JP6730043B2 - Fiber reinforced resin prepreg sheet - Google Patents

Description

The present invention relates to a fiber reinforced resin prepreg sheet. More specifically, the present invention relates to a fiber reinforced resin prepreg sheet that is attached to an object to reinforce the object.

Conventionally, a resin sheet reinforced with glass fiber, aramid fiber, carbon fiber or the like has been attached to the surface of concrete or steel structure whose strength has deteriorated due to aging deterioration for repair or reinforcement.

In particular, as a reinforcing method, it is known to use an epoxy resin reinforced with carbon fiber. As an example in which such a fiber-reinforced resin is used, JP-A-1-197532 (Patent Document 1) describes a reinforcing method using a site-hardened soft carbon fiber-reinforced prepreg.

JP-A-1-197532

The conventional fiber reinforced resin prepreg is substantially composed of only the fiber reinforced resin layer. And when sticking to a concrete structure, it is preferable to apply and use the adhesive agent of 2-5 mm thickness. Although the above-mentioned Patent Document 1 describes pressing at 0.02 to 0.1 kg/cm ² when it is attached to the surface of the concrete slab, the prepreg is substantially composed of only the fiber reinforced resin layer. Therefore, if the adhesive is not applied in advance, it cannot be actually applied with the above pressing force. Therefore, the conventional fiber reinforced resin prepreg cannot be said to be excellent in simplicity during construction.

Therefore, an object of the present invention is to provide a fiber reinforced resin prepreg sheet that can be attached to an object with a light load.

In order to achieve the above object, the present invention includes the following inventions.
(1)
The fiber reinforced resin prepreg sheet of the present invention includes a first resin layer, a fiber reinforced resin layer laminated on the first resin layer, and a second resin layer laminated on the fiber reinforced resin layer. The first resin layer has a thickness of 50 μm or more. Further, the viscosity of the resin forming the first resin layer at 30° C. is 200 Pa·s or more and 50,000 Pa·s or less.

As described above, the fiber-reinforced resin prepreg sheet of the present invention is provided with a first resin layer that does not substantially contain fibers as a configuration different from the fiber-reinforced resin layer, and the first resin layer is 200 Pa at 30° C. By having a viscosity of s or more and 50,000 Pa·s or less and a thickness of 50 μm or more, it can be attached to a target object that is a target with a light load (ease of sticking). Therefore, the fiber-reinforced resin prepreg sheet of the present invention has excellent workability.

The viscosity at 30° C. refers to the complex viscosity measured by dynamic viscoelasticity measurement at a measurement frequency of 1 Hz.
Further, the light load may be a force of, for example, less than 50,000 Pa, preferably less than 10,000 Pa. It means that it can be attached to an object even if gravity is applied during attachment (before curing) (that is, even if the prepreg sheet is applied with its own weight in the direction of peeling it). It refers to maintaining a stable attachment state without shifting the attachment position or peeling from the object.

(2)
In the fiber-reinforced resin prepreg sheet according to (1) above, the weight ratio of the fibers contained in the fiber-reinforced resin layer to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer is 20% or more. It may be 60% or less.

By thus setting the weight ratio of the fibers within the predetermined range, it is possible to preferably obtain the ease of sticking to the object and the strengthening property of the object.

(3)
In the fiber-reinforced resin prepreg sheet described in (1) or (2) above, the fibers contained in the fiber-reinforced resin layer may be a unidirectional fiber material.

This makes it easy for the fiber-reinforced resin prepreg sheet to follow the crevices of the cracks when the object to be adhered has a linear crack such as a hardened cement product.

(4)
In the fiber-reinforced resin prepreg sheet according to any one of (1) to (3), the first resin layer may have a thickness of 60 μm or more.

Thereby, the fiber reinforced resin prepreg sheet can be attached to the object with a lighter load.

(5)
In the fiber-reinforced resin prepreg sheet according to any one of (1) to (4) above, the viscosity of the resin forming the first resin layer at 30° C. may be 10,000 Pa·s or more and 50,000 Pa·s or less.

Thereby, the fiber reinforced resin prepreg sheet can be attached to the object with a lighter load.

(6)
The fiber-reinforced resin prepreg sheet according to any one of (1) to (5) above may include a barrier layer provided on the opposite side of the second resin layer from the fiber-reinforced resin layer.

This makes it possible to better protect the object.

(7)
The fiber-reinforced resin prepreg sheet according to any one of (1) to (6) above may be used for attaching and reinforcing the surface of the metal structure.

Thereby, the fiber reinforced resin prepreg sheet can be attached to the object with a lighter load.

According to the present invention, there is provided a fiber reinforced resin prepreg sheet that can be attached to an object with a light load.

It is a typical sectional view showing an example of a fiber reinforced resin prepreg sheet of the present invention. It is a typical sectional view showing other examples of the fiber reinforced resin prepreg sheet of the present invention.

[1. Fiber reinforced resin prepreg sheet]
[1-1. Basic structure]
FIG. 1 is a schematic cross-sectional view showing an example of the fiber-reinforced resin prepreg sheet of the present invention. The fiber-reinforced resin prepreg sheet 100 shown in FIG. 1 includes a first resin layer 210, a fiber-reinforced resin layer 250, and a second resin layer 220. The first resin layer 210, the fiber reinforced resin layer 250, and the second resin layer 220 are laminated in this order. The total thickness of the first resin layer 210, the fiber-reinforced resin layer 250, and the second resin layer 220 is, for example, 0.1 mm or more and 3 mm or less, preferably 0.5 mm or more and 1.5 mm or less. It is preferable that the total thickness is equal to or more than the above lower limit because it is easy to secure the first resin total 210 with an appropriate thickness, and if the total thickness is equal to or less than the above upper limit, the prepreg sheet is particularly preferable when the surface is a curved surface. This is preferable because it is easy to follow without causing creases on the concave curved surface side due to the difference between the inner and outer peripheries, and it is possible to suppress an increase in the sheet area to be attached to the outer layer in the case of multi-layered attachment to the columnar structure. The fiber-reinforced resin prepreg sheet 100 of this embodiment further includes a barrier layer 290. The barrier layer 290 is laminated on the second resin layer 220. In the fiber-reinforced resin prepreg sheet 100, the release sheet 300 is attached to the first resin layer 210.

