JP2000280385A - Production of fiber reinforced resin laminated material and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laminated material capable of also shaping a reinforced layer simultaneously with the shaping of a thermoplastic resin sheet, cured by ultraviolet rays and visible light, having high design effect and excellent appearance and reduced in thickness and wt. SOLUTION: A fiber reinforced resin laminated material is formed by laminating a thermoplastic resin sheet and a fiber reinforced resin sheet. In this case, the fiber reinforced resin sheet consists of a resin selected from an unsaturated polyester resin, a vinyl ester resin and an acrylic resin, a photopolymerization initiator, a thickner containing a thermoplastic resin powder as an effective component and a fiber reinforcing material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin sheet (a) and a fiber-reinforced resin sheet used for a surface material of furniture, household goods, etc., a surface of an interior material of a vehicle, or a surface of a bathtub.
And (b) a photo-curable fiber-reinforced resin laminate, and a method for producing a molded article using the same.

[0002]

2. Description of the Related Art As a conventional technique, a method of manufacturing a laminated thermoplastic resin product reinforced with FRP is, for example, a method of laminating an FRP layer on a back surface of a thermoplastic resin sheet by a hand lay-up method or a spray-up method. Alternatively, a method of bonding a thermoplastic resin sheet to an FRP molded material that has been formed in advance with an adhesive, or a method of laminating a thermoplastic resin sheet on a sheet molding compound (SMC) and performing heat compression molding may be used.

[0003] However, these techniques have some disadvantages. For example, in the hand lay-up method or the spray-up method, since a liquid resin is used, there is a problem in the working environment due to the odor, and low productivity due to manual work and long curing time. The method of bonding an FRP molded product has a problem in economical efficiency due to a high bonding cost of the molded product.

On the other hand, the compression molding method using SMC can be said to be a technique excellent in workability and economy because SMC is easy to handle and inexpensive. However, in this method, the unsaturated polyester resin used for the SMC has a high viscosity due to its nature, and it is necessary to raise the temperature sufficiently to facilitate the shaping. If not, there are drawbacks such as a problem in shaping and filling of details. Accordingly, there is a serious drawback in that the thermoplastic resin may be melted during the heat compression molding or the color or embossed pattern for surface decoration may be changed due to the partial softening of the thermoplastic resin.

In order to solve these disadvantages, Japanese Patent Laid-Open No.
In JP-A-182036, a sheet-like prepreg made of glass fiber impregnated with a photocurable vinyl ester resin is adhered to the back surface of a thermoplastic resin sheet, shaped by vacuum molding or vacuum / pressure-air molding, and cured by ultraviolet light. The method of releasing, cooling and cooling is shown. However, in this method, since the sheet-like prepreg uses a conventional thickener, when the prepreg is attached to the thermoplastic resin sheet, the release film on one side must be peeled off.
At this time, the adhesiveness of the sheet is high, and the resin or the like adheres to the release film, causing a partial non-uniformity of the resin, and also has problems in terms of workability and economy.

Further, when cured by ultraviolet rays, the FRP layer undergoes curing shrinkage as compared with the thermoplastic resin sheet,
Problems such as separation between sheets and generation of fine cracks in the FRP also occur. To prevent this, a method such as adding a low-shrinking agent such as polyvinyl acetate, polystyrene, or polymethyl methacrylate can be considered. However, in practice, the FRP layer is separated due to separation or generation of microcracks or voids. Problems such as cloudiness occur.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to provide, among the above-mentioned conventional techniques, a thermoplastic resin for maintaining the quality of a laminated molded product obtained in terms of workability, productivity and economy. Provided are a method for producing a fiber-reinforced resin laminate and a molded product which can be used at a low temperature at which melting does not occur and at a low pressure under which the shape or pattern of the resin surface does not change.

[0008]

Means for Solving the Problems The present inventors have a photocuring property suitable for a laminate with a thermoplastic resin sheet suitable for low-temperature low-pressure molding, have excellent workability, and have a low shrinkage effect. As a result of intensive studies on the fiber reinforced resin sheet, the present invention has been completed.

