JP2001240815A - Method of producing double-layered material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which a double-layered material excellent in workability, sufficiently suppressed in an adhesive failure to various kind of base materials and moreover providing a cured material having sufficient basic performances can simply be produced while applying to various uses. SOLUTION: This method for producing the double-layered material is a method for producing the double-layered material comprising a curable molding material layer obtained by including a curable resin, a reinforcing fiber and a photosensitizer and a pressure sensitive adhesive layer and comprises a forming process of curable molding material layer forming the curable molding material layer and a laminating process of pressure sensitive adhesive layer laminating the pressure sensitive adhesive layer and the laminating process of pressure sensitive adhesive layer is carried out in different process after the forming process of curable molding material layer is finished.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a multilayer material.

[0002]

2. Description of the Related Art A multilayer material containing a curable molding material layer has flexibility before curing, so that it can be processed into an arbitrary size or shape, or the processed material is applied to a base material. Can be easily done, and
After curing, excellent mechanical equivalent to fiber reinforced plastic,
It has basic performance such as chemical and electrical characteristics.

[0003] A multilayer material containing such a curable molding material layer is easy to process and work, and can secure a sufficient working time. In addition, metal, plastic, rubber, glass, ceramics, As long as it has sufficient adhesiveness corresponding to various surface conditions and complicated shapes of various base materials such as stone and wood, and the occurrence of problems due to poor adhesion to the base material is sufficiently suppressed. That can be used in various applications as structural members, pipes, lining materials, etc. in various types of buildings, machinery, automobiles, ships, household goods, etc., and reinforcing materials for reinforcing or repairing them Becomes

JP-A-59-1250 discloses that a curable molding material layer obtained by impregnating a reinforcing fiber with a mixture of an unsaturated polyester resin and a photosensitizer is sealed with a release film that does not allow styrene to pass through. It is disclosed that, by slightly swelling a curable prepreg manufactured by aging after aging with a primer, poor adhesion of the prepreg to a steel sheet can be suppressed to some extent.

JP-A-63-186744 discloses a polyester having a release film on the outside on a curable molding material layer obtained by impregnating reinforcing fibers with a mixture of a vinyl ester resin and a photosensitizer. It is disclosed that a photocurable prepreg produced by aging after a film is placed thereon has a cured sheet having a smooth surface due to a transparent sheet.

Japanese Patent Application Laid-Open No. 57-99375 discloses that a reinforcing fiber is sandwiched between resin-adhered films in which a mixture of an epoxy vinyl ester resin and a photosensitizer is adhered to upper and lower two-layer release films. The curable molding material layer produced by aging the impregnated curable molding material layer is turned into a thin steel sheet using a photocurable epoxy vinyl ester resin containing a specific dibasic acid or oligoester in the resin skeleton. It is disclosed that the bonding strength of the curable molding material layer to a thin steel plate can be improved to some extent by bonding.

[0007] These prepregs can improve the adhesive strength to a specific substrate to some extent.
However, depending on the base material, sufficient adhesiveness is not ensured, or the prepreg and the primer harden during application, so that the application time is restricted and the prepreg cannot be sufficiently adhered to the substrate. Also, there is a possibility that the adhesion failure cannot be sufficiently suppressed. In addition, since it is necessary to perform the construction using a primer, the work in the construction is complicated. Furthermore, even in their production, they cannot be easily produced so as to be suitable for various uses.

That is, in the application of a curable molding material,
It is necessary to deal with the ease of handling of the material, the shortening of the working time, the surface condition of the base material, the shape, etc.However, in order to develop sufficient adhesive strength, before applying the curable molding material, In addition, there is a need for a step of performing a pre-treatment such as a primer treatment which requires a coating technique, and there is a problem of easy handling and work time. In addition, there is a problem that it is necessary to change the step of performing the pretreatment according to the base material on which the curable molding material is to be applied, or that the application cannot be performed in some cases. On the other hand, in the production of a curable molding material, if it can be produced so as to be compatible with the base material and application in which it is used,
Adhesion failure can be sufficiently suppressed, and a curable molding material can be supplied in accordance with required basic performance and the like.

[0009]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above situation, has excellent workability, sufficiently suppresses poor adhesion to various base materials, and has a sufficient basic property for a cured product. It is an object of the present invention to provide a method capable of easily producing a multilayer material having performance and adapting it to various uses.

[0010]

The present invention provides a curable resin,
A method for producing a multilayer material including a curable molding material layer containing a reinforcing fiber and a photosensitizer, and a pressure-sensitive adhesive layer, the curable molding material layer forming the curable molding material layer Forming a pressure-sensitive adhesive layer laminating step of laminating the pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer laminating step is performed in a separate step after the curable molding material layer forming step is completed. This is a method for producing a multilayer material.

The inventors of the present invention have scrutinized the problems of the method for producing a multi-layered material, and have conducted extensive studies. As a result, the method for producing a multi-layered material described above is complicated. A multilayer material that can easily form a cured layer having high adhesive strength and excellent durability on various substrates without applying a primer treatment or the like can be easily manufactured for each application. We have encountered the fact that dramatic effects occur and arrived at the present invention. Hereinafter, the present invention will be described in detail.

The method for producing a multilayer material of the present invention is a method for producing a multilayer material including a curable molding material layer and a pressure-sensitive adhesive layer. Each layer constituting the multilayer material is in the form of a film or a sheet. The curable molding material layer contains a curable resin, a reinforcing fiber, and a photosensitizer. It is preferable that the composition further contains a filler. Such a curable molding material layer may be formed by laminating different molding materials.

The curable resin is not particularly limited as long as it can be used as a molding material. For example, unsaturated polyester resin, vinyl ester resin (epoxy acrylate resin), (meth) acryl syrup, diallyl phthalate Radical polymerizable resins such as resins;
Epoxy resins, urea resins, melamine resins, acrylic urethane resins, polyurethanes, polybutadienes and the like can be mentioned. These may be used alone or in combination of two or more. Among these, a photocurable resin such as a radical polymerization type resin is preferable. More preferably, it is an unsaturated polyester resin because the workability and workability of the multilayer material are improved and the cured product has sufficient basic performance.