FIG. 2 is a schematic cross-sectional view showing another example of the fiber-reinforced resin prepreg sheet of the present invention. The fiber-reinforced resin prepreg sheet 100a shown in FIG. 2 is the same as the fiber-reinforced resin prepreg sheet 100 described above except that it does not have the barrier layer 290.
The fiber-reinforced resin prepreg sheet 100 will be described below.

[1-2. First resin layer]
The first resin layer 210 not only smoothes the surface of the fiber reinforced resin layer 250, but also has a predetermined thickness and a predetermined viscosity, thereby serving as an adhesive layer for bonding the fiber reinforced resin prepreg sheet 100 to an object. Function.

The thickness of the first resin layer 210 is 50 μm or more, preferably 60 μm or more. When the thickness of the first resin layer 210 is in the above range, the fiber reinforced resin prepreg sheet 100 can be attached to an object with a light load, and further, it is possible to follow the unevenness of the object to be adhered, resulting in poor adhesion. It is possible to prevent the resin tank from peeling from the surface of the carbon fiber during the peeling work. The upper limit in the thickness range of the first resin layer 210 is not particularly limited, but may be, for example, 500 μm, preferably 200 μm from the viewpoint of preventing the total thickness of the fiber reinforced resin prepreg sheet 100 from being enlarged.

The resin composition forming the first resin layer 210 is maintained in a pregelled state. The pre-gelled state is a state in which the resin composition is not completely cured and can retain its own shape by thickening. As a result, the first resin layer 210 has adhesiveness.

The storage elastic modulus of the resin forming the first resin layer 210 at 30° C. and a frequency of 100 Hz may be 30,000 Pa or higher, preferably 35,000 Pa or higher. This allows the release sheet 300 to be easily released.
The storage elastic modulus of the resin forming the first resin layer 210 at 30° C. and a frequency of 1 Hz may be 200,000 Pa or less, preferably 100,000 Pa or less. As a result, it can be firmly adhered to the object.

The viscosity of the resin forming the first resin layer 210 at 30° C. and a frequency of 1 Hz is 200 Pa·s or more and 50,000 Pa·s or less, preferably 10,000 Pa·s or more and 50,000 Pa·s or less. It is preferable that the viscosity is equal to or higher than the lower limit in terms of maintaining the thickness of the first resin layer 210 and that the release sheet 300 can be easily peeled off, and if the viscosity is equal to or lower than the upper limit, conformability to the surface of the object is preferable. Is preferable and the fiber-reinforced resin prepreg sheet 100 can be attached to an object with a light load.

The resin forming the first resin layer 210 may exhibit a minimum viscosity of 1 Pa·s or higher, preferably 30 Pa·s or higher at 130° C. or higher and 150° C. or lower. Accordingly, the thickness of the first resin layer 210 is appropriately maintained even when the first resin layer 210 is subjected to heating conditions during curing, and thus it is possible to favorably prevent the fiber reinforced resin prepreg sheet 100 from shifting during construction.
Further, the resin forming the first resin layer 210 may exhibit a minimum viscosity of 130 Pa or higher and 165° C. or lower, of 1 Pa·s or more, preferably 50 Pa·s or more, and more preferably 500 Pa·s or more. Accordingly, the thickness of the first resin layer 210 is appropriately maintained even when subjected to heating and pressurizing conditions during curing, so that the pressure applied during curing can be effectively applied. Therefore, the adhesive strength to the object is excellent. Further, it is possible to prevent the displacement after the attachment.

The resin composition forming the first resin layer 210 is a one-component resin composition, and is a thermosetting resin and/or an energy ray curable resin in an uncured state (hereinafter sometimes simply referred to as an uncured resin). ), hardeners and thickeners, and may also include other additives.
The uncured resin is not particularly limited, and examples thereof include epoxy resin, unsaturated polyester resin, phenol resin, vinyl ester resin, cyanate ester resin, urethane acrylate resin, phenoxy resin, alkyd resin, urethane resin, maleimide resin and cyanic acid. Examples thereof include prepolymerized resins of ester resins, bismaleimide resins, acetylene-terminated polyimide resins and polyisoimide resins, and nadic acid-terminated polyimide resins. These resins may be used alone or in combination of two or more.

In this embodiment, an epoxy resin is preferably used as a main component from the viewpoint of adhesiveness to different materials. The epoxy resin is an epoxy prepolymer compound having one or more functional epoxy groups, preferably two or more functional groups. Specifically, it means at least one of a monomer having an epoxy group, an oligomer having an epoxy group, and a polymer having an epoxy group. Since the resin composition is thickened by the thickener, the epoxy prepolymer compound preferably contains at least a monomer or an oligomer, and may be a monomer or an oligomer only.
Further, the epoxy prepolymer compound includes glycidyl ether type, glycidyl amine type, glycidyl ester type, and alicyclic epoxy compounds.

The glycidyl ether type, glycidyl amine type and glycidyl ester type epoxy compounds can be obtained from a halide having a glycidyl alkyl group and an active hydrogen compound (alcohol, amine and carboxylic acid, respectively).

Examples of the glycidyl ether type epoxy compound include a bisphenol A type epoxy compound, a bisphenol A type epoxy compound bromide, a bisphenol A type epoxy compound hydrogenated product, a bisphenol F type epoxy compound, a bisphenol F type epoxy compound bromide, and a bisphenol F type epoxy compound. Hydrogenated compounds, bisphenol S type epoxy compounds, o-, m-, p-cresol novolac type epoxy compounds, phenol novolac type epoxy compounds, naphthalene ring-containing epoxy compounds, biphenyl type epoxy compounds, biphenyl novolac type epoxy compounds, di- Cyclopentadiene type epoxy compound, phenol aralkyl type epoxy compound, dihydroxypentadiene type epoxy compound, triphenylmethane type epoxy compound, etc., and phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl Examples thereof include ether and allyl glycidyl ether.

