JP2012091418A - Method for manufacturing fiber reinforced resin sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing a transparent fiber reinforced resin sheet for reinforcement or repair with little bubble in a sheet-like transparent resin layer which contains mesh objects, and allows observation on a surface of a concrete structure, and to provide a fiber reinforced resin sheet.SOLUTION: The manufacturing method of a fiber reinforced resin sheet contains following steps (1)-(4): (1) a liquid layer forming step of applying on a carrier film or, a barrier layer formed on the carrier film, transparency thermosetting resin composition A for body including urethane acrylate resin, vinyl ester resin, polymerizable monomer, photopolymerization initiator, and thermal polymerization initiator; (2) a step of making a mesh object contact with the liquid layer formed in the above liquid layer forming step, cover the upper part with a cover film, carry out impregnating of the transparency thermosetting resin composition A for bodies by pressurization impregnation roller; (3) a step of irradiating the transparency thermosetting resin composition A for body with un-white fluorescent lamp to carry out optical curing; and further (4) a step of carrying out thermosetting of the transparency thermosetting resin composition A for body.

Description

  The present invention relates to a method for manufacturing a fiber reinforced resin sheet for repairing or reinforcing concrete structures such as concrete tunnels, elevated carriageways, bridges, and buildings.

  In recent years, reinforced concrete structures at or near the coast are damaged by sea salt particles, or the structures deteriorate due to corrosion and expansion of the reinforcing bars caused by salt intrusion into reinforced concrete structures in contact with seawater. Or deterioration of concrete due to weakening of the surface layer due to substances that are harmful to concrete, such as acid rain and chemicals in factories, or excessive traffic to structures due to increased vehicle traffic, increased loading capacity, speeding up, etc. A major problem is that the surface portion of the concrete structure is cracked or peeled off due to a load or the like, and the concrete structure itself is deteriorated.

  Various methods for preventing the peeling of the deteriorated concrete, various methods for repairing the cracked portion and the peeled portion, and materials thereof have been studied. Among them, in a sheet for repair or reinforcement in which a protective layer serving as a surface layer and an adhesive layer to a concrete structure are provided in advance and a reinforcing layer composed of a fiber base material is interposed between these layers, the fiber As a base material, a method using a nonwoven fabric or a woven fabric processed sheet of organic fiber or inorganic fiber has been proposed as a construction method capable of facilitating construction and stabilizing quality (Patent Document 1). reference).

On the other hand, after repairing the cracked portion of the deteriorated concrete, it is also important for the management of the concrete structure to visually observe the progress of defects such as cracks at the repaired site. However, in the conventional general repair method, since the surface is covered with a covering material such as a fiber base material, it is difficult to visually observe them.
As a solution to this problem, Patent Document 2 proposes a method for forming a concrete reinforcing layer in which a reinforcing net is directly attached to a concrete surface with a visible light curable vinyl ester resin having a total light transmittance of 30% or more ( Patent Document 2).

  In addition, a fiber reinforcement for repairing / reinforcing a concrete structure, comprising a mesh body in which monofilaments of sea-island type composite organic fibers are arranged in a net-like manner at intervals, and a sheet-like transparent resin enclosing the mesh body A resin sheet has been proposed (see Patent Document 3).

JP 2002-256707 A JP 2007-2514 A JP 2009-61718 A

However, the repair / reinforcing sheet described in Patent Document 1 does not take into account the visual observation of the concrete surface after construction, and it is impossible to observe the presence or absence of cracks, their degree, changes with time, and the like.
In addition, the method described in Patent Document 2 inevitably involves applying a visible light curable vinyl ester resin for fixing the reinforcing net and the reinforcing sheet at the construction site, and repairing the site with an unstable scaffold. Or the simplification and shortening of the reinforcement work have been requested.
On the other hand, the fiber reinforced resin sheet described in Patent Document 3 can be visually observed on the concrete surface, but it is difficult to completely eliminate many pinhole-shaped through holes in the fiber reinforced resin sheet. It is done. If there is a through-hole, uncured adhesive is likely to leak out, and when the surface is rubbed with a roller or the like during construction application, the adhesive will be spread on the surface where the adhesive has leaked. This may cause trouble in construction such as wiping off the adhesive, and if the adhesive is not completely wiped off, dirt will easily adhere to the surface. There was a thing.

Therefore, according to Japanese Patent Application No. 2009-68817 (filed on Mar. 19, 2009), the present applicant provided a barrier layer as a method for preventing a through hole, and repaired or reinforced fiber reinforcement for a concrete structure that blocked the penetration. A resin sheet was provided. However, even in this fiber reinforced resin sheet, though the through holes are blocked, it is inevitable that bubbles are generated in the transparent resin layer, and there is an appearance problem (including misunderstanding that there may be through holes). ) And other issues. Furthermore, when the acrylic resin or vinyl ester resin constituting the transparent resin layer was cured by heat curing, the resin whose resin viscosity was reduced by heating replaced the gas contained in the mesh, leading to the generation of bubbles.
In other words, there is a need for a transparent fiber reinforced resin sheet for reinforcing or repairing low-cost reinforcing or repairing because it is easy to observe the surface of a concrete structure because it is a sheet-like material that encloses a mesh body but has few bubbles in the transparent layer. It was.

  Therefore, in the present invention, as a result of earnestly examining the method for repairing concrete structures such as concrete tunnels, elevated roadways, bridges, buildings, or the like, which can solve the above problems, or manufacturing a reinforcing fiber reinforced resin sheet, the mesh body When the resin composition is impregnated with a predetermined transparent curable resin composition and cured, a resin sheet containing mesh-like reinforcing fibers without bubbles can be obtained by photocuring with a predetermined light source and then thermosetting, and curing. The inventors have found that the time can be shortened and have completed the present invention.