The unsaturated polyester resin is not particularly limited. For example, a polymer having a weight average molecular weight (Mw) of several hundreds to several tens of thousands obtained by condensing an acid component and an alcohol component is converted into a vinyl monomer. Examples thereof include a radical polymerization type resin obtained by dissolution. The acid component is not particularly restricted but includes, for example, unsaturated dibasic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, mesaconic acid, citraconic acid, citraconic anhydride; phthalic acid, anhydride Phthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, succinic acid, adipic acid, sebacic acid, heptic acid, methyltetrahydrophthalic anhydride, endomethylenetetrahydro Saturated dibasic acids such as phthalic anhydride; and trifunctional or higher polybasic acids such as trimellitic acid, trimellitic anhydride, pyromellitic acid, and pyromellitic dianhydride. 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 vinyl monomer is not particularly limited as long as it is a reactive monomer and can undergo a crosslinking reaction with the unsaturated group of the polymer at the time of curing. For example, styrene, α-methylstyrene, vinyltoluene, 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 unsaturated monocarboxylic acids thereof Monoesters of 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,
Polyfunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and 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.

The types and amounts of the acid component, alcohol component and vinyl monomer in the unsaturated polyester resin are not particularly limited, and may be appropriately set according to, for example, the basic performance required for the cured product. It is preferable that 5 to 100% by weight of the acid component is 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. The polymer is, for example, a diene compound such as dicyclopentadiene,
It may be modified with various components such as a rubber component such as a terminal functional butadiene-acrylonitrile copolymer.

The vinyl ester resin is not particularly limited. For example, a radical polymerization type resin obtained by dissolving a reaction product obtained by addition-polymerizing a vinyl-based unsaturated carboxylic acid at the terminal of an epoxy resin into the vinyl monomer is used. Resins. 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, and examples thereof include acrylic acid and methacrylic acid. The vinyl monomer is not particularly limited, and examples thereof include the same ones as described above.
These may be used alone or in combination of two or more.

The type and amount of the epoxy resin, vinyl unsaturated carboxylic acid and vinyl monomer in the vinyl ester resin are not particularly limited, and may be appropriately set according to the basic performance required for the cured product. I just need. The method of addition polymerization of the epoxy resin and the vinyl-based unsaturated carboxylic acid is not particularly limited. 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 above (meth) acrylic syrup is not particularly limited, and is, for example, a mixture containing a monomer (meth) acrylate and a polymer of (meth) acrylate, and if necessary, And a radical polymerization type resin further containing a crosslinking agent and the above-mentioned vinyl monomer.

The above (meth) acrylate 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 is preferable because the basic performance, appearance, safety, and the like of the cured material layer of the multilayer material can be further improved. .

The polymer of the above (meth) acrylic ester can be obtained by polymerizing a polymer containing a (meth) acrylic ester or, if necessary, a vinyl monomer as a monomer component. The polymerization degree of the (meth) acrylic acid ester polymer is not particularly limited.

The crosslinking agent is not particularly restricted but includes, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol. Multifunctional (meth) acrylates such as di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and 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.

The type and amount of the (meth) acrylic acid ester, the polymer of the (meth) acrylic acid ester, the crosslinking agent, and the vinyl monomer used if necessary in the (meth) acrylic syrup are not particularly limited. Instead, it may be appropriately set according to the basic performance and the like required for the cured product.

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

The reinforcing fibers in the curable molding material layer are not particularly limited, and include, for example, inorganic fibers such as glass fibers, carbon fibers, metal fibers, and fibers made of ceramics;
Organic fibers composed of aramid, polyester, vinylon, phenol, Teflon and the like; natural fibers and the like. The form of these fibers is not particularly limited, and may be, for example, a cloth (woven); chopped strand mat,
Mats such as preformable mats, continuous strand mats, and facing mats; chops; rovings; and nonwovens. These may be used alone or in combination of two or more. Of these, glass fibers are preferred.

The photosensitizer in the curable molding material layer is not particularly limited, and may be, for example, “surface”, 27 [7].
(1989) Yamaoka, p. 548, and “Visible light polymerization initiators having photosensitivity in the visible light region” described in Sato, IBP18, and the like in “Third Polymer Material Forum Abstracts” (1994). The photosensitizer may be used alone,
Two or more kinds may be used in combination. Note that the photosensitizer is sometimes called a photocuring agent, and in this specification, the terms “photosensitizer” and “photocuring agent” are used in a unified manner. The visible light polymerization 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, dimethoxyacetophenone,
Dimethoxyphenylacetophenone, diethoxyacetophenone, benzyldimethylketone, benzophenone,
Carbonyl compounds such as trimethylbenzoyldiphenylphosphine oxide; compounds having a sulfur atom such as diphenylsulfide, diphenyldisulfide, diphenylsulfide, dithiocarbamate and methylthioxanthone; halides of polycondensed ring hydrocarbons such as α-chloromethylnaphthalene Dyes such as acrylic flavin and fluorescein; metal salts such as uranyl nitrate, iron chloride, and silver chloride; onium salts such as p-methoxybenzenediazonium, hexafluorophosphate, diphenyliodonium, and triphenylsulfonium; Pentadienyltitanium-di (pentafluorophenyl); Also, organic peroxide / dye system, diphenyliodonium salt / dye, imidazole /
Keto compound, hexaarylbiimidazole compound / hydrogen donating compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye,
Known composite initiator systems such as hexaarylbiimidazole / radical generators described in JP-A-37377 are also included.

As the above-mentioned photosensitizer, those having photosensitivity from the ultraviolet light region to the visible light region can also be used. Examples of such a photosensitizer include bis (2,
6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -methylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, 2,6 -Dimethoxybenzoyl-
Examples include acyl phosphine oxide compounds such as diphenyl phosphine oxide. These can use a commercial item, for example, Darocur1173
(Product name, Ciba Specialty Chemicals,
2-hydroxy-2-methyl-1-phenylpropane-
1-one) and bis (2,6-dimethoxybenzoyl)-
75% of 2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals)
Irgacure 170 mixed at a ratio of / 25 (weight ratio)
0 (trade name, manufactured by Ciba Specialty Chemicals); Irgacure 184 (trade name, manufactured by Ciba Specialty Chemicals, 1-hydroxy-cyclohexyl-phenyl ketone) and bis (2,6-dimethoxybenzoyl)- Irgacure 1800 (trade name, Ciba Specialty Chemicals) mixed with 2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals) at a ratio of 75/25 (weight ratio)
Irgacure 1850 (trade name, manufactured by Ciba Specialty Chemicals); Irgacure 819 (trade name, manufactured by Ciba Specialty Chemicals, manufactured by Ciba Chemicals Co., Ltd.) 2,4,6-trimethylbenzoyl) -phenylphosphine oxide); Lucirin TPO (trade name, manufactured by BASF, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide); Darocur
1173 (trade name, manufactured by Ciba Specialty Chemicals, 2-hydroxy-2-methyl-1-phenylpropan-1-one) and Lucirin TPO were mixed with 50.
Darocur 42 mixed at a ratio of / 50 (weight ratio)
65 (trade name, manufactured by Ciba Specialty Chemicals) can be used.

