing and construction are easy and sufficient work time can be secured, and various surface conditions and complex shapes on various base materials such as metal, plastic, rubber, glass, porcelain, stone, wood, etc. Correspondingly sufficient adhesiveness, if the occurrence of defects due to poor adhesion to the base material is sufficiently suppressed, various buildings, machinery,
Structural members, piping, etc. in automobiles, ships, household goods, etc.
It can be used for various applications as a lining material, a reinforcing material for reinforcing or repairing them, and the like.

As a technique relating to a sheet-like reinforcing material, for example, JP-A-59-1250 discloses a method in which a curable and lipophilic primer is applied to a curable prepreg, and the coated surface is brought into close contact with a steel plate. Then, a method of attaching a prepreg to a steel plate, in which the prepreg and the primer are cured, is disclosed. JP-A-63-186744 discloses a photocurable prepreg formed by laminating a transparent sheet on one side. Further, JP-A-57-993
No. 75 discloses that a photocurable molding material layer is adhered to a thin steel plate using a photocurable vinyl ester resin containing a specific dibasic acid or oligoester in a resin skeleton, and then cured by light irradiation. Thus, a method of reinforcing a thin steel plate has been disclosed.

[0005] However, in these techniques, there is a possibility that sufficient adhesiveness may not be secured depending on the base material, and since it is necessary to perform the work using a primer or an adhesive, the work in the work is complicated. Furthermore, the photocurable molding material layer itself can be colored sufficiently, and the coloring of the photocurable molding material layer itself can be performed. There was room to do it.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, and has excellent workability, sufficiently suppresses poor adhesion to various substrates, and has an adhesive strength and durability. The object of the present invention is to provide a sheet-like reinforcing material which can improve photo-curing, can sufficiently perform photo-curing, and can color the photo-curable molding material layer itself to meet various uses. It is.

[0007]

Means for Solving the Problems In the case of a thermosetting molding material, a glass filler is used to make the cured product transparent, and coloring is performed using a small amount of toner or pigment. It has been considered that molding materials are unsuitable for coloring because coloring with toner, pigment or the like impairs photocurability. In addition, in the application of photocurable molding materials, ease of handling of materials, shortening of work time,
It is necessary to respond to the surface condition and shape of the substrate, but before applying the photocurable molding material to develop a sufficient adhesive strength, it is necessary to apply coating technology to the substrate before primer treatment etc. A process for performing the treatment is required, and there are problems of easy handling and work time.

The present inventors have scrutinized the above facts and conducted intensive studies. As a result, the photocurable molding material layer in the sheet-like reinforcing material was filled with a filler having a specified light transmittance of a specific wavelength. It has been found that when incorporated, photocuring can be sufficiently performed and the photocurable molding material layer itself can be colored. It has also been found that specific frit and / or glass particles are suitable as such a filler. It is new to use a specific frit or a specific glass particle as a filler so that the sheet-like reinforcing material is colored, and further, it has an adhesive layer and a release layer. If the adhesive layer is also photo-curable, it becomes possible to easily form a cured layer with high adhesive strength and durability on various substrates, and for complicated primer treatment and coloring. The present inventors have come across the fact that a dramatic effect that can be easily used for various applications without post-coating or the like occurs, and the present invention has been achieved.

That is, the present invention relates to a sheet-like reinforcing material comprising a photocurable resin, a filler, and a photocurable molding material layer essentially including reinforcing fibers, wherein the filler is a melt-molded article. It is a sheet-like reinforcing material containing a transparent filler having an average light transmittance of 15 to 90% at a wavelength of 400 to 500 nm. Hereinafter, the present invention will be described in detail.

First, the configuration of the sheet-like reinforcing material of the present invention will be described. The sheet-like reinforcing material of the present invention has a photocurable molding material layer as a structure, and preferably has a pressure-sensitive adhesive layer and a release layer on one side from the inside in this order. Thereby, the performance of the photocurable molding material layer can be sufficiently exhibited on various substrates.
These photocurable molding material layers, pressure-sensitive adhesive layers and release layers are layered materials that are sheet-like or film-like, and as long as the effects of the present invention are achieved, they are sheet-like or film-like other than these. Layered materials may be included between the layers or on the outer surface of the sheet-like reinforcement. These layered materials may be used alone or in combination of two or more.

It is preferable that the sheet-like reinforcing material has a protective layer on one side. In this case, when it has an adhesive layer and a release layer, it will have a protective layer on one other side of the surface having the adhesive layer and the release layer. Such a protective layer prevents curing inhibition due to oxygen in the air on the surface of the photocurable molding material layer. It is possible to more reliably cure the photocurable molding material layer by suppressing volatilization from occurring. Further, it has an effect of smoothing the surface of the photocurable molding material layer and an effect of blocking odor.

It is preferable that the sheet-like reinforcing material further has a light-shielding layer on a surface to which light is applied. Such a light-shielding layer prevents the photo-curing of the sheet-like reinforcing material, allows a sufficient application time, and allows the photo-curable molding material layer to be quickly cured by removing the light-shielding layer after the application. It is not necessary to block all light rays as the light-blocking level, and if the light transmittance in a wavelength band of 500 nm or less is adjusted to be 10% or less, a sufficient effect of preventing the photo-curing of the sheet-like reinforcing material can be obtained. Will be provided.

The preferred form of the sheet-like reinforcing material is (1) a form having an adhesive layer and a release layer in this order on one surface of the photocurable molding material layer, and (2) a photocurable molding material layer. One side has an adhesive layer and a release layer in this order from the inside, and the other side has a protective layer. (3) One side of the photocurable molding material layer has an adhesive layer and a release layer in this order from the inside. In addition, a mode in which a protective layer and a light-shielding layer are provided on the other side from the inside, and the like can be given.

Next, each layer constituting the sheet-like reinforcing material of the present invention will be described. The photocurable molding material layer in the present invention has a plasticity or flexibility that allows the sheet-like reinforcing material to be sufficiently processed and applied before curing, and a sufficient flexural strength and flexural modulus after curing. It has sufficient durability, such as weather resistance, water resistance, abrasion resistance, and high electrical characteristics, depending on the type of resin and filler. It is preferable that the photocurable molding material layer has no surface stickiness that hinders processing and construction work.

The photocurable molding material layer is formed essentially of a photocurable resin, a filler, and a reinforcing fiber.
Such a photocurable molding material layer is preferably a prepreg sheet obtained by increasing the viscosity of a photocurable resin. Also,
A sheet formed by laminating different molding materials may be used.

Among the constituent elements forming the photocurable molding material layer, the filler exerts the function and effect of the present invention. The filler in the present invention has a mean light transmittance at a wavelength of 400 to 500 nm of 15 to 50 when a melt molded product is used.
Contains 90% transparent filler. By using such a filler, a coloring effect can be obtained without reducing the photocurability of the sheet-like reinforcing material. Wavelength 400-5
When the average light transmittance at 00 nm is 15 to 90%,
It means that the average light transmittance satisfies 15 to 90% in the wavelength region of 400 to 500 nm. If the average light transmittance is less than 15%, the photocurability will be significantly reduced, and if it exceeds 90%, the coloring effect will not be sufficiently obtained. More preferably, the wavelength 40
The average light transmittance from 0 to 500 nm is 25 to 70%. The filler may have a function of reinforcing the photocurable molding material layer together with a filler used for reinforcement described later.

In the photocurable molding material layer of the present invention,
The transparent filler is a frit and / or glass particle having an average particle size of 1 to 1000 μm,
It is preferable to use 1 to 150 parts by weight with respect to parts by weight. The frit and / or the glass particles have a function of coloring the photocurable molding material layer and a function of introducing light, and thus are suitable as a filler that can be colored without impairing photocurability. . If the average particle size of the frit and / or the glass particles is less than 1 μm, light propagation is poor and the effect of maintaining photocurability at a desired level is poor, which is not preferable. On the other hand, if it exceeds 1000 μm, it becomes difficult to uniformly disperse the particles, which is not preferable. More preferably, the average particle size is 10 to 1000 μm, and more preferably 20 to
９００900 μm, more preferably 50-800 μm. In addition, the frit and / or the glass particles are formed of the photocurable resin 10.
If the amount is less than 1 part by weight with respect to 0 part by weight, the coloring effect may not be sufficiently obtained. On the other hand, if the amount exceeds 150 parts by weight, the workability in producing the photocurable molding material layer is reduced. There is a possibility that the effect of maintaining the photocurability at a desired level may be poor. The average particle size and the amount of these frit and / or glass particles are preferably selected within the above range according to the use in which the sheet-like reinforcing material is used. The average particle size is a direction in which the particle size increases from the minimum particle size when the horizontal axis represents the particle size and the vertical axis represents the weight ratio (% by weight) of the particles having each particle size to represent the particle size distribution of the filler. The weight ratio (% by weight) of each particle size is accumulated, and the total is 50% by weight. The particle size distribution means the distribution of the particle size of each particle constituting the filler, and the horizontal axis represents the particle size, and the vertical axis represents the weight ratio (% by weight) of the particles having each particle size. You can do it. The particle size distribution is in accordance with JIS Z8815.
Can be measured in accordance with the sieving method.

The above-mentioned frit is a glassy particle in a crushed state obtained by half-melting or completely melting a raw material and quenching the raw material. For example, a commercially available product can be used. Specific examples include Frit JH-1922 and EH-1040 (both are trade names, manufactured by Nippon Frit Co., Ltd.). Also,
Examples of the glass particles whose light transmittance is specified as described above include finely crushed blue glass bottles and the like, and colored glass fillers. Since the above frit and glass particles pass a specific range of wavelengths, when viewed as a transparent filler, specifically, as a light-transmitting filler, they are colored to a light gray or transparent blue. May be observed. For example, even a glass powder having a specific particle size can be used as the transparent filler of the present invention as long as the glass powder is colored and can satisfy the requirements as the transparent filler of the present invention. These may be used alone,
Two or more kinds may be used in combination.

