JP2002088176A - Photocurable prepreg and water-proof material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable prepreg which has a multi-layered structure, has excellent adhesivity to a top coating layer, can eliminate a process of intermediate coating, and can control the evaporation of styrene monomer or the like, and to provide a water-proof material comprising the prepreg. SOLUTION: This photocurable prepreg characterized by laminating into two or more layers a photocurable resin compound consisting essentially of (A) a resin selected from an unsaturated polyester resin, a vinyl ester resin, a vinyl urethane resin and an acrylic resin, (B) a polymerizable unsaturated monomer, (C) a photopolymerization initiator, and (D) a thickening agent containing the powder of a thermoplastic resin as an active component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable prepreg and a waterproof material which can be used for various applications.

[0002]

2. Description of the Related Art As a prior art of a photocurable sheet, for example, Japanese Patent Application Laid-Open No.
No. 1345 and JP-A-10-339001. These applications are used for repairing, reinforcing, or waterproofing lining materials for various steel, concrete and plastic pipes and various structural members, for repairing automobiles and ships, and for waterproofing roofs and tanks. ,
Used for repairing surfboards, boats, etc.

[0003] For so-called lining work for construction and civil engineering, asphalt waterproof coating and vinyl chloride sheet have been applied as waterproofing applications. However, because of their low mechanical strength and severe deterioration, they are waterproof in a short period of time. There is a problem that the effect is impaired and frequent maintenance work is required. In addition, waterproofing is performed by impregnating the glass fiber chopped strand mat with wet waterproofing unsaturated polyester resin on site and curing and molding the FRP layer. Although a method of forming a layer is also known, the working environment is deteriorated due to the volatilization of volatile substances such as styrene monomer in the unsaturated polyester resin, skin irritation of glass fiber used as a reinforcing material, and scattering of chopped strands. There was such a problem. Further, after the FRP layer is laminated, an intermediate coating layer, a top coat layer and a styrene monomer-based resin coating step are further applied to impart properties such as surface water resistance, abrasion resistance and weather resistance.

The above-mentioned publication is cited as a means for solving these problems, and has a certain effect as a measure for improving the working environment. However, since the sheet configuration is a single-layer structure,
There is a defect that the performance such as water resistance, abrasion resistance, and weather resistance of the surface is inferior to that of a laminated structure including a multi-layer coating process in a wet construction. Japanese Unexamined Patent Application Publication No. 10-71661 also proposes a multi-layered waterproof sheet, which has the effect of improving the base followability, but has a surface durability that often poses a problem in practical use, particularly, a top coat layer. However, it cannot be said that a sufficient effect has been obtained with respect to the adhesiveness. That is, in the normal FRP waterproofing, after the FRP layer is laminated, the middle coat layer and the top coat layer are applied, and then the waterproof laminated structure is completed. However, if the adhesion of the middle coat layer to the FRP layer and the top coat layer is insufficient. In practice, a problem such as peeling of the intermediate coat layer and the FRP layer or peeling of the intermediate coat layer and the top coat occurs.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a multilayer structure having excellent adhesion to a top coat layer, omitting the step of applying an intermediate coating layer, and suppressing volatilization of styrene monomer and the like. To provide a photocurable prepreg and a waterproof material therefor.

[0006]

The present invention provides (1) a resin (A) selected from unsaturated polyester resins, vinyl ester resins, vinyl urethane resins and acrylic resins, a polymerizable unsaturated monomer (B), A polymerization initiator (C), a photocurable prepreg characterized by being laminated with two or more layers of a photocurable resin compound containing a thickener (D) as an essential component and a thermoplastic resin powder as an active ingredient; and It relates to a waterproof material using the same. Next, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated polyester resin used in the present invention is not particularly limited, and a known unsaturated polyester resin conventionally used in general unsaturated polyester resin molded articles can be used. The unsaturated polyester resin is obtained from an α, β-unsaturated carboxylic acid or an α, β-unsaturated carboxylic acid containing a saturated carboxylic acid 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.

[0010] The unsaturated polyester resin is a solution of the polymerizable unsaturated monomer (B). Their mixing ratio is preferably unsaturated polyester resin: polymerizable monomer = 40-80% by weight: 60-20% by weight.