That is, the present invention relates to a fiber reinforced resin laminate obtained by laminating (1) (a) a thermoplastic resin sheet and (b) a fiber reinforced resin sheet, wherein the fiber reinforced resin sheet (b) is not Resin (A) selected from saturated polyester resin, vinyl ester resin, or acrylic resin, photopolymerization initiator
(B), a fiber-reinforced resin laminate comprising a thickener (C) containing a thermoplastic resin powder as an active ingredient, and a fiber-reinforced material (D); (2) a fiber-reinforced resin sheet (b) But 80 ° C
Thickened below, B-staged,
(3) After adhering the fiber reinforced resin sheet (b) to the back side of the thermoplastic resin sheet (a), the fiber reinforced resin sheet (b) is heated, and the surface of the thermoplastic resin sheet is brought into contact with the mold surface to form a vacuum, a pressure forming, Forming by either pressure, then irradiating the fiber reinforced resin sheet surface with ultraviolet light or visible light to cure the fiber reinforced resin sheet, and then release and cool the fiber. (4) A method for producing a resin laminate molded article, (4) after adhering the fiber-reinforced resin laminate to a mold, heating and pressurizing it, and then shaping the fiber-reinforced resin sheet
(B) irradiating the surface with ultraviolet light or visible light to cure the fiber reinforced resin sheet (b), and then release the mold and cool it, and provide a method for producing a fiber reinforced resin laminate molded article. Is what you do. Next, the present invention will be described in detail.

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The thermoplastic resin sheet of the present invention (a)
Is, for example, polyvinyl chloride, polyethylene, polypropylene and its copolymer, acrylic (PMMA and others)
Resin, ABS, polystyrene, polycarbonate resin,
It is obtained from a thermoplastic polyurethane resin, AS (acrylonitrile / styrene copolymer) and acrylic / vinyl chloride copolymer, and its thickness is preferably 0.1 to 5 mm.

The thermoplastic resin sheet (a) of the present invention is preferably a soft surface material having a decorative pattern by embossing in addition to color on the surface. For forming the sheet, a method is preferred in which the sheet is heated to a temperature lower than the melting temperature of the resin and higher than the temperature at which softening starts, and then formed by vacuum or vacuum / pressure-air forming. Under the conditions of the vacuum forming or the vacuum / pressure forming, the curing reaction of the FRP layer is performed to improve the workability such as film peeling property and to reduce the shrinkage effect. It is the gist of the present invention to utilize photocuring at a low temperature by using.

The fiber reinforced resin of the fiber reinforced resin sheet (b) of the present invention is a resin selected from unsaturated polyester resins, vinyl ester resins and acrylic resins, and these resins are used as a polymerizable vinyl monomer solution. Is what you do. These resins are cured by the photopolymerization initiator (B).

The unsaturated polyester resin of the present invention is not particularly limited, and a known unsaturated polyester resin commonly used in conventional general unsaturated polyester resin molded articles can be used. This unsaturated polyester resin has α,
It is obtained from β-unsaturated carboxylic acids or α, β-unsaturated carboxylic acids, optionally containing saturated carboxylic acids, and alcohols.

Examples of the α, β-unsaturated carboxylic acid include fumaric acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, chloromaleic acid, and dimethyl esters thereof.
These α, β-unsaturated carboxylic acids may be used alone or in combination of two or more.
Examples of the saturated carboxylic acid include, for example, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid,
Hexahydrophthalic anhydride, adipic acid, sebacic acid,
Azelaic acid and the like. These saturated carboxylic acids may be used alone or in combination of two or more.

On the other hand, examples of alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,3-pentanediol, , 6-hexanediol, cyclohexanediol, neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, glycerin monoallyl ether, hydrogenated bisphenol A, 2,2-bis (4-hydroxypropoxy Examples thereof include diols such as phenyl) propane and 2,2-bis (4-hydroxyethoxyphenyl) propane, triols such as trimethylolpropane, and tetraols such as pentaerythritol. These alcohols may be used alone or in combination of two or more.

The unsaturated polyester is made into a solution of a polymerizable monomer described below, and is used as an unsaturated polyester resin. The mixing ratio is preferably unsaturated polyester:
Polymerizable monomer = 40 to 80% by weight: 60 to 20% by weight.

When a commonly used alkaline earth metal oxide or the like is used as a thickener, the unsaturated polyester must have a molecular weight of about 2,000 or more. When the thickener (C) as an active ingredient is used, it is possible to prepreg even an unsaturated polyester having a molecular weight of 1,000 to 2,000.