The curable molding material layer may contain, for example, a curing agent or the like in order to have thermosetting properties. It has curability. The curing agent is not particularly limited, for example, benzoyl peroxide,
Lauroyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy octoate, t-butyl peroxy benzoate, cumene hydroperoxide, cyclohexanone peroxide, dicumyl peroxide, Organic peroxides such as bis (4-t-butylcyclohexyl) peroxydicarbonate and 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; 2,2'-azobisiso Examples include radical polymerization initiators such as azo compounds such as butyronitrile and 2-phenylazo-2,4-dimethyl-4-methoxyvaleronitrile.

The filler is not particularly restricted but includes, for example, aluminum hydroxide, calcium carbonate, calcium sulfate, barium sulfate, alumina, clay, talc, glass powder, milled fiber, cristobalite, silica (silica sand), river sand, diatomaceous earth. And inorganic fillers such as mica powder, gypsum and glass powder; and organic fillers. 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 performance such as mechanical properties of the multilayer material is improved. In addition, cristobalite, silica, river sand and the like are preferable for wear resistance. Thus, it is preferable to select these depending on the application in which the multilayer material is used.

The curable molding material layer may further contain other additives, if necessary. The other additives are not particularly limited, for example, a thickener, a low-shrinking agent, an internal release agent, a coloring agent, a chain transfer agent, a polymerization inhibitor,
Examples include an ultraviolet absorber, a viscosity reducing agent, a coupling agent, and an antibacterial agent. These may be used alone or in combination of two or more. When the curable molding material layer is a photocurable one, it is preferable to appropriately set the type and amount of other additives so as not to impair the photocurability.

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 above-mentioned low-shrinking 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 colorant is not particularly restricted but includes, for example, inorganic pigments, organic pigments and toners which can be used in the curable resin. The polymerization inhibitor is not particularly limited and includes, for example, pt-butylcatechol, p-methoxyphenol, hydroquinone, p-
Examples include benzoquinone, chloranil, m-dinitrobenzene, nitrobenzene, p-phenyldiamine, sulfur, diphenylpicrylhydrazyl, di-p-fluorophenylamine, tri-p-nitrophenylmethyl and the like.

The ultraviolet absorber is not particularly limited, and for example, those which can be used for a benzophenone-based or benzotriazole-based curable resin can be used. The viscosity reducing agent, the coupling agent, and the antibacterial agent are not particularly limited, and for example, those that can be used for a curable resin can be used.

The curable molding material layer in the multilayer material has plasticity and flexibility before curing so that the multilayer material can be sufficiently processed and applied, and has sufficient flexural strength and flexural modulus after curing. It has sufficient basic performance such as weather resistance, water resistance, abrasion resistance, and high electrical properties depending on the type of resin and filler. The curable molding material layer preferably has no surface stickiness that hinders processing and construction work, and preferably has rapid curability.

Examples of the pressure-sensitive adhesive layer in the multilayer material include a film formed of only an adhesive (without a support); a film formed of a support having an adhesive layer, and the like. Further, these may be laminated. The pressure-sensitive adhesive layer is formed of a pressure-sensitive adhesive.

The above-mentioned pressure-sensitive adhesive is not particularly restricted but includes, for example, rubber-based pressure-sensitive adhesives mainly composed of synthetic rubber such as styrene-butadiene rubber, isobutylene rubber, isoprene rubber, butyl rubber and natural rubber; acrylic resin, polyvinyl alcohol, Polyacrylamide, polyvinyl methyl ether, styrene-isoprene block copolymer, styrene-butadiene block copolymer, styrene-ethylene-butylene block copolymer, synthetic resin-based adhesive containing ethylene-vinyl acetate, etc. as a main component No. These may be any of a solvent type, an emulsion type, a hot melt type, a water soluble type and the like, or may be used alone.
Two or more kinds may be used in combination. 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 a 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 support is not particularly limited as long as it has strength and flexibility which do not impair the workability of the multilayer material and durability against the monomers and solvents contained in the curable molding material. Examples thereof include films, woven fabrics, nonwoven fabrics, and foams formed of paper and resin materials, and may be those subjected to press working, embossing, or the like.

The paper is not particularly limited.
Examples include those formed of natural fibers, synthetic fibers, inorganic fibers, and the like, and may be surface-treated by silicon treatment or the like. The resin material is not particularly limited and includes, for example, polyethylene, polypropylene, polybutene, polystyrene, polyolefins such as ethylene-α-olefin copolymer; polyethylene terephthalate, polyesters such as polybutylene terephthalate; tetrafluoroethylene, polyvinylidene fluoride, Fluororesins such as polymonochlorotrifluoroethylene; polybutadiene, polycarbonate, polyacetal, polyamide, polyphenylene ether, polyphenylene sulfide, polyether sulfone, polyurethane, polyimide, polyether ether ketone, polymethylpentene, ionomer resin, polyvinyl butyral, polyvinyl alcohol , Cellulose diacetate, polyvinyl chloride, polyvinylidene chloride, polyvinyl chloride Body, ethylene - vinyl acetate copolymer, ethylene - (meth) acrylic acid copolymer, ethylene - (meth) acrylic acid ester copolymer and the like. These may be used alone or in combination of two or more.

The pressure-sensitive adhesive layer has sufficient adhesiveness to a substrate on which a multilayer material is used, and also has flexibility so that the multilayer material can be sufficiently applied. By the pressure-sensitive adhesive layer, the multilayer material has adhesion to the substrate, and after the adhesion, the curable molding material layer and the pressure-sensitive adhesive layer have shape retention. Further, due to the strength of the pressure-sensitive adhesive itself, the adhesion to the curable molding material layer after curing, and the adhesion to the substrate, excellent adhesive strength is obtained.