When an unsaturated polyester resin is used alone with an alkaline earth metal oxide or the like commonly used as a normal thickener, the unsaturated polyester resin must have a molecular weight of about 2,000 or more. However, a thickener comprising the thermoplastic resin powder as an essential component in the present invention as an active ingredient
When (C) is used, a sheet can be formed even with an unsaturated polyester resin having a molecular weight of 500 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 contains a polybutadiene type vinyl ester resin and the like, and is excellent in corrosion resistance and mechanical strength. The vinyl ester resin is a solution of the polymerizable unsaturated monomer (B). 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. 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) acrylic ester such as isobutyl acrylate and cyclohexyl (meth) acrylate are essential components, and if necessary, other polymerizable monomers copolymerizable with the above (meth) acrylic esters. . The acrylic resin is preferably obtained by polymerizing the monomer mixture to obtain a so-called acrylic syrup.

The polymerizable monomer which can be copolymerized is, 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.

When the acrylic resin is used in the form of a syrup dissolved in a polymerizable unsaturated monomer (B), it preferably has a molecular weight of 100,000 or less. Can be obtained in a way. A syrup obtained by prepolymerizing the monomer at 10 to 40% can be used as it is.

The polymerizable unsaturated monomer (B) serving as a resin solvent and a polymerization component in the resin (A) includes methyl (meth) acrylate, ethyl (meth) acrylate, and (meth) acrylic acid. Propyl, isopropyl (meth) acrylate,
(Meth) butyl, (meth) acrylate, isobutyl (meth) acrylate, cyclohexyl (meth) acrylate, etc.
One or more (meth) acrylic esters selected from acrylic esters are essential components in the case of an acrylic resin. Furthermore, other polymerizable monomers, for example, a (meth) acrylic ester having an alkyl group having 1 to 12 carbon atoms, styrene, α-methylstyrene, (meth) acrylamide, an alkyl having 1 to 4 carbon atoms Maleic esters and fumaric esters having a group are also included.

Further, 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 resin and the polymerizable unsaturated monomer is preferably such that the resin ratio is 5 to 75% by weight.

The vinyl urethane resin used in the present invention is obtained by reacting a functional group-containing vinyl compound with a functional group-containing urethane compound and then subjecting the compound to radical polymerization. The urethane compound is preferably a reaction product of the above polyisocyanate and a polyol and / or a polyol having a functional group,
It has a functional group such as an isocyanate group, a hydroxyl group, a carboxyl group, and an amino group. On the other hand, as the vinyl compound having a functional group, those having a functional group that reacts with the urethane compound, for example, an acrylic monomer having a functional group such as a hydroxyl group, a carboxyl group, and an amino group,
Maleic acid, itaconic acid and the like can be mentioned.

The mixing ratio of the vinyl urethane resin and the polymerizable monomer is preferably such that the ratio of the resin is 30 to 80% by weight.

Examples of the photopolymerization initiator (C) 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 natural light and light in the ultraviolet region, whereby the polymerization reaction proceeds. When used, the resin (A) may further contain additives and fillers for adjusting the viscosity, tackiness, shrinkage of the impregnation molding, etc. as long as the photoreaction is not hindered.

The addition amount of the photopolymerization initiator (C) depends on the total amount of the resin (A) selected from unsaturated polyester resins, vinyl ester resins, vinyl urethane resins and acrylic resins and the polymerizable unsaturated monomer (B). 0.01 to 100 parts by weight
The range is 10 parts by weight.

Thickener containing thermoplastic resin powder as an active ingredient
As (D), for example, acrylic polymer fine powder (ZEON products Zeon F301, F303, F320, F3
25, F340, F345, F351). Resin (A) and polymerizable unsaturated monomer (B) total 100
It is preferably used in an amount of 10 to 40 parts by weight based on parts by weight.

Furthermore, in order to improve the stability of the compound against light during shaping, the compound is placed within a transparent range.
A facial dye having an absorption band of not more than 00 nm can be added.

The inorganic filler is selected from unsaturated polyester resins, vinyl ester resins, vinyl urethane resins and acrylic resins (A) as long as the transparency of the photocurable compound after thickening is not significantly reduced. And 100 parts by weight of the total of the polymerizable unsaturated monomer (B) and 1
It is also possible to add up to 00 parts by weight.