That is, the present invention provides the following [1] to [9].
[1] A method for producing a fiber reinforced resin sheet for repairing or reinforcing a concrete structure obtained by impregnating and curing a transparent curable resin in a mesh body, the production method comprising the following steps (1) to (4) The manufacturing method of the fiber reinforced resin sheet characterized by including.
(1) On the carrier film or on the barrier layer formed on the carrier film, urethane acrylate resin (a), vinyl ester resin (b), polymerizable monomer (c), photopolymerization initiator (d), And a liquid layer forming step of applying the transparent curable resin composition for main body (A), comprising the thermal polymerization initiator (e), and (2) contacting the mesh body with the liquid layer formed by the liquid layer forming step. And covering the upper part with a first cover film and impregnating the transparent curable resin composition for main body (A) with a pressure impregnation roller, (3) at least one selected from non-white fluorescent lamps A step of photocuring the transparent curable resin composition for main body (A) by irradiating light from a light source; and (4) a step of thermosetting the transparent curable resin composition for main body (A).
[2] The method for producing a fiber-reinforced resin sheet according to [1], wherein the non-white fluorescent lamp is a black light fluorescent lamp and is photocured by the black light fluorescent lamp.
[3] The method for producing a fiber-reinforced resin sheet according to [1] or [2], wherein the polymerizable monomer (c) is at least one selected from methyl methacrylate, methyl acrylate, and styrene.
[4] Before the liquid layer forming step of (1), including the following barrier layer forming step (5) for forming a barrier layer on the upper part of the carrier film, the above [1] to [3] A method for producing the fiber-reinforced resin sheet according to any one of the above,
(5) After applying the transparent curable resin composition (B) for the barrier layer on the carrier film and sandwiching and curing with the second cover film to form the barrier layer, the second cover film is peeled and removed. The barrier layer forming step of subjecting the formed barrier layer to the step (1).
[5] The transparent curable resin composition for the barrier layer (B) is the same as the transparent curable resin composition for the main body (A), and receives light from at least one light source selected from non-white fluorescent lamps. The method for producing a fiber-reinforced resin sheet according to [4], which is cured by irradiation.
[6] In the step of impregnating the mesh body of (2) with the transparent curable resin composition for main body (A), the mesh body is in a wet state after the pre-impregnation step of (6) described below. The method for producing a fiber-reinforced resin sheet according to any one of [1] to [5],
(6) The transparent curable resin composition for pre-impregnation (C) having compatibility with the transparent curable resin composition for main body (A) and having a viscosity of 50 to 15000 cP is applied to the mesh body, and between the impregnating rollers And a pre-impregnation step of impregnating and defoaming with a roller linear pressure of 3 to 30 N / cm.
[7] The mesh body is a laminated fabric, in which sea-island type composite yarns are laminated in at least three directions of warp direction, oblique direction, and reverse oblique direction, and the laminated sea-island type composite yarns are heat-sealed. The method for producing a fiber-reinforced resin sheet according to any one of 1 to 6, which is a warp or bilayer triaxial laminated fabric.
[8] The method for producing a fiber-reinforced resin sheet according to any one of [1] to [7], wherein the mesh body is hydrophilized.
[9] The fiber reinforced resin according to the above [4], wherein the first cover film is obtained by continuously reusing a film obtained by peeling off the second cover film used in the barrier layer forming step of (5). Sheet manufacturing method.

According to the method for producing a fiber-reinforced resin sheet of the present invention, the transparent curable resin composition for main body (A) impregnated in the mesh body is photocured by irradiating light from a predetermined light source, and then heated. Since it has been cured, the phenomenon that bubbles contained in the mesh body aggregate due to a decrease in viscosity accompanying the temperature rise of the uncured transparent curable resin composition for main body (A) and many bubbles of 2 mm or more appear. Thus, a fiber-reinforced resin sheet with few bubbles can be obtained at the opening of the mesh body.
Since the fiber reinforced resin sheet of the present invention is a fiber reinforced resin sheet with few bubbles obtained by the method for producing a fiber reinforced resin sheet of the present invention, it is effective as a fiber reinforced resin sheet for reinforcement or repair that enables observation of the concrete structure surface. Can be provided.

(A) The top view of an example of the fiber reinforced resin sheet for repair or reinforcement of the concrete structure of this invention, (B) AA sectional view taken on the line. (A) The cross-sectional enlarged schematic diagram of the fiber reinforced resin sheet obtained in Example 1 of this invention, (B) The cross-sectional enlarged schematic diagram of the fiber reinforced resin sheet obtained by the manufacturing method of the comparative example 2. FIG. It is an enlarged photograph which shows the pinhole (penetrating bubble) which generate | occur | produced in the fiber reinforced resin sheet obtained by the comparative example 2. (A) The core-sheath type composite fiber explanatory drawing which comprises the sea-island type composite yarn as an example of a reinforcing fiber, (B) It is explanatory drawing of the sea-island type composite yarn which united the sheath component. It is process explanatory drawing of an example of the manufacturing method of this invention.

  Hereinafter, preferred embodiments of the present invention will be described. Each embodiment shown in the accompanying drawings shows an example of a typical embodiment according to the present invention, and the scope of the present invention is not interpreted narrowly.

Repairing or manufacturing method of the reinforcing fiber-reinforced resin sheet of the concrete structure of the present invention, (1) the key catcher rear films or on a carrier barrier layer formed on the film, a urethane acrylate resin (a), vinyl ester resin ( b), a liquid layer forming step of applying the transparent curable resin composition (A) for the main body, including the polymerizable monomer (c), the photopolymerization initiator (d), and the thermal polymerization initiator (e);
(2) The mesh body is brought into contact with the liquid layer formed in the liquid layer forming step, the upper part thereof is covered with a first cover film, and the transparent curable resin composition for the main body (A) by a pressure impregnation roller. Impregnating step,
(3) a step of photocuring the transparent curable resin composition for main body (A) by irradiating light from at least one light source selected from non-white fluorescent lamps; and (4) further for the main body. A step of thermosetting the transparent curable resin composition (A),
It is characterized by including.

In the present invention, the mesh body can be selected from one or a combination of two or more of woven fabric, net, knitted fabric, and laminated fabric.
The mesh body has a predetermined opening formed of reinforcing fibers, and the opening preferably has an opening ratio of 30% or more with respect to the total projected area of the mesh body. The transparent curable resin composition (A) for use hardly penetrates into the mesh body and cannot be expected to have a reinforcing effect, and it is difficult to observe the concrete surface layer.
The laminated fabric is also referred to as a braided fabric, and a three-axis fabric laminated in at least three directions of warp direction, oblique direction, and reverse oblique direction can be generally used. Since the laminated fabric has low cost as a mesh body, there is also an economic merit. The laminated fabric can be produced, for example, by the method described in JP-A-11-20059.

The mesh body is a one-layer or two-ply triaxial laminated fabric obtained by laminating reinforcing fibers in at least three directions of warp direction, oblique direction, and reverse oblique direction, and heat-sealing the laminated sea-island type composite yarns. It can be.
FIG. 1A is a top view of an example of a fiber reinforced resin sheet for repairing or reinforcing a concrete structure of the present invention, and shows a state in which the mesh body 10 is visible through a transparent resin layer. Mesh body 10 shown in the figure, the constituent yarn reinforcing fibers 1, on the lower warp layer 11, oblique yarn layer 13 and Gyakuhasu交糸layer 14, the upper warp layer 12 are stacked, heated intersection of each layer Is heat-sealed.
After the mesh body 10 is formed, the whole mesh body 10 may be thinned by further heating and pressing. Thereby, the softness | flexibility and flexibility of the mesh body 10 can be improved further. The heating temperature at that time is preferably close to the melting point of the thermoplastic resin constituting the sea. The pressurization can be performed by a method such as roller pressing.

