JP2002029867A - Method for reinforcing concrete structure and radical- polymerizable primer and radical-polymerized hardened resin-forming composition, for use in the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for reinforcing an existing concrete structure such as pier or tunnel. SOLUTION: This concrete structure reinforcing method comprises: coating the surface of a concrete structure with a radical-polymerizable primer composition, executing impregnation work of the coated concrete structure with a fibrous base material and a radical-polymerized hardened resin-forming composition, and subjecting these compositions (i.e., the radical-polymerizable primer composition and radical-polymerized hardened resin-forming composition) to polymerization and hardening, to form a composite material layer consisting of the fibrous base material and the hardening compositions on the surface of the concrete structured radical-polymerizable primer composition is a hardening composition containing a polymerizable unsaturated monomer, a vinyl ester resin, benzoyl peroxide used as a radical polymerization initiator and a tertiary amine used as a hardening promoter, and the radical-polymerized hardened resin-forming composition is a hardening composition containing a polymerizable unsaturated monomer, a vinyl ester resin, benzoyl peroxide used as a radical polymerization initiator, a thixotropy-providing agent component and a tertiary amine used as a hardening promoter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method and a reinforcing material for reinforcing an existing concrete structure such as a pier or a tunnel.

[0002]

2. Description of the Related Art Conventionally, as a method of reinforcing concrete bridge piers on a highway, a steel plate is attached after anchor bolts are attached to existing concrete, and an epoxy resin or the like is injected into a gap between the concrete and the steel plate and hardened. Methods are known. Also, recently, instead of the method of reinforcing steel sheet adhesion, Japanese Patent Application Laid-Open Nos. Hei 3-212568 and Hei 5-
39677, JP-A-5-32804, JP-A-6-271
As seen in 373, a reinforcing method of attaching carbon fiber to an existing concrete surface using epoxy resin as an adhesive has been spotlighted, and the results thereof have been gradually increasing. This method has the advantage that, compared to the conventional method of bonding and reinforcing steel sheets, it is possible to eliminate the work of transporting and assembling heavy objects such as steel sheets and to eliminate the need for welding work.

[0003]

However, epoxy resins generally require one day or more to cure at room temperature, and particularly when the temperature falls to 5 ° C. or less in winter, the curing speed becomes extremely slow. In addition to the long working period, there is a possibility that curing failure may occur. In addition, when performing the bonding operation using an epoxy resin, there are the following problems. (I) The construction surface must be clean, and dirt, dust, latencies, and oils and fats on the concrete surface must be completely removed. (Ii) When mixing the main agent and the curing agent, it is necessary to strictly adhere to the prescribed mixing ratio and to sufficiently stir. (Iii) Since the curing speed of the epoxy resin is low, it is necessary to set the viscosity and thixotropy of the adhesive to be high when repairing the vertical surface and the ceiling surface to prevent dripping before the adhesive is cured. When the viscosity is increased, the impregnation of the adhesive into the carbon fiber sheet becomes worse, and the air entrapped at the time of applying the adhesive becomes difficult to escape, so that there is a concern that a defective portion may be left in the cured reinforced composite.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, when reinforcing a concrete structure with carbon fibers, an acrylic monomer-containing mold coating having a specific composition has been used. It has been found that it is extremely effective to use a film-forming agent as a primer on a concrete surface and as a matrix component of a cured composite with carbon fibers, and the present invention has been completed. That is, the present invention first applies a radical polymerizable primer composition to the surface of a concrete structure, then impregnates and constructs a fiber base material and a radical polymerizable resin-forming composition, cures and cures the fiber base material. The present invention relates to a reinforcing method for reinforcing an existing concrete structure by forming a composite material layer of a material and a polymerizable coating film forming agent so as to adhere and integrate with a concrete surface. Here, "impregnating and constructing" means that after fixing the fiber base material to the construction surface, a polymerizable film forming agent may be applied and impregnated, or the fiber impregnated with the polymerizable film forming agent may be impregnated. This means that the base material may be fixed to the construction surface. Radical polymerization-curable resin-forming composition can be a low-viscosity composition as compared with epoxy resin-based adhesives, easily impregnates the fiber substrate used, and wets the concrete substrate. Good, evenly adheres to the surface even if there are irregularities, dust, oils and fats, and its reaction and curing are less affected by environmental temperature compared to epoxy resin adhesives, and cures quickly in winter. .

[0005] The fiber base material used in the present invention is not particularly limited as long as the strength when a composite material is formed has a predetermined numerical value. It is preferable to use a base material such as a yarn using a fiber or a sheet using the yarn. While carbon fiber has high rigidity, it also has a brittle surface.
Those formed into a sheet using a resin binder or the like as necessary are preferable. In the case of other fibers, a yarn obtained by twisting long fibers into a yarn, which is formed into a woven fabric, can also be used.

The radical polymerizable primer composition and the radical polymerizable resin-forming composition used in the method for reinforcing a concrete structure of the present invention include the following (a):
To (c), (a) a polymerizable unsaturated monomer, (b) a vinyl ester resin, and (c) a radical polymerization initiator. The composition is a low-viscosity composition that is a feature of the present invention, easily impregnated into a fiber base material to be used, has good wettability to a concrete base material, and has irregularities and dust on its surface, and oils and fats. Evenly adheres even if
In addition, the reaction and curing are less affected by the environmental temperature than the epoxy resin-based adhesive, and cure quickly even in winter.