Usually, the upper and lower sides of the photocurable prepreg sheet of the present invention are covered with a thermoplastic resin film, but the thickness of the film is not particularly limited. From the viewpoint of workability at the time of shaping and curing the photocurable sheet in the present invention, a film having a thickness of preferably 15 μm to 50 μm is used.

As the fiber reinforcing material (E), 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. Fiber reinforcing material (D) is a photocurable prepreg 10
It is preferably used in an amount of 20 to 30% by weight based on 0% by weight.

The photocurable prepreg sheet according to the present invention comprises a compound layer obtained by mixing a resin (A), a photocuring agent (C), a thickener (D) containing a thermoplastic resin powder as an active ingredient, and the like. It is a sheet material that is laminated and multilayered and sandwiched and fixed between two thermoplastic resin films such as polyethylene, polypropylene, polyester, and polyvinyl alcohol. Specifically, for example, a prepreg compound having a different composition is applied to each of two resin films, and the two resin films are laminated and integrated. As the thermoplastic resin film for fixing, a film subjected to release treatment with silicon or the like can be used as the compound surface in consideration of the releasability from the photocurable compound. In these cases, in order to ensure the storage stability of the sheet, a film obtained by adding an ultraviolet absorber to one or both surfaces of the film or a film obtained by applying a paint containing the ultraviolet absorber to a thermoplastic resin film may be used.

When the photocurable prepreg sheet is used for lining or the like, preferably the resin (A), the photocuring agent (C) and the thermoplastic resin powder are added to the above-mentioned fiber reinforcing material (E) by an ordinary method as an active ingredient. The mixture is impregnated with a mixture such as a thickener (D) to form a sheet material sandwiched and fixed between two films of polyethylene, polypropylene, polyester, polyvinyl alcohol and the like. Also in this case, there is a method of impregnating a fiber reinforced material with different prepreg compounds on two resin films, and laminating and integrating the two resin films.

The obtained photocurable prepreg sheet can be stored in a long form by winding it on a pipe such as a paper tube or an iron tube, or by folding it at a fixed length. In particular, a long sheet is effective for constructing a laminated structure having a large area. In the case of continuously manufacturing a sheet, a compound is applied to each of two long upper and lower resin films, and the sheet is continuously manufactured while a fiber reinforcing material is inserted therebetween. At this time, compounds having different compositions can be laminated on the upper and lower compounds. The obtained sheet must be wrapped with a film that does not transmit light, such as an aluminum vapor-deposited film, to prevent the volatile monomer from volatilizing.

The obtained photocurable prepreg sheet is
B-stage (prepreg) preferably at a temperature of 80 ° C. or lower, preferably a warmed room temperature to 50 ° C., more preferably 30 ° C. to 45 ° C., and a prepreg sheet having no liquid content. Become.

The obtained photocurable prepreg is useful as various waterproof materials, for example, floors, roofs, outer walls, and the like of factories and the like.
Rooftop, open corridor, veranda, outer wall, eaves, bathroom,
Bases for kitchens, aquariums, pools, bridge piers, decks, athletics stadiums, tennis courts, for example, concrete, asphalt, ALC boards, PC boards, FRP, plastic, wood,
It is installed on metal, existing waterproof sheet, etc. as follows. In addition, it is also useful for repairing wall materials and pipes, repairing and reinforcing various structural members, waterproofing materials for tanks, and repairing boats and the like.

When the prepreg of the present invention is used as a waterproofing material, a step of first applying a material called a primer on a substrate may be mentioned. The primer may be a urethane-based, epoxy-based or polyester-based material. There are various types, such as systems, which are appropriately selected from the viewpoints of workability, substrate condition, and the like. After the primer has dried,
The photocurable prepreg of the present invention is bonded to a substrate.

As a joining method, one side of the protective film can be peeled off and adhered to the substrate by contact pressure.
If necessary, an operation of applying a low pressure of about 1 kg / cm ² with a roller or the like to remove air bubbles or the like remaining between the substrate and the substrate can be performed. After fully adhered to the substrate, natural light (sunlight)
Alternatively, the photocurable sheet is irradiated with an ultraviolet irradiation lamp such as a high-pressure mercury lamp to be cured, and the upper resin film is peeled off. Usually, a top coat layer is applied from above for surface protection and aesthetics. At this time, in a normal waterproofing construction, a layer called an intermediate coating layer is provided between the FRP layer and the top coat layer,
Although measures are taken to improve the adhesion between the layers, in the sheet of the present invention, since the composition having good adhesion is arranged on the surface where the top coat is applied by multilayering the sheet, the intermediate coating layer The application step can be omitted. Examples of the topcoat include a polyester-based, vinylester-based topcoat, and a paint-based topcoat such as acrylic urethane.