The vinyl ester resin is most typically produced by the reaction of an epoxy resin with acrylic acid or methacrylic acid. In addition, for example, the vinyl ester resin is produced by the reaction of terminal carboxypolybutadiene with glycidyl methacrylate. It is a group of resins having corrosion resistance and mechanical strength. Vinyl ester resin
This is a solution of a polymerizable monomer described below. The mixing ratio is
Preferably vinyl ester resin: polymerizable monomer = 40 to
80% by weight: 60 to 20% by weight.

The acrylic resin is a thermoplastic acrylic polymer derived from a polymerizable monomer containing methacrylic acid ester and acrylic acid ester as main components, and a polymerizable monomer. Monomers used in the polymer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and (meth) butyl. (Meth) acrylate such as isobutyl acrylate and cyclohexyl (meth) acrylate is an essential component, and if necessary, other polymerizable monomers copolymerizable with the (meth) acrylates are used in combination. It is obtained by polymerizing a monomer mixture.

Examples of the copolymerizable polymerizable monomer include, for example, a functional monomer such as hydroxyethyl (meth)
Hydroxyl group-containing monomers such as acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate, and monomers having a carboxyl group such as (meth) acrylic acid can also be used. Further, other (meth) acrylic acid esters, styrene, α-methylstyrene, vinyl toluene, paramethylstyrene, chlorostyrene and other aromatic monomers, vinyl acetate, vinyl propionate and other vinyl esters, vinyl chloride, A vinyl halide monomer such as vinylidene chloride and an unsaturated nitrile such as acrylonitrile and methacrylonitrile can be used in combination.

Since the acrylic polymer is used in the form of a syrup dissolved in the polymerizable monomer, it preferably has a molecular weight of 100,000 or less, and is obtained by a general polymerization method such as suspension polymerization or solution polymerization. be able to. In addition, the monomer is
A syrup prepolymerized by 40% can be used as it is.

In the resin (A) described above, the polymerizable monomer serving as a resin solvent and a polymerization component includes methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylate. One or more (meth) acrylates selected from (meth) acrylates such as isopropyl acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and cyclohexyl (meth) acrylate In the case of acrylic resin, it is an essential component. Furthermore, other polymerizable monomers, for example, having 1 to 1 carbon atoms
(Meth) acrylic acid ester having 2 alkyl groups,
Styrene, α-methylstyrene, (meth) acrylic acid amide, maleic acid ester having an alkyl group having 1 to 4 carbon atoms, fumaric acid ester and the like are also included.

Also, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Butylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene di (meth) acrylate, etc. May be used in combination.

The mixing ratio of the acrylic polymer and the polymerizable monomer is such that the ratio of the polymer is 5 to 75% by weight.

Examples of the photopolymerization initiator (B) include, for example, benzophenone, acetophenone, and derivatives thereof. Photopolymerization initiator of the present invention
(B) is to cure the resin (A) at room temperature even when irradiated with visible light and light in the ultraviolet region having a wavelength up to about 500 nm. When used in resin (A),
Furthermore, additives and fillers for controlling viscosity, tackiness, impregnation molding shrinkage, etc. may be blended within a range that does not inhibit the photoreaction.

Thickener containing thermoplastic resin powder as an active ingredient
As (C), for example, acrylic polymer fine powder (ZEON products Zeon F301, F303, F320, F3
25, F340, F345, F351). Preferably 10 to 10 parts by weight of the resin (A)
40 parts by weight are used.

As the fiber reinforcing material (D), those usually used as a fiber reinforcing material may be used, and examples thereof include glass fiber, polyester fiber, phenol fiber, polyvinyl alcohol fiber, aromatic polyamide fiber, nylon fiber and carbon fiber. . Examples of these forms include chopped strands, chopped strand mats, rovings, and woven fabrics. These fiber reinforcing materials are selected in consideration of the viscosity of the resin composition, the strength of the obtained molded article, and the like. The amount of fiber reinforcement (D) used is (A) + (B) + (C) 1
It is preferably used in an amount of 20 to 30% by weight based on 00 parts by weight.

The fiber reinforced resin sheet (b) is preferably prepared by adding a resin (A) and a photo-curing agent to the fiber reinforced material (D) by an ordinary method.
(B) and a thickener containing a thermoplastic resin powder as an active ingredient (C)
Impregnated with polyethylene, polyester, P
A sheet material sandwiched and fixed between two films such as VA. Preservation is usually sandwiched between two thin films and wound as a long sheet on a pipe such as a paper tube or iron tube, or a double-sided peelable film is placed on one side of the sheet (b). The film is laminated and wound up with the film facing out.