In the above-mentioned filler, as a method for measuring the light transmittance, a spectral colorimeter SQ-300H (trade name, manufactured by Nippon Denshoku Industries Co., Ltd.) is used in accordance with JIS Z8722 to measure every 20 nm from 400 nm as a starting point. 6 to 500nm
Measure the light transmittance of the point. Lambbe for each value
the following equation according to rt-Beer's law:

[0020]

(Equation 1)

The average value of the light transmittance at each of the six wavelengths obtained by converting the thickness of the medium, ie, the sample, to 0.7 mm was defined as the average light transmittance of the present invention. As a sample, the frit or the glass particles are heated to 1000 ° C. or more to be melted.
It is possible to use a plate cooled with a mold so as to form a plate of 5 to 0.8 mm, or a plate of 0.5 to 0.8 mm thick before becoming a frit or glass particles. . An example of measuring the light transmittance of the filler in this way is shown in the graph of FIG. In the graph of FIG. 1, the fillers 1 and 3 are fillers whose average light transmittance satisfies the above-mentioned range in a wavelength region of 400 to 500 nm and can exert the effects of the present invention. Filling material 2
Is a filler whose average light transmittance does not satisfy the above range in the wavelength region of 400 to 500 nm and cannot exert the effects of the present invention. Filler 1 is a frit JH-1922 (trade name, average particle size 100 μm) used in Examples.
Frit), filler 3 is fritted EH-1040
(Trade name, frit having an average particle size of 100 μm). The average light transmittance was determined by averaging and rounding off the first decimal place.

[0022]

[Table 1]

The sheet-like reinforcing material of the present invention is a sheet-like reinforcing material having a structure of a photo-curable resin material, a filler, and a photo-curable molding material layer essentially including reinforcing fibers. The photocurable resin constituting the photocurable molding material layer is preferably a photocurable resin essentially containing a polymer and a polymerizable unsaturated monomer. More preferably, the polymer has a radical polymerizable double bond. The amount of the photocurable resin is 20 to 9 with the photocurable molding material layer being 100% by weight.
5% by weight. More preferably, 20 to 80% by weight,
More preferably, it is 20 to 70% by weight. Based on the photocurable resin to be compounded, the contents of various compounding materials can be appropriately set.

The photocurable resin is not particularly limited as long as it is a photocurable resin that can be used as a molding material. Examples of the radical polymerizable resin include unsaturated polyester resins and vinyl ester resins (epoxy acrylate). Resin), polyester (meth) acrylate resin, (meth) acryl syrup, diallyl phthalate resin, and the like. These may be used alone or in combination of two or more. Among these, unsaturated polyester resins are preferred because the workability and workability of the sheet-like reinforcing material are improved, and the cured product has sufficient basic performance.

The unsaturated polyester resin is not particularly limited. For example, unsaturated polyester having a weight average molecular weight (Mw) of several hundreds to tens of thousands obtained by condensing an acid component and an alcohol component is polymerizable. A radical polymerizable resin dissolved in an unsaturated monomer may be used. The acid component used in the unsaturated polyester is not particularly limited, and examples thereof include unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, mesaconic acid, citraconic acid, and citraconic anhydride; Phthalic acid, phthalic anhydride, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, heptic acid, methyltetrahydrophthalic anhydride And tribasic or higher polybasic acids such as trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride and the like. These may be used alone or in combination of two or more.

The alcohol component is not particularly restricted but includes, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol,
Triethylene glycol, neopentyl glycol,
1,3-butanediol, 1,4-butanediol,
Glycols such as 1,6-hexanediol, bisphenol A, hydrogenated bisphenol A, propylene oxide adduct of bisphenol A, and ethylene oxide adduct of bisphenol A; trifunctional or higher alcohols such as glycerin, trimethylolpropane, and pentaerythritol; Epoxides such as ethylene oxide, propylene oxide, and epichlorohydrin are exemplified. These may be used alone or in combination of two or more.

The types and amounts of the acid component and the alcohol component in the unsaturated polyester are not particularly limited, and may be appropriately set according to, for example, the basic performance required for the cured product. 5 to 100% by weight of the acid component
Is preferably an unsaturated dibasic acid. The method for condensing the acid component and the alcohol component is not particularly limited, and for example, reaction conditions such as a reaction temperature and a reaction time may be appropriately set. Further, it may be modified with various components such as a diene compound such as dicyclopentadiene and a rubber component such as a terminal functional butadiene-acrylonitrile copolymer.

The vinyl ester resin is not particularly limited. For example, a vinyl ester obtained by adding a vinyl unsaturated carboxylic acid to an epoxy group of an epoxy resin is dissolved in a polymerizable unsaturated monomer. Radical polymerization type resins and the like can be mentioned. The epoxy resin is not particularly limited, and examples thereof include a bisphenol type, a novolak type, a cycloaliphatic type, and an epoxidized polybutadiene type. The vinyl unsaturated carboxylic acid is not particularly limited, for example, acrylic acid,
Methacrylic acid and the like can be mentioned. These may be used alone or in combination of two or more.

The type and amount of the epoxy resin and the vinyl-based unsaturated carboxylic acid in the vinyl ester are not particularly limited, and may be appropriately set according to the basic performance required for the cured product. The method for addition polymerization of the epoxy resin and the vinyl-based unsaturated carboxylic acid is not particularly limited, and for example, reaction conditions such as a reaction temperature and a reaction time may be appropriately set in the same manner as described above.

The polyester (meth) acrylate is obtained, for example, by the dehydration condensation of a polyester polyol and (meth) acrylic acid, and has a polyester structure in the main chain skeleton and at least one of the molecular terminals.
Finally, it is a compound having a structure in which (meth) acrylic acid is introduced via an ester bond.

The (meth) acrylic syrup is not particularly limited, and is, for example, a mixture containing a polymer of a (meth) acrylic acid ester which is a polymerizable unsaturated monomer and a polymer of a (meth) acrylic acid ester. Yes, as needed
A radical polymerizable resin further containing a polymerizable unsaturated monomer other than the (meth) acrylate ester is exemplified.

The above (meth) acrylic acid ester is not particularly restricted but includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate , Lauryl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl (meth) acrylate and the like. Also,
(Meth) acrylamide can also be used. These may be used alone or in combination of two or more. Among these, methyl methacrylate or (meth) acrylic acid ester containing methyl methacrylate as a main component can be further improved in basic performance, appearance, safety and the like by the cured product layer of the sheet-like reinforcing material. preferable.

The polymer of the (meth) acrylic ester is obtained by polymerizing a polymer containing a (meth) acrylic ester or, if necessary, another polymerizable unsaturated monomer as a monomer component. The degree of polymerization is not particularly limited. The type and amount of the (meth) acrylic acid ester, the polymer of the (meth) acrylic acid ester and the like in the (meth) acrylic syrup are not particularly limited, and are appropriately set according to the basic performance and the like required for the cured product. do it.

When the photocurable resin contains two or more resins and forms a mixture, the content of each resin is not particularly limited. Further, a radical polymerizable resin other than the above-described radical polymerizable resin may be contained.

The polymerizable unsaturated monomer means a monomer having a polymerizable unsaturated bond such as a vinyl monomer and a crosslinking agent contained in the photocurable resin. The polymerizable unsaturated monomer is a reactive monomer, and is not particularly limited as long as it undergoes a crosslinking reaction with an unsaturated group of the polymer at the time of curing.For example, styrene, α-methylstyrene, vinyl Toluene, chlorostyrene, vinyl acetate, allyl alcohol, ethylene glycol monoallyl ether, propylene glycol monoallyl ether, acrylonitrile, maleimides; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and the like; Monoesters of carboxylic acids; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid and citraconic acid, and monoesters of these unsaturated dicarboxylic acids;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyfunctional (meth) acrylates such as pentaerythritol tetra (meth) acrylate; divinylbenzene, diallyl phthalate, diallyl isophthalate, triallyl cyanurate, triallyl isocyanurate and the like. These may be used alone or in combination of two or more. Among these, it is preferable to use those containing styrene.

The content ratio of the total amount of polymerizable unsaturated monomers such as a vinyl monomer and a crosslinking agent in the photocurable resin is not particularly limited, and may be, for example, 1 to 80% by weight based on the total weight of the photocurable resin. %. If it is less than 1% by weight, the photocurability may be inferior and 80% by weight.
If it exceeds 3, the viscosity of the resin mixture solution of the photocurable resin and the filler becomes too low, making it difficult to handle, and the cured product may have poor basic performance such as strength. More preferably, it is 5 to 70% by weight, and further preferably, 10 to 70% by weight.
60% by weight. Further, a resin mixed solution in which the above-mentioned photocurable resin is mixed with a filler and other additives included as desired (a curing agent, a low-shrinkage agent, a coupling agent, a release agent, etc.) is used in the present invention. May be described as a compound.