In the present invention, in order to prevent a phenomenon in which the applied composition causes curing inhibition due to the influence of oxygen in the air and causes poor drying of the surface portion and "stickiness", the above-mentioned component vinyl ester resin is used. It is preferable to introduce a component having an air drying function into (b). When the component vinyl ester resin (b) does not contain a component having an air drying function, it is preferable to separately add a component (d) having an air drying function to the composition.

The radical polymerizable primer composition and the radical polymerizable resin-forming composition are preferably curable at room temperature. However, the composition is heated by using a heating means such as an infrared heater or a hot air blowing device. It may be one that polymerizes by polymerization.

In the present invention, a concrete structure is coated with a radically polymerizable primer composition, then impregnated with a fiber base material and a radically polymerizable resin-forming composition, polymerized and cured to form a concrete structure. A polymerizable primer composition and a polymer-curable resin-forming composition used in a method for reinforcing a concrete structure to be integrated, comprising the following components (a) to (c): (a) a polymerizable unsaturated monomer (b) ) Vinyl ester resin (c) A radical polymerizable primer composition and a radical polymerizable curable resin-forming composition containing a polymerization initiator, wherein a component having an air drying function is not introduced into the vinyl ester resin. The composition is preferably a composition to which the component (d) having an air drying function is added.

The (a) polymerizable unsaturated monomer used in the radical polymerizable primer composition and the radical polymerizable resin-forming composition is at least one selected from glycidyl, carboxyl, hydroxyl and alkoxysilyl groups. It is preferable that the composition contains at least one or more functional monomers having a functional group of These functional monomers are incorporated into the skeleton of the polymerized and cured product by copolymerization.In the primer, they exhibit the effect of improving the adhesiveness to the concrete surface, and in the radically polymerizable resin-forming composition, It has the effect of increasing the adhesiveness to a fiber base material as a reinforcing fiber such as carbon fiber and glass fiber.

The vinyl ester resin (b) used in the radical polymerizable primer composition and the radical polymerizable resin-forming composition is an epoxy acrylate having at least one acrylate group or methacrylate group in the molecule. Is preferred. The vinyl ester resin is combined with a fiber base material using carbon fiber or the like to form a reinforced resin, and exerts an effect of strongly reinforcing a concrete structure.

In the present invention, at least one of the radically polymerizable primer composition and the radically polymerizable resin-forming composition is further soluble or homogeneously dispersed in the component mixture of (a) to (c). Preferably, it contains at least one type of coupling agent component (g) selected from the group consisting of a silane coupling agent, a titanate coupling agent, a zirconate coupling agent, and an organoaluminum coupling agent. By adding the component (g), an effect of improving the adhesiveness can be further obtained.

The radical polymerizable primer further contains a polymer component (e) soluble or homogeneously dispersed in the component mixture (a) to (c), or a thixotropic agent component (f). Is preferred. On the other hand, the radical polymerization curable resin-forming composition contains the thixotropy-imparting component (f), and preferably further contains the polymer component (e).
When the component (d) having an air drying function is used in combination, the component (e) and the component (f) are soluble or uniformly dispersed in the component mixture of (a) to (d). . The polymer component (e) exerts effects such as viscosity adjustment, imparting toughness, and improving durability, and also has an action as a polymerization accelerator by the Trommsdorff effect in the polymerization process of these compositions. The thixotropic agent component (f) is effective in preventing dripping when applied to a vertical surface, an inclined surface, or the like.

The above (a) to (c) or (a) to (c) which are added as necessary to the radical polymerizable primer composition and the radical polymerizable resin forming composition.
(D) The polymer component (e) soluble or homogeneously dispersed in the component mixture is particularly preferably a polymer having rubber elasticity. By adding the polymer component (e) having rubber elasticity, particularly the toughness and durability of the reinforcing layer including the fiber base material are greatly improved.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION In the method for reinforcing a concrete structure according to the present invention, first, a radical polymerizable primer composition is applied to the surface of a concrete structure, and then a fibrous base material and a radical polymerizable resin-forming composition are applied. Impregnating and constructing, polymerizing and curing the radical polymerizable primer composition and the radical polymerizable resin-forming composition, and bonding the fiber base material and the cured product of the curable composition to a concrete structure to be integrated. It is to make it. By forming the fiber base material and the curable composition into a fiber reinforced resin layer and bonding and integrating with the concrete structure via the primer layer,
The concrete structure is reinforced. Further, the reinforcing layer formed according to the present invention has waterproofness and does not cause cracks, so that water is prevented from penetrating into the concrete structure as a secondary result, thereby improving the durability of the structure. An effect also occurs.

The radical polymerization-curable primer used in the present invention is composed of a composition containing (a) a polymerizable unsaturated monomer, (b) a vinyl ester resin, and (c) a radical polymerization initiator. The polymerization-curable resin-forming composition is composed of a composition containing (a) a polymerizable unsaturated monomer, (b) a vinyl ester resin, (c) a radical polymerization initiator, and (f) a thixotropic agent. You. In any case, when a component having an air drying function is not introduced into the vinyl ester resin (b), a component (d) having an air drying function is separately added.