The reinforcing fiber used for the mesh body 10 may be vinylon fiber, polyester fiber, polyamide fiber, polyolefin fiber, aromatic if the physical properties such as fiber strength and elongation have a reinforcing effect as the constituent yarn of the mesh body 10. It does not ask | require the kind, such as a polyamide fiber.
Especially, the mesh body 10 is a core-sheath type comprising (a) a core component made of a polyolefin resin and (b) a sheath component made of a polyolefin resin having a melting point lower by 20 ° C. than the melting point of the core component. It is preferable to use a sea-island type composite yarn in which the sheath component of the composite fiber is fused, and to form a mesh body, particularly a triaxial laminated fabric, obtained by heat-sealing the intersection of the composite yarn.
Examples of the polyolefin-based resin that can be used for the sea-island composite yarn of the present invention include binary copolymers of olefins such as polyethylene, polypropylene, ethylene, propylene, and butene-1, and ternary copolymers.
Suitable combinations of the core component and the sheath component include, for example, a combination using isotactic polypropylene (mp = 163 ° C.) as the core component and linear low density polyethylene (mp = 110 ° C.) as the sheath component.
Such a sea-island type composite yarn is spun to have a predetermined sheath / core cross-section ratio by using, for example, a spin draw method, using a conventional composite spinning equipment and a core-sheath type composite spinning nozzle, and led to a drawing apparatus that is directly connected. It can be obtained by stretching under saturated water vapor pressure and fusing a plurality of fibers with a sheath component together with stretching. Moreover, it can manufacture by the method as described in Unexamined-Japanese-Patent No. 2003-326609.

In the sea-island type composite yarn, the mass ratio of the island part to the sea part is preferably 20:80 to 80:20. If the mass ratio of the island part to the total mass of the island part and the sea part is less than 20% by mass, the reinforcing effect by the mesh body 10 tends to be small, and if it exceeds 80% by mass, the thermal bond strength tends to be low. . From the same viewpoint, the mass ratio between the island and the sea is more preferably 40:60 to 70:30.
The fineness of the sea-island type composite yarn is preferably 100 to 5000 dtex. If it is less than 100 dtex, the intended physical properties tend to be difficult to obtain, and if it exceeds 5000 dtex, flexibility and followability tend to be impaired. A fineness of 500 to 3000 dtex is more preferable.

FIG. 4 is a perspective view showing an embodiment of a method for producing a monofilament.
In the embodiment of FIG. 4, a plurality of core-sheath type composite single fibers 9 having a core-sheath structure composed of a single core part (island part) 3 and a sheath part 5 a covering the outer peripheral surface of the single core part (island part) 3 are concentrated. The step of preparing the sheath-type composite single fiber bundle 15 ((a) of FIG. 4), the sheath portion 5a is melted while stretching the core-sheath composite single fiber bundle 15, and the sheath portions 5a are fused to form a plurality of And a step of forming a sea part 5 including the island part 3 ((b) of FIG. 4). In addition, this process may be performed prior to the manufacturing process of the mesh body 10 mentioned later, and may be performed by the heat processing in the manufacturing process of the mesh body 10.

  When applying the transparent curable resin composition for main body (A) on the barrier layer formed on the carrier film, the barrier layer also needs to be adhered to the main body layer and be transparent. A transparent curable resin having compatibility with the main body transparent curable resin composition (A) may be applied on the film, and then cured to form a barrier layer.

The main body transparent curable resin composition (A) comprises a urethane acrylate resin (a), a vinyl ester resin (b), a polymerizable monomer (c), a photopolymerization initiator (d), and a thermal polymerization initiator ( e).
The urethane acrylate resin (a) and the vinyl ester resin (b) constitute the main body of the transparent curable resin, and the mass ratio of the urethane acrylate resin (a) and the vinyl ester resin (b) is the urethane acrylate resin. (A) / Vinyl ester resin (b) is approximately 9/1 to 5/5, and if the mass ratio is less than 9/1, the rigidity of the fiber-reinforced resin sheet after curing is insufficient, exceeding 5/5 to vinyl As the ratio of the ester resin (b) increases, the flexibility decreases.

  In the present invention, the urethane acrylate resin (a) is a polyhydric alcohol used in the production of an unsaturated polyester, or a saturated dibasic acid or anhydride thereof used in the production of an unsaturated polyester and the polyhydric alcohol. Saturated polyester polyols obtained by esterification reaction with tolylene diisocyanate (commonly called TDI), 4,4-diphenylmethane diisocyanate (commonly called MDI) or 3-isocyanate methyl- 3,5,5-Trimethylcyclohexyl-isocyanate (generally called IPDI) is subjected to an addition reaction to synthesize a urethane compound having an isocyanate group at the end of the molecule, and then 2-hydroxyethyl methacrylate or Addition reaction of 2-hydroxyethyl acrylate First, 2-hydroxyethyl methacrylate or 2-hydroxyethyl acrylate and TDI, MDI or IPDI are subjected to an addition reaction to synthesize a compound having an isocyanate group at one end of the molecule, It is a liquid resin in which a urethane acrylate obtained by addition reaction of a monohydric alcohol or the saturated polyester polyol is dissolved in a polymerizable monomer used as a crosslinking agent.

  Examples of the vinyl ester resin (b) that can be used in the present invention include an epoxy (meth) acrylate resin produced by a reaction between an epoxy resin and (meth) acrylic acid, polybutadiene having a terminal carboxyl group, and glycidyl (meth) acrylate. And polybutadiene type vinyl ester resin produced by the above reaction, and has excellent corrosion resistance and mechanical strength.

  As such an epoxy (meth) acrylate resin, a reaction of a bisphenol type epoxy resin and a carboxylic acid having a (meth) acrylol group, a reaction of a novolac type epoxy resin and a carboxylic acid having a (meth) acrylol group Can be mentioned.

  Examples of the bisphenol type epoxy resin include glycidyl ether type epoxy resins having substantially two or more epoxy groups in one molecule obtained by reaction of epichlorohydrin and bisphenol A or bisphenol F, methyl epichlorohydrin and bisphenol A, for example. Or the dimethyl glycidyl ether type epoxy resin obtained by reaction with bisphenol F, the epoxy resin obtained from the alkylene oxide adduct of bisphenol A, and epichlorohydrin or methyl epichlorohydrin, etc. are mentioned.

  Examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of a novolak type phenol resin or a novolac type cresol resin with epichlorohydrin or methyl epichlorohydrin.