In addition, the sheet (b) can be stored while being folded at a fixed length. Obtained sheet (b)
Must be wrapped in a film that does not transmit light, such as an aluminum vapor-deposited film, to prevent gelation.

The obtained sheet (b) is preferably at 80 ° C.
B-stage (prepreg) at the following temperature, preferably from room temperature to 50 ° C, more preferably from 30 ° C to
Viscosity is increased by 45 ° C., and a prepreg fiber-reinforced resin sheet (b) having no liquid content is obtained. Upon lamination molding of the fiber-reinforced resin sheet after the thickening (b), a primer may be applied to the back surface of the thermoplastic resin sheet (a) which has been heated to a softening temperature in advance, and then a fixing film on one side is formed. The fiber reinforced resin sheet (b) surface that has been peeled off and exposed is pressed and adhered, or the laminated material in which the thermoplastic resin sheet (a) and the fiber reinforced resin sheet (b) are pressed and adhered at room temperature in the same manner as the thermoplastic resin Heat the sheet (a) to the softening temperature, fix it in a vacuum forming mold with the surface of the thermoplastic resin sheet (a) facing the mold face, and depressurize and suction, or Fiber reinforced resin sheet on the back of the laminated material
(2) The laminated material is shaped into the shape of the mold surface by pressurizing / pressing from the surface. After shaping, the surface of the fiber reinforced resin sheet (b) is irradiated with ultraviolet light or visible light to cure the sheet. In this case, the light irradiation may be performed while the laminate is attached to the vacuum forming mold, or the laminate may be removed from the mold,
It may be performed after cooling and solidifying the thermoplastic resin. If the film left on the back surface of the fiber reinforced resin sheet (b) does not hinder light transmission and is a soft thin transparent film, it may be attached until this operation is completed.

The pressure is preferably 0.1 to 10
The shaping is performed by a pressure of kg / cm2. Similarly, in laminating the prepreg-formed sheet (b) after thickening, a thermoplastic resin sheet previously heated to a softening temperature
(A) After applying a primer on the back side in some cases, the fixing film on one side is peeled off, and the exposed prepreg-formed fiber reinforced resin sheet (b) is pressed and adhered to the surface, or a thermoplastic resin at room temperature. After heating the laminated material in which the sheet (a) and the fiber-reinforced resin sheet (b) are similarly pressed and adhered to the softening temperature of the thermoplastic resin sheet (a), the thermoplastic resin is applied to a molding mold such as an FRP mold or a mold. The surface of the sheet (a) is fixed to face the mold surface, and shaped by heating and compression. After the shaping, one side of the mold is removed, and the fiber-reinforced resin sheet (b) is cured by irradiating ultraviolet light or visible light from the surface. Also in this case, light irradiation is performed while the laminated material remains on the mold.
The heat treatment may be performed, or the heat treatment may be performed after the laminate is removed from the mold and the thermoplastic resin sheet (a) is cooled and solidified.

The light irradiation lamp is not particularly limited, but a commercially available high-pressure mercury lamp is preferred.

The photocurable fiber-reinforced resin sheet of the present invention (b)
Has moderate tackiness, and its viscosity decreases when heated, making it easy to flow under low pressure. Further, it has flexibility even at normal temperature, and has extremely good followability to the thermoplastic resin sheet (a). The adhesiveness is easy to adhere to the sheet and easy to integrate with the sheet. In spite of such adhesiveness, when the sheet (b) holding film is peeled off, there is no adhesion of the resin to the film at all, and thus the workability is excellent and the economy is superior.

Furthermore, since the sheet (b) is provided in a form sandwiched between films, it is convenient because it can be easily handled such as cutting and stacking before molding, and it does not hinder the irradiation of ultraviolet rays very much.

As the fiber reinforced resin sheet (b), various kinds of resin (A), additives, fiber reinforced material (D), or their contents, and the total thickness can be varied. So a thermoplastic resin sheet (a) or a fiber reinforced resin sheet suitable for the thickness, rigidity, feel, etc. of the reinforced composite material of the product
(B) can be selected. In the production of the sheet,
By changing the amount of the thickener (C) added, the degree of thickening can be changed, and the tackiness and handleability can be changed.