Component (a) Among these, the polymerizable unsaturated monomer component (a) forms a skeleton of a cured product by polymerization, and includes alkyl acrylate, methacrylate, styrene, vinyl toluene and the like. Examples of the monomer include aromatic monomers and acrylonitrile.In addition to these monomers, it is possible to use a monomer that contributes to the formation of a crosslinked structure such as divinylbenzene, diallyl phthalate, and ethylene glycol dimethacrylate, if necessary. it can. Among these monomers, the use of aromatic monomers, particularly styrene, is preferable in terms of cost and low cost, good compatibility with other components, and contribution to improving the water resistance of the composite material after curing. .

As the alkyl acrylate, for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isobonyl acrylate and the like can be used. Examples of the methacrylate include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, isobonyl methacrylate, and tetrahydrofurfuryl methacrylate. These may be used alone or in combination of two or more. Above all, monomers having a glass transition temperature of 0 ° C. or less, such as homopolymers having a glass transition temperature of 80 ° C. or higher (eg, methyl methacrylate, t-butyl methacrylate, isobornyl methacrylate, styrene, etc.) A mixture of n-butyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, etc.) is preferable because it can impart appropriate strength and flexibility to the obtained coating film. The mixing ratio of the monomer (M) having a glass transition temperature of 80 ° C. or higher and the monomer (N) having a glass transition temperature of 0 ° C. or lower is a weight ratio of M / N = 30/70 to
It is preferable to set the ratio to 90/10. In addition,
The content of the component (a) can be appropriately set.
８０80% by weight (hereinafter abbreviated as “%”), and more preferably 55-75%.
If the content of the component (a) is less than 40%, the curable primer obtained tends to have a high viscosity, and the permeability to the concrete surface tends to decrease.
This is because the permeability to the concrete becomes remarkable, and the curability of the concrete surface tends to deteriorate. 55 content
Particularly in the range of 75%, particularly stable characteristics can be obtained.

On the other hand, in the radical polymerization curable resin-forming composition, the content of the component (a) is preferably set to 20 to 70%, more preferably 35 to 55%. When the content of the component (a) is less than 20%, the viscosity of the obtained radical polymerization-curable resin-forming composition becomes too high, so that it is difficult to impregnate a fiber base material, particularly a sheet such as a woven fabric, The mixed solubility of other components in the curable composition also decreases.

The component (a) of the present invention contains at least one or more functional monomers (a ') having at least one functional group selected from glycidyl group, carboxyl group, hydroxyl group and alkoxysilyl group. Among them, those having an epoxy group, a carboxyl group, a methoxysilyl group, an ethoxysilyl group, a methoxyethoxysilyl group or the like in the molecule are particularly effective.

Examples of the functional monomer (a ') having an epoxy group include glycidyl methacrylate and glycidyl acrylate. Examples of those having a carboxyl group include acrylic acid, methacrylic acid, and oligoester acrylate (for example, Aronix M5600 and M6500 manufactured by Toagosei Co., Ltd.).
And the like, and examples of the alkoxysilyl group-containing compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane,
γ-methacryloxypropyltrimethoxysilane and the like can be exemplified. Examples of the compound having a hydroxyl group include hydroxyethyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl methacrylate.

The content of these functional monomers (a ') in the radical polymerizable primer composition and the radical polymerizable resin-forming composition is preferably set to 0.5 to 10%, more preferably 1 to 5%. Is more preferably set to. At 0.5% or less, the effect of improving the adhesiveness is small, and
%, The hardness and water resistance of the cured product are reduced and the cost is increased. When it is set in the range of 1 to 5%, good characteristics can be obtained at a relatively low cost.

Component (b) The vinyl ester resin component (b) is one of the main components of the radical polymerizable primer composition and the radical polymerizable resin-forming composition, and is a polymerizable unsaturated monomer, particularly By using in combination with acrylic monomers, etc., the mechanical strength, hardness, thermal deformation, alkali resistance, acid resistance, chemical resistance, and weather resistance of the cured product are improved, and compared with the cured product of the acrylic monomer alone. The effect of reducing the curing shrinkage is also exerted. As such a vinyl ester resin as the component (b), an epoxy acrylate having a (meth) acrylate group in a molecule is known and can be used.

An epoxy acrylate having a (meth) acrylate group (meaning "acrylate group and / or methacrylate group") in the molecule is a bisphenol type epoxy resin or a bisphenol type epoxy resin and a novolak type epoxy resin. A resin obtained by reacting an epoxy resin having an average epoxy equivalent preferably in the range of 150 to 450 with an unsaturated monobasic acid in the presence of an esterification catalyst. Here, a typical example of the bisphenol type epoxy resin is a glycidyl ether type epoxy resin obtained by reacting epichlorohydrin with bisphenol A or bisphenol F and having substantially two or more epoxy groups in one molecule. And dimethyl glycidyl ether type epoxy resin obtained by reacting methyl epichlorohydrin with bisphenol A or bisphenol F, or epoxy resin obtained from an alkylene oxide adduct of bisphenol A and epichlorohydrin or metaepichlorohydrin. Representative examples of the unsaturated monobasic acid used for the synthesis of epoxy acrylate having a (meth) acrylate group include acrylic acid, methacrylic acid, crotonic acid, monomethylmalate, monopropylmalate, and sorbin. Examples include acid or mono (2-ethylhexyl) malate. These unsaturated monobasic acids can be used alone or in combination of two or more.