Examples of the glycidyl amine type epoxy compound include tetraglycidyl diaminodiphenylmethane, triglycidyl aminophenol, tetraglycidyl xylene diamine, glycidyl aniline, and glycidyl o-toluidine.
Examples of the glycidyl ester type epoxy compound include phthalic acid diglycidyl ester, terephthalic acid diglycidyl ester, and dimer acid diglycidyl ester.

The alicyclic epoxy compound is a compound having an alicyclic ring and an epoxy group, and more specifically, an alicyclic epoxy group (epoxy composed of two adjacent carbon atoms and oxygen atoms forming an alicyclic ring). Group) and a compound having an epoxy group which is directly or indirectly single-bonded to an aliphatic ring.

The compound having an alicyclic epoxy group is preferably a compound in which two alicyclic epoxy groups are linked by a single bond or a divalent linking group. A cyclohexene oxide group is mentioned as an alicyclic epoxy group. Examples of the divalent linking group include a divalent hydrocarbon group, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and groups in which a plurality of these groups are linked. For example, 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (for example, Celoxide 2021P manufactured by Daicel Corporation), ε-caprolactone-modified 3′,4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxy. A rate (for example, Celoxide 2081 manufactured by Daicel Corporation) is preferable. In addition, as a compound having an alicyclic epoxy group, 1,2-epoxy-4-vinylcyclohexane (for example, Cellecide 2000 manufactured by Daicel Corp.) and 3-methacryloyloxymethylcyclohexene having one alicyclic epoxy group are used. Examples thereof include oxide, 3-acryloyloxymethylcyclohexene oxide, and 3-vinylcyclohexene oxide.

Examples of the compound having an epoxy group directly or indirectly single-bonded to an aliphatic ring include epoxynorbornene (for example, Celoxide 3000 manufactured by Daicel Corp.), 1,2-bis(hydroxymethyl)-1-butanol 2-epoxy-4-(2-oxiranyl)cyclohexane adduct (for example, EHPE3150 manufactured by Daicel Corp.) and the like can be mentioned.

A so-called latent curing agent is used as the curing agent. The latent curing agent is a compound that is activated by dissolution, decomposition, transfer reaction or the like upon heating and/or irradiation with active energy rays, and functions as a curing accelerator for a thermosetting or energy ray curable resin. .. Therefore, the fiber-reinforced resin prepreg sheet 100 is contained in an inactive state as a curing agent until it is attached to an object and subjected to curing conditions.

The curing agent may be a compound which is activated by the action of heat, or a compound which is activated by the action of active energy rays such as light (especially ultraviolet rays), electromagnetic waves (especially X-rays) and electron rays. Or both may be combined. More specifically, dicyandiamide, BF ₃ -amine complex, modified imidazole compound (for example, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl5-hydroxymethylimidazole, 2,4-diamino). Compounds such as -6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole) and onium salts can be mentioned. In addition, these compounds may be microencapsulated or may be made into an inclusion compound with an organic polymer from the viewpoint of storage stability and fast curing performance.

Thickeners are thickeners that thicken with increasing temperature and exclude solid epoxy resins. As a result, it is possible to prevent defective adhesion due to a decrease in viscosity due to a temperature rise during curing, such as a solid epoxy resin. Specific examples thereof include core-shell type thermoplastic resin particles and vinyl chloride resin particles.

The core component of the core-shell type thermoplastic resin particles is not particularly limited, but for example, one or more selected from (meth)acrylic acid esters, dienes and monomers copolymerizable therewith are used as the monomer component. It may be a resin (particularly poly(meth)acrylic acid ester-based organic fine particles).
Examples of the (meth)acrylic acid ester include ethyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, n-propyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and n-decyl. Methacrylate, isobutyl (meth)acrylate, n-amyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate and the like can be mentioned. To be
Examples of the diene include conjugated diene compounds such as butadiene, isoprene, 1,3-pentadiene, cyclopentadiene and dicyclopentadiene, and non-conjugated diene compounds such as 1,4-hexadiene and ethylidene norbornene.
Examples of monomers copolymerizable with these are aromatic vinyl compounds such as styrene, α-methylstyrene, vinyltoluene, pt-butylstyrene, and chlorostyrene, acrylamide, N-methylolacrylamide, N-butoxymethylacrylamide. And methacrylamide compounds such as methacrylamide, N-methylolmethacrylamide, N-butoxymethylmethacrylamide, and glycidyl acrylate, glycidyl methacrylate, allyl glycidyl acrylate, and the like.

The shell component of the core-shell type thermoplastic resin is not particularly limited, but it may be a resin containing two or more kinds selected from the above monomers as the monomer component. The shell layer should be copolymerized with N-substituted acrylamide, a (meth)acrylic acid ester-based crosslinkable monomer having at least two radically polymerizable double bonds, and a monomer having a free carboxyl group. You can This tends to result in a structure that exhibits solubility in the thermosetting resin or the energy ray curable resin.
Examples of the N-substituted acrylamide include N-acryloylpyrrolidine, N,N-dimethylacrylamide, N-isopropylacrylamide, N-hexylacrylamide, N-octylacrylamide, N-dodecylacrylamide and the like.
Examples of the crosslinkable monomer having at least two double bonds capable of radical polymerization with the (meth)acrylic acid ester-based monomer include ethylene glycol diacrylate, butylene glycol diacrylate, trimethylolpropane diacrylate, and trimethylol. Propane triacrylate Hexanediol diacrylate, oligoethylene diacrylate, ethylene glycol dimethacrylate, butylene glycol dimethacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, hexanediol dimethacrylate, oligoethylenedimethacrylate, divinylbenzene, etc. Group divinyl monomers, triallyl trimellitate, triallyl isocyanurate and the like can be mentioned.
The monomer having a free carboxyl group, (meth) acrylic acid, crotonic acid, unsaturated monocarboxylic acids such as cinnamic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, dicarboxylic acids such as chloromaleic acid, Examples thereof include monoesters of unsaturated dicarboxylic acids such as monomethyl maleate, monoethyl maleate, monobutyl maleate, monomethyl fumarate, monomethyl itaconate, monoethyl itaconate and monobutyl itaconate.