It is preferable that the pressure-sensitive adhesive layer has curability, since its performance is excellent. The method for imparting curability to the pressure-sensitive adhesive layer is not particularly limited. For example, it is preferable that the pressure-sensitive adhesive be photocurable by including a curable resin or a photosensitizer. In this case, since the strength of the pressure-sensitive adhesive layer is improved, as the vinyl monomer contained in the curable resin,
It is preferably a polyfunctional (meth) acrylate. In addition, even if vinyl monomers such as styrene contained in the curable molding material layer migrate to the pressure-sensitive adhesive layer, the vinyl monomer contributes to the curing of the pressure-sensitive adhesive layer and sufficiently cures the pressure-sensitive adhesive layer. Will be able to do that.

The multilayer material preferably includes a light-shielding layer and a release layer in addition to the curable molding material layer and the pressure-sensitive adhesive layer. In the multilayer material, having a light-shielding layer on one side,
By having the pressure-sensitive adhesive layer and the release layer in this order on the other side, in order to shield the curable molding material layer from light, it has a light-shielding layer on one side and adheres the curable molding material layer to the substrate. Therefore, it has an adhesive layer on the other side, and has a release layer on one side outside the adhesive layer to protect the adhesive layer until the multilayer material is processed or applied.

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, as a film obtained by vapor-depositing a light-shielding material on such a paper or resin material, 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, and a film coated with a light-shielding material is used. Examples of the light-shielding material include a film in which a pigment or the like is dispersed or a film in which an ink film is formed on one or both sides, and examples of the film in which the light-shielding material is dispersed include a film in which a pigment or the like is dispersed as a light-shielding material.

The pigment is not particularly limited as long as it can impart light-shielding properties to the film. Examples thereof 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 fibers; These may be used alone or in combination of two or more. The paper or film is not particularly limited, and includes, for example, the same ones as described above.

The light-shielding layer is formed of a curable molding material so that the workability and workability of the multilayer material are not impaired by the curing of the curable molding material layer during processing and construction of the multilayer material. It has the function of shielding the layer from light (light-shielding property), and has the flexibility to sufficiently process and construct a multilayer material.

The release layer in the multilayer material is not particularly limited, and is, for example, paper or a film formed of the above-described resin material such as polyethylene or polypropylene; a film formed of a metal material such as an aluminum foil. And the like, which are treated with a release agent.

The release agent is not particularly restricted but includes, for example, those containing as a main component a release resin such as a silicone resin, a fluororesin or a polyethylene wax. These may be used alone or in combination of two or more. The release layer protects the pressure-sensitive adhesive layer while the multilayer material is processed, and can release the pressure-sensitive adhesive layer and the release layer while maintaining the pressure-sensitive adhesive layer's tackiness. (Releasability), and has the flexibility to allow the multilayer material to be sufficiently applied.

The pressure-sensitive adhesive layer and the release layer are formed by shielding both sides of the curable molding material layer with the light-shielding layer.
Since the workability, workability, adhesiveness, and the like of the multilayer material can be improved and adhesion failure can be sufficiently suppressed, it is preferable that the material has a light-shielding property. In this case, both the pressure-sensitive adhesive layer and the release layer may have a light-shielding property, or at least one of the pressure-sensitive adhesive layer and the release layer may have a light-shielding property.

The method for imparting light-shielding properties to the pressure-sensitive adhesive layer is not particularly limited. For example, it can be carried out by using an adhesive in which a pigment is dispersed or by using a support having light-shielding properties. 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.

In the above-mentioned multilayer material, the curable molding material layer and the pressure-sensitive adhesive layer are used as long as they do not hinder the curing of the multilayer material and do not hinder the adhesion of the multilayer material to the substrate. Alternatively, a film layer other than the light-shielding layer and the release layer may be included, and a light-transmitting film such as a transparent film may be provided between the light-shielding layer and the curable molding material layer.

The method for producing a multilayer material according to the present invention comprises: a step of forming a curable molding material layer for forming the curable molding material layer;
And a step of laminating the pressure-sensitive adhesive layer. The step of laminating the pressure-sensitive adhesive layer is performed in another step after the step of forming the curable molding material layer is completed.

The curable molding material layer forming step includes:
The process is not particularly limited as long as the process is capable of forming a curable molding material layer. For example, the above-described components including a curable resin, a reinforcing fiber, and a photosensitizer are mixed to form a resin mixed solution to form 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, it can be carried out by spraying or stacking reinforcing fibers on a carrier film and applying a resin mixed solution, followed by pressure bonding, impregnation or the like.

The pressure-sensitive adhesive layer laminating step is not particularly limited as long as the pressure-sensitive adhesive layer can be laminated. For example, the pressure-sensitive adhesive layer may be laminated or the pressure-sensitive adhesive layer may be laminated. It can be performed by coating. The method for producing a multilayer material preferably includes an aging step of aging and thickening the curable molding material layer.
Thereby, the multi-layered material becomes easy to handle, and there is no surface stickiness that hinders the work of processing and construction. Further, if necessary, the method may include a step of adjusting the shape of the multilayer material, a step of treating the curable molding material layer with light or heat, and adjusting the flexibility of the multilayer material.

The step of laminating the pressure-sensitive adhesive layer is performed in another step after the step of forming the curable molding material layer is completed. Thus, by being performed in a separate process,
The curable molding material layer forming step can be easily performed by a normal SMC manufacturing apparatus, and a pressure-sensitive adhesive layer is selected and laminated for each application on a sheet produced by the curable molding material layer forming step. Will be able to do it. Therefore,
A multi-layered material with excellent workability, sufficient adhesion to various substrates, and sufficient basic performance, can be efficiently used for various applications without increasing manufacturing costs. It will be possible to manufacture it.

The method of making the curable molding material layer forming step and the pressure-sensitive adhesive layer laminating step different from each other is not particularly limited. For example, after the curable molding material layer forming step is completed, It is preferable to temporarily store the produced sheet and then perform a pressure-sensitive adhesive layer laminating step. This allows the aging process during temporary storage,
The sheet having the curable molding material layer formed thereon can be easily handled in the pressure-sensitive adhesive layer laminating step.

[0059]

1 and 2 show an embodiment of the present invention. FIG. 1 is an example of a curable molding material layer forming step, and shows a state in which a curable molding material layer is produced by an SMC (sheet molding compound) manufacturing apparatus. In this manufacturing apparatus, between the carrier film supply device 1a and the sheet winding device 10a,
The carrier film 2a moves on the flat portion 14 at a constant speed. In the position (1), the resin mixed solution 3a is applied onto the carrier film 2a supplied from the carrier film supply device 1a using a knife coater 4a as an application device. In the position (2), the chopped reinforcing fibers are used. 7 is sprayed on the resin mixed solution on the carrier film 2a, and at a point (3), the resin mixed solution 3b is applied onto the carrier film 2b supplied from the carrier film supplying device 1b using a knife coater 4b as a coating device. The applied films are bonded and pressed together, and at the point (4), the reinforcing fibers are sufficiently impregnated with the resin mixed solution by applying pressure by the impregnation roll 9.