  The polymerizable monomer (c) that can be used in the present invention is a liquid polymerizable monomer that can be polymerized with the urethane acrylate resin (a) and the vinyl ester resin (b), such as styrene; methyl methacrylate. Methacrylic acid esters such as ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, and hydroxyethyl methacrylate, and (meth) acrylic acid. Of these, methyl methacrylate is preferred from the viewpoint of reacting at a low temperature, or styrene is preferred from the viewpoint of high boiling point, and these can be used alone or in combination of two or more.

The transparent curable resin composition for main body (A) of the present invention contains a photopolymerization initiator (d).
As the photopolymerization initiator (d) that can be used, a chemical change occurs through the action of light or interaction with the electronically excited state of the sensitizing dye, and at least one of radical, acid, and base is selected. It is a compound to be formed. In the present invention, the photopolymerization initiator is an actinic ray to be irradiated, for example, 400 to 200 nm ultraviolet ray, far ultraviolet ray, g ray, h ray, i ray, KrF excimer laser beam, ArF excimer laser beam, electron beam, X ray. Those having sensitivity to a molecular beam, an ion beam, or the like can be appropriately selected and used. However, it is mentioned as a condition that it penetrates the cover film 22 (23).

Examples of the photopolymerization initiator (d) include aromatic ketones, aromatic onium salt compounds, organic peroxides, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, and active esters. Examples thereof include compounds and compounds having a carbon halogen bond.
More specifically, for example, benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine And oxides. Among these, photopolymerization initiators such as 1-hydroxycyclohexyl phenyl ketone and 2,4,6-trimethylbenzoyldiphenylphosphine oxide are particularly preferable. These photopolymerization initiators may be used alone or in combination of two or more.

  The photopolymerization initiator (d) is preferably used in the range of 0.1 to 2 parts by mass with respect to 100 parts by mass in total of the urethane acrylate resin (a) and the vinyl ester resin (b). If the photopolymerization initiator (d) is in the range of 0.1 to 2 parts by mass, the curing rate and production rate can be balanced, the generation of bubbles can be suppressed, and the fiber-reinforced resin sheet does not become insufficiently cured. Too much and it will not be uneconomical.

The transparent curable resin composition (A) for main body of the present invention contains a thermal polymerization initiator (e).
Examples of the thermal polymerization initiator that can be used include medium temperature curable organic peroxides that can be cured at about 50 to 100 ° C., esters thereof, and organic azo compounds.
As the organic peroxide, 1,1-bis (t-butylperoxy) -2,2,5-trimethylcyclohexane (Perhexa 3M-95 manufactured by NOF Corporation), 1,1-bis (t-butylperoxy) cyclo Dodecane (Perhexa CD manufactured by NOF Corporation), 1,1,3,3-tetramethyl hydroperoxide (Perocta H manufactured by NOF Corporation), 1,1-dimethylbutyl peroxide (Perhexyl H manufactured by NOF Corporation), bis (1 -T-butylperoxy-1-methylethyl) benzene (Nippon Yushi Co., Ltd., Perbutyl P), Dicumyl peroxide (Nippon Yushi Co., Ltd., Park Mill D), 2,5-dimethyl-2,5-bis (t-butylperoxy) Hexane (Perhexa 25B manufactured by NOF Corporation), t-butylcumyl peroxide (Perbutyl C manufactured by NOF Corporation), di-t-butylpe Oxide (Nippon Yushi Co., Ltd., Perbutyl D), 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne (Nippon Yushi Co., Ltd., Perhexine 25B), Benzoyl peroxide, Lauroyl peroxide (Nippon Yushi Co., Ltd., Parroyl) L), decanoyl peroxide (Sanpelox-DPO manufactured by Sanken Chemical Co., Ltd.), dicyclohexyl peroxydicarbonate (Sanperox-CD manufactured by Sanken Chemical Co., Ltd.), bis (4-t-butylcyclohexyl) peroxydicarbonate (Nippon Yushi Co., Ltd.) Parroyl TCP), t-butyl 2-ethylperhexanoate (Nippon Yushi Co., Ltd. perbutyl O), (1,1-dimethylpropyl) 2-ethylperhexanoate (Kagoya Akzo Trigonox 121), ( 1,1-dimethylbutyl) 2-ethylperhexanoate (a chemical manufactured by Kayaku Akzo) Ester HO), t-butyl 3,5,5-trimethylperhexanoate (Nippon Yushi Co., Ltd., Perbutyl 355), t-hexyl peroxyisopropyl monocarbonate (Nippon Yushi Co., Ltd., Perhexyl I), t-butyl peroxyisopropyl Monocarbonate (Nippon Yushi Co., Ltd., Perbutyl I), t-butyl peroxy 2-ethylhexyl monocarbonate (Nippon Yushi Co., Ltd., Perbutyl E), t-butyl permaleate (Nippon Yushi Co., Ltd., Perbutyl MA), 1,1,3 , 3-tetramethylbutyl peroxy-2-ethylhexanoate (Perocta O manufactured by NOF Corporation), t-butyl perlaurate (Perbutyl L manufactured by NOF Corporation), t-butyl perbenzoate (manufactured by NOF Corporation) Perbutyl Z) and the like. These thermal polymerization initiators may be used alone or in combination.

  The thermal polymerization initiator is preferably used in the range of 0.1 to 5 parts by mass with respect to 100 parts by mass in total of the urethane acrylate resin (a) and the vinyl ester resin (b). If the thermal polymerization initiator is in the range of 0.1 to 5 parts by mass, the fiber-reinforced resin sheet will not be insufficiently cured and will not be uneconomical because it is too much.

In order to further control the reactivity of the thermal polymerization initiator, a polymerization inhibitor or an accelerator can be added to the transparent curable resin composition (A) for the main body. As the polymerization inhibitor, 2,6-di-t-butyl-p-cresol, 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2,2′-methylenebis (4-ethyl-6) -T-butylphenol), 4,4'-thiobis (2-methyl-6-t-butylphenol), hydroquinone, 2-t-butylhydroquinone, 2,5-di-t-butylhydroquinone, p-benzoquinone, 2- Examples include ethyl anthraquinone, dilauryl thiodipropionate, and cuperone.
As the promoter, a transition metal salt such as cobalt naphthenate can be used.

Moreover, the transparent curable resin composition for main body (A) may further contain an ultraviolet absorber, an antioxidant and the like within a range in which desired transparency can be obtained. The viscosity of the transparent curable resin composition for main body (A) is preferably 100 to 15000 cP, and more preferably 800 to 1000 cP.
When the viscosity of the transparent curable resin composition (A) for the main body is low, dripping tends to occur, and when the viscosity of the transparent curable resin composition (A) for the main body is high, impregnation is poor and formed. There is a tendency that bubbles are easily generated in the transparent resin layer.