Commercially available vinyl ester resins include, for example, Lipoxy R-800 series, H-600 series (manufactured by Showa Kogaku), Dicklight series, Diova series (manufactured by Dainippon Ink) and the like.

The content of the component (b) can be appropriately set according to the molecular weight and viscosity, but is generally preferably set to 5 to 50% by weight in the radically polymerizable primer composition. That is, if the content of the component (b) is less than 5%, the obtained cured product has insufficient mechanical strength and chemical resistance, and if it is 50% or more, the permeability to the concrete surface layer tends to be poor. On the other hand, in the radical polymerization curable resin-forming composition component, it is preferably set to 10 to 60%, and if it is 10% or less, the strength as the radical polymerization curable resin-forming composition tends to be insufficient, If it is 60% or more, the solubility of other components (for example, the component (e)) in the radical polymerization curable resin-forming composition will decrease.

Component (c) The component (c) is a radical polymerization initiator component for polymerizing and curing the radical polymerizable primer composition and the radical polymerization curable resin-forming composition. Immediately before the polymerization-curable resin-forming composition is applied, it is added and mixed. As such a component, an organic peroxide is generally used. Specifically, ketone peroxide, peroxyketal, hydroperoxide, diacyl peroxide, peroxyester, peroxydicarbonate are used. Although the organic peroxides are known and can be used, these organic peroxides are appropriately selected according to various conditions at the time of construction. In order to avoid the danger of handling these organic peroxides, pastes or powders diluted with an inert liquid or powder to a concentration of 50% or less, preferably 30% or less, are used. Preferably, benzoyl peroxide surface-treated with an inorganic powder having water of crystallization is particularly preferred. Inorganic powders used for such applications include calcium phosphate, calcium sulfate, magnesium carbonate, aluminum hydroxide and the like.

Further, these radical polymerization initiators are generally used in combination with a curing accelerator and utilizing a redox reaction. The curing accelerator used is not particularly limited, but includes metals such as tertiary amines, quaternary ammonium salts, cobalt, vanadium, manganese, and copper, such as cobalt naphthenate, cobalt octenoate, copper naphthenate, and naphthenic acid. Metal soaps such as manganese and vanadium accelerators; As the tertiary amine, it is preferable to use one in which at least one aromatic acid group is directly bonded to a nitrogen atom, and particularly preferably, N-dimethylaniline, N-dimethyl-p-toluidine, N-dihydroxyethyl-p-toluidine, N-di (2-hydroxypropyl) -p-toluidine and the like can be mentioned. These may be used alone or in combination of two or more, and are usually previously blended in the primer composition and the radical polymerization curable resin-forming composition.

The amount of the radical polymerization initiator component (c) to be added can be appropriately set according to the conditions at the time of construction, such as the temperature, but the amount of the radical polymerization initiator composition or the radical polymerization curable resin-forming composition in the components is not limited. It is preferably set to 0.1 to 10%, more preferably in the range of 0.5 to 7%.

Component (d) The component (d) having an air drying function is that the radical polymerizable composition comes into contact with air during the polymerization, whereby oxygen in the air acts as a polymerization inhibitor and the cured product It is a component that prevents the phenomenon that the surface becomes uncured. Paraffin wax has been conventionally used as a component having such an air drying function. However, in the method of adding only paraffin wax, the curing reaction is easily affected by temperature, monomer concentration, humidity, and the like. In this method, a method of introducing a component having an air drying function into a vinyl ester resin as the component (b) and a method of separately adding a component having an air drying function are used. The component (d) having the air drying function may not be added when the component having the air drying function is introduced into the component (b). The components having an air drying function are:
It is preferable to use it in combination with paraffin wax because of its great effect.

As a method for introducing a component having an air drying function into a vinyl ester resin, there is known a method in which the following compound is added and reacted in the synthesis of a vinyl ester. (1) A method of adding a compound containing an allyl ether group to a glycol component. (2) A method of adding a compound containing a cyclic aliphatic unsaturated polybasic acid and a derivative thereof to an acid component. (3) A method of adding a dicyclopentadiene derivative.

Examples of the compound having an allyl ether group used in the above method (1) include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyoxyethylene glycol monoallyl ether, Propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polyoxypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol monoallyl ether, hexylene Glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpro Allyl ether compounds of polyhydric alcohols such as diallyl ether, glycerin monoallyl ether, glycerin diallyl ether, pentaerythritol monoallyl ether, pentaerythritol diallyl ether, pentaerythritol triallyl ether, and oxiranes such as allyl glycidyl ether Allyl ether compounds having a ring are exemplified. Among them, triethylene glycol monoallyl ether, trimethylolpropane monoallyl ether, trimethylolpropane diallyl ether, allyl glycidyl ether, and glycerin diallyl ether are preferable from the viewpoint of air drying function and economy, and trimethylol propane diallyl ether and allyl Glycidyl ether is particularly preferred. The above allyl ether compounds can be used alone or in combination of two or more.