The carrier films 2a and 2b are not particularly limited, and include, for example, a film formed of paper or a resin material, a film formed of a metal material such as an aluminum foil, or the like. Evaporation material,
It may be a coated or dispersed film or a film treated with a release agent. Further, a laminate of these materials, or a product subjected to press working, embossing, or the like may be used.

The film formed of the above resin material may be, for example, a resin film mixed with a pigment, an additive or the like, and a calender film; an extruded film; a cast film;
It can be obtained as a film or the like by a T-die method or an inflation method. Further, it may be a stretched film such as a uniaxially stretched film or a biaxially stretched film.

As a film obtained by vapor-depositing, coating or dispersing a light-shielding material on the above-mentioned paper or resin material, for example, the vapor-deposited film can be obtained by vapor-depositing a metal such as aluminum on one or both sides of the film. The resulting film can be obtained by applying or printing a paint or ink in which a pigment is dispersed on one or both sides of the film. Further, the film treated with the release agent can be obtained by applying a release agent to one surface to which the curable molding material layer is applied. In these cases, the surface of the film may be subjected to a plasma treatment, a corona discharge treatment, a chemical treatment, or the like before the deposition, application, printing, or release agent treatment.

The method of preparing the resin mixed solution 3a to be supplied to the point (1) is not particularly limited. For example, the method can be performed by mixing the components in the resin mixed solution with a stirrer such as a disper. . In this case, the mixing order and mixing method of each component are not particularly limited as long as the curable molding material layer has the function.

The type and amount of each component in the resin mixed solution 3a are determined according to the combination thereof, the conditions for forming the curable molding material layer, or the basic performance required for the cured product and its use. It is not particularly limited as long as it is appropriately set according to the requirements. For example, the amount of the photosensitizer used is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the curable resin. If the amount is less than 0.01 part by weight, the photocurability of the curable molding material layer may be inferior. If the amount exceeds 20 parts by weight, the photocurability of the curable molding material layer is expected to be further improved. Can not do. More preferably, it is 0.05 to 15 parts by weight, and still more preferably 1 to 10 parts by weight. The amount of the filler used is 3 parts per 100 parts by weight of the curable resin.
It is preferable that the amount is not more than 00 parts by weight. 30
If the amount exceeds 0 parts by weight, the fluidity of the resin mixed solution is inferior, so that the workability in producing the curable molding material layer may be reduced.

In the above item (1), the coating device is not particularly limited as long as it can apply the resin mixed solution with a constant thickness. For example, in addition to a knife coater, a roll coater and a curtain coater And various coaters such as a flow coater, a spray coater and a die coater; and a coating device such as a spray, a brush and a roller. These may be used alone or in combination of two or more. Among these, a knife coater is preferable because the resin mixed solution can be easily and efficiently applied with a uniform thickness. The means for supplying the resin mixed solution to these coating apparatuses is not particularly limited.

In the above (2), the method of spraying the reinforcing fibers is not particularly limited. For example, as shown in FIG. 1 (2), the roving reinforcing fibers 5 are cut to a length of about 6 to 50 mm. It is preferable that the cutting is performed by forming the chopped reinforcing fibers 7 using a cutting device. Examples of such a cutting device include a device that cuts by rotating a cutter roll 6a having a plurality of cutters and a rubber roll 6b so as to sandwich the same from both the left and right, and the like.
A rubber roll or a metal roll on one side can also be used. In addition, in the portion (2), it is sufficient that reinforcing fibers can be supplied onto the carrier film. For example, various types of fibers such as chopped strand mats and continuous strand mats formed into a cloth with a binder, It can also be carried out by loading a woven or non-woven fabric.

The method of pressing the carrier film coated with the resin mixed solution 3b at the position (3) above is not particularly limited, and may be performed by, for example, a pressing roll 8a. The method for preparing the resin mixed solution 3b and the method for applying the resin mixed solution are not particularly limited.
This can be performed in the same manner as in the case of (2). Further, the carrier film 2b is not particularly limited, for example, a film formed of paper or a resin material,
Films formed of a metal material such as aluminum foil and the like may be mentioned, and a light-shielding material may be vapor-deposited on paper or a resin material, or a film obtained by coating or dispersing or a film treated with a release agent may be used. It may be one that has been subjected to press working, embossing, or the like.

The method for sufficiently impregnating the reinforcing fibers with the resin mixed solution in the above-mentioned point (4) is not particularly limited, other than the method of applying pressure by the impregnation roll 9.
The impregnating roll 9 used in this case is not particularly limited. For example, a roll having a smooth surface or a corrugated surface can be used. In order to perform sufficient impregnation, it is preferable to use a plurality of corrugated rolls. Further, the impregnation rolls may be arranged so as to be sandwiched from above and below the sheet, or a plurality of impregnation rolls may be belted. In the above point (4), in addition to the impregnation operation,
Operations such as defoaming can be performed.

In the curable molding material layer forming step, it is preferable to use a light-shielding film for either the carrier film 2a or 2b. As a result, this film can be used as a light-shielding layer in the multilayer material, light curing of the multilayer material is prevented, sufficient application time is taken, and the curable molding material layer is quickly removed by removing the light-shielding layer after application. It can be cured.
The thickness of such a 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 multilayer material may be impaired. More preferably, 1
0 to 500 μm.

In the step of forming the curable molding material layer, a light-transmitting film may be used for either the carrier film 2a or 2b, or a multi-layer film having a light-shielding film and a light-transmitting film may be used. Then, one side of the curable molding material layer can be made to be a light transmitting film. Further, the carrier film 2a
Or 2b using a film having a light-shielding property,
A light transmissive film may be laminated on this film. Thereby, after the light-shielding layer is peeled off, the light-shielding layer is cured with the light-transmitting film attached thereto, and the surface state of the multilayer material can be made smoother by peeling off after the curing.