The photocurable resin preferably contains a curing agent. As the curing agent, a photosensitizer or the like for imparting photocurability to the resin is suitable. The photosensitizer is not particularly limited, and examples thereof include “surface”, 27 [7] (1
989) Yamaoka, p. 548 and “The 3rd Polymer Material Forum Abstracts” (1994) Sato, IBP18 and the like, and visible light initiators having photosensitivity in the visible light region. Preferably, it is used. The photosensitizers may be used alone or in combination of two or more. The photosensitizer is sometimes called a photocuring agent, and in this specification, the terms “photosensitizer” and “photocuring agent” are used as a photosensitizing agent. The visible light initiator is not particularly limited as long as it is a photopolymerization initiator having photosensitivity in a wavelength range of 380 to 780 nm.
For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, α-methylbenzoin, α-phenylbenzoin, benzyl, diacetyl, anthraquinone, methylanthraquinone, chloroanthraquinone, camphorquinone, acetophenone, acetophenone benzyl, Carbonyl compounds such as dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, benzyldimethylketone, benzophenone, trimethylbenzoyldiphenylphosphine oxide; compounds having a sulfur atom such as diphenylsulfide, diphenyldisulfide, diphenylsulfide, dithiocarbamate and methylthioxanthone; α-chloro Halides of polycondensed ring hydrocarbons such as tilnaphthalene; dyes such as acrylflavin and fluorescein; metal salts such as uranyl nitrate, iron chloride and silver chloride; p-methoxybenzenediazonium, hexafluorophosphate and diphenyleye Odonium,
Onium salts such as triphenylsulfonium; dicyclopentadienyltitanium-di (pentafluorophenyl); Also, organic peroxides / dye systems, diphenyliodonium salts / dyes, imidazole / keto compounds, hexaarylbiimidazole compounds / hydrogen-donating compounds, mercaptobenzothiazole / thiopyrylium salts, metal arenes / cyanine dyes, JP-B-45-37
No. 377, hexaarylbiimidazole /
Known composite initiator systems such as radical generators are also included.

As the photosensitizer, a wide-area photosensitive agent having photosensitivity from the ultraviolet light region to the visible light region can be used. Examples of such a photosensitizer include bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and bis (2,4,
Acyl phosphine oxide compounds such as 6-trimethylbenzoyl) -methylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, and 2,6-dimethoxybenzoyl-diphenylphosphine oxide. These can use a commercial item, for example, Darocur11
73 (trade name, manufactured by Ciba Specialty Chemicals, 2-hydroxy-2-methyl-1-phenylpropan-1-one) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentyl Irgacure 1700 (trade name, Ciba Specialty Chemicals) mixed with phosphine oxide (Ciba Specialty Chemicals) at a ratio of 75/25 (weight ratio); Irgacure 184 (trade name, Ciba. Specialty Chemicals, 1-hydroxy-cyclohexyl-phenyl ketone) and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide (Ciba Specialty Chemicals) Irgacure 180 mixed at a ratio of 75/25 (weight ratio) (Trade name, Ciba Specialty Chemicals, Inc.) (trade name, manufactured by Ciba Specialty Chemicals, Inc.) and 50/50 Irgacure 1850 was mixed at a ratio of (weight ratio); Irgacure 819
(Product name, manufactured by Ciba Specialty Chemicals,
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide); Lucirin TPO (trade name, manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide); Darocu
r1173 (trade name, manufactured by Ciba Specialty Chemicals, 2-hydroxy-2-methyl-1-phenylpropan-1-one) and Lucirin TPO in 5
Darocur4 mixed at a ratio of 0/50 (weight ratio)
265 (trade name, manufactured by Ciba Specialty Chemicals) can be used.

The content ratio of the photosensitizer is not particularly limited, and is preferably, for example, 0.01 to 10 parts by weight based on 100 parts by weight of the photocurable resin. 0.01
If it is less than 10 parts by weight, the photocurability of the photocurable molding material layer may be inferior. If it exceeds 10 parts by weight, the basic performance of the cured product may be inferior. More preferably, 0.05 to
8 parts by weight, more preferably 0.1 to 5 parts by weight.

The photocurable resin may also contain a thermosetting agent or the like in addition to the photosensitizer, in which case the photocurable molding material layer also has thermosetting properties. The thermosetting agent is not particularly limited, and examples thereof include benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, t-butylperoxy-2-ethylhexanoate, t-butylperoxyoctoate, and t-butylperoxide. Oxybenzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, 1,1-bis (t
Organic peroxides such as -hexylperoxy) -3,3,5-trimethylcyclohexane; and 2,2'-azobisisobutyronitrile, 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile and the like. Examples include radical polymerization initiators such as azo compounds. The content ratio of the thermosetting agent is not particularly limited.
It is preferably 0 to 10 parts by weight with respect to 0 parts by weight. If it exceeds 10 parts by weight, the basic performance of the cured product may be inferior. More preferably, it is 0.01 to 8 parts by weight, and still more preferably 0.05 to 5 parts by weight.

The above-mentioned photocurable resin may further contain, as other additives, a low-shrinking agent, an internal release agent, a chain transfer agent, a polymerization inhibitor, an ultraviolet absorber, a thickener, a coupling agent, a thickener. ,
It may contain an additive such as an antibacterial agent or a halogen-based, phosphorus-based or inorganic flame retardant. The photocurable molding material layer of the present invention,
These additives may be contained as necessary in addition to the photocurable resin, filler, glass particles, and frit. These may be used alone or in combination of two or more. In this case, it is preferable to appropriately set the type, the usage amount, and the like so as not to impair the photocurability.

The above-mentioned low shrinkage agent is not particularly limited.
For example, heat of polyethylene, polypropylene, polystyrene, three-dimensional cross-linked polystyrene, polymethyl methacrylate, polyethylene glycol, polypropylene glycol, cellulose butyrate, acetate (acetylcellulose), polyvinyl chloride, polyvinyl acetate, polycaprolactone, saturated polyester, etc. And a plastic polymer. The content ratio of the low shrinkage agent is not particularly limited, and for example, is preferably 0 to 30 parts by weight based on 100 parts by weight of the photocurable resin. If it exceeds 30 parts by weight, the basic performance such as the strength of the cured product may be reduced. More preferably, it is 0 to 15 parts by weight. The internal release agent is not particularly limited, and includes, for example, a silicone resin and a stearate. The content ratio of the internal release agent is not particularly limited, and for example, is preferably 0 to 10 parts by weight based on 100 parts by weight of the photocurable resin. If it exceeds 10 parts by weight, the basic performance of the cured product may be reduced. More preferably, it is 0 to 5 parts by weight.

The chain transfer agent is not particularly limited.
For example, α-methylstyrene dimer; carbon tetrachloride; t
-Butyl mercaptan, n-octyl mercaptan, n
Alkyl mercaptans such as dodecyl mercaptan; aromatic mercaptans such as thiophenol and thionaphthol; thioglycolic acid; octyl thioglycolate, ethylene glycol dithioglycolate, tolmethylolpropane tris- (thioglycolate), pentaerythritol tetrakis- ( Alkyl esters of thioglycolic acid such as thioglycolate); β-mercaptopropionic acid; octyl β-mercaptopropionate;
And β-mecaptopropionic acid alkyl esters such as butanediol di (β-thiopropionate) and pentaerythritol tetrakis- (β-thiopropionate). The content ratio of the chain transfer agent is not particularly limited, and for example, is preferably 0 to 5 parts by weight based on 100 parts by weight of the photocurable resin. If it exceeds 5 parts by weight, the curability of the photocurable resin may be poor. More preferably, it is 0 to 2 parts by weight.

The polymerization inhibitor is not particularly limited.
For example, pt-butylcatechol, p-methoxyphenol, hydroquinone, p-benzoquinone, chloranil, m-dinitrobenzene, nitrobenzene, p-phenyldiamine, sulfur, diphenylpicrylhydrazyl,
Di-p-fluorophenylamine, tri-p-nitrophenylmethyl and the like. The content ratio of the polymerization inhibitor is not particularly limited.
It is preferably 0 to 5 parts by weight with respect to 0 parts by weight.
If it exceeds 5 parts by weight, the curability of the photocurable resin may be poor. More preferably, it is 0.001 to 2 parts by weight.

The ultraviolet absorber is not particularly limited, and for example, those which can be used for photocurable resins such as benzophenone type and benzotriazole type can be used. The coupling agent is not particularly limited, and for example, those that can be used for a photocurable resin can be used, and the content ratio of each of these is not particularly limited. 0 to 100 parts by weight of resin
Preferably it is 5 parts by weight. If it exceeds 5 parts by weight,
The curability of the photocurable resin may be poor. More preferably, it is 0.05 to 2 parts by weight.

The thickener is not particularly restricted but includes, for example, polyvalent metal oxides such as magnesium oxide, calcium oxide and zinc oxide; polyvalent metal hydroxides such as magnesium hydroxide and calcium hydroxide; And isocyanate. The amount of the thickener used is not particularly limited. For example, in the case of a polyvalent metal oxide or a polyvalent metal hydroxide, 0.1 to 10 parts by weight based on 100 parts by weight of the photocurable resin.
Parts by weight, more preferably 0.5 parts by weight.
-5 parts by weight. In the case of a polyfunctional isocyanate or the like, it is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the photocurable resin.
Parts by weight, and more preferably 5 to 15 parts by weight. If the amount is less than the above amount, the resin mixed solution of the photocurable resin and the filler may not easily increase in viscosity. If the amount is more than the above amount, the resin mixed solution may be too thick. In order to further increase the viscosity, the photocurable molding material layer using the thickener undergoes a so-called aging step in which the thickening reaction proceeds at room temperature or by heating for a certain period of time.

When a polyvalent metal oxide or a polyvalent hydroxide is used as a thickener, a succinic acid derivative having a total carbon number of 8 to 30 may be used as a thickener if necessary. Can be. When such a succinic acid derivative is used,
In the thickening form based on the reaction of an acid-metal salt, where a polyvalent metal oxide or a polyvalent hydroxide acts, a rapid thickening effect will be obtained in synergy with an appropriate water content, It is possible to form the photocurable molding material layer while preserving the distribution state of the reinforcing fibers such as glass fibers as much as possible. This makes it possible to form a photocurable molding material layer in which glass fibers and the like are more appropriately distributed in the layer than a conventional SMC (sheet molding compound) without the bias of the glass fibers and the like. Product value can be increased. Specific examples of the succinic acid derivative include, for example, octylsuccinic acid, octenylsuccinic acid, hexylsuccinic acid, hexenylsuccinic acid, nonylsuccinic acid, nonenylsuccinic acid, decylsuccinic acid, decenylsuccinic acid, dodecylsuccinic acid, dodecenylsuccinic acid, and tetradecylsuccinic acid. , Tetradecenyl succinic acid, cyclododecyl succinic acid, cyclododecenyl succinic acid, hexadecyl succinic acid, hexadecenyl succinic acid, heptadecyl succinic acid,
Heptadecenyl succinic acid, octadecyl succinic acid, octadecenyl succinic acid, eicosyl succinic acid, eicosenyl succinic acid, diphenylbutenyl succinic acid, pentadodecyl succinic acid, pentadodecenyl succinic acid, and, These salts and the like can be mentioned. These succinic acid derivatives may be used alone or as a mixture of two or more. The method for synthesizing the succinic acid derivative is not particularly limited.