As the glycol component used in combination with the allyl ether compound, in addition to the above-mentioned pentaerythritol and the like, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4- Examples thereof include butanediol, triethylene glycol, tetraethylene glycol, bisphenol A, hydrogenated bisphenol A, and ethylene glycol carbonate, and those obtained by adding ethylene oxide or propylene oxide to them can also be used. Among them, from an economic point of view,
General-purpose products mass-produced industrially are preferable, and particularly preferably, propylene glycol, triethylene glycol,
Bisphenol A, 1,4-butanediol. The glycol components are used alone or in combination of two or more.

The compound containing a cyclic aliphatic unsaturated polybasic acid and its derivative used in the above (2) includes tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, α-
Terpinene-maleic anhydride adduct, rosin, ester gum and the like. Among them, from the viewpoint of industrial or physical properties, particularly weather resistance, tetrahydrophthalic anhydride,
Endomethylenetetrahydrophthalic anhydride and methyltetrahydrophthalic anhydride are preferred, and tetrahydrophthalic anhydride is particularly preferred. The cycloaliphatic unsaturated polybasic acids and the like are used alone or in combination of two or more. When these cycloaliphatic unsaturated polybasic acids are used, it is preferable to use diethylene glycol or triethylene glycol as a glycol component to be a reaction partner.

Examples of the acid used together with the above-mentioned cycloaliphatic unsaturated polybasic acid and the like include those described above in connection with the component (b), and specifically, the following acids are used. . That is, examples of the α, β-unsaturated dibasic acid or acid anhydride include maleic acid, maleic anhydride, fumaric acid, itaconic acid, chlormaleic acid, and esters of these acids or acid anhydrides. . Further, examples of the aromatic saturated dibasic acid or its acid anhydride include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, nitrophthalic acid, halogenated phthalic anhydride, and these acids or acid anhydrides. . Examples of aliphatic or alicyclic saturated dibasic acids include oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, glutaric acid, hexahydrophthalic anhydride, and anhydrides of these acids. can give. Among these, maleic anhydride, maleic acid, phthalic acid, phthalic anhydride, adipic acid, and fumaric acid are preferred from the viewpoint of physical properties and economics, and maleic anhydride and phthalic anhydride are particularly preferred. These acids and acid anhydrides are used alone or in combination of two or more. The compound containing dicyclopentadiene used in the above (3) is not particularly limited, and examples thereof include hydroxylated dicyclopentadiene.
Introduced into vinyl esters.

Examples of the compound used as a component having an air drying function which can be added as the component (d) include an acrylic acid derivative of dicyclopentadiene, a drying oil or an epoxy-reactive diluent. Examples of the drying oil include linseed oil, soybean oil, cottonseed oil, peanut oil, coconut oil, and the like, and a reaction product of these fatty oils with a polyhydric alcohol such as glycerin or a reaction product of cyclopentadiene with cyclopentadiene. Oil. Of these, cyclopentadiene oil is preferred from the viewpoint of the effect. As the epoxy-reactive diluent, a monoepoxy compound, a polyepoxy compound, or the like can be used. Specific examples of the monoepoxy compound include allyl glycidyl ether, n-butyl glycidyl ether, phenyl glycidyl ether, and glycidyl methacrylate. And specific examples of the polyepoxy compound include diglycidyl ether. Of these, monoepoxy compounds are preferred, and glycidyl methacrylate and allyl glycidyl ether are particularly preferred. The epoxy reactive diluents may be used alone or in combination of two or more. Having air drying function (d)
As a component, addition of a commercially available product such as Lipoxy AC-201 and Lipoxy 501 (manufactured by Showa Polymer) is also effective.

The amount of the component (d) to be added to the radical-polymerizable primer or the radical-polymerizable curable resin-forming composition can be appropriately set, but is generally preferably 1 to 20% of the composition.
More preferably, it is in the range of 2 to 10%. If the content of the component (d) is less than 1%, the air-drying property becomes insufficient, so that the polymerization-curable component on the surface of the coating film may become uncured. And the uniformity of the cured coating surface tends to decrease. In the range of 2 to 10%, stable characteristics can be obtained.

Component (e) The polymer as component (e) is a component added for the purpose of adjusting the viscosity of the composition and improving the toughness and durability of the cured product. It must be soluble or uniformly dispersed in each composition until it is added to the product or the radical polymerization-curable resin-forming composition, stirred, and the cured coating film is formed. .

Such polymers include acrylic polymers, polyvinyl acetate resins, ethylene vinyl acetate resins,
Ethylene-vinyl acetate-vinyl chloride copolymer, urethane resin, urethane prepolymer, acrylic urethane oligomer, reactive epoxy resin, acrylonitrile-butadiene rubber, styrene-butadiene rubber, styrene block copolymer, isoprene rubber, chlorosulfonated polyethylene One or two or more polymers can be selected and used from polymers such as epichlorohydrin rubber and chloroprene rubber.

Examples of the acrylic polymer include methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, methyl acrylate,
Polymers obtained by polymerizing monomers such as ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and copolymers obtained by combining two or more of these. Coalescence. Among them, methyl methacrylate polymer, a monomer having low glass transition temperature of methyl methacrylate and homopolymer (for example, methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, 2-ethylhexyl acrylate, It is preferable to use a copolymer with lauryl methacrylate). The molecular weight of these polymers is preferably from 2,000 to 8,000. Such various acrylic polymers are commercially available, for example, Paraloid B-60 (MMA / R & H MMA /
BMA copolymer), paraloid A-21 (MMA polymer) and the like can be used.