In order to increase the adhesive strength between the thermoplastic resin sheet (a) and the fiber reinforced resin sheet (b), the thermoplastic resin sheet (a)
It is very effective to apply a primer to the primer, and in the present invention, the primer and the prepreg can be simultaneously cured by ultraviolet irradiation using a photocurable primer varnish.

Hereinafter, the present invention will be described in detail with reference to examples.

(Reference Example 1) (Production of fiber-reinforced resin sheet) Unsaturated polyester resin (Polylite CN325, Dainippon Ink and Chemicals, Inc.)
100 parts by weight of an acrylic thickener (Zeon F)
303 (manufactured by Zeon Corporation) and 30 minutes by weight, and sufficiently stirred. 1 part by weight of Irgacure 651 (manufactured by Ciba Geigy) was further added as an ultraviolet curing agent, and after stirring and mixing,
Using an MC manufacturing apparatus, a 1-inch glass chopped strand was impregnated, and the sheet was taken out into a storage box while being folded. The obtained sheet was heated to 45 ° C., stored for 2 hours and thickened to prepare a fiber reinforced resin sheet. Although the fiber-reinforced resin sheet is sticky,
The peelability of the protective film was good, and there was no adhesion of the resin component.

Reference Example 2 (Production of Fiber Reinforced Resin Sheet) The monomer component in the unsaturated polyester resin was converted from styrene monomer to methyl methacrylate / β-hydroxyethyl methacrylate (9
5/5: weight ratio), except that the fiber reinforced resin sheet was prepared in the same manner as in Reference Example 1. The workability (film peelability) was good due to the thickening.

(Reference Example 3) (Production of fiber reinforced resin sheet) An acrylic syrup obtained by polymerizing 30% of methyl methacrylate by bulk polymerization was used instead of the unsaturated polyester.
A fiber reinforced resin sheet was prepared in the same manner as in Reference Example 1.
The workability of the obtained sheet was good.

(Reference Example 4) (Production of a fiber-reinforced resin sheet) A reference was made except that a vinyl ester resin (Dicklight MUE-3563: manufactured by Dainippon Ink and Chemicals, Inc.) was used instead of the unsaturated polyester resin. A fiber reinforced resin sheet was prepared in the same manner as in Example 1. The workability of the obtained sheet was good.

Reference Example 5 (Production of Fiber-Reinforced Resin Sheet) A fiber-reinforced resin sheet was prepared in the same manner as in Reference Example 1, except that the glass chopped strand was changed to a glass chopped strand mat.

Reference Example 6 Production of Fiber-Reinforced Resin Sheet A fiber-reinforced resin sheet was prepared in the same manner as in Reference Example 1, except that the glass chopped strand was changed to carbon fiber.

(Reference Example 7) (Production of fiber-reinforced resin sheet) A fiber-reinforced resin sheet was prepared in the same manner as in Reference Example 4, except that acrylic powder as a thickener was removed. It was very difficult to remove the film from the obtained sheet.

Example 1 A sheet of polymethyl methacrylate having a thickness of 3 mm and a fiber reinforced resin sheet having a thickness of 1 mm prepared in Reference Example 1 were overlaid, pressed with a roller, and cut into a predetermined area. After heating this laminated product by leaving it in an air bath at 150 ° C. for 5 minutes, the surface of polymethyl methacrylate was placed on the FRP mold so as to face the mold, and suction was performed at a reduced pressure of 30 mmHg from the hole of the mold. . In order to sufficiently shape the laminate, the mold was covered with an iron lid provided with a hole in the center, and evacuated at 5 kg / cm ² . After complete shaping, the lid was removed, and a sun lamp SSL250A (manufactured by Stanley Electric Co., Ltd.) was placed on the prepreg surface with the release film attached.
The laminate was removed from the mold by irradiation for 0 minutes. Curing and interlayer adhesion were sufficient.

Example 2 A laminated product was obtained in the same manner as in Example 1 except that the fiber reinforced resin sheet was changed to the sheet prepared in Reference Example 2. Curing and interlayer adhesion were sufficient.

Example 3 A laminated product was obtained in the same manner as in Example 1 except that the fiber reinforced resin sheet was changed to the sheet prepared in Reference Example 3. Curing and interlayer adhesion were sufficient.

Example 4 A laminated product was obtained in the same manner as in Example 1 except that the fiber reinforced resin sheet was changed to the sheet prepared in Reference Example 4. Curing and interlayer adhesion were sufficient.