The vinyl chloride resin is not particularly limited, and other than a homopolymer of vinyl chloride monomer, for example, a copolymer of vinyl chloride monomer and a polymerizable monomer other than vinyl chloride monomer, chloride Examples thereof include a graft copolymer obtained by grafting a vinyl chloride monomer or a vinyl chloride resin on a polymer other than the vinyl resin. Furthermore, chlorinated vinyl chloride resins obtained by chlorinating these vinyl chloride resins are also included. These vinyl chloride resins may be used alone or in combination of two or more.

The polymerizable monomer in the copolymer of the vinyl chloride monomer and the polymerizable monomer other than the vinyl chloride monomer is not particularly limited, but α-olefin having 2 to 16 carbon atoms (for example, ethylene , Propylene, and butylene); vinyl esters of aliphatic carboxylic acids having 2 to 16 carbon atoms (for example, vinyl acetate and vinyl propionate); alkyl vinyl ethers having 2 to 16 carbon atoms (for example, butyl vinyl ether and cetyl vinyl ether) An alkyl (meth)acrylate having 1 to 16 carbon atoms (for example, methyl (meth)acrylate, ethyl (meth)acrylate and butyl acrylate); an aryl (meth)acrylate (for example, phenyl methacrylate); an aromatic vinyl (for example, Styrene and α-substituted styrenes (eg α-methylstyrene); vinyl halides (eg vinylidene chloride and vinylidene fluoride); and N-substituted maleimides (N-phenylmaleimide and N-cyclohexylmaleimide).

As the polymer which gives the graft copolymer together with the vinyl chloride monomer or the vinyl chloride resin, any polymer can be used, regardless of homopolymer or copolymer, as long as it is a polymer which can be graft-polymerized to the vinyl chloride monomer. Be done. For example, a copolymer of α-olefin and vinyl ester (for example, ethylene-vinyl acetate copolymer); a copolymer of α-olefin, vinyl ester and carbon monoxide (for example, ethylene-vinyl acetate-monoxide). Carbon copolymer); Copolymer of α-olefin and alkyl (meth)acrylate (for example, ethylene-methyl methacrylate copolymer and ethylene-ethyl acrylate copolymer); α-olefin and alkyl (meth)acrylate Copolymer with carbon monoxide (for example, ethylene-butyl acrylate-carbon monoxide copolymer); Copolymer of two or more different α-olefins (for example, ethylene-propylene copolymer); Unsaturated nitrile And diene copolymers (eg acrylonitrile-butadiene copolymer); polyurethanes; and chlorinated polyolefins (eg chlorinated polyethylene and chlorinated polypropylene).

The average degree of polymerization of the vinyl chloride resin is not particularly limited, but is, for example, 400 or more and 1500 or less, preferably 600 or more and 1300 or less. When the average degree of polymerization is at least the above lower limit value, it is easy to obtain preferable physical properties (for example, toughness) of the vinyl chloride resin, and it is easy to obtain the tackiness suitable for the application with an appropriate addition amount. When the average degree of polymerization is less than or equal to the above upper limit value, a mode of compatibility or swelling with respect to the uncured resin can be easily obtained with a small amount of addition. Since the above-mentioned characteristics are influenced by the composition of the uncured resin, even an average degree of polymerization exceeding the above range may be appropriately selected by those skilled in the art.

Since the thickener is in the form of particles, it is easy to obtain a compatibility state or a swelling state with the uncured resin in the production of the fiber reinforced resin prepreg sheet 100, and the handling property is also excellent. From the viewpoint of obtaining these conditions more preferably, the average particle diameter of the thickener particles may be 0.2 μm or more and 200 μm or less. The average particle diameter means a volume-based 50% cumulative distribution diameter measured by a dynamic scattering method using laser light.

The content of the thickener is not particularly limited, but may be, for example, 5 parts by weight or more and less than 50 parts by weight, preferably 15 parts by weight or more and less than 35 parts by weight, relative to 100 parts by weight of the above uncured resin. It is preferable that the content is equal to or more than the above lower limit in terms of obtaining a thickening effect satisfactorily and reducing the load at the time of sticking the fiber reinforced resin prepreg sheet 100, and if less than the above upper limit, the target surface It is preferable in that the following property can be obtained well and the load at the time of attaching the fiber reinforced resin prepreg sheet 100 is reduced.

A filler may be added to the resin composition for the purpose of reducing curing stress due to curing shrinkage. Examples of the filler include calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolin, clay, celite, barlite, baryta, silica, silica sand, dolomite limestone, gypsum, hollow balloon, alumina, glass powder, aluminum hydroxide. , Zirconium oxide, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder and the like.

[1-3. Fiber-reinforced resin layer]
The fiber reinforced resin layer 250 is composed of fibers and a matrix resin impregnated in the fibers. In the present embodiment, the matrix resin and the resin composition forming the above-mentioned first resin layer 210 are advantageous in that the fiber-reinforced resin prepreg sheet 100 can be easily manufactured, the interlayer compatibility can be obtained, and an integrated curing mode can be obtained after curing. It is the same. However, the matrix resin is allowed to be different from the resin composition forming the first resin layer 210 as long as it is selected from those that can be the resin composition forming the first resin layer 210 described above. ..

In particular, the matrix resin of the fiber-reinforced resin layer 250 exhibits a minimum viscosity of 1 Pa·s or more, preferably 30 Pa·s or more at 130° C. or higher and 150° C. or lower, so that the fiber-reinforced resin is hardened even when subjected to heating conditions during curing. Since the resin is prevented from leaching from the resin layer, it is possible to favorably prevent the fiber-reinforced resin prepreg sheet 100 from being displaced during construction.

The weight ratio of the fibers contained in the fiber-reinforced resin layer 250 to the total weight of the first resin layer 210, the fiber-reinforced resin layer 250, and the second resin layer 220 is, for example, 5% or more and 60% or less, preferably 20%. The above may be 60% or less, more preferably 20% or more and 35% or less, and further preferably 10% or more and 30% or less. It is preferable that the weight ratio is equal to or more than the lower limit value in order to obtain good strengthening property of the object as an object, and if the weight ratio is equal to or less than the upper limit value, it is easy to secure the thickness of the first resin layer 210. It is preferable in that it is easy to attach.