According to the present invention, two or more layers of a photocurable prepreg compound containing a photopolymerization initiator and capable of increasing viscosity are laminated to form a multilayer structure, and a compound composition and a top coat on the side to be bonded to the substrate are applied. If the side compound is used as a waterproofing material by using a different composition, the step of applying an intermediate coating layer on a normal waterproof laminated structure can be omitted because of excellent adhesion to the top coat.

The prepreg of the present invention has a structure in which two or more photocurable prepreg compound layers are laminated, and the composition of each compound layer is cured according to the required performance of the laminated structure completed after curing. The same composition may be used even if the type and amount of resin (A), polymerizable unsaturated monomer (B), photopolymerization initiator (C), thickener (D), etc. are changed, and each compound layer may be used if necessary. May also contain a fiber reinforcement (E).
This photocurable multilayer prepreg sheet is bonded to a substrate,
It can be cured by irradiation with ultraviolet light and natural light to provide a waterproof laminated structure.

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

(Example 1: Two-layer sheet of unsaturated polyester resin and vinyl ester resin) Unsaturated polyester resin (Polylite FW-281: 40% by weight of polymerizable unsaturated monomer, Dainippon Ink and Chemicals, Inc.) )), And 30 parts by weight of an acrylic thickener (Zeon F303, manufactured by Zeon Corporation) are added to 100 parts by weight, followed by sufficient stirring. Irgacure 651 as a photopolymerization initiator (ultraviolet curing agent)
1 part by weight (manufactured by Ciba Specialty Chemical) was further added, and after stirring and mixing, the mixture was impregnated into a 1-inch glass chopped strand using an SMC manufacturing apparatus, and fixed on a PET film having a film thickness of 16 μm to form the first layer. And 0.5% by weight of tinuvin 328 (manufactured by Ciba Specialty Chemicals), which is a benzotriazole-based ultraviolet absorber, is melt-mixed and formed into a 16 μm PET film, and a vinyl ester resin (Dion 9102-01) is formed on the PET film.
NP: 45 parts by weight of polymerizable unsaturated monomer, 100 parts by weight of Dainippon Ink and Chemicals, Inc., 30 parts by weight of an acrylic thickener (Zeon F303, made by Nippon Zeon), and an ultraviolet curing agent One part by weight of Irgacure 651 (manufactured by Ciba Specialty Chemicals) was added, and the compound obtained by stirring and mixing was applied to form a second layer.

The two layers were superposed on each other to obtain a photocurable prepreg sheet sandwiched between PET films. In this case, the PET film on one side contains an ultraviolet absorber, and the storage stability of the prepreg layer is secured. To prevent the volatilization of styrene, store it wrapped in aluminized film. The obtained sheet was heated to 45 ° C., stored for 2 hours and thickened to prepare a photocurable prepreg sheet.
The photocurable sheet had a sheet thickness of 1.2 mm, a glass content of 23%, and was tacky, but had good peeling properties of the protective film and no adhesion of resin.

(Example 2: Two-layered sheet of vinyl urethane resin and vinyl ester resin) 60 parts of vinyl urethane obtained from propylene glycol (molecular weight: 600), isophorone diisocyanate and 2-hydroxyethyl methacrylate and 40 parts of methyl methacrylate A photocurable prepreg sheet was prepared in the same manner as in Example 1, except that a vinyl urethane resin in which was mixed and dissolved was used instead of the unsaturated polyester resin. The workability of the obtained sheet was the same as that of the sheet example 1 and was good.

Example 3 Double-Layered Sheet of Acrylic Resin and Vinyl Ester Resin Acrylic syrup (about 70% by weight of polymerizable unsaturated monomer) obtained by polymerizing 30% of methyl methacrylate by bulk polymerization was used. A photocurable prepreg sheet was prepared in the same manner as in Example 1 except that the unsaturated polyester was used instead. The workability of the obtained sheet was the same as in Example 1 and was good.