The amount of the succinic acid derivative used depends on the type and combination, but is preferably in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the photocurable resin.
The content is more preferably in the range of 1 part by weight to 10 parts by weight. When the amount of the succinic acid derivative used is less than 0.01 parts by weight, the expected action and effect of using the succinic acid derivative become poor. That is, the initial viscosity of the resin mixed solution becomes too high, and the mixed solution cannot be sufficiently impregnated into the reinforcing fibers, which is not preferable. If the amount of the succinic acid derivative is more than 10 parts by weight, the initial viscosity of the resin mixed solution can be suppressed to a low value, but the physical properties such as water resistance are undesirably reduced.

In order to increase the rate of thickening as an auxiliary agent of the thickening modifier, the water content in the resin mixed solution should be 0.1% by weight or less.
0.45% by weight, more preferably 0.12% to 0.42% by weight, even more preferably 0.15% by weight.
The used amount may be set so as to be in the range of from 0.4% by weight to 0.4% by weight. That is, the water content of the resin mixed solution is preferably 0.1% by weight or more and 0.45% by weight or less, more preferably 0.12% by weight or more and 0.42% by weight or less, and 0.15% by weight or more. The content is more preferably 0.4% by weight or less. If the water content is less than 0.1% by weight, the expected action and effect are poor, which is not preferable. When the content is 0.45% by weight or more, physical properties such as water resistance are undesirably reduced. For example, it can be adjusted by measuring the moisture content of the resin mixed solution and adding water as needed so that the desired total moisture content is obtained. The moisture content can be measured using a Karl Fischer moisture meter. With these combinations, the aging step can be remarkably shortened if the resin mixture solution undergoes a thickening reaction at 60 ° C to 100 ° C. The measurement of the moisture content is preferably performed on a compound that is a resin mixed solution in which various additives and fillers are blended as necessary. Also, the thickener is
It is a preferable usage form that the moisture content is measured, and the water content is adjusted and then added to the compound. After that, it is a preferred embodiment to obtain a sheet-like reinforcing material of the present invention by applying to a carrier film and adding a predetermined amount of reinforcing fibers.

The antibacterial agent is not particularly limited, and for example, those which can be used for a photocurable resin can be used. The amount of each of the above antibacterial agents is not particularly limited, and for example, is preferably 0 to 10 parts by weight based on 100 parts by weight of the photocurable resin. More preferably, it is 0.1 to 5 parts by weight.

The reinforcing fibers in the photocurable molding material layer act as a reinforcing material, whereby the resin and the reinforcing fibers are compounded, and the photocurable molding material layer has a basic performance such as strength. It will be excellent. Examples of the use form of such reinforcing fibers include a form in which reinforcing fibers are mixed in a compound; a form in which a compound is impregnated into a reinforcing fiber; and the like.

The reinforcing fibers are not particularly limited, and include, for example, inorganic fibers such as glass fibers, carbon fibers, metal fibers, and ceramic fibers; and organic fibers such as aramid, polyester, vinylon, phenol, and Teflon (registered trademark). Fiber; natural fiber and the like. The form of these fibers is not particularly limited, and may be, for example, a cloth (woven fabric); a mat such as a chop strand mat, a preformable mat, a continuous strand mat, or a surfacing mat; a chop; a roving; Non-woven fabrics and the like can be mentioned. These may be used alone or in combination of two or more. Of these, glass fibers are preferred.

The shape of the reinforcing fiber is not particularly limited, but the aspect ratio is preferably 100 or more as a ratio of the diameter to the length. Thereby, the light propagation property of the reinforcing fiber is improved, and the photocurability of the photocurable molding material layer can be improved. If it is less than 100, it may not be possible to sufficiently contribute to improvement in photocurability, and more preferably 1500 or more.

The amount of the reinforcing fiber used is, for example,
It is preferable that the amount be 5 to 100 parts by weight based on 100 parts by weight of the photocurable resin. If the amount is less than 5 parts by weight or exceeds 100 parts by weight, the basic performance of the cured product may be reduced. More preferably, it is 10 to 65 parts by weight.

The photocurable molding material layer preferably further contains, as a reinforcing material, a normal filler other than the transparent filler used in the present invention as long as the photocurability is not impaired.
Such fillers are not particularly limited as long as they are used for reinforcing the molding material, and include, for example, aluminum hydroxide, calcium carbonate, calcium sulfate, barium sulfate, alumina, clay, talc, milled fiber, Inorganic fillers such as cristobalite, silica (silica sand), river sand, diatomaceous earth, mica powder, and gypsum; and organic fillers. In addition, highly transparent glass powder can be used for the purpose of reinforcement. These may be used alone or in combination of two or more. Among these, aluminum hydroxide is preferably used as an essential component because the basic properties such as mechanical properties of the cured product are improved. When aluminum hydroxide is used, flame retardancy can be imparted to the photocurable molding material layer, which is a preferred embodiment. In addition, cristobalite, silica, river sand and the like are preferable for wear resistance. Further, since the amount of the highly transparent filler such as glass powder does not basically affect the photocurability of the reinforcing material of the present invention, the amount of the filler can be appropriately set as desired.

It is preferable that the amount of the ordinary filler is, for example, 0 to 300 parts by weight based on 100 parts by weight of the photocurable resin. More preferably,
It is 2 to 300 parts by weight. If the amount exceeds 300 parts by weight, the workability in producing the photocurable molding material layer, that is, the workability of curing by active energy rays may be reduced. More preferably, it is 30 to 280 parts by weight. More preferably, it is 50 to 200 parts by weight. In a preferred embodiment of the present invention, in the sheet-like reinforcing material that requires a transparent filler, the transparent filler and other normal fillers can also be used together. The amount used is preferably from 1 to 450 parts by weight. More preferably,
30 to 350 parts by weight. Particularly preferably, 40 to 3
00 parts by weight, most preferably 50 to 200 parts by weight. In addition, the mixing ratio of the transparent filler to other ordinary fillers can be appropriately set depending on desired physical properties such as desired photocurability, flame retardancy and strength of the obtained sheet-like reinforcing material.

The photocurable molding material layer can be obtained, for example, by mixing the above-described components and impregnating the reinforcing fibers as a resin mixed solution, that is, by a method of producing an SMC (sheet molding compound). Such a method is not particularly limited, for example, a resin mixed solution is applied on a carrier film, and the reinforcing fibers are scattered or stacked, and the other mixed carrier film is sandwiched by applying the resin mixed solution, Alternatively, the method can be carried out by spraying or loading reinforcing fibers on a carrier film and applying a resin mixed solution, followed by pressure bonding, impregnation, aging, and thickening.

In the production of the photocurable molding material layer,
The viscosity of the resin mixed solution is not particularly limited, but is preferably adjusted appropriately according to the use of the sheet-like reinforcing material. For example, the sheet-like reinforcing material of the present invention can be used for base materials having various shapes such as a flat surface, a three-dimensional curved surface, and an uneven surface. In the case of a sheet-like reinforcing material that can be used, that is, not only can it be used on a flat surface, but if it is a sheet-like reinforcing material that sufficiently follows a three-dimensional curved surface or uneven surface, a flexible sheet It is preferable that the photocurable molding material layer is also formed so as to have flexibility. In this case, if the amount of the thickener used is reduced, the viscosity of the compound is lowered,
The flexibility of the photocurable molding material layer will be improved,
There is a possibility that the sheet containing the photocurable molding material layer produced may not be able to be wound up due to a low viscosity increase rate.
For this reason, by using the above-mentioned thickening modifier and its auxiliary agent having a quick thickening effect, it is possible to wind up the manufactured sheet, and it is preferable to easily manufacture the sheet-like reinforcing material. . By the way, in the production of SMC, usually, an aging step is performed after winding, so that external force such as winding is applied to the sheet-like reinforcing material before aging, but the viscosity of the compound is low. Occasionally, there is a possibility that reinforcing fibers such as glass are unevenly distributed, wrinkles are generated in a sheet, and air enters and bubbles are generated. It is preferable to manufacture a sheet-like reinforcing material by winding up a sheet including a photocurable molding material layer after the step of sticking. Thereby, it becomes possible to manufacture a sheet-like reinforcing material that can cope with base materials of various shapes without causing the above-mentioned problems.

The thickness of the photocurable molding material layer is not particularly limited, and is preferably, for example, 0.1 to 10 mm. When the thickness is less than 0.1 mm, the cured product may not have sufficient strength. Curability may decrease. More preferably, it is 0.5 to 5 mm.

The pressure-sensitive adhesive layer in the present invention has sufficient adhesiveness to a substrate on which the sheet-like reinforcing material is used, and has flexibility so that the sheet-like reinforcing material can be sufficiently applied. By the adhesive layer, the sheet-like reinforcing material has adhesiveness to the substrate, and after the adhesion, the photocurable molding material layer and the adhesive layer have shape retention. In addition, due to the strength of the pressure-sensitive adhesive itself, the adhesiveness to the photocurable molding material layer after curing, and the adhesiveness to the substrate, excellent adhesive strength is obtained. That is, the pressure-sensitive adhesive layer has an adhesive force before the sheet-like reinforcing material is cured, so that the pressure-sensitive adhesive layer and the photocurable molding material layer or the base material adhere to each other, and after the sheet-like reinforcing material is cured,
An adhesive layer is formed to have an adhesive force for permanently attaching the photocurable molding material layer and the substrate.