The thickness of the curable molding material layer produced in the step of forming the curable molding material layer is not particularly limited, and is preferably, for example, 0.1 to 10 mm.
If the thickness is less than 0.1 mm, the cured product may not have sufficient strength. If the thickness exceeds 10 mm, the workability and workability of the multilayer material are reduced, and the photocurability of the curable molding material layer is reduced. May decrease. More preferably, 0.5 to
5 mm. Thereby, the application thickness of the resin mixed solution in the locations (1) and (3) and the amount of the reinforcing fibers sprayed in the location (2) may be appropriately set.

It is preferable that the amount of the reinforcing fibers to be sprayed is, for example, 5 to 100 parts by weight based on 100 parts by weight of the curable resin. If the amount is less than 5 parts by weight or exceeds 100 parts by weight, the basic performance of the multilayer material may be deteriorated. More preferably, 10-6
5 parts by weight.

In FIG. 1, after the point (4),
It is preferable to perform an aging step for aging and thickening the curable molding material layer. The aging step is preferably performed by temporarily storing the wound roll after winding the sheet. The ripening conditions in the ripening step are not particularly limited.
It can be performed by allowing to stand for a period of time to 4 days.
In this case, it is preferable that the sheet is put in a packaging material or a can made of an aluminum vapor-deposited film having a light-shielding property during aging.

By performing the curable molding material layer forming step using the SMC manufacturing apparatus shown in FIG. 1, a sheet including the curable molding material layer can be easily produced. The multi-layer material of the present invention can be produced by supplying the pressure-sensitive adhesive layer laminating step which is a separate step from the material layer forming step.

The sheet containing the curable molding material layer is obtained by, for example, cutting the sheet wound by a sheet winding device into a predetermined size as required and supplying the cut sheet to the pressure-sensitive adhesive layer laminating step. The multilayer material in the present invention,
It can be manufactured simply for each application. In this case, the sheet cut to a predetermined size can be supplied to the pressure-sensitive adhesive layer laminating step as it is or after being wound around a paper tube or the like. Further, the sheet wound in the curable molding material layer forming step may be supplied as it is.

In FIG. 2A, as an example of the step of laminating the pressure-sensitive adhesive layer, a sheet including the curable molding material layer produced in the curable molding material layer forming step is provided on one side with a release layer 16a.
Shows a state in which the other side of the pressure-sensitive adhesive layer 17 having the following is bonded and wound. Thereby, the multilayer material has a release layer and a pressure-sensitive adhesive layer on one side in this order. FIG. 2B shows a state in which the pressure-sensitive adhesive 18 is applied to form a pressure-sensitive adhesive layer, and then the release layer 16b is laminated and wound. The steps shown in FIGS. 2A and 2B complete the production of the multilayer material. After this, while storing and transporting the multilayer material,
It is preferable that the multilayer material is put in a packaging material such as an aluminum vapor-deposited film having a light-shielding property or a can.

In FIGS. 2A and 2B, since the sheet containing the curable molding material layer produced in the curable molding material layer forming step has the protective films (carrier films) on both surfaces thereof, When supplying the sheet containing the curable molding material layer, the protective film on one side is peeled off by the protective film peeling device 12, and an adhesive layer is formed thereon. In FIG. 2 (1),
The method for laminating the pressure-sensitive adhesive layer 17 having the release layer 16b on one side is not particularly limited.
The pressure can be increased by b. In this case,
The press roll is not particularly limited as long as it is a roll that can sufficiently bond the sheets. For example, a roll having a smooth surface or a corrugated surface can be used.

In FIG. 2B, the pressure-sensitive adhesive 18
The method of applying is not particularly limited, and for example, can be performed in the same manner as the method of applying the resin mixed solution described above. The method for laminating the release layer 16b is not particularly limited. For example, the release layer 16b can be applied by applying pressure using a pressure roll 8c.

In FIGS. 2 (1) and 2 (2), the pressure-sensitive adhesive layer and the release layer may be those subjected to press working, embossing or the like. Before lamination, these processes may be applied to the pressure-sensitive adhesive layer and the release layer. After laminating the pressure-sensitive adhesive layer and the release layer, a pressing operation may be further performed by the pressing roll 13 or the like, or a defoaming operation may be performed.

In FIGS. 2A and 2B, the thickness of the pressure-sensitive adhesive layer is not particularly limited.
It is preferably from 10 to 10 mm. If it is less than 3 μm, poor adhesion of the multilayer material to the substrate may not be suppressed, and if it exceeds 10 mm, the workability and workability of the multilayer material will be reduced, and the basic performance of the cured product will be reduced. There is a risk. More preferably, it is 10 μm to 5 mm. 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 releasability, and if it exceeds 2000 μm, the workability and workability of the multilayer material may be reduced. More preferably, 10
It is 500 μm.

In the above embodiment, FIG.
2 (1), an apparatus for applying the pressure-sensitive adhesive layer is used, and in FIG. 2 (2), an apparatus for applying the pressure-sensitive adhesive layer is used. The production method is not limited to these, for example, the structure and size of each device, the order and the number of times in the application of the resin mixed solution or the application of the reinforcing fibers are not particularly limited, and, apart from the above steps, An operation of laminating a film or the like having another function may be performed.

As shown in FIGS. 2A and 2B,
The pressure-sensitive adhesive layer laminating step is performed in a separate step after completing the curable molding material layer forming step, so that the pressure-sensitive adhesive layer is selected in accordance with the base material and application in which the multilayer material is used. Thus, a multilayer material can be easily manufactured. Therefore, the multilayer material produced by such a production method is excellent in workability, the cured product has a sufficient basic performance, and various types of metals, plastics, rubber, glass, ceramics, stones, woods, etc. It has sufficient adhesiveness in response to various surface conditions and complex shapes of the base material, and structural members, pipes, lining materials, etc. in various buildings, machinery, automobiles, ships, household goods, etc., Even if it is used in various applications as a reinforcing material for reinforcing or repairing them, the occurrence of problems due to poor adhesion to the base material is suppressed.

[0083]

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. Note that “parts” indicates “parts by weight”.

Synthesis Example 1 498 parts of isophthalic acid as a saturated dibasic acid and propylene as a polyhydric alcohol were placed in a four-necked flask as a reactor equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer. After charging 418 parts of glycol and 670 parts of dipropylene glycol, the inside of the flask was replaced with nitrogen gas. Next, the mixture was stirred and the maximum temperature was increased to 21.
The mixture was heated to 5 ° C. to perform a dehydration reaction. Thereby, when the acid value reached 10, the temperature was lowered to 50 ° C,
Further, 686 of maleic anhydride as an unsaturated dibasic acid was added.
The components were heated to a maximum temperature of 215 ° C., and the dehydration reaction was continued to obtain an unsaturated polyester resin having an acid value of 28. And 60 parts of this unsaturated polyester resin,
Unsaturated polyester resin A was obtained by mixing 40 parts of styrene as a vinyl monomer and 0.02 parts of hydroquinone as a stabilizer.