Fibers include carbon fibers such as PAN (polyacrylonitrile)-based carbon fibers and pitch-based carbon fibers; metal fibers such as steel fibers; inorganic fibers such as glass fibers, ceramic fibers, boron fibers; and aramid, polyester, polyethylene, nylon. , Vinylon, polyacetal, polyparaphenylenebenzoxazole, high-strength polypropylene, and other organic fibers; kenaf, hemp, and other natural fibers. These fibers may be used alone or in combination of two or more. From the viewpoint of specific strength, carbon fiber is preferable.

The form of the fiber is not particularly limited, and examples thereof include a form in which fibers such as tows, cloths, chopped fibers, and continuous fibers are aligned in one direction; a form in which continuous fibers are formed into a woven fabric; Alignment in one direction Hold with weft auxiliary yarns; Multi-axial warp knit in which a plurality of fiber sheets in which the fiber directions are aligned in one direction are stitched together with overlapping auxiliary yarns so that the fiber directions are different And the form of a non-woven fabric of fibers. Among these, the one in which the fibers are aligned in one direction and the one in which the tows are aligned in one direction and held by the weft auxiliary yarn (unidirectional fiber material) are preferable. In this case, the fibers are unidirectional in the entire fiber reinforced resin prepreg sheet 100. The fiber-reinforced resin prepreg sheet 100 containing a unidirectional fiber material as a reinforcing fiber makes it easy to cause the fiber direction to follow the crevice of the crack when the object to be attached causes a linear crack, such as a cement hardened material, For example, when the object to be attached is an axial body such as a tube, the fiber direction is easily aligned with the axial direction.

The basis weight of the fibers may be, for example, 100 g/m ² or more and 600 g/m ² or less. It is preferable that the basis weight is equal to or more than the lower limit value in that an appropriate amount can be applied with a small number of construction treatments depending on the degree of deterioration of reinforcement or repair hardening, and if it is less than or equal to the upper limit value, impregnability is improved. It is preferable in terms of obtaining good results.

[1-4. Second resin layer]
The second resin layer 220 in the present embodiment not only smoothes the surface of the fiber reinforced resin layer 250, but also functions as an adhesive layer that adheres the barrier layer 290.
In the present embodiment, the resin constituting the second resin layer 220 is the above-mentioned first resin in view of the ease of manufacturing the fiber reinforced resin prepreg sheet 100, the interlayer compatibility, and the fact that an integrated curing mode is obtained after curing. It is the same as the resin composition constituting the matrix resin of the layer 210 and the fiber reinforced resin layer 250. However, as long as the resin forming the second resin layer 220 is selected from those that can be the resin composition forming the matrix resin of the first resin layer 210 and/or the fiber reinforced resin layer 250 described above, It may be different from the resin composition constituting the matrix resin of the 1 resin layer 210 and/or the fiber reinforced resin layer 250. Alternatively, the resin forming the second resin layer 220 may be different from the resin that can be the resin composition forming the matrix resin of the first resin layer 210 and/or the fiber-reinforced resin layer 250 described above.

[1-5. Barrier layer]
The substance forming the barrier layer 290 is not particularly limited as long as it has a barrier function as a layer. Examples of the barrier properties include ultraviolet barrier properties; gas barrier properties such as carbon dioxide barrier properties, oxygen barrier properties, and water vapor barrier properties. The barrier layer 290 may have a single-layer structure or a laminated structure of a plurality of layers having different barrier properties.

When the barrier layer 290 has an ultraviolet barrier property, a base resin such as an acrylic resin can contain an ultraviolet shielding agent. Examples of the ultraviolet ray shielding agent include those generally called pigments and ultraviolet ray absorbing agents.

As the pigment, phthalocyanine-based, isoindolinone-based, perylene-based, azo-based, condensed azo-based, quinacridone-based, anthraquinone-based, aniline black-based, triphenylmethane-based, dioxazine-based, titanium oxide-based, iron oxide-based, oxidized Pigments such as chromium type, lead chromate type, spinel type firing type, diketopyrrolopyrrole type, manganese oxide-bismuth oxide complex salt type, manganese oxide-yttrium complex salt type, iron oxide-chromium oxide complex salt type and the like. .. The pigment may be used alone or in combination of two or more.

As the ultraviolet absorber, an inorganic ultraviolet absorber such as zinc oxide, titanium oxide, calcium carbonate, cerium oxide, silica, aluminum hydroxide, magnesium hydroxide, calcium hydroxide, carbon black, white carbon, zeolite, graphite; phenyl Salicylates such as salicylate, p-tert-butylphenyl salicylate and p-octylphenyl salicylate; Benzophenones such as 2,4-gihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone; 2-(2'-Hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-5-tert-butylphenyl)benzotriazole and other benzotriazoles; 2-ethylhexyl-2- Examples include cyanoacrylate-based organic UV absorbers such as cyano-3,3'-diphenyl acrylate and ethyl-2-cyano-3,3'-diphenyl acrylate. The ultraviolet absorber may be used alone or in combination of two or more.

When the barrier layer 290 has a gas barrier property, the resin forming the barrier layer 290 includes polyvinyl alcohol (PVA), ethylene vinyl alcohol copolymer (EVOH), polyvinylidene chloride resin (PVDC), and polyacrylonitrile ( Examples thereof include gas barrier resins such as PAN).

[1-6. Release sheet]
The release sheet may be a resin film, and specific examples thereof include a polyester film such as a polyethylene terephthalate film and a resin film such as a polyolefin film such as a polypropylene film. The surface of the resin film may be subjected to a release treatment by providing a release control agent layer such as a silicone resin.

[2. Manufacturing method of fiber reinforced resin prepreg sheet]
The fiber-reinforced resin prepreg sheet 100 can be manufactured by, for example, a resin mixing step, an impregnation step, and a thickening step.