The form of the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include a film usually formed of a pressure-sensitive adhesive layer having a support. Further, two or more films may be laminated. The support is a film-shaped or sheet-shaped layer used to improve the shape retention and strength of the pressure-sensitive adhesive layer, handleability, and the like.For example, a film formed of paper or a resin material, Woven fabrics, non-woven fabrics, foams, and the like formed of fibers such as natural fibers, synthetic fibers, and inorganic fibers may be used, and may be subjected to press working, embossing, or the like.

The pressure-sensitive adhesive layer contains a pressure-sensitive adhesive. The pressure-sensitive adhesive is not particularly limited, and includes, for example, a rubber-based pressure-sensitive adhesive mainly containing a synthetic rubber such as styrene-butadiene rubber, isobutylene rubber, isoprene rubber, and butyl rubber or a natural rubber; acrylic resin, polyvinyl alcohol, polyacrylamide, Polyvinyl methyl ether,
Synthetic resin-based pressure-sensitive adhesives containing styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butylene block copolymer, ethylene-vinyl acetate or the like as a main component are exemplified. They are,
Any of a solvent type, an emulsion type, a hot melt type, a water soluble type and the like may be used, or they may be used alone or in combination of two or more. Among these, an acrylic pressure-sensitive adhesive is preferable.

The pressure-sensitive adhesive may contain a tackifier, a plasticizer, the above-mentioned additives, and the like, if necessary. These may be used alone or in combination of two or more. The tackifier and the plasticizer are not particularly limited as long as they can be generally used for the pressure-sensitive adhesive. Examples of the tackifier include natural resins such as rosin and terpene-based resins; Petroleum hydrocarbon resins such as resins; phenolic resins; xylene resins; and the like. Examples of plasticizers include petroleum plasticizers such as process oil; liquid rubber plasticizers such as liquid polyisobutylene and liquid polybutene; Resin-based plasticizers such as basic acid esters are exemplified.

The pressure-sensitive adhesive layer may further contain a filler, a flame retardant, and the like. These may be used alone or in combination of two or more. When the pressure-sensitive adhesive layer contains a filler and a flame retardant, the heat resistance and the flame retardancy of the pressure-sensitive adhesive layer are improved. The filler is not particularly limited,
For example, those described above can be used, and among them, aluminum hydroxide is preferably used.

The flame retardant is not particularly limited, and examples thereof include halogen-based flame retardants; phosphorus-based flame retardants; and non-halogen-based flame retardants such as inorganic flame retardants. Among them, it is preferable to use a non-halogen flame retardant in order not to pollute the environment. The amount of the filler or the flame retardant is, for example, 0 to 100 parts by weight of the adhesive.
Preferably, the amount is 100 parts by weight. More preferably, it is 20 to 80 parts by weight. If the amount of the filler or the flame retardant exceeds the above range, the adhesiveness of the pressure-sensitive adhesive layer may be reduced.

The pressure-sensitive adhesive layer is preferably one having photocurability, in which case the adhesive strength can be further improved. The method for imparting photocurability to the adhesive layer is not particularly limited. For example, it is preferable to impart photocurability by including the above-mentioned photocurable resin or photosensitizer in an adhesive. . Furthermore, when a polymerizable unsaturated monomer such as polyfunctional (meth) acrylate or styrene contained in the photocurable molding material layer moves to the adhesive layer, the polymerizable unsaturated monomer cures the adhesive layer. This contributes to sufficient curing of the adhesive layer.

In order to impart photocurability to the pressure-sensitive adhesive layer, the pressure-sensitive adhesive layer must have no support in the photocurable molding material layer to block polymerizable unsaturated monomers and the like. Is preferred. As a result, the polymerizable unsaturated monomer that has permeated into the adhesive layer is not prevented from penetrating by the support, so that the entire adhesive layer uniformly contains the polymerizable unsaturated monomer. As a result, the pressure-sensitive adhesive and the polymerizable unsaturated monomer are integrated and cured, so that the pressure-sensitive adhesive becomes rigid and the adhesive layer as a whole has sufficient adhesive strength, heat resistance, flame retardancy and durability. The sheet-like reinforcing material containing such an adhesive layer has sufficient flexibility at the time of construction, and at the time of adhesion to the substrate, the adhesive layer uniformly swells with the polymerizable unsaturated monomer and adheres to the substrate. In addition, the adhesiveness is improved, and the adhesive strength is improved, so that a shift between the photocurable molding material layer and the adhesive layer and a shift between the base material and the adhesive layer hardly occur, and it is difficult to peel off the base material. Further, since the entire pressure-sensitive adhesive layer is integrally cured, there is no problem that the pressure-sensitive adhesive layer is separated from the support in the pressure-sensitive adhesive layer.

In the above embodiment, for example, (a) a film formed by a pressure-sensitive adhesive layer having no support;
(B) The form of a film or the like formed by a pressure-sensitive adhesive layer having a support such as paper or nonwoven fabric through which the polymerizable unsaturated monomer permeates. Further, these may be laminated. In the embodiment (a), a transfer tape can be used, and it is preferable to use a pressure-sensitive adhesive containing a resin having an improved molecular weight or a degree of crosslinking, and the sheet-like reinforcing material follows the surface shape of the base material. Is improved,
Since the construction is easy, sufficient adhesive strength can be stably exhibited. In addition, the above-mentioned mode (b) is preferable because the strength and shape retention of the pressure-sensitive adhesive layer, and workability such as cutting when applying the sheet-like reinforcing material are improved. It is preferable to use paper or nonwoven fabric from the viewpoint of followability to the surface shape of the substrate in the sheet-like reinforcing material.

The thickness of the pressure-sensitive adhesive layer is not particularly limited, but is preferably, for example, 3 μm to 10 mm.
If it is less than 3 μm, poor adhesion of the sheet-like reinforcing material to the substrate may not be suppressed, and if it exceeds 10 mm, the workability and workability of the sheet-like reinforcing material may be reduced,
There is a possibility that the basic performance of the sheet-like reinforcing material is reduced. More preferably, it is 10 μm to 5 mm.

The release layer in the present invention protects the adhesive layer while the sheet-like reinforcing material is processed, and can release the adhesive layer and the release layer while maintaining the adhesiveness of the adhesive layer. (Releasability), and has the flexibility to allow the sheet-like reinforcing material to be sufficiently applied.

The form of the release layer is not particularly limited. For example, paper or a film formed of the above-mentioned resin material such as polyethylene or polypropylene; a film formed of a metal material such as an aluminum foil; Films treated with a release agent are exemplified.

The release agent is not particularly limited, and examples thereof include those containing a release resin such as a silicone resin, a fluororesin, or a polyethylene wax as a main component. These may be used alone or in combination of two or more. The release agent layer can be formed, for example, by applying a release agent to one surface of a support such as a film or paper. In these cases, the surface of the film may be subjected to plasma treatment, corona discharge treatment, chemical treatment, or the like before coating.

The thickness of the release layer is not particularly limited, and is preferably, for example, 3 to 2000 μm.
If it is less than 3 μm, the release layer may not have sufficient release properties, and if it exceeds 2000 μm, the workability and workability of the sheet-like reinforcing material may be reduced. More preferably, it is 10 to 500 μm.

The release layer, together with the light-shielding layer, shields both sides of the photocurable molding material layer from light, thereby improving the workability, workability, adhesiveness, etc. of the sheet-like reinforcing material and sufficiently suppressing poor adhesion. It is preferable that the material has a light-shielding property. It is not necessary to block all light rays as in the light-blocking layer as in the light-blocking layer.
It is effective if the light transmittance in the wavelength band of m or less is adjusted to be 10% or less. The method for imparting light-shielding properties to the release layer is not particularly limited. For example, the method can be performed by using paper or a film having light-shielding properties.

The protective layer in the present invention has a function of improving the curability on the surface of the photocurable molding material layer, improving the surface condition, and sufficiently suppressing odor. In the sheet-like reinforcing material of the present invention, when such a protective layer is provided, it is preferable to perform photo-curing in a state where the protective layer is provided. In this case, the protective layer has a light-transmitting property. Will be used. As such a light-transmitting protective layer, for example, the protective layer is a film formed of a resin material, and the film does not include a material such as a pigment that reduces the light transmitting property, or a photo-curing property. A material that does not impair the photocurability of the molding material layer can be used.

The protective layer in the present invention is one that is peeled off after the sheet-like reinforcing material is applied and the photocurable molding material layer is cured, and that that is left as a permanent protective layer of the sheet-like reinforcing material without being peeled off. There is. If it is to be peeled off, it has release properties to the photocurable molding material layer, and
It has the flexibility that the sheet-like reinforcing material can be sufficiently applied.

The form of the protective layer in the case of being peeled off is not particularly limited, and examples thereof include an odor blocking film formed of a resin material and a laminated film obtained by laminating the same.

The resin material in the odor blocking film is not particularly limited as long as the protective layer in the case of being peeled off does not easily transmit the polymerizable unsaturated monomer contained in the photocurable molding material layer. However, for example, polyamide resins such as nylon; polyesters such as polyethylene terephthalate and polybutylene terephthalate; polyvinyl chloride, polyvinylidene chloride, vinyl chloride copolymer, cellophane, polyvinyl acetal (vinylon), and the like are preferable.

When the odor blocking film is a film made of the above resin material, the protective layer in the case of being peeled off has a mold releasing property with respect to the photocurable molding material layer. It is preferable to form a multilayer film in which a release film having a release property for the material layer is laminated on an odor blocking film. In this case,
The release film is located on the surface in contact with the photocurable molding material layer.

In the case where the protective layer is peeled off, the protective layer also has a function of blocking moisture in order to prevent the odor-blocking film from absorbing wrinkles and warping when the film has hygroscopicity. It is preferable that the moisture barrier film is a multilayer film laminated on one or both sides of the odor barrier film. In this case, the moisture barrier film is located at least on the other surface in contact with the photocurable molding material layer.