Synthesis Example 2 A four-necked flask as a reactor equipped with a thermometer, a nitrogen gas inlet tube and a stirrer was charged with an epoxy equivalent of 18 obtained by the reaction of bisphenol A with epichlorohydrin.
No. 9 Epicron 850 (trade name, manufactured by Dainippon Ink and Chemicals, Inc.) 458 parts, methacrylic acid 215 parts, hydroquinone 0.35 part and triethylamine 2.1 parts were added,
The temperature was raised to 110 ° C. in an oxygen-containing gas stream, and the reaction was carried out for 6 hours to obtain an epoxy acrylate resin having a polymerizable vinyl group. Then, 65 parts of this epoxy acrylate resin, 35 parts of styrene as a vinyl monomer, and 0.02 parts of hydroquinone as a stabilizer were mixed to obtain an epoxy acrylate resin B.

Example 1 100 parts of the unsaturated polyester resin A obtained in Synthesis Example 1 as a curable resin, 1.4 parts of MgO # 20 (trade name, manufactured by Kyowa Chemical Industry Co., Ltd.) as a thickener, and as a filler 110 parts of aluminum hydroxide B-308 (trade name, manufactured by Alcoa Chemical Co., Ltd.), Darocur 1173 as a photoinitiator
(Product name, Ciba Specialty Chemicals)
1.0 part, methylhydroquinone 50 as a polymerization inhibitor
0 ppm and 5 parts of styrene were added, and the mixture was stirred with a disper for 10 minutes to obtain a resin mixed solution. The viscosity of this solution was 35.5 poise (25 ° C.).

Then, the SMC manufacturing apparatus was set to a width of 500 mm.
As a carrier film, a polyethylene film provided with a light-shielding property by dispersing a black pigment as a light-shielding material was set. The carrier film is moved, the above-mentioned resin mixed solution is uniformly applied thereon with a knife coater at a width of 400 mm, and glass roving AF is applied on the layer.
210 W (trade name, manufactured by Asahi Fiber Glass Co., Ltd.) was cut into approximately 1 inch by an automatic cutter, and a glass chop was sprayed. The same polyethylene film as the above was used as a carrier film on the laminate, covered with a layer coated with a resin mixed solution in the same manner, defoamed and impregnated with an impregnating roll, and then wound around a paper tube. Next, the whole paper tube was hermetically sealed with a packaging material made of an aluminum vapor-deposited polyester film, and then aged at 40 ° C. for 48 hours to increase the viscosity. Thereafter, DCT-210 (trade name, manufactured by Chugoku Kako Co., Ltd.), which is a double-sided adhesive tape, is adhered to the laminate so that the release layer is on the outside, and the release paper of the double-sided adhesive tape is on the outside, and a paper tube is formed. Take up the multilayer material (photo-cured prepreg F) of the present invention.
RP sheet). Thereafter, the entire paper tube was hermetically sealed with an aluminum-evaporated polyester film packaging material and stored.

The obtained light-cured prepreg FRP sheet was used as a substrate in a place where sunlight was well exposed, with a diameter of 200 mm.
A 150 mm wide cylinder (made of a cold-rolled steel sheet having a thickness of 1 mm) was used to bond the entire circumference of the cylinder. The base material had been sufficiently removed in advance of dirt, oiliness, wax and the like. The application process is to take out the photo-cured prepreg FRP sheet from the packaging material and cut it to the size required for the adhesive application, the adhesive process to peel off the release paper and adhere to the base material, and the solar Work time required for curing by a curing step of curing with light and an auxiliary curing step of curing a part lacking sunlight (shade part) using a handy type ultraviolet irradiation device (Handicure 800: manufactured by Ushio Electric Co., Ltd.) Was 45 minutes. FIG.
(1) shows the cylinder after applying the photocurable prepreg FRP sheet. Workability (workability) in this construction was evaluated according to the following criteria.

A: Since the photocurable prepreg FRP sheet maintained sufficient flexibility and the bonding operation was easy, the operation could be performed easily. ○: Flexibility was impaired due to the start of curing of the photocurable prepreg FRP sheet, but the work could be performed because the bonding work was easy. Δ: The photocurable prepreg FRP sheet maintained sufficient flexibility, but the bonding operation was not easy, so that the operation was not easy. ×: The curing of the photocurable prepreg FRP sheet was started, the flexibility was impaired, and the bonding operation was not easy, so that it was difficult to perform the operation.

Example 2 In Example 1, the unsaturated polyester resin A was used as the epoxy acrylate resin B obtained in Synthesis Example 2, and 1.4 parts of MgO # 20 was used as a thickener, and Sumidur 44V20 (methylene diisocyanate) was used. A photocurable prepreg FRP sheet was obtained in the same manner except that 11 parts (trade name, manufactured by Sumitomo Chemical Co., Ltd.) were used. The obtained photocurable prepreg FRP sheet was evaluated in the same manner as in Example 1. The results are shown in Table 1. In the evaluation, the test conditions were the same as in Example 1.

Example 3 The photo-cured prepreg FRP sheet obtained in Example 1 was used as a base material in a place exposed to sunlight to a size of 30 × 3.
Using a steel plate of 0 cm (made of a cold-rolled steel plate having a thickness of 1 mm), the entire surface was bonded and worked. Fig. 3 (2) shows the photo-cured prepreg F
The steel sheet after applying the RP sheet is shown. Since there was no sun-deficient portion, no auxiliary curing process was required. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Example 4 In Example 1, the double-sided adhesive tape was replaced with DCT-410.
(Product name, manufactured by Chugoku Kako Co., Ltd.)
A light-cured prepreg FRP sheet was subjected to adhesive curing in the same manner except that urethane foam 10 times mm was used. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 1 A mixed solution of a photocurable resin was prepared in the same manner as in Example 1. Then, as a carrier film having a width of 500 mm, a polyethylene film in which a black pigment was dispersed to impart light-shielding properties was set as an SMC impregnating machine. This carrier film is moved, the above-mentioned resin mixed solution is uniformly applied with a knife coater in a width of 400 mm, and a glass chopping AF210W, which is a glass roving, cut to about 1 inch with an automatic cutter is sprayed on the layer. did. The same polyethylene film as the above was used as a carrier film on the laminate, covered with a layer coated with a resin mixed solution in the same manner, defoamed and impregnated with an impregnating roll, and then wound around a paper tube. The whole paper tube was hermetically packaged with a packaging material made of an aluminum vapor-deposited polyester film, which was then aged at 40 ° C. for 48 hours and thickened to obtain a comparative light-cured prepreg FRP sheet.