(Application Example 1) The PET film on the back side of the photocurable prepreg sheet prepared in Example 1 was peeled off, leaving the film containing the ultraviolet absorber, and treated with a primer (polylite primer PD 0.2 kg / m ²⁾ , Manufactured by Dainippon Ink and Chemicals, Inc.). At this time, it is necessary to perform sufficient defoaming work with a rubber roller or the like so that no bubbles remain between the base surface and the photocurable sheet. However, due to the effect of the film containing the ultraviolet absorber, outdoor work is required. , A sufficient defoaming operation was possible. Also, the odor of the monomer was suppressed by the effect of thickening the protective film and the resin. After completion of the laminating operation, the ultraviolet absorbent-containing film was peeled off, and the prepreg FRP layer was cured for about 2 hours. Next, a polyester resin (Polylight T-250, manufactured by Dainippon Ink and Chemicals, Inc.) / Gray toner (9B-3345, manufactured by Nippon Fellow Co., Ltd.) / Additive RS-401 (Dainippon Ink) A mixture of 100% / 5/5/1 parts by weight of a chemical industry (manufactured by Chemical Industry Co., Ltd.) / 55% MEKPO (methyl ethyl ketone peroxide) was applied at 0.4 kg / m ² and finished to obtain a laminated structure.

(Application Example 2) The PET film on the back side of the photocurable prepreg sheet prepared in Example 1 was peeled off, leaving the film containing the ultraviolet absorbent, and laminated on a primer-treated concrete substrate. At this time, it is necessary to perform sufficient defoaming work with a rubber roller or the like so that no bubbles remain between the base surface and the photocurable sheet. However, due to the effect of the film containing the ultraviolet absorber, outdoor work is required. , A sufficient defoaming operation was possible. Also, the odor of the monomer was suppressed by the effect of thickening the protective film and the resin. After completion of the laminating operation, the ultraviolet absorbent-containing film was peeled off, and the prepreg FRP layer was cured for about 2 hours. Next, as a top coat layer, an acrylic urethane paint (compo top AU main agent / curing agent, manufactured by Dainippon Ink and Chemicals, Inc.) was applied at 0.2 kg / m ² and finished to obtain a laminated structure.

(Application Example 3) The PET film on the back side of the photocurable prepreg sheet prepared in Example 2 was peeled off except for the film containing the ultraviolet absorbent, and the primer was treated in the same manner as in Application Example 1 to give a concrete substrate. Laminated on
A polyester resin was applied and finished as the top coat layer in the same manner as in Application Example 1 to obtain a laminated structure.

(Application Example 4) The PET film on the back side of the photocurable prepreg sheet prepared in Example 2 was peeled off except for the film containing the ultraviolet absorber, and the primer was treated in the same manner as in Application Example 2 to form a concrete substrate. Laminated on
An acrylic urethane paint was applied and finished in the same manner as in Application Example 2 as a top coat layer to obtain a laminated structure.

(Application Example 5) The PET film on the back side of the photocurable prepreg sheet prepared in Example 3 was peeled off except for the film containing the ultraviolet absorbent, and the primer was treated in the same manner as in Application Example 1 to give a concrete base. Laminated on
A polyester resin was applied and finished as the top coat layer in the same manner as in Application Example 1 to obtain a laminated structure.

(Application Example 6) The PET film on the back side of the photocurable prepreg sheet prepared in Example 3 was peeled off except for the film containing the ultraviolet absorbent, and the primer was treated in the same manner as in Application Example 2 for the concrete substrate. Laminated on
An acrylic urethane paint was applied and finished in the same manner as in Application Example 2 as a top coat layer to obtain a laminated structure.

Comparative Example 1 An acrylic thickener (100 parts by weight of unsaturated polyester resin (Polylite FW-281: polymerizable unsaturated monomer weight%, manufactured by Dainippon Ink and Chemicals, Inc.) was used. Zeon F303, manufactured by Zeon Japan) 30
Add parts by weight and stir well. 1 part by weight of Irgacure 651 (manufactured by Ciba Specialty Chemicals) as an ultraviolet curing agent was further added, and after stirring and mixing, the mixture was impregnated into a 1-inch glass chopped strand using an SMC manufacturing apparatus, and was placed on a PET film having a thickness of 16 μm. And 0.5% by weight of Tinuvin 328 (manufactured by Ciba Specialty Chemicals), which is a benzotriazole-based ultraviolet absorber, was melted and mixed to form a film.
A photocurable prepreg sheet was obtained by covering with a μm PET film.