The release film and the moisture barrier film are not particularly restricted but include, for example, films formed of resin materials such as polyethylene and polypropylene. Examples of these multilayer films include a film obtained by laminating an odor blocking film and a release film; a film obtained by laminating a moisture blocking film, an odor blocking film, and a release film in this order.

The formation of the protective layer in the case of being peeled off, for example, in the case of a laminated film, can be carried out by an ordinary method for producing a laminated film. The protective layer that remains as a permanent protective layer of the sheet-like reinforcement without being peeled off is
After curing of the photocurable molding material layer, it remains on its surface,
It imparts performance such as weather resistance and chemical resistance. Further, in the sheet-like reinforcing material of the present invention, since the photocurable molding material layer is colored, the appearance can be imparted without using the permanent protective layer as a surface covering material. The appearance may be provided in combination with the curable molding material layer.

The surface of the permanent protective layer, which is in contact with the photocurable molding material layer, has been subjected to a surface treatment so that the permanent protective layer has sufficient adhesion to the cured molding material layer. Is preferred. Examples of the form include a film subjected to a chemical treatment and a film subjected to a physical treatment.
Also, a film obtained by combining these surface treatments can be used.

By these surface treatments, the adhesiveness between the permanent protective layer and the photocurable molding material layer is improved, and the above-mentioned effects are exerted. Examples of the chemical treatment include various chemical treatments, acid treatment, solvent treatment, treatment with a coupling agent, and the like. Further, as the physical treatment, for example, mechanical surface roughening treatment, ultraviolet irradiation treatment,
Plasma treatment, corona discharge treatment, ion beam treatment and the like can be mentioned. Among these, it is preferable to apply a chemical treatment, a plasma treatment, a corona discharge treatment or the like to the film.

The permanent protective layer can be subjected to a surface treatment, has strength and flexibility not to impair the workability of the sheet-like reinforcing material, and has excellent weather resistance and chemical resistance. If not particularly limited, for example, polyethylene terephthalate, polyesters such as polybutylene terephthalate, polyvinyl fluoride, polyvinylidene fluoride,
Fluororesins such as vinyl fluoride copolymers;

The thickness of the protective layer is not particularly limited, and is preferably, for example, 3 to 3000 μm.
If it is less than 3 μm, the protective layer may not be able to improve the curability on the surface of the photocurable molding material layer or improve the surface condition, and may not be able to sufficiently suppress the odor. is there. 3000 μm
If it exceeds 300, the workability and workability of the sheet-like reinforcing material may be reduced. More preferably, it is 10 to 500 μm. Further, the thickness of the odor blocking film in the protective layer is not particularly limited, and is preferably, for example, 3 to 2000 μm. When the thickness is less than 3 μm, the protective layer may not be able to sufficiently suppress odor, and 200
If it exceeds 0 μm, the workability and workability of the sheet-like reinforcing material may be reduced when the protective layer is a multilayer film. More preferably, it is 5 to 500 μm.

The light-shielding layer in the present invention does not impair the workability and workability of the sheet-like reinforcing material due to the curing of the photocurable molding material layer while the sheet-like reinforcing material is being worked and applied. In addition, it has an effect of shielding the photocurable molding material layer from light (light shielding property) and has sufficient flexibility to sufficiently process and construct a sheet-like reinforcing material.

The form of the light-shielding layer is not particularly limited, and examples thereof include a film obtained by depositing, coating or dispersing a light-shielding material on paper or a resin material. Further, these may be laminated. For example, such a film in which a light-shielding material is deposited on paper or a resin material includes a film in which a vapor-deposited film made of a metal such as aluminum is formed on one or both sides as a light-shielding material. As a light-shielding material, a film or the like in which a coating film or an ink film in which a pigment or the like is dispersed is formed on one surface or both surfaces, and the like.
Examples of the light shielding material include a film in which a pigment or the like is dispersed.

The pigment is not particularly limited as long as it can impart light-shielding properties to the film. Examples of the pigment include carbon black; titanium oxide, iron oxide, zinc oxide, lead oxide, calcium carbonate, barium sulfate, and the like. Inorganic pigments such as alumina, kaolin clay, talc, and mica; metal powders such as aluminum and stainless steel; organic pigments such as phthalocyanine blue; milled fiber; These may be used alone or in combination of two or more.

The film is not particularly limited as long as it has strength and flexibility which do not impair the workability of the sheet-like reinforcing material, and durability against monomers and solvents contained in the photocurable molding material. For example, a film formed of paper or a resin material may be used. The paper is not particularly limited, and includes, for example, those formed of natural fibers, synthetic fibers, inorganic fibers, and the like. It may be. The resin material is not particularly limited. For example, polyethylene, polypropylene, polybutene, polystyrene, ethylene-α
-Polyolefins such as olefin copolymers; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Fluororesins such as tetrafluoroethylene, polyvinylidene fluoride and polymonochlorotrifluoroethylene; Polybutadiene, polycarbonate, polyacetal, polyamide, polyphenylene ether, polyphenylene sulfide , Polyether sulfone, polyurethane, polyimide, polyether ether ketone, polymethyl pentene, ionomer resin, polyvinyl butyral, polyvinyl alcohol, cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, vinyl copolymer, ethylene-vinyl acetate Copolymer, ethylene-
(Meth) acrylic acid copolymer, ethylene- (meth) acrylic acid ester copolymer and the like can be mentioned. These may be used alone or in combination of two or more.

The above-mentioned film can be obtained, for example, by mixing a resin material with a pigment, an additive, etc., to obtain a calender film; an extruded film; a cast film; Further, it may be a stretched film such as a uniaxially stretched film or a biaxially stretched film. The deposited film can be obtained, for example, by depositing a metal such as aluminum on one or both sides of the film. The coated film can be obtained by, for example, applying or printing a paint or ink in which a pigment is dispersed on one or both sides of the film. In these cases, the surface of the film is subjected to plasma treatment, corona discharge treatment,
Chemical treatment may be performed.

The thickness of the light-shielding layer is not particularly limited, and is preferably, for example, 5 to 2000 μm.
If it is less than 5 μm, the light-shielding layer may not have sufficient strength to withstand sufficient peeling, and if it exceeds 2000 μm, the workability of the sheet-like reinforcing material may be impaired. More preferably, it is 10 to 500 μm.

In the production of the sheet-like reinforcing material of the present invention,
The order and method of laminating each layer are not particularly limited. For example, in the method of manufacturing the SMC described above,
By using a film in which a protective layer, an adhesive layer, and a release layer are laminated as a carrier film, the protective layer, the adhesive layer, and the release layer can be laminated on both sides of the photocurable molding material layer. Further, by using a film in which a light-shielding layer and a protective layer are laminated and a film in which an adhesive layer and a release layer are laminated as a carrier film, the light-shielding layer and the protective layer, and the adhesive layer and the release layer can be cured by photocuring. It can be laminated on both sides of the molding material layer.

The sheet-like reinforcing material of the present invention can be easily processed and constructed, can secure a sufficient working time and has excellent workability, and can be made of metal, plastic, rubber, glass,
It has sufficient adhesion to various surface conditions and complicated shapes of various base materials such as ceramics, stone materials, wood, etc., so that the occurrence of defects due to poor adhesion to the base material is sufficiently suppressed. In addition, the photocurable molding material layer itself is colored while photocuring can be sufficiently performed. In addition, the cured product has sufficient basic performance such as mechanical, chemical, and electrical properties, and has improved adhesive strength and durability. It can be used for structural members, pipes, lining materials, etc. in automobiles, ships, household goods, etc., and can be used for various applications.

The sheet-like reinforcing material of the present invention can be used as a reinforcing material for reinforcing or repairing the above-mentioned various materials. In this case, the sheet-like reinforcing material itself can be attached to various substrates, or the sheet-like reinforcing material can be used to attach the reinforcing material to various substrates. The reinforcing material is not particularly limited, and examples thereof include a bar-shaped, pipe-shaped, plate-shaped, and net-shaped reinforcing material. These may be used alone or in combination of two or more. Moreover, it may be combined in advance with the sheet-like reinforcing material of the present invention, or may be combined at the time of construction.

The reinforcing material contains the sheet-like reinforcing material of the present invention and, if necessary, a reinforcing material and the like. Since the sheet-like reinforcing material of the present invention has the above-mentioned action, Sufficient reinforcement and repair can be easily performed on various base materials. Such a reinforcing material is one of preferred embodiments of the present invention. The construction method and the repair method using the sheet-like reinforcing material of the present invention are also one of the preferred embodiments of the present invention.

[0097]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention are shown in FIGS. FIG. 2A shows a state before the sheet-like reinforcing material of the present invention is applied. In this state, the sheet-shaped reinforcing material has a protective layer on one side of the photocurable molding material layer, and has an adhesive layer and a release layer in this order on the other side from the inside. In this case, it is preferable to put the sheet-like reinforcing material in a packaging material or a can made of an aluminum vapor-deposited film or the like having a light-shielding property while storing or transporting the sheet-like reinforcing material.

FIG. 2 (2) shows a state in which the release layer is peeled off from the sheet-like reinforcing material of the present invention and applied to the base material. In this state, the sheet-like reinforcing material has a protective layer on one side of the photocurable molding material layer and an adhesive layer on the other side. In this case, in order to improve the adhesiveness of the sheet-like reinforcing material, the surface of the base material may be subjected to a base treatment, and the occurrence of problems due to poor adhesion of the sheet-like reinforcing material is sufficiently suppressed. As long as this is the case, the surface of the base material does not need to have been subjected to a base treatment.