Example 5 When a fiber reinforced resin sheet and a polymethyl methacrylate sheet were bonded, a photocurable varnish (Lipoxy VS) was applied to the bonding surface of the polymethyl methacrylate.
-200: Showa Polymer Co., Ltd.), and molding was performed in the same manner as in Example 1 except that a fiber-reinforced resin sheet was adhered after brush-coating. However, since the adhesion between the layers was further improved, compressed air was not required at the time of shaping under reduced pressure.

Example 6 A laminated product was obtained in the same manner as in Example 1 except that the fiber reinforced resin sheet was changed to the sheet prepared in Reference Example 5. Curing and interlayer adhesion were sufficient.

Example 7 A laminated product was obtained in the same manner as in Example 1 except that the fiber reinforced resin sheet was changed to the sheet prepared in Reference Example 6. Curing and interlayer adhesion were sufficient.

(Embodiment 8) Using the same laminated material as in Embodiment 1, after leaving it to stand in an air bath at 150 ° C. for 5 minutes and heating, face the polymethyl methacrylate surface on the FRP mold. So that the FRP female mold
Pressure was applied to obtain a surface pressure of kg / cm ² , and the mixture was shaped. After complete shaping, the upper mold was removed, and the prepreg surface was irradiated with a sun lamp SSL250A (Stanley Electric) for 20 minutes while the release film was attached to remove the laminate from the mold. Curing and interlayer adhesion were sufficient.

(Comparative Example 1) The release film of the fiber-reinforced resin sheet prepared in Reference Example 7 was peeled off, attached to a polymethyl methacrylate sheet, and molded in the same manner as in Example 1. The resin component attached to the release film leads to non-uniform film thickness, and the non-uniform thickness of the prepreg layer occurs during vacuum molding. For this reason, the color of the decorated polymethyl acrylate is non-uniform, and sometimes the prepreg layer is broken, and a satisfactory molded product cannot be obtained.

[0054]

According to the fiber-reinforced resin laminate of the present invention, the reinforcing layer can be simultaneously formed under a low pressure at the same time as the formation of the thermoplastic resin sheet, and is cured by ultraviolet light and visible light. It is possible to obtain a large-sized molded product having high quality, excellent appearance, thin thickness and light weight by a simple process.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) B32B 27/36 101 B32B 31/20 31/20 31/28 31/28 B29C 67/14 G // B29L 9 : 00 F term (for reference) 4F100 AG00 AK01A AK01B AK21B AK25B AK44B BA02 CA02B CA30B DE01B DG01B DG03 DH01B DH02B EH012 EJ082 EJ172 EJ242 EJ422 EJ502 EJ522 EJ541 HA09 HA14 HA25 HA33 HA34 HA35 HA44 HA45 HB01 HB11 HC04 HC16 HK03 HK04 HK05 HK10 HK31 HT03

Claims (4)

[Claims] 1. A fiber reinforced resin laminate comprising (a) a thermoplastic resin sheet and (b) a fiber reinforced resin sheet, wherein the fiber reinforced resin sheet (b) is an unsaturated polyester resin, vinyl ester Resin, or a resin selected from acrylic resin (A), a photopolymerization initiator (B), a thickener (C) containing a thermoplastic resin powder as an active ingredient, and a fiber reinforcement (D) Fiber reinforced resin laminate. 2. The fiber-reinforced resin laminate according to claim 1, wherein the fiber-reinforced resin sheet (b) is thickened at 80 ° C. or lower and B-staged. 3. A fiber reinforced resin sheet (b) is closely adhered to the back side of the thermoplastic resin sheet (a), and then heated, and the surface of the thermoplastic resin sheet is brought into contact with the mold surface to form a vacuum, and to form a compressed air. Molding, shaping by pressure, and then irradiating the surface of the fiber-reinforced resin sheet with ultraviolet light or visible light to cure the fiber-reinforced resin sheet, and then release and cool it. A method for producing a fiber-reinforced resin laminate. 4. After the fiber-reinforced resin laminate according to claim 1 is brought into close contact with a mold, it is shaped by heating and pressing, and then the surface of the fiber-reinforced resin sheet (b) is irradiated with ultraviolet light or visible light. Then, the fiber reinforced resin sheet (b) is cured, and then released from the mold and cooled, thereby producing a fiber reinforced resin laminate molded article.