In order to prevent volatilization of styrene, it is wrapped and stored in an aluminum vapor-deposited film. 45 sheets obtained
C., heated for 2 hours and thickened to prepare a photocurable sheet. The photocurable sheet has a sheet thickness of 1.2 mm,
Although the glass content was 23% and the film was tacky, the peelability of the protective film was good and there was no adhesion of the resin component. The PET film on the back side was peeled off, leaving the film containing the ultraviolet absorbent of the photocurable sheet, and laminated on a primer-treated concrete substrate in the same manner as in Example 1, and as a top coat layer in the same manner as in Example 1 A polyester resin was applied and finished to obtain a laminated structure.

Comparative Example 2 A photocurable sheet obtained in the same manner as in Comparative Example 1 was laminated on a primer-treated concrete substrate in the same manner as in Example 2, and acrylic urethane was used as the top coat layer in the same manner as in Example 2. A paint was applied and finished to obtain a laminated structure.

(Comparative Example 3) A vinyl urethane resin obtained by mixing and dissolving 60 parts of vinyl urethane obtained from propylene glycol (molecular weight: 600), isophorone diisocyanate and 2-hydroxyethyl methacrylate and 40 parts of methyl methacrylate was used instead of the unsaturated polyester. A photocurable sheet was prepared in the same manner as in Comparative Example 1 except that it was used in Example 1. The photocurable sheet was laminated on a primer-treated concrete substrate in the same manner as in Example 1, and was used as a top coat layer in Example 1.
In the same manner as described above, a polyester resin was applied and finished to obtain a laminated structure.

(Comparative Example 4) A photocurable sheet obtained in the same manner as in Comparative Example 3 was laminated on a primer-treated concrete substrate in the same manner as in Example 2, and acrylic urethane was used as the top coat layer in the same manner as in Example 2. A paint was applied and finished to obtain a laminated structure.

Comparative Example 5 Comparative Example 5 was repeated except that an acrylic syrup (about 70% by weight of a polymerizable unsaturated monomer) obtained by polymerizing 30% of methyl methacrylate by bulk polymerization was used instead of the unsaturated polyester. The photocurable sheet obtained in the same manner as in Example 1 was laminated on a primer-treated concrete substrate in the same manner as in Example 1, and a polyester resin was applied and finished as a top coat layer in the same manner as in Example 1 to obtain a laminated structure. Was.

(Comparative Example 6) A photocurable sheet obtained in the same manner as in Comparative Example 5 was laminated on a primer-treated concrete base in the same manner as in Example 2, and acrylic urethane was used as the top coat layer in the same manner as in Example 2. A paint was applied and finished to obtain a laminated structure.

<Test and Evaluation Method> 1) Water Resistance Adhesion Test with Top Coat Each laminated structure was immersed in hot water at 95 ° C., and the state of the top coat layer was visually observed 1, 3, 5, and 7 days later. .

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

[Table 3]

[0059]

According to the present invention, there is provided a photocurable prepreg excellent in adhesiveness to a top coat layer and capable of suppressing volatilization of monomers and the like, and a waterproof material therefor.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08K 7/02 C08K 7/02 C08L 101/00 C08L 101/00 F term (Reference) 4F072 AA02 AB04 AB05 AB06 AB09 AB10 AD09 AD23 AD38 AD43 AG03 AH21 AJ04 AJ16 AK05 AL17 4J002 BE022 BG021 CC042 CD201 CF002 CF221 CK021 CL002 DA016 DL006 FA046 FD012 FD016 4J011 AA05 AC04 PA69 PB38 QA02 QA03 QA08 QA09 QA34 QA34 QA34 QA35 QB34 AE01 AG03 AG04 BA05 BA07 BA08 CA03 CC05 CD02

Claims (3)

[Claims] 1. A resin (A) selected from unsaturated polyester resins, vinyl ester resins, vinyl urethane resins and acrylic resins, a polymerizable unsaturated monomer (B), and a photopolymerization initiator.
(C) A photocurable prepreg comprising two or more layers of a photocurable resin compound containing a thickener (D) containing a thermoplastic resin powder as an active ingredient as an essential component. 2. The photocurable prepreg according to claim 1, further comprising a fiber reinforcement (E). 3. A waterproof material comprising the photocurable prepreg according to claim 1.