FIG. 2 (3) shows a state in which the sheet-like reinforcing material of the present invention is adhered to a base material and is being cured. In this state, the sheet-like reinforcing material has a protective layer on one side of the photocurable molding material layer and an adhesive layer on the other side, and the adhesive layer is adhered to the substrate. In this case, pressure is applied to the sheet-like reinforcing material, or air that has entered between the base material and the adhesive layer is evacuated so that the occurrence of defects due to poor adhesion of the sheet-like reinforcing material is sufficiently suppressed. Operation or the like may be performed. In such a state, the sheet-like reinforcing material is cured. In this case, the photocurable molding material layer is cured by the active energy rays.

FIG. 2D shows a state in which the protective layer is peeled off after the sheet-like reinforcing material of the present invention is cured.
In this state, the sheet-shaped reinforcing material has an adhesive layer on one side of the photocurable molding material layer, and the adhesive layer is adhered to the base material.

The active energy rays are not particularly limited, and include, for example, sunlight, ultraviolet rays, infrared rays, electron beams, radiation, laser beams, high frequencies, microwaves and the like. These may be used alone or in combination of two or more. Irradiation of the active energy ray can be performed using sunlight in the outdoors or the like. Can be performed using, for example, an active energy ray irradiation device.

The irradiation device for the active energy ray is not particularly limited, and examples thereof include an ultraviolet fluorescent lamp, a low-pressure mercury lamp, a (ultra) high-pressure mercury lamp, a xenon lamp, a Mercury halogen lamp, an argon glow lamp, a photographic lighting lamp, Examples include a carbon arc lamp, a tungsten lamp, an incandescent lamp, and an excimer laser irradiation device.

The curing time of the sheet-like reinforcing material of the present invention is not particularly limited. For example, in the case of curing using sunlight, it is preferable to set the curing time in 1 minute to 10 hours. When curing with
It is preferable to set so as to cure in 1 minute to 5 hours. In addition, it is preferable that the setting is made such that the composition is cured within one hour in direct sunlight. After curing, the sheet-like reinforcing material of the present invention has a colored appearance without being coated on its surface. However, if necessary, it may be subjected to a clear coating or the like.

FIGS. 3 (1) to 3 (5) show an embodiment having a light shielding layer. In this embodiment, the same operation as in FIG. 2 is performed except that the light-shielding layer is peeled off before the photocurable molding material layer is cured. In the state of (4) in FIG. 3 described above, the photocurable molding material layer starts to cure after the light-shielding layer is peeled off. Thus, the photocurability of the photocurable molding material layer can be set. As a result, the working time can be reduced.

In FIGS. 2 and 3, when the pressure-sensitive adhesive layer has curability, the pressure-sensitive adhesive layer is hardened more strongly together with the photocurable molding material layer, and the adhesiveness to the base material is improved. Since it can be improved, the sheet-like reinforcing material has excellent adhesiveness. Thereby, the basic performance of the sheet-like reinforcing material can be further improved. In addition, in the states of (1), (2) and (3) in FIG. 3, since the curability of the adhesive layer is also preserved until the light-shielding layer is peeled off, the adhesive layer is removed after the light-shielding layer is peeled off. It is possible to sufficiently exert the curing action having the same. In this case, in order to make the adhesiveness of the sheet-like reinforcing material sufficient, it is preferable that the setting of the photocurable molding material layer be faster than the curing of the adhesive layer.

In FIG. 4A, FIG. 2D and FIG.
The same state as (5) is shown, and in this case, the substrate
A sheet-like reinforcing material is adhered to the corners of. FIG.
In (2), a sheet-like reinforcing material is bonded to a substrate having a curved surface
Have been. 4 (1) and (2) above
The sheet-like reinforcing material of the present invention is adhered to the substrate by the adhesive layer.
The present invention
In the sheet-like reinforcing material of
Can be easily constructed. Ma
In addition, the workability is excellent, and the adhesive layer
Because it has excellent adhesion to substrates with complicated shapes,
Adhesion failure is sufficiently suppressed and adhesive strength and durability are excellent.
Will be.

[0107]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. “Parts” means “parts by weight”, and “%”
Indicates "% by weight".

Synthesis Example 1 Reactor equipped with thermometer, nitrogen gas inlet tube and stirrer
In a four-necked flask as
498 parts of phthalic acid and polyhydric alcohol
418 parts of propylene glycol and dipropylene glyco
After charging 670 parts, the inside of the flask is replaced with nitrogen gas.
did. Then, while stirring the mixture, the maximum temperature was set at 21.
The mixture was heated to 5 ° C. to perform a dehydration reaction. This
When the acid value reaches 10, the temperature is lowered to 50 ° C,
Further, 686 of maleic anhydride as an unsaturated dibasic acid was added.
Heat the parts so that the maximum temperature is 215 ° C, and remove
By continuing the water reaction, an unsaturated polyester having an acid value of 28 was obtained.
Was. And 60 parts of this unsaturated polyester, vinyl
40 parts of styrene as a nomer, and as a stabilizer
By mixing 0.02 parts of hydroquinone,
A polyester resin A was obtained.

Synthesis Example 2 462 parts of hexahydrophthalic anhydride as a saturated dibasic acid was placed in a four-necked flask as a reactor equipped with a thermometer, a nitrogen gas inlet tube, a reflux condenser, and a stirrer. Propylene glycol 41 as polyhydric alcohol
After charging 8 parts and 520 parts of neopentyl glycol, the inside of the flask was purged with nitrogen gas. Next, the mixture was heated to a maximum temperature of 215 ° C. with stirring to perform a dehydration reaction. Thus, when the acid value reached 8, the temperature was lowered to 50 ° C. Further, 686 parts of maleic anhydride as an unsaturated dibasic acid was charged, and the maximum temperature was 2
The mixture was heated to 15 ° C., and the dehydration reaction was continued to obtain an unsaturated polyester having an acid value of 28. Then, 60 parts of the unsaturated polyester, 40 parts of styrene as a vinyl monomer, and 0.02 parts of hydroquinone as a stabilizer were used.
By mixing the parts, an unsaturated polyester resin B was obtained.

Example 1 After stirring the following (1) to (10) with a disper for 10 minutes, the water content of all the compounds was measured.
Since it was 055%, 0.375 parts of pure water was added to adjust to 0.2%, and the mixture was further stirred for 5 minutes to obtain a resin mixed solution before thickening. This solution is 1.9 Pa · s (25
° C). (1) 90 parts of unsaturated polyester resin A (2) 15 parts of styrene monomer (3) Thickening regulator: 2 parts of pentadodecyl succinic acid (4) 40 parts of frit JH-1922 (frit having an average particle size of 100 μm) (5) Filler: 25 parts of aluminum hydroxide B-308 (6) Filler: 50 parts of aluminum hydroxide B-325 (7) Filler: 35 parts of aluminum hydroxide B-30-S (8) Photoinitiator: Irgacure 1700 0.5 part (9) Photoinitiator: Darocure 1173 1.5 parts (10) Polymerization inhibitor: Parapenzoquinone 0.03 part (11) Thickener: Magmicron MD-502 1.4 parts Frit JH -1922 is manufactured by Nippon Frit Co., Ltd. under the trade name of aluminum hydroxide B-308, aluminum hydroxide B-325 and aluminum hydroxide B-
0-S is a product name of Alcoa Chemical Co., Ltd.,
Irgacure 1700 and Darocur 1173
Both are manufactured by Ciba Specialty Chemicals under the trade name, and Magmicron MD-502 is manufactured by Okunikoseigaku under the trade name.

Next, the thickener of (11) was added to the resin mixed solution, and the mixture was stirred for 5 minutes to prepare a resin mixed solution.
A double-sided adhesive tape unwinder, a film transfer device equipped with a knife coater, and a sheet-like reinforcing material manufacturing device equipped with a heating and aging furnace, an acrylic adhesive, a rayon nonwoven fabric, an acrylic adhesive as a carrier film having a width of 500 mm,
Then, a double-sided pressure-sensitive adhesive tape obtained by combining a paper separator as a release layer in this order was set such that the release layer was on the lower side. The carrier film was moved, and the above resin mixed solution was uniformly applied thereon with a knife coater in a width of 400 mm.
30N-572-AN (trade name, manufactured by Nitto Boshoku Co., Ltd.) was cut into 1-inch pieces by an automatic cutter and sprayed so as to have a weight of 12% by weight. A glass using a resin mixed solution as a reinforcing fiber using a Teflon grooved roll having a diameter of 150 mm from above while supplying a glass nonwoven fabric FPL-4025 (trade name, manufactured by Japan Vilene Co., Ltd.) onto the laminate. The fiber is impregnated and defoamed, and transferred while forming a photocurable molding material layer. Next, a nylon film as a protective layer is supplied while being pressed onto the laminate with a roll having a diameter of 200 mm to supply the nylon film. The light-curable molding material layer was sealed and exposed to a predetermined thickness, and was led to a heating and aging furnace in the next step as a sheet. After aging for 20 minutes while transferring the sheet in a heating aging furnace maintained at 80 ° C., it is rapidly cooled to 35 ° C. or less with cold air, and an aluminum vapor-deposited polyester film as a light-shielding layer is supplied on the protective layer. Then, it was wound around a paper tube with the release paper of the double-sided pressure-sensitive adhesive tape facing outward while being attached to the protective layer. The paper tube was further hermetically sealed and packaged with an aluminum-evaporated polyester film to obtain a sheet-like reinforcing material (light-cured prepreg FRP sheet) of the present invention. In addition, the viscosity at 40 degreeC which aged the resin mixed solution used for this sheet-shaped reinforcement under the same conditions was 380 Pa * s.