Further, the ultraviolet absorber is useful for preventing deterioration of the fiber reinforced resin sheet due to direct sunlight outdoors. Specific examples of such ultraviolet absorbers are not particularly limited as long as they are soluble in the above-mentioned transparent curable resin composition for main body (A), and various ultraviolet absorbers can be used. Specific examples include salicylic acid ester, benzophenone, triazole, hydroxybenzoate, and cyanoacrylate. These ultraviolet absorbers may be used in combination. Among these, in terms of compatibility with urethane acrylate compounds, benzophenone or triazole, specifically, (2-hydroxy-4-octyloxy-phenyl) -phenyl-methanone, 2-benzotriazole-2- Ultraviolet absorbers such as yl-4-tert-octyl-phenol are preferred.
It is preferable that the content rate of a ultraviolet absorber is 0.1-3 mass parts normally with respect to 100 mass parts of transparent curable resin compositions for main bodies (A), Most preferably, it is 1-2 mass parts. . If the amount of the ultraviolet absorber is too small, the light resistance tends to be lowered. If the amount is too large, the ultraviolet irradiation energy is consumed at the time of photocuring of the main body resin, and the curing tends to be difficult.

As the carrier film 21 and the cover film 22 (23) that can be used in the present invention, a transparent film that can transmit 70% or more of light of 300 nm or more, for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate can be used.
These carrier film 21 and cover film 22 (23) may be used as they are as protective films. The protective film protects the surface of the fiber-reinforced resin sheet in operations such as inspection, storage, transportation, and cutting after the fiber-reinforced resin sheet is manufactured, and is removed during construction.

In the method for producing a fiber-reinforced resin sheet of the present invention, the transparent curable resin composition for main body (A) is photocured by irradiating light from at least one light source selected from non-white fluorescent lamps.
The non-white fluorescent lamp used in the present invention is a non-white fluorescent lamp that absorbs ultraviolet light having a wavelength of 253.7 nm and is converted into another specific wavelength and the energy thereof is amplified. And a fluorescent lamp for photochemistry. The black fluorescent lamp is a light source that efficiently emits near-ultraviolet light (peak wavelength: 352 nm) having a strong fluorescent action without emitting almost any visible light. For example, “FL20SBLB”, “FL40SBLB” manufactured by Toshiba Lighting & Technology Corporation is preferably used. be able to.
As the color fluorescent lamp, a blue fluorescent lamp (“FL20SB”, “FL40SB” manufactured by Toshiba Lighting & Technology Corporation), etc., a blue white fluorescent lamp (“FL20SBW”, “FL40SBW” manufactured by Toshiba Lighting & Technology Corporation), etc. are preferably used. Can do.
The photochemical fluorescent lamp is a light source that generates near-ultraviolet radiation near 360 nm that is effective for promoting a photochemical reaction. For example, “FL20SBL-360” and “FL40SBL-360” manufactured by Mitsubishi Electric OSRAM Co., Ltd. Etc. can be preferably used.

That is, the non-white fluorescent lamp in the present invention does not include a sterilizing lamp, a low-pressure mercury lamp, a high-pressure mercury lamp, or a metahalide lamp that directly uses ultraviolet light without wavelength conversion. These require time (about 15 minutes) to turn on, and more time (about 5 to 10 minutes) until the output stabilizes, while non-white fluorescent lights turn on immediately and are on demand. Is possible. The power consumption of the non-white fluorescent lamp is preferably 10 to 100W, more preferably 20 to 60W. If the fluorescent lamp is within the above range and the irradiation intensity is 6 W / cm ² or more, the above-mentioned transparent curable resin composition for main body (A) can be cured in 2 to 6 minutes, and further, low energy. Since it is light, it does not boil the polymerizable monomer to generate bubbles or damage the substrate.

  In particular, the low-pressure mercury lamp, the high-pressure mercury lamp, the ultra-high pressure mercury lamp, and the metal halide lamp described above may cause thermal damage to the base material due to irradiation when 50% or more of the consumed energy becomes infrared rays or heat loss. There was a problem that it was necessary to install a cooling device, and the device was enlarged. On the other hand, when a non-white fluorescent lamp is used, it is not necessary to install a cooling device, and the equipment can be downsized.

  In the method for producing a fiber-reinforced resin sheet of the present invention, the thermosetting step is a step of further thermosetting the photocured transparent curable resin composition for main body (A). This thermosetting is performed in order to develop the strength of the curable resin and to reduce the remaining polymerizable monomer (monomer).

  FIG. 5 is a process explanatory diagram of an example of the manufacturing method of the present invention. In the manufacturing method according to FIG. 5, after the barrier layer transparent curable resin composition (B) is applied onto the carrier film 21, sandwiched and cured by the second cover film 23 to form the barrier layer 101, Through the barrier layer forming step (5) for peeling the cover film 23 of No. 2, the transparent curable resin composition for main body (A) is supplied from the pump 43 through the nozzle 48 onto the barrier layer.

In the barrier layer forming step (5), first, a transparent curable resin composition for a barrier layer (B) containing a polymerizable monomer for forming a barrier layer having a predetermined thickness on the carrier film 21 [in this embodiment] The transparent curable resin composition for barrier layer (B) and the transparent curable resin composition for main body (A) are the same. ] 20b was prepared in the preparation tank 40a, charged into the reserve tank 40, applied by the pump 41 onto the carrier film 21 from the nozzle 42, adjusted to a predetermined application thickness with the squeeze roll 50, and inserted into the curing furnace 70. A barrier layer 101 made of a cured transparent cured resin for the barrier layer is formed.
For application of the transparent curable resin composition for barrier layer (B) or the transparent curable resin composition for main body (A) on the carrier film 21, a general coating apparatus can be used, for example, gravure reverse, gravure You can choose from direct, triple reverse, and die coat.

Next, after supplying (applying) the main body transparent curable resin composition (A) 20a for forming a fiber reinforced resin main body layer having a predetermined thickness on the barrier layer 101, the pre-impregnating transparent curable resin composition ( The pre-impregnated mesh body 10a impregnated with C) is supplied, and the pre-impregnated mesh body 10a is further impregnated with the squeeze roll 55 into the main body transparent curable resin composition (A) 20a, and then the first cover film 22 is sandwiched between the pre-impregnated mesh body 10a, impregnated and defoamed with a squeeze roll 56, and adjusted in thickness, irradiated with light from a non-white fluorescent lamp in a curing furnace 71, and photocured. Further, after-curing such as uncured monomer and the process for improving the thermal stability of the fiber reinforced resin sheet are performed in the thermosetting furnace 72 and wound.
In this embodiment, the first cover film 22 peels off the second cover film 23 used for forming the barrier layer at the portion of the roll 53a after the barrier layer is cured, and passes through the guide rolls 53b to 53c. The squeeze roll 56 is reused as the first cover film 22. A tension roll (not shown) is provided between the guide rolls 53b to 53c to adjust the tension of the cover film 22 (23) and adjust the speed balance with the carrier film 21 side.