When a polymer having rubber elasticity is used as the component (e) and the polymer is dissolved or uniformly dispersed and cured in a radical-polymerizable resin-forming composition, a rubber-like polymer micro-dispersed in the cured resin is obtained. Domains are generated, and toughness can be imparted to the matrix layer of the composite with carbon fibers and the like. As a result, the fracture resistance of the composite layer when tensile force, shear force, impact force, and peeling force are applied is greatly improved.

Examples of such polymers having rubber elasticity include thermoplastic polyurethane elastomers such as Pandex T-5201 and 5202 (manufactured by Dainippon Ink and Chemicals), Desmocol 406 (manufactured by Sumitomo Bayer Urethane), and urethane prepolymer. Death module T
Examples include EC41 (manufactured by Sumitomo Bayer), Hypren R305 (manufactured by Mitsui Toatsu Chemicals), Polyflex MT (manufactured by Daiichi Kogyo Seiyaku), and acrylonitrile butadiene rubbers such as Nippol 1072J, DN219 (manufactured by Nippon Zeon), and styrene. As the block copolymer, Kraton GX1726 (manufactured by Shell Chemical), Solprene T40
6. Asaprene T450, Tufprene A (Asahi Kasei Kogyo, styrene-butadiene-based plastic elastomer), and Hypalon 20 as chlorosulfonated polyethylene
(Manufactured by DuPont), as epichlorohydrin rubber,
Examples include Zeklon 1000 and 1100 (manufactured by Zeon Corporation). These polymers having rubber elasticity can be dissolved or dispersed in the radical polymerization curable resin-forming composition alone or in combination with a compatibilizer suitable for each polymer. For a polymer having poor dispersion stability in the radical polymerization curable resin-forming composition, the polymer is dissolved in a part of the component (a) in advance, and a monomer solution of this polymer is dissolved in the radical polymerization curable resin-forming composition. Immediately before the coating of the product, the polymerization initiator (c) is added together with the component to the radical polymerization-curable resin-forming composition, uniformly mixed, stirred, and dispersed.
The purpose can be achieved by using it immediately.

This component (e) is particularly effective when it is added to a radical-polymerized curable resin-forming composition, and its addition amount can be appropriately set.
It is preferably set in the range of 25%, more preferably in the range of 5 to 15%. When the component (e) is less than 1%, the thickening effect and the toughness-imparting effect after curing may not be sufficiently exhibited, and when it is 25% or more, the viscosity of the radical-polymerized curable resin-forming composition may be reduced. Too high, the coating workability of the composition, the impregnation property of the fiber base material, especially carbon fiber, and the toughness of the composite after curing are reduced. Further, the stability of the radical polymerization curable resin-forming composition is lowered, and the tendency of the separation of the component (e) becomes remarkable. On the other hand, it is effective to add the component (e) to the radical polymerization-curable primer composition. However, if it is added in excess, the viscosity of the composition increases, and the impregnation property to the concrete surface layer decreases. When the addition rate is adjusted in the range of 0 to 5%, the degree of thickening is small, and the polymerization and curing reaction is accelerated and effective.

Component (f) The component (f) is contained in the radical polymerization curable resin-forming composition and enhances the thixotropy of the curable composition, and is particularly hardened when applied to a vertical surface or a ceiling surface. In the meantime, the composition exhibits an effect of preventing dripping of the radical polymerization curable resin-forming composition. As the component (f), an inorganic type,
Any organic or thixotropy-imparting agent can be used.
(Manufactured by Nippon Aerosil Co., Ltd.), Nipsil LP, VN3,
Examples thereof include finely divided silica such as L300 (manufactured by Nippon Silica Industry Co., Ltd.), finely divided calcium carbonate such as Nanox 25 (manufactured by Maruo Calcium), and graphite white CC (manufactured by Shiraishi Calcium). Manufacture, hydrogenated castor oil system), DISPARON 6500 (Kusumoto Kasei, fatty acid amide wax system), BYK-P10
4, BYK-410 (manufactured by BYK-Chemie) and the like.

The addition amount of the component (f) can be appropriately set.
Generally, in the radical polymerization-curable resin-forming composition (B),
The content is preferably set to 0.5 to 10%. In particular, when finely divided silica such as Aerosil 200 is used, a sufficient effect can be obtained by adding 5% or less. If it is 0.5% or less, the effect of imparting thixotropic properties is small, and it may be difficult to perform the work on a surface having a large inclination. On the other hand, if it is 10% or more, the thixotropic property becomes too large, and the fluidity and coating workability of the radical polymerizable resin-forming composition deteriorate.