The obtained light-cured prepreg FRP sheet was used as a substrate in a place where sunlight was well exposed, with a radius of curvature of 1
Using a bent tube (made of a cold-rolled steel plate having a thickness of 1 mm) having a diameter of 000 mm and a tube diameter of 200 mm, one ply was adhered to the entire periphery of the bent tube with a width of 150 mm. In addition, the base material had sufficiently removed dirt, oil, wax and the like in advance.
Processing is a processing step of taking out the photocurable prepreg FRP sheet from the packaging material and cutting it into the size required for bonding
An adhesive process in which the release paper is peeled off and closely adhered to the substrate,
A curing process in which the light-shielding film is peeled off and cured with sunlight, and an auxiliary curing process in which the sunlight-deficient portion (shaded portion) is cured with a handy type ultraviolet irradiation device (Handicure 800: manufactured by Ushio Inc.) It took 70 minutes to work. The actual irradiation time was 30 minutes, the work was completed by removing the protective layer after curing, and the total work time was 80 minutes. FIG. 5 shows the cylinder after applying the photocurable prepreg FRP sheet. The cured product of the sheet-shaped reinforcing material was colored to a value equivalent to Munsell N7.5. Workability (workability) and adhesiveness in this construction were evaluated according to the following criteria.

[0113]Workability  ◎: Photo-cured prepreg FRP sheet maintains sufficient flexibility
In other words, the work is easy because the bonding work is also easy.
I was able to. ○: Curing of the photocurable prepreg FRP sheet has started.
The flexibility is impaired, but the bonding work is easy
I was able to work. Δ: The photocurable prepreg FRP sheet has sufficient flexibility.
But the work is not easy because the bonding work is not easy
It was not easy. ×: Curing of the photocurable prepreg FRP sheet started.
Flexibility is impaired and bonding is not easy.
Business was difficult.

[0114]Adhesiveness  ：: The photocurable prepreg FRP sheet is cured against the substrate after curing.
And the adhesive layer is fully cured as a whole,
It was hard to peel off and slipped. ：: The photo-cured prepreg FRP sheet is hardened against the substrate after curing.
And adhered enough, the adhesive layer partially cured and peeled off
It was difficult but slightly easy to shift. Δ: The photo-cured prepreg FRP sheet is opposed to the substrate after curing.
The adhesive layer did not cure, but slightly peeled off.
It was easy to come off and slip off. ×: The photo-cured prepreg FRP sheet is cured against the substrate
But the adhesion was not uniform enough and peeled off
It was easy to shift.

Example 2 Unsaturated polyester resin B in place of unsaturated polyester resin A in Example 1, frit EH1040 in place of frit JH-1922, aluminum hydroxide B-30-S
75 parts instead of 35 parts. After stirring with a disper for 10 minutes in the same manner as in Example 1, the water content of all the compounds was measured and found to be 0.07%.
0.39 parts of pure water was added to adjust to 2%, and the mixture was further stirred for 5 minutes to obtain a resin mixed solution before thickening. This solution is
It was 2.5 Pa · s (25 ° C.). Others are the same,
A sheet-like reinforcing material (light-cured prepreg sheet) of the present invention was obtained. The viscosity at 40 ° C. when the resin mixed solution used for the sheet-like reinforcing material was aged under the same conditions was 650 Pa · s.
Met. Processing, adhesion, curing, and auxiliary curing were performed in the same manner as in Example 1. The evaluation was the same as in Example 1. In addition,
The cured product of the sheet-like reinforcing material is Munsell 6.25PB5
It was colored to a color equivalent to / 10, and was found to be "extremely flame-retardant" as a result of a railway vehicle material combustion test by the Japan Railway Rolling Stock Machine Technology Association.

Example 3 A sheet of the present invention was prepared in the same manner as in Example 1 except that a nylon film having a black pigment dispersed therein to impart light-shielding properties was used instead of the double-sided pressure-sensitive adhesive tape used as the carrier film in Example 1. A reinforcing material (light-cured prepreg sheet) was obtained. This sheet-like reinforcing material was subjected to adhesive curing treatment in the same manner as in Example 1. The substrate was subjected to a primer treatment step after sufficiently removing dirt, oil, wax, and the like in advance at the portion where the photocurable prepreg FRP sheet was bonded. A primer (Mighty Grip-9036, trade name, manufactured by E-Tech Co.) was applied in an amount of 300 g / m ² and dried sufficiently. The evaluation was the same as in Example 1.

Comparative Example 1 Except for frit JH1922 of Example 1, 75 parts were used instead of 35 parts of aluminum hydroxide B-30-S. After stirring with a disper for 10 minutes in the same manner as in Example 1,
The water content of all compounds was measured to be 0.062
% Pure water to adjust to 0.2%.
And stirred for 5 minutes to obtain a resin mixed solution before thickening. This solution had a pressure of 1.9 Pa · s (25 ° C.).
Other than that obtained the comparative photocurable prepreg FRP sheet similarly. In addition, the viscosity at 40 degreeC which aged the resin mixed solution used for the obtained photocurable prepreg FRP sheet on the same conditions was 423 Pa * s. Processing, adhesion, curing, and auxiliary curing were performed in the same manner as in Example 1. The working time required for curing was 50 minutes. After curing, the protective layer was removed, sanding was performed entirely with # 240 sandpaper, and a topcoat HiArt # 4000 (trade name, manufactured by Isamu Paint Co., Ltd.) toned to Munsell N7.5 was applied. It took 15 hours at 20 ° C. to cure the coating film by natural standing. The construction time until the completion of the painting operation was 3 hours.

Comparative Example 2 Munsell N instead of frit EH1040 of Example 2
A sheet-like reinforcing material was obtained in the same manner as in Example 2, except that 10 parts of a toner toned to a color equivalent to 7.5 was used.
In order to process, adhere, and cure in the same manner as in Example 1, irradiation was performed for 3 hours using a hand-held ultraviolet irradiation apparatus, but the sheet portion on the adhesive layer side remained uncured.

Comparative Example 3 Munsell N instead of frit EH1040 of Example 2
A sheet-like reinforcing material was obtained in the same manner as in Example 2, except that 7 parts of a toner toned to 6.25 PB 5/10 was used. In order to process, adhere and cure in the same manner as in Example 1, irradiation was performed for 3 hours using a handy type ultraviolet irradiation apparatus, but the sheet portion on the adhesive layer side remained uncured.

Comparative Example 4 Frit EH was used in place of frit EH1040 of Example 2.
A sheet-like reinforcing material was obtained in the same manner as in Example 2 except that 1088 was used. In order to process, adhere and cure in the same manner as in Example 1, curing was performed by irradiating for 3 hours using a handy type ultraviolet irradiation apparatus, but the adhesive layer portion was not cured and did not exhibit sufficient adhesive strength. Examples 1 and 2 and Comparative Examples 1 and 2
Table 2 shows the evaluation results.

[0121]

[Table 2]

In Example 1, the sheet-like reinforcing material of the present invention has a small number of construction steps and a short working time.
Because of its excellent workability, it can stably adhere to the base material and sufficiently suppress poor adhesion. Moreover, since it has a light gray color, it has the advantage that post-painting can be omitted. From the confirmation, it was found that it could be used for various uses in various base materials.

Since the sheet-like reinforcing material of the present invention has the above-mentioned structure, it is excellent in workability, and adhesion failure to various substrates is sufficiently suppressed to improve the adhesive strength and durability. Can be sufficiently cured, and since the photocurable molding material layer itself is colored, it can be used in various structures, machinery, automobiles, ships, household goods, etc. It is a material that can be used for members, piping, lining materials, etc., and can respond to various uses.

[Brief description of the drawings]

FIG. 1 is a graph showing an example of measuring the light transmittance of a frit.

FIG. 2 is a schematic cross-sectional view of an embodiment showing a state in which the sheet-like reinforcing material of the present invention adheres to a substrate and is cured.

FIG. 3 is a schematic cross-sectional view of one embodiment showing a state in which the sheet-like reinforcing material of the present invention adheres to a substrate and is cured.

FIG. 4 is a schematic cross-sectional view of one embodiment showing a state in which the sheet-like reinforcing material of the present invention is adhered to a substrate having an end portion or a curved surface of the substrate.

FIG. 5 is a schematic diagram showing a state after a photocurable prepreg FRP sheet has been applied to the cylindrical steel plate used in the examples.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Protective layer 2 Photocurable molding material layer 3 Adhesive layer 4 Release layer 5 Base material 6 Joining part 7 Light shielding layer 8 Center line

Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat II (Reference) C08L 101: 00 C08L 101: 00 (72) Inventor Sadami Tao 5-8 Nishiomiboricho, Suita-shi, Osaka Japan Inside the catalyst (72) Inventor Yukio Ozaki 5-8, Nishiobari-cho, Suita-shi, Osaka F-term (reference) 4F072 AA02 AA05 AA07 AB09 AD38 AE23 AE25 AF06 AG03 AJ16 AJ22 AK05 4F100 AG00A AG00H AK01A AK01B AR00B AR00C BA03 BA07 BA10A BA10C CA23A DE01A DE01H DG01A DG01H EJ91C GB07 GB31 GB32. FA10 GA01 4J040 DC092 DF041 DF051 EB052 ED002 ED111 EG022 FA061 FA101 FA131 FA261 FA271 HA026 HA066 HA346 HA366 JA09 JB08 JB09 KA03 KA04 KA42 LA03

Claims (4)

[Claims] 1. A sheet-shaped reinforcing material having a photocurable resin material, a filler, and a photocurable molding material layer having a reinforcing fiber as an essential component, wherein the filler is a melt-molded product. The average light transmittance at a wavelength of 400 to 500 nm is 15
A sheet-like reinforcing material comprising a transparent filler of up to 90%. 2. The transparent filler has an average particle size of 1 to 10.
2. The sheet-like reinforcing material according to claim 1, wherein the sheet-like reinforcing material is a frit and / or glass particles having a size of 00 μm and is used in an amount of 1 to 150 parts by weight based on 100 parts by weight of the photocurable resin. 3. The sheet-like reinforcing material according to claim 1, wherein the sheet-like reinforcing material includes an adhesive layer and a release layer on one side from the inside in this order. 4. The sheet-like reinforcing material according to claim 3, wherein the adhesive layer is photocurable.