Next, the pre-impregnation step (6) in which the mesh body 10 is impregnated and defoamed with the transparent curable resin composition for pre-impregnation (C) will be described.
The pre-impregnating transparent curable resin composition (C) is selected from compositions having compatibility with the main body transparent curable resin composition (A) and a viscosity of 50 to 15000 cP.
The transparent curable resin composition (C) for pre-impregnation is prepared by using a solvent such as a styrene monomer (viscosity 50 cP or less, 25 ° C.) and a thermosetting resin (viscosity 100 to 6000 cP, 25 ° C.) such as vinyl ester or unsaturated polyester. What is necessary is just a composition which is compatible and is compatible with the transparent curable resin composition for main body (A). The lower the viscosity of the pre-impregnating transparent curable resin composition (C), the higher the deaeration effect. Therefore, the transparent curable resin composition for main body (A) may be heated to lower the viscosity. . However, the thermosetting resin needs to be at a temperature at which no curing reaction occurs. The pre-impregnated mesh body 10a is preliminarily impregnated with the transparent curable resin composition (A) until it is sent to the main impregnation step of introducing and impregnating the pre-impregnated mesh body 10a into the liquid layer 20a ′ of the transparent curable resin composition (A). Since it is important to be wet in C), when a solvent is used, it is necessary to promptly send it to the impregnation step before volatilization.

From the viewpoint of impregnating the mesh body 10 and removing bubbles contained in the mesh body 10, the pre-impregnation transparent curable resin composition (C) has a viscosity of 50 to 15000 cP, and the squeeze roller 47 has a linear pressure of 3 to 3. 30 N / cm is preferable. Here, the roller linear pressure is obtained by dividing the weight (N) for pressing the roller by the length (cm) of the roller.
If the viscosity is less than 50 cP, dripping tends to occur, and the amount of resin retained by the mesh body 10 becomes insufficient. If the viscosity exceeds 15000 cP, impregnation is poor, and bubbles are generated in the formed transparent resin layer. It tends to be easy to do.
If the linear pressure is less than 3 N / cm, the impregnation step is performed in a state where a large amount of bubbles are contained in the resin held by the mesh body 10, and bubbles appear in the cured fiber-reinforced resin sheet. On the other hand, if the linear pressure exceeds 30 N / cm, the pre-impregnation roller 47 deforms the mesh body and causes defects such as wrinkles.

The pre-impregnated pre-impregnated mesh main body 10a is a liquid layer 20a ′ formed by applying the main body transparent curable resin composition (A) on the carrier film 21 or a barrier layer formed on the carrier film 21. Then, the squeeze roller 55 sandwiches the first cover film 22 and the squeeze roller 56 performs the main impregnation.
Subsequently, it passes through the curing furnace 71 and the thermosetting furnace 72 and is taken up via the roller 60 and wound up.

  As the carrier film 21, the first cover film 22, and the second cover film 23, as described above, for example, a polyester film such as polyethylene terephthalate or polyethylene naphthalate can be used. In FIG. 5, the first cover film 22 is peeled off after the second cover film 23 used for forming the barrier layer is cured, and this is introduced again from the site of the squeeze roll 56 to perform the main impregnation and curing. Used after the process. These carrier films 21 may be used as they are as the protective films 21 and 22 (23) after the take-up. The protective film protects the surface of the fiber-reinforced resin sheet in operations such as inspection, storage, transportation, and cutting after the fiber-reinforced resin sheet is manufactured, and is removed during construction.

  Furthermore, the curable resin composition for main body (A) and / or the curable resin composition for barrier layer (B) may contain an adhesive component. By including a pressure-sensitive adhesive component (for example, a tackifier), it becomes easy to adhere to the adhesive layer on the concrete structure side during construction, and effects such as rapid construction can be expected. Moreover, a fiber reinforced resin sheet can be effectively protected by adhesion with a protective film.

  Subsequently, the transparent curable resin composition for main body (A) and the transparent curable resin composition for pre-impregnation (C) are cured in the curing furnace 71 by irradiation with ultraviolet rays. Polymerization of the polymerizable monomer proceeds in the curable resin compositions 20a and 20c by irradiation with the ultraviolet rays. The fiber reinforced resin sheet 100 in which the transparent resin layer is formed as the fiber reinforced resin main body layer, after coming out of the curing furnace 71, is further subjected to after-curing and dimensional stabilization heat treatment in the thermosetting furnace 72. Taken over and taken up. When passing through the curing furnace 71 and the thermosetting furnace 72, both ends of the fiber reinforced resin sheet 100 are sandwiched between clips, and the fiber reinforced resin sheet is processed in a tension state without wrinkles and with a certain width. It is preferable at the point which obtains a fiber reinforced resin sheet.

  FIG. 2A shows an enlarged cross-sectional view of the fiber-reinforced resin sheet obtained by the production method of the present invention. In the drawing, the constituent fibers 1 of the mesh body 10 are also embedded in the barrier layer 101 side. This is because the surface of the barrier layer 101 once cured is uncured transparent curable resin composition for main body. Since it swells due to the compatibility with each other by contact with (A), the pre-impregnated mesh body 10a is subjected to the action of the impregnation rollers 55, 56, etc., and a part thereof is embedded also on the barrier layer side. Such an interface state with the barrier layer is preferable as the fiber reinforced resin sheet hardly causes interface peeling. In the figure, the protective films 21 and 22 (23) also serve as the carrier film 21 and the cover film 22 (23) at the time of manufacture, and are peeled off during construction as a fiber reinforced resin sheet.

In the production method of the present invention, the carrier film 21 and / or the first cover film 22 can be a transparent (meth) acrylic resin film.
In this case, a liquid curable resin composition (A) for forming a main body is applied as a transparent curable resin on the (meth) acrylic resin film as the carrier film 21 to form the liquid layer 20a ′, and pre-impregnated The fiber reinforced resin sheet is subjected to the main impregnation, curing, and heat treatment steps after being sandwiched between the first cover film 22 together with the pre-impregnated mesh body 10a impregnated with the transparent curable resin composition (C) for use. Can be manufactured.
When the (meth) acrylic resin film is used, the (meth) acrylic resin film can have a function of serving as the carrier film 21, the barrier layer, and further the protective layer.

  Hereinafter, although an example and a comparative example explain the present invention, the present invention is not limited to these examples.