Component (g) Component (g), which is a coupling agent component, is selected from silane-based coupling agents, titanate-based coupling agents, zirconate-based coupling agents, and organoaluminum-based coupling agents, and is selected from one or more. Is used. Examples of each compound include the following. Silane-based coupling agents γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N- (β
Aminoethyl) γ-aminopropyltrimethoxysilane, N- (βaminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyl Trimethoxysilane,
γ-chloropropyltrimethoxysilane, β- (3,4
Epoxycyclohexyl) ethyltrimethoxysilane and the like. Titanate-based coupling agents (a) Monoalkoxy type: isopropyl triisostearoyl titanate, isopropyl tristearoyl titanate, isopropyl tri (dioctyl phosphate) titanate, isopropyl tri (dibutyl pyrophosphate) titanate, isopropyl trimethacryl titanate and the like. (B) Chelate titanate type: titanium diisostearate oxyacetate, titanium di (dioctyl phosphate) oxyacetate, titanium di (octyl pyrophosphate) oxyacetate, titanium isostearate, diisostearoylethylene titanate, di (dioctyl) (Phosphate) ethylene titanate, di (dioctyl pyrophosphate) ethylene titanate, titanium isostearate methacrylate oxyacetate, dimethacrylethylene titanate and the like. (C) Coordination type titanates: tetraisopropyl di (dilauryl phosphite) titanate, tetraisopropyl di (dioctyl phosphite) titanate, tetraoctyloxytitanium di (lauryl phosphite) titanate and the like. (D) In addition, neoalkoxy titanate, heterocyclic titanate and the like. Zirconium-based coupling agents Zirconium alkoxides such as ethoxyzirconium stearate, zirconium chelate compounds such as zirconium tetraacetylacetonate and zirconium α-hydroxycarboxylate, zirconium soaps, zirconium acetate and the like. Organic aluminum-based coupling agent Aluminum isopropylate, monosec-butoxyaluminum diisopropylate, aluminum sec
Aluminum alkoxides such as butyrate; aluminum chelate compounds such as ethyl acetoacetate aluminum diisopropylate and aluminum tris (ethyl acetoacetate);

The above-mentioned coupling agent component (g) is added to the radical-polymerizable primer composition and the polymer-curable resin-forming composition so that the content in the composition is 0.5 to 10%. Is added. As with the component (a ′), 0.
If the content is 5% or less, the effect of improving the adhesiveness may be small.
Addition of 0% or more may lower the physical properties of the cured product and increase the cost of the composition. In particular, addition in the range of 1 to 5% is preferable because of its relatively low cost and good characteristics.

The radical-polymerizable primer composition and the radical-polymerized curable resin-forming composition of the present invention include, in addition to the above components, calcium carbonate, clay, alumina powder, silica powder, talc, barium sulfate, mica, and aluminum hydroxide. And inorganic powders such as silica sand, cement, blast furnace slag, and gypsum, or pigments such as titanium oxide, barium sulfate, carbon black, red iron oxide, ultramarine, cobalt blue, phthalocyanine blue, and graphite.

If necessary, an antifoaming agent, a pigment dispersant,
An anti-settling agent, a discoloration inhibitor, a paraffin wax, and a polymerization inhibitor can be added. In particular, the polymerization inhibitor is preferably added in order to stably store the radically polymerizable primer composition and the radically polymerizable resin-forming composition in the distribution stage.

The radical polymerizable primer composition and the radical polymerizable curable resin-forming composition of the present invention comprise at least two components of a composition containing a radical polymerization initiator such as peroxide and other components containing a polymerizable monomer at the distribution stage. It is preferably a component type.

PAN-based carbon fiber, pitch-based carbon fiber, aramid fiber (aromatic polyamide), glass fiber, polyvinyl alcohol fiber or the like is used as a fiber base material having a function as a reinforcing fiber applied to the concrete surface. Although carbon fibers are preferred, carbon fibers are preferred in view of tensile strength, Young's modulus and workability, and PAN-based carbon fibers are preferred. Examples of such carbon fibers include PAN-based Torayca T200, T300, high elasticity type (manufactured by Toray), Pyrofil TR30, MR40 (manufactured by Mitsubishi Rayon), Vesfight ST-3, IM500 (manufactured by Toho Rayon). Yes, it can be used. Further, as pitch-based carbon fiber, FORCA toe sheet FT500, FT
700 (made by Tonen), Granock TU cloth ST200,
HM300 (manufactured by Nippon Petrochemical) is suitable. These fibers are preferably used in the form of a sheet material in which long fibers are arranged in one direction or a woven fabric using the yarn, and the direction of the fibers is appropriately selected according to the direction in which stress is applied to the concrete structure. Will be constructed. Generally, taking a pier as an example, it is preferable to stack a vertical layer and at least two layers in a direction crossing the vertical layer.