The obtained photo-cured prepreg FRP sheet was subjected to adhesive curing in the same manner as in Example 1. still,
The base material was subjected to a primer treatment step after sufficient removal of dirt, oiliness, wax, etc. in advance at the portion where the photocurable prepreg FRP sheet was bonded. 3 primers (Mighty Grip 9036, trade name, manufactured by E-Tech)
After application of an amount of 00 gr / m ² and sufficient drying, processing, adhesion, curing, and auxiliary curing were performed in the same manner as in Example 1. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 2 A comparative photocurable prepreg FRP sheet was subjected to adhesive curing in the same manner as in Comparative Example 1, except that a transparent polyethylene film was used as the carrier film.
The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

Comparative Example 3 In Comparative Example 1, Darocur 117 was used as a photoinitiator.
In the same manner except that No. 3 was changed from 1.0 part to 0.5 part, a comparative light-cured prepreg FRP sheet was subjected to adhesive curing. The evaluation was performed in the same manner as in Example 1, and the results are shown in Table 1.

[0097]

[Table 1]

As is clear from Table 1, in Examples 1 to 4, the multilayer material of the present invention has a small number of construction steps, a short working time, and excellent workability. In addition, it was found that it was possible to stably adhere to the base material, to sufficiently suppress poor adhesion, and to cope with various uses of various base materials. Further, in Examples 1 and 4, it was found that the pressure-sensitive adhesive layer in the multilayer material can be selected and easily manufactured.

[0099]

According to the method for producing a multilayer material of the present invention, since it has the above-described structure, it is excellent in workability, the cured product has sufficient basic performance, and metal, plastic, rubber, glass, ceramic, stone, and the like are obtained. Has sufficient adhesion to various surface conditions and complicated shapes of various base materials such as wood, structural members and pipes in various buildings, machinery, automobiles, ships, household goods, etc. , A lining material, or a multilayer material that can be used for various purposes as a reinforcing material to reinforce or repair them, but that can suppress the occurrence of defects due to poor adhesion to the base material It can be manufactured simply and in accordance with the base material and application in which it is used.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view of one embodiment showing a state in which a curable molding material layer is produced in a curable molding material layer forming step in the method for producing a multilayer material of the present invention.

FIG. 2 is a schematic cross-sectional view of one embodiment showing a state in which a pressure-sensitive adhesive layer is laminated in a pressure-sensitive adhesive layer laminating step in the method for producing a multilayer material of the present invention.

FIG. 3A is a schematic diagram illustrating a state after a photocurable prepreg FRP sheet is applied to a cylindrical steel plate used in an example. (2) is a schematic diagram showing a state after applying a photocurable prepreg FRP sheet to the steel plate used in the example.

[Explanation of symbols]

 1a, 1b Carrier film supply device 1c Curable molding material layer supply device 1d Pressure-sensitive adhesive layer and release layer supply device 1e Release layer supply device 2a, 2b Carrier film 3a, 3b Resin mixed solution 4a, 4b, 4c Knife coater Reference Signs List 5 Roving reinforcing fiber 6a Cutter roll 6b Rubber roll 7 Chop reinforcing fiber 8a, 8b, 8c Crimping roll 9 Impregnation roll 10a, 10b, 10c Sheet take-up device 11 Tension roll 12 Protective film peeling device 13 Pressing roll 14 Flat portion 15 Curable molding material layer 16a, 16b Release layer 17 Pressure-sensitive adhesive layer 18 Pressure-sensitive adhesive 19 Base material 20 Joint

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08F 2/50 C08F 2/50 C08J 5/24 CEZ C08J 5/24 CEZ // C08L 101: 00 C08L 101: 00 (72 ) Inventor Toshio Awaji 5-8 Nishiburi-cho, Suita-shi, Osaka F-term (reference) 4F072 AA02 AA07 AB03 AB04 AB05 AB06 AB07 AB08 AB09 AB10 AB11 AB28 AB29 AD09 AD34 AD38 AE02 AG03 AG20 AH04 AH25 AH26 AK05 AL09 AL12 4F100 AG00 AK01A AK01B AK04 AK44 AR00C AR00D BA03 BA07 BA08 BA10A BA10C BA10D CA30B CB05C DG01B DH00B DH01B EA041 EA051 EH112 EH462 EH762 EJ182 EJ912 EJ942 EK03 EK04 GB07 GB51 JB12B JB14B JL01 JL11 JL13C JL14D JN30A 4J004 AA05 AA07 AA08 AA09 AA10 AB01 AB07 CA06 CB03 DA02 DA04 DA06 DB02 FA08 4J011 QA01 QA02 QA03 QA05 QA06 QA09 QA13 QA20 QA21 QA23 QA27 QA39 QB12 QB19 QB20 QB22 RA03 RA14 SA01 SA12 SA21 SA22 SA31 SA32 SA34 SA41 SA42 SA63 SA76 SA78 SA83 SA90 SA07 SA87 SA83 SA01 SA86

Claims (4)

[Claims] 1. A method for producing a multilayer material comprising a curable molding material layer comprising a curable resin, a reinforcing fiber and a photosensitizer, and a pressure-sensitive adhesive layer, the method comprising: A curable molding material layer forming step of forming a layer, and a pressure-sensitive adhesive layer laminating step of laminating the pressure-sensitive adhesive layer, wherein the pressure-sensitive adhesive layer laminating step ends the curable molding material layer forming step. A method for producing a multilayer material, which is performed in a separate step after the formation. 2. The method according to claim 1, wherein the curable molding material layer is formed on a carrier film. 3. The method according to claim 2, wherein the carrier film is a light-shielding film. 4. The pressure-sensitive adhesive layer laminating step is performed by bonding another surface of the pressure-sensitive adhesive layer having a release layer on one surface to a curable molding material layer. The method for producing a multilayer material according to claim 1, 2 or 3.