[2-1. Resin mixing process]
In the resin mixing step, the uncured resin and the thickener are mixed to obtain a mixed resin liquid. The mixed resin liquid may be solvent-free, but when the mixed resin liquid alone has too high a viscosity, a solvent may be added to prepare the mixed resin liquid. This facilitates the impregnation of the fibers in the impregnation step. In this case, the solvent may be a low boiling point solvent. Specific examples of the low boiling point solvent include organic solvents such as ethanol, toluene, and acetone. When an acrylic thickener is used together, a solvent that is incompatible with the thickener is preferable. The amount of the solvent is appropriately adjusted for the purpose of obtaining good impregnating ability for the reinforcing fiber, but if it is too large, a large amount of heat and time are required for the drying treatment, so the minimum amount that enables the impregnation of the fiber. It is preferable that

The temperature of the mixed resin liquid may be, for example, 20° C. or higher and 60° C. or lower, preferably 30° C. or higher and 50° C. or lower. It is preferable that the temperature is equal to or higher than the lower limit value in order to lower the resin viscosity and obtain good impregnating ability to the fiber, and if the temperature is equal to or lower than the upper limit value, the thickening of the mixed resin liquid is prevented to the fiber. Is preferable in terms of obtaining good impregnating property.

[2-2. Impregnation process]
In the impregnation step, the fibers are impregnated with the mixed resin liquid. The temperature condition allowed in the supporting process may be the same as the temperature condition in the resin mixing process. For example, the same temperature may be maintained in the resin mixing step and the impregnation step, or the temperature of the mixed resin liquid may be increased within the above temperature range in order to improve the impregnation property into the resin, The temperature of the mixed resin liquid may be lowered within the above-mentioned temperature range in order to favorably hold the fibers and to secure the thickness of the first resin layer 210.

The method of impregnation is not particularly limited and is appropriately selected by those skilled in the art. For example, the fibers can be immersed in a liquid tank containing the mixed resin liquid, and if necessary, the impregnation can be made efficient by using a technique such as a treatment of the fibers and a pressure change treatment such as pressurization or vacuum. it can. After the fiber impregnated with the mixed resin liquid is pulled out from the liquid tank, the amount of the mixed resin liquid adhering to the surface of the fiber is adjusted by a doctor knife or the like to secure the thickness of the first resin layer 210. it can.

[2-3. Thickening process]
In the thickening step, the mixed resin liquid impregnated in the fibers is thickened. Specifically, by heating, the thickener contained in the mixed resin liquid is preferably swollen with the uncured resin. Alternatively, it is allowed to be compatible with the uncured resin.

The heating temperature may be any temperature at which a compatible or swollen state is obtained. For example, it is 80°C or higher, preferably 100°C or higher. As a result, the solvent is evaporated and at least a swollen state can be easily obtained. On the other hand, the higher the temperature, the easier it is to obtain a compatible state. Furthermore, the upper limit within the range of the heating temperature may be, for example, 140° C. or lower, preferably 120° C. or lower. The upper limit of the heating temperature can be appropriately adjusted by those skilled in the art in consideration of the curing temperature of the uncured resin.

The heating time may be appropriately adjusted in accordance with the above temperature so that a compatible or swelled state can be obtained and the effect of the curing reaction does not appear. For example, the heating time may be 10 minutes or more and 60 minutes or less.

The barrier layer 290 may be laminated by coating a coating layer of the barrier resin composition, or may be laminated by laminating a barrier film.

After the thickening is completed, the release sheet 300 is provided to obtain the fiber reinforced resin prepreg sheet 100. The obtained fiber reinforced resin prepreg sheet 100 may be divided into a predetermined size and size, or may be wound into a roll shape.

[3. Method of reinforcing or repairing an object using fiber reinforced resin prepreg sheet]
The fiber reinforced resin prepreg sheet 100 can be used for reinforcing or repairing an object. Reinforcement refers to a process for imparting mechanical properties that are better than the sound state (non-deteriorated state) of the target regardless of the degree of deterioration of the target, and repair is due to deterioration of the target. A process for recovering the deterioration of mechanical properties to the same level as a sound state (non-deteriorated state). The method of reinforcing or repairing an object includes a sticking step and a hardening step.

[3-1. Pasting process]
In the attaching step, the fiber reinforced resin prepreg sheet 100 described above is attached to an object to be reinforced or repaired. The object may be a building structure, building material, structure such as piping. The material of the object may be a metal or a hardened cement. Examples of the metal include carbon steel and cast steel. Examples of hardened cement include mortar and concrete.

The surface to be attached may be subjected to surface removal (kelen treatment) to smooth or roughen it in advance, or may be treated with a primer. Examples of the skeleton treatment include a treatment with a wire brush, a disc grinder, a sand blast and a bristol blast. Since the first resin layer 210 of the fiber-reinforced resin prepreg sheet 100 of the present invention functions as an adhesive layer, another layer such as an adhesive layer is interposed between the object and the fiber-reinforced resin prepreg sheet 100 to assist adhesion. Adhesion is possible without this, but the present invention also allows an embodiment in which another layer that assists the adhesion is interposed.

In the attaching step, the fiber reinforced resin prepreg sheet 100 is attached to an object. The fiber reinforced resin prepreg sheet 100 can be pressed against the target object by a roller or the like in order to surely bond the target object to the target object. The pressing pressure of the fiber reinforced resin prepreg sheet 100 is, for example, less than 50,000 Pa, preferably less than 10,000 Pa. Since the fiber reinforced resin prepreg sheet 100 is excellent in easy attachment, it can be attached with such a light force. The lower limit value within the range of the pressing pressure is not particularly limited, but is 1,000 Pa, preferably 10,000 Pa, from the viewpoint of sure attachment.

One fiber reinforced resin prepreg sheet 100 may be used for a specific portion of the target object, or a plurality of fiber reinforced resin prepreg sheets 100 may be used by being stacked at the specific portion. When stacking a plurality of sheets, the above fiber-reinforced resin prepreg sheet 100 having the barrier layer 290 on the outermost fiber-reinforced resin prepreg sheet is used, and the other fiber-reinforced resin prepreg sheets do not have the barrier layer 290. The reinforced resin prepreg sheet 100a can be used.

[3-2. Curing process]
In the curing step, the resin composite in the pasted state is subjected to the activation condition of the curing agent. Thereby, the resin composition contained in the fiber reinforced resin prepreg sheet 100 is completely cured. Therefore, the object is reinforced or repaired with the completely cured body of the fiber-reinforced resin firmly adhered to the surface.