The procedure of the reinforcing method according to the present invention will be described. Here, an example in which a carbon fiber sheet is used as a fiber base material will be described. First, steps, defects, cracks, etc. on the concrete surface are corrected using an injectant, mortar, or the like. Next, immediately before use, the radical polymerization initiator component (c) was added, and the uniformly mixed radically polymerizable primer composition was added to the mixture by a known method such as roller brushing or spraying.
It applied in an amount of 05~0.3kg / ^{m 2.} The pot life of the primer composition can be appropriately adjusted depending on the temperature at the time of construction, the type of the component (c), the amount added, the combination with the curing accelerator, and the like, but usually after the component (c) is added and mixed. It is desirable to complete the application within 30 minutes. Since the primer composition is usually adjusted to be cured within one hour, it is possible to immediately proceed to the next carbon fiber sheet construction work step after the primer application and curing. Various procedures can be considered for attaching the carbon fiber sheet. Usually, first, the radical polymerization curable resin-forming composition to which the component (c) is added and mixed is applied to the primer cured surface by a known means such as a roller brush. After coating, a carbon fiber sheet is stuck thereon, and immediately before that, a component (c) is added and mixed to form a radical polymerization-curable resin-forming composition,
Impregnated into carbon fiber sheet. At this time, a coating operation is performed so that the radical polymerization-curable resin-forming composition is sufficiently impregnated in the carbon fiber, and air is completely extruded using a defoaming roller. This operation is repeated as necessary by changing the vertical and horizontal directions of application of the carbon fiber sheet, for example, so that the desired carbon fiber sheet laminated cured composite layer can be formed. In general, it is desirable that the operation of attaching the carbon fiber using the radical polymerization-curable resin-forming composition is performed within 30 minutes after the addition and mixing of the component (c) as in the case of the primer coating.

By repeating such a series of operation steps, the operation time can be remarkably reduced as compared with the conventional method using an epoxy resin-forming composition, and the reinforcing method using an epoxy adhesive can be used. The same or better performance and effect can be obtained. In addition, the carbon fiber may be immersed in the radical polymerization curable resin-forming composition, and the impregnated composition may be adhered to the construction surface.

In the present invention, it is possible to add a colorant to the radical polymerization curable resin-forming composition as appropriate to form a colored cured coating film. Surface protection coating.
For example, acrylic paints, urethane paints, and acrylic urethane paints can be used.

[0055]

Embodiments of the present invention will be described below. (Examples 1 to 10) [1] Preparation of monomer mixture containing component (a) The following (a-) was prepared as a monomer mixture containing component (a).
1) and (a-2) were blended. The compounding amounts are indicated in parts by weight. (A-1) Methyl methacrylate 80 Butyl acrylate 15 Ethylene glycol dimethacrylate 4.4 N-di (2-hydroxypropyl) -p-toluidine 0.5 Hydroquinone 0.1

(A-2) Methyl methacrylate 37 Styrene 50 2-ethylhexyl acrylate 10 Divinylbenzene 2.5 N-dimethyl-p-toluidine 0.5 Hydroquinone 0.02

[2] Preparation of Component (b) Components (b) and (b-2) were prepared as the component (b) vinyl ester resin as follows. (B-1) Preparation of Epoxy Acrylate In a four-necked flask equipped with a stirrer, a thermometer, a cooling condenser, and a gas inlet tube, an epoxy resin having an epoxy equivalent of 265 obtained by the reaction of bisphenol A and epichlorohydrin (DER337, Dow Chemical Company) 13
3 parts, methacrylic acid (epoxy group / carboxyl group = 1
/ 1; equivalent ratio) 43 parts, hydroquinone monomethyl ether 0.24 part, and triethylmethylammonium iodide 1.69 part as an esterification catalyst were charged and reacted in air at 110 ° C for 5 hours, and the reaction rate was 99.8%. As a result, a slightly brown liquid epoxy acrylate having a viscosity of 55 poise was obtained.

(B-2) Commercially available vinyl ester resin Dicklight UE3505 (manufactured by Dainippon Ink and Chemicals, viscosity: 300 to 600 cps) was used as (b-2).

[3] Preparation of Curing Agent Containing Component (c) A benzoyl peroxide powder is treated with magnesium carbonate having water of crystallization, uniformly mixed, and a curing agent containing 30% pure benzoyl peroxide (hereinafter referred to as “BPO powder”). ").

[4] Preparation of Component (d) The following components (d-1), (d-2) and (d-3) were prepared as component (d) (a component having an air drying function). (D-1) Synthesis of saturated polyester 2.0 mol of terephthalic acid, 1.5 g of diethylene glycol
Mol, pentaerythritol triallyl ether 1.0
The moles were heated and dehydrated and condensed under known conditions to obtain a saturated polyester having an acid value of 20.

Preparation of (d-2) and (d-3) As a commercially available component having an air drying function, Showa Polymer's Lipoxy AC-501 (viscosity: 1200 to 1700 c
ps) to (c-2), Lipoxy AC-201 (viscosity: 3)
(00-500 cps) as (c-3).

[5] Preparation of Monomer Solution Containing Component (e) The following various commercially available polymers are dissolved in the above monomer mixture (a-1) to give (e-1) to (e-1). e-4) A polymer solution was prepared.

(E-1): Paraloid B66 (Rome
(Acrylic resin manufactured by Andhas Japan) (polymer concentration = 50%) (e-2): Pandex T5201 (thermoplastic polyurethane manufactured by Dainippon Ink and Chemicals, Inc.) (polymer concentration = 25%) (e -3): Zeklon 1100 (Epichlorohydrin rubber manufactured by Zeon Corporation) (polymer concentration = 12.5%) (e-4): Nippol 1072J (acrylonitrile-butadiene rubber manufactured by Zeon Corporation) (polymer concentration = 2)
0%)

[6] Preparation of Radical-Polymerizable Primer Composition and Coating on Concrete Surface The various components prepared as described above were weighed as shown in the upper row of Table 1, and the tabletop dispersion was