<Manufacture of sea-island type composite yarn>
Isotactic polypropylene (mp = 163 ° C.) is used for the core component, and linear low density polyethylene (mp = 110 ° C.) using a metallocene catalyst is used for the sheath component, and a conventional composite spinning equipment, core-sheath type composite spinning nozzle (240 Hole), spinning at 260 ° C. so that the sheath / core cross-section ratio is 35/65, and guiding to a stretching apparatus that is directly connected, and stretching at a stretching ratio of 13 times under a saturated water vapor pressure of 0.42 MPa and 145 ° C. A sea-island type composite yarn having a total fineness of 1,850 dtex and a filament number of 240, which is drawn and fused with fibers by a sheath component, and having a core polypropylene as an island component and a sheath linear low-density polyethylene as a sea component. Obtained (spin draw method).
The sea-island type composite yarn had a tensile strength of 6.5 cN / dtex, an elongation of 15%, a Young's modulus of 92.0 cN / dtex, and a heat shrinkage measured at 140 ° C. of 6.8%. .

<Preparation of mesh body and hydrophilization>
The obtained sea-island type composite yarn is placed in a laminated fabric manufacturing apparatus, and warp yarns, oblique yarns and reverse oblique yarns are laminated at a pitch of 10 mm in three directions of warp direction, oblique direction and reverse direction, and then the surface temperature A triaxial mesh body 10 in which the composite yarn sea part resin was melted by contact heating with a heating roller at 150 ° C. and the composite yarn of each layer was bonded was obtained. The mesh was 10 mm, and the mass per unit area was 65 g / m ² .
The obtained triaxial laminated fabric mesh body 10 was passed through a corona discharge treatment apparatus (manufactured by Kasuga Denki Co., Ltd., model name: oscillator AGI-023, 6 aluminum electrodes), and the voltage, treatment speed, etc. were changed, The modification degree of the mesh body 10 was adjusted to a wetting index of 56 mN / m. The surface modification degree (wetting index) was evaluated by a wettability test method according to JIS K6768.

Example 1
(Barrier layer formation process)
A polyethylene terephthalate film (thickness 50 μm) was fed out as the carrier film 21, and a liquid 20b of the transparent curable resin composition for barrier layer (B) was applied to form a barrier layer (barrier layer) 101 on the film.
The transparent curable resin composition for barrier layer (B) is a mass ratio (a) of urethane acrylate resin (a) and vinyl ester resin (b) containing 20% by mass of methyl methacrylate as the polymerizable monomer (c). ) / (B) is a mixture of 80/20 (manufactured by Nippon Iupika: Neopole 8136) 100 parts by mass (viscosity 1000 cP, 25 ° C.), 1-hydroxy-cyclohexyl-phenyl ketone (product) as photocuring initiator (d) Name Irgacure 184: Ciba Specialty Chemicals Co., Ltd.) 2 parts by mass, and 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (as a thermosetting initiator (e)) 2 parts by mass of Nippon Oil & Fats Co., Ltd .: Perocta O) was added, stirred in the mixing tank 40a, and poured into the reserve tank 40. After being supplied from the reserve tank 40 by the pump 41 onto the carrier film 21 from the nozzle 42 and adjusted by the squeeze roller 50 so that the thickness after curing is 50 μm, the second cover film (polyethylene terephthalate film (thickness) 25 μm)) 23, and the entire film thickness was adjusted to 125 μm. This is guided to a curing furnace 70, and both sides are irradiated with black light for 1 minute (maximum wavelength 352 nm, irradiation energy 400 mJ / cm ² ) and photocured, and then the second cover film 23 is peeled off at the position of the roller 53a. Thus, a film 101 having a 50 μm thick barrier layer supported by the carrier film 21 was obtained.

(Resin impregnation and curing of mesh body)
Then, the carrier film 21 and the film 101 having a barrier layer formed thereon are continuously supplied, and the same resin composition 20a as the transparent curable resin composition (B) is used as the transparent curable resin for the main body. The composition (A) is supplied from the nozzle 48 by the pump 43 while being supplied with the mesh body 10 and is sandwiched between the first cover film (polyethylene terephthalate film (thickness 25 μm)) 22 to form the entire film. The thickness was adjusted by the pressure roller 56 so as to be 400 μm, and the mesh body 10 was impregnated with the liquid composition.
Thereafter, both surfaces are irradiated with black light in the curing furnace 71 for 5 minutes (irradiation energy: 2400 mJ / cm ² ) and photocured, and then thermally cured by heating at 100 ° C. for 10 minutes in the thermosetting furnace 72. A fiber reinforced resin sheet was obtained.
Bubbles of the obtained sheet were as small as 1 mm or less, and the number was small, and when used as a sheet for repairing or reinforcing a concrete structure, the visibility of the concrete surface was hardly hindered.

Example 2
The composition of Example 1 with the same composition of the transparent curable resin composition for barrier layer (B) and the transparent curable resin composition for main body (A), and 2-methyl-1- A fiber-reinforced resin sheet was obtained in the same manner as in Example 1 except that 1 part by mass of [4- (methylthio) phenyl] -2-morpholinopropanone-1 (manufactured by Ciba Geigy: trade name Irgacure 907) was added. .
The outer diameter of the bubbles in the obtained sheet is as small as 1 mm or less and the number is small. When used as a sheet for repairing or reinforcing concrete structures, the visibility of the concrete surface is hardly impaired. It was.

Comparative Example 1
The film 101 in which the barrier layer is formed on the carrier film 21 is supplied in the same manner as in Example 1. The main body transparent curable resin composition (A) having the same composition as in Example 1 is supplied from the nozzle 48 by the pump 43. On the other hand, the mesh body 10 is supplied and sandwiched between the first cover films (polyethylene terephthalate film (thickness 25 μm)) 22 and adjusted by the pressure roller 56 so that the total film thickness becomes 400 μm. The mesh body 10 was impregnated with the liquid composition.
After that, when one side was irradiated with a high-pressure mercury lamp in the curing furnace 71 for 5 seconds (irradiation energy 2500 mJ / cm ² ), the resin generated heat and burned.

Comparative Example 2
The film 101 in which the barrier layer is formed on the carrier film 21 is supplied in the same manner as in Example 1. The main body transparent curable resin composition (A) having the same composition as in Example 1 is supplied from the nozzle 48 by the pump 43. On the other hand, the mesh body 10 is supplied and sandwiched between the first cover films (polyethylene terephthalate film (thickness 25 μm)) 22 and adjusted by the pressure roller 56 so that the total film thickness becomes 400 μm. The mesh body 10 was impregnated with the liquid composition.
Then, without curing in the curing furnace 71, heat curing was performed by heating at 100 ° C. for 10 minutes in the thermosetting furnace 72 to obtain a fiber reinforced resin sheet.
There are many bubbles in the obtained sheet, and the outer diameter of the bubbles is almost 2 mm or more. When used as a sheet for repairing or reinforcing a concrete structure, the visibility of the concrete surface is hindered. It was.