The activation condition of the curing agent can be appropriately determined by those skilled in the art based on the resin composition and the curing agent used in the fiber reinforced resin prepreg sheet 100.

When the fiber-reinforced resin prepreg sheet 100 has a minimum viscosity at 130° C. or higher and 150° C. or lower, and the minimum viscosity is 1 Pa·s or higher, preferably 30 Pa·s or higher, a relatively high viscosity is maintained. Since the thickness of the resin layer 210 is appropriately maintained and the resin can be prevented from leaching from the fiber reinforced resin layer 250, it is suitable for thermosetting.

Further, in the above case, since the thickness of the first resin layer 210 is appropriately maintained even after curing, and it is possible to prevent the resin from leaching from the fiber reinforced resin layer, the pressing is performed in the curing step. It is possible to obtain a good fixed state even without the use. In this case, since a tool or the like for pressing is not required, on-site construction is easy and the degree of freedom in the shape of the construction object is significantly increased.

Furthermore, when the fiber-reinforced resin prepreg sheet 100 has a minimum viscosity of 30 Pa·s or higher, preferably 50 Pa·s or higher at 130° C. or higher and 150° C. or lower, the applied pressure is heated by heating and pressurizing. The fiber-reinforced resin prepreg sheet 100 can be used to efficiently act on the object. Thereby, the fiber-reinforced resin can be firmly fixed to the object.

When the pressurization is performed, the pressurization condition may be 1,000 Pa or more and 200,000 Pa or less, preferably 10,000 Pa or more. It is preferable that the pressure condition is equal to or higher than the lower limit value in that the fiber-reinforced resin prepreg sheet 100 is satisfactorily pressed against the object and the adhesive strength to the object becomes good, and the pressure condition is equal to or lower than the upper limit value. It is preferable because the adhesive strength to the object is improved by not crushing the thickness of the first resin layer 210. At the time of pressurization, it is preferable to interpose a release sheet or the like for the purpose of preventing the prepreg sheet from adhering to a device for pressing. Examples of the release sheet include a sheet whose surface is subjected to a release treatment, and a Teflon (registered trademark) sheet having excellent non-adhesiveness.

In the case of heat curing, the curing conditions may be heating conditions of 100°C or higher and 200°C or lower, preferably 130°C or higher and 200°C or lower. It is preferable that the temperature is equal to or higher than the lower limit value because the first adhesive layer 210 of the fiber-reinforced resin prepreg sheet 100 can easily follow the surface of the object, and if the temperature is equal to or lower than the upper limit value, the fiber-reinforced resin prepreg sheet. It is preferable in that the resin and/or the fibers constituting 100 are prevented from being modified. Therefore, the fiber-reinforced resin prepreg sheet 100 can be firmly fixed to a different material. The heating time may be 5 minutes or more and 60 minutes or less, preferably 10 minutes or more and 30 minutes or less. It is preferable that the heating time is at least the above lower limit value in order to sufficiently advance the curing reaction to obtain adhesive strength, and it is preferable that the heating time is at most the above upper limit value in order to prevent denaturation of the cured resin.

The heating method is not particularly limited, but a non-contact heating method such as hot air or an infrared heater is preferable in order to ensure a high degree of freedom with respect to the shape of the object.

[3-3. Reattaching-Temporary attaching process and resetting process]
In the fiber-reinforced resin prepreg sheet 100, since the first resin layer 210 has a high viscosity when uncured, it can be reattached before being cured. For example, it is useful when it is desired to correct the attachment position and/or the attachment direction of the fiber reinforced resin prepreg sheet 100. When performing such reattachment, the method of reinforcing or repairing the object using the fiber reinforced resin prepreg sheet further includes a temporary attaching step and a resetting step before the above-mentioned attaching step (main attaching step). ..

In the temporary attaching step, the fiber reinforced resin prepreg sheet 100 is attached to an object at a temporary position and/or direction. In the reset step, the temporarily attached fiber-reinforced resin prepreg sheet 100 is peeled off from the object. Further, after this, in the above-mentioned attaching step (main attaching step), the peeled fiber reinforced resin prepreg sheet 100 is attached again to the target object at a position/and/or direction that is judged to be more appropriate.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following inventions.

[Example 1]
Epoxy resin jER828 (Mitsubishi Chemical Co., Ltd.) 100 parts by weight, dicyandiamide DICY-7 (Mitsubishi Chemical Co., Ltd.) 7 parts by weight, 2-phenyl-4,5-dihydroxymethylimidazole 2PHZ-PW (Shikoku Kasei) (Manufactured by Co., Ltd.) and 15 parts by weight of polymethacrylic acid ester-based organic fine particles Zefiac F301 (manufactured by Aika Kogyo Co., Ltd.) are stirred and defoamed in a planetary mixer at 20° C. and 2000 rpm for 10 minutes. A mixed resin solution was prepared.

As the carbon fiber sheet, a unidirectional cloth (PAN-based, 300 g/m ² ) was used and immersed in a liquid tank containing the above-mentioned mixed resin liquid heated to 40°C. The immersed carbon fiber sheet was handled while passing it through a roll for defoaming and resin impregnation, subsequently pulled up from the liquid tank, and the thickness of the mixed resin liquid adhering to the surface was adjusted with a doctor knife.

Then, the carbon fiber sheet impregnated with the mixed resin solution was left to stand in an environment of 110° C. for 30 minutes for thickening. Thus, a fiber reinforced resin prepreg sheet composed of the first resin layer, the fiber reinforced resin layer and the second resin layer was obtained. The thickness of the first resin layer was 60 μm, the thickness of the fiber-reinforced resin layer was 700 μm, and the total thickness was 860 μm. The weight ratio of the carbon fiber sheet was 28% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Example 2]
A fiber-reinforced resin prepreg sheet was obtained in the same manner as in Example 1 except that 20 parts by weight of polymethacrylic acid ester-based organic fine particles Zefiac F301 (manufactured by Aika Kogyo Co., Ltd.) was used and the thickness of the first resin layer was 100 μm. It was created.
In the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 900 μm. The weight ratio of the carbon fiber sheet was 30% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Example 3]
Fiber-reinforced resin prepreg sheet was obtained in the same manner as in Example 1 except that 25 parts by weight of polymethacrylic acid ester-based organic fine particles Zefiac F301 (manufactured by Aika Kogyo Co., Ltd.) was used and the thickness of the first resin layer was 100 μm. It was created.
In the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 900 μm. The weight ratio of the carbon fiber sheet was 30% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Example 4]
Fiber-reinforced resin prepreg sheet was prepared in the same manner as in Example 1 except that 35 parts by weight of polymethacrylic acid ester-based organic fine particles Zefiac F301 (manufactured by Aika Kogyo Co., Ltd.) was used and the thickness of the first resin layer was 100 μm. It was created.
In the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 900 μm. The weight ratio of the carbon fiber sheet was 30% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Comparative Example 1]
A fiber reinforced resin prepreg sheet was prepared in the same manner as in Example 1 except that the thickness of the first resin layer was 20 μm.
In the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 820 μm. The weight ratio of the carbon fiber sheet was 26% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Comparative example 2]
Fiber-reinforced resin prepreg sheet was prepared in the same manner as in Example 1 except that 25 parts by weight of polymethacrylic acid ester-based organic fine particles Zefiac F301 (manufactured by Aika Kogyo Co., Ltd.) was used and the thickness of the first resin layer was 20 μm. It was created.
In the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 820 μm. The weight ratio of the carbon fiber sheet was 26% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Comparative Example 3]
Epoxy resin CES (manufactured by Showbond Chemical Co., Ltd.) and a curing agent were mixed in a weight ratio of 2:1 and stirred at 300 rpm with a stirrer for about 3 minutes. This resin was adhered to a keeled object with a Bristol blaster, carbon fiber was placed on it, resin was further applied, impregnation treatment was performed from above with a defoaming roller, and curing was performed for 1 week while applying a pressure of 5,700 Pa. .. At this time, the resin thickness on the adhesive surface to the steel plate was about 20 μm.
Therefore, in the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 820 μm. The weight ratio of the carbon fiber sheet was 26% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Comparative Example 4]
Fiber-reinforced resin prepreg sheet was prepared in the same manner as in Example 1 except that 50 parts by weight of polymethacrylic acid ester-based organic fine particles Zefiac F301 (manufactured by Aika Kogyo Co., Ltd.) was used and the thickness of the first resin layer was 100 μm. It was created.
In the obtained fiber reinforced resin prepreg sheet, the thickness of the fiber reinforced resin layer was 700 μm, and the total thickness was 900 μm. The weight ratio of the carbon fiber sheet was 30% with respect to the total weight of the first resin layer, the fiber-reinforced resin layer, and the second resin layer.

[Viscosity measurement of resin]
The mixed resin liquids used in Examples 1 to 4 and Comparative Examples 1 to 4 were separately prepared as measurement samples, heated to 110° C. at 5° C./min, and maintained for 1 hour to increase. After viscous, the temperature was lowered to 30° C. to prepare a thickened resin composition.
Using a viscoelasticity measuring device (MCR102 Anton Paar), the viscosity of the thickened resin composition was measured under the conditions of a parallel plate radius of 25 mm, a parallel distance of 1 mm and a frequency of 1 Hz.

[Pasteability evaluation]
The fiber reinforced resin prepregs prepared in Examples 1 to 4 and Comparative Examples 1 to 4 were attached to the surface of a steel plate that had been scraped with a Bristol blaster. A roller was used at the time of sticking (the sticking pressure by the roller was less than 100,000 Pa).
"⊚" is required for those applied at an application pressure of less than 10,000 Pa, "○" is required for those applied at 10,000 Pa or more and less than 50,000 Pa, and an application pressure of 50,000 Pa or more is required. The thing was rated as "x".
In addition, the term “adhered” means that when the steel sheet is attached (before hardening) with the side with the prepreg attached facing vertically or downward, it withstands its own weight and maintains the state of attachment without shifting from the attachment position. The state.

Table 1 below shows an outline of Examples 1 to 4 and Comparative Examples 1 to 4 as well as the results of viscosity measurement and sticking property evaluation.

Although the preferred embodiments of the present invention are as described above, the present invention is not limited thereto and various other embodiments may be made without departing from the spirit of the present invention.

100, 100a... Fiber reinforced prepreg sheet 210... First resin layer 220... Second resin layer 250... Fiber reinforced resin layer

Claims (6)

A first resin layer,
A fiber-reinforced resin layer laminated on the first resin layer,
A second resin layer laminated on the fiber reinforced resin layer,
The resin composition forming the first resin layer contains core-shell type thermoplastic resin particles or vinyl chloride resin particles,
Wherein the first resin layer has a thickness of at least 50 [mu] m, and state, and are viscosity less 200 Pa · s or more 50,000 Pa · s at 30 ° C. of the resin constituting the first resin layer,
The minimum viscosity of the resin constituting the first resin layer at 130° C. or higher and 150° C. or lower is 30 Pa·s or higher,
A fiber-reinforced resin prepreg sheet in which the matrix resin of the fiber-reinforced resin layer has a minimum viscosity of 30 Pa·s or higher at 130°C or higher and 150°C or lower . The content of the core-shell type thermoplastic resin particles or vinyl chloride resin particles in the first resin layer is 5 parts by weight or more and 35 parts by weight or less with respect to 100 parts by weight of the uncured resin. Fiber reinforced resin prepreg sheet of. The fiber-reinforced resin prepreg sheet according to claim 1 or 2, wherein the fibers contained in the fiber-reinforced resin layer are unidirectional fiber materials. The fiber-reinforced resin prepreg sheet according to any one of claims 1 to 3, wherein the fiber-reinforced resin layer contains carbon fibers. The fiber reinforced resin prepreg sheet according to any one of claims 1 to 4, comprising a barrier layer provided on the side of the second resin layer opposite to the fiber reinforced resin layer. The fiber-reinforced resin prepreg sheet according to any one of claims 1 to 5, which is used for sticking and reinforcing the surface of a metal structure.

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