Comparative Example 3 and Comparative Example 4
In Comparative Example 2, the thermosetting conditions were changed to 110 ° C. for 10 minutes (Comparative Example 3) and 90 ° C. for 15 minutes (Comparative Example 4) in a thermosetting furnace 72 to obtain a fiber reinforced resin sheet. Any fiber reinforced resin sheet has a large number of bubbles, and most of the bubbles have an outer diameter of 2 mm or more. When used as a sheet for repairing or reinforcing a concrete structure, the visibility of the concrete surface is hindered. It was a thing.
Table 1 summarizes the configuration, composition and curing conditions, and the degree of influence on the visibility due to the generation of bubbles for the above Examples and Comparative Examples.

Curing by UV irradiation depends on the amount of energy applied and the amount and type of curing initiator. Since the amount of energy is determined by the wavelength, illuminance, and irradiation time, it is necessary to use a light source with a short wavelength and high brightness in order to shorten the irradiation time. However, in Comparative Example 1 using a high-pressure mercury lamp (manufactured by Oak Manufacturing Co., Ltd., output 30 W / cm ² ), the amount of heat generated by the lamp itself was considerably increased, so that the acrylic resin burned even when the distance was 1 m. In addition, when using a high-intensity light source, measures such as flowing water between them can be taken, but it is unavoidable that the heat generated by curing cannot be controlled, and that the device is complicated and large in size and expensive. Absent.

  In Example 2, a photocuring accelerator was added, but the curing was slightly faster, but there was no noticeable change in the air bubbles and the like. It was confirmed that after-curing must be performed later because polymerization is incomplete by only photocuring.

  The method for producing a fiber-reinforced resin sheet of the present invention can be effectively used as a method for producing a reinforcing or repairing fiber-reinforced resin sheet capable of observing the surface of a concrete structure with few bubbles in the opening of the mesh body.

1 Reinforcing fiber (Umijima type composite yarn)
3 core (island)
5a sheath part 5 sea part 10 mesh body 10a pre-impregnated mesh body 11 lower warp (layer)
12 Upper warp (layer)
13 Oblique yarn (layer)
14 Reverse diagonal thread (layer)
15 Core-sheath type composite single fiber bundle 20a Transparent curable resin composition for main body (A)
20b Transparent curable resin composition for barrier layer (B)
20c Transparent curable resin composition for pre-impregnation (C)
20a ′ Liquid layer of transparent curable resin composition (A) for main body 20b ′ Liquid layer of transparent curable resin composition (B) for barrier layer 20c ′ Liquid layer of transparent curable resin composition (C) for pre-impregnation 21 Carrier film 22 First cover film 23 Second cover film 25 Air bubbles 40, 44 Reserve tank 40a Mixing tank 41, 43, 45 Pump (resin supply pump)
42, 48 Nozzle 46 Pre-impregnation tank 47 Pre-impregnation roller 52 First squeeze roller 53a, 53b, 53c Guide roller 55 Impregnation roller 56 Second squeeze roller 60 Take-up roller 61 Winder 70, 71 Curing furnace 72 Thermosetting furnace 100 Fiber reinforced resin sheet 101 Barrier layer 102 Fiber reinforced resin main body layer

Claims (9)

A method of manufacturing a fiber structure reinforced resin sheet for repairing or reinforcing a concrete structure formed by impregnating and curing a transparent curable resin in a mesh body, the manufacturing method including the following steps (1) to (4) A method for producing a fiber-reinforced resin sheet.
(1) On the carrier film or on the barrier layer formed on the carrier film, urethane acrylate resin (a), vinyl ester resin (b), polymerizable monomer (c), photopolymerization initiator (d), And a liquid layer forming step of applying the transparent curable resin composition (A) for the main body, including the thermal polymerization initiator (e),
(2) A barrier formed on the carrier film or on the carrier film by allowing the mesh body to enter the liquid layer formed by the liquid layer forming step and further placing the first cover film on the upper surface thereof. A step of impregnating the transparent curable resin composition for main body (A) into a mesh body sandwiched between layers,
(3) a step of photocuring the transparent curable resin composition for main body (A) by irradiating light from at least one light source selected from non-white fluorescent lamps; and (4) further for the main body. A step of thermosetting the transparent curable resin composition (A).   The method for producing a fiber-reinforced resin sheet according to claim 1, wherein the non-white fluorescent lamp is a black light fluorescent lamp and is photocured by the black light fluorescent lamp.   The method for producing a fiber-reinforced resin sheet according to claim 1 or 2, wherein the polymerizable monomer (c) is at least one selected from methyl methacrylate, methyl acrylate, and styrene. The fiber according to any one of claims 1 to 3, further comprising the following barrier layer forming step (5) for forming a barrier layer on the carrier film before the liquid layer forming step (1). A method for producing a reinforced resin sheet.
(5) After applying the transparent curable resin composition (B) for the barrier layer on the carrier film and sandwiching and curing with the second cover film to form the barrier layer, the second cover film is peeled and removed. The barrier layer forming step of subjecting the formed barrier layer to the step (1).   The transparent curable resin composition (B) is the same as the transparent curable resin composition for main body (A), and is cured by irradiating light from at least one light source selected from non-white fluorescent lamps. The method for producing a fiber-reinforced resin sheet according to claim 4. 2. In the step of impregnating the transparent curable resin composition (A) for main body into the mesh body of (2), the mesh body is in a wet state through the pre-impregnation step of (6) described below. The manufacturing method of the fiber reinforced resin sheet in any one of -5.
(6) The transparent curable resin composition for pre-impregnation (C) having compatibility with the transparent curable resin composition for main body (A) and having a viscosity of 50 to 15000 cP is applied to the mesh body, and between the impregnating rollers And a pre-impregnation step of impregnating and defoaming with a roller linear pressure of 3 to 30 N / cm.   The mesh body is a laminated fabric, and the sea-island type composite yarn is laminated in at least three directions of warp direction, oblique direction, and reverse oblique direction, and the sea-island type composite yarns are heat-sealed to each other or The method for producing a fiber-reinforced resin sheet according to any one of claims 1 to 6, which is a bilayer triaxial laminated fabric.   The method for producing a fiber-reinforced resin sheet according to any one of claims 1 to 7, wherein the mesh body is hydrophilized.   The method for producing a fiber-reinforced resin sheet according to claim 4, wherein the first cover film is obtained by continuously reusing the film from which the second cover film used in the barrier layer forming step (5) is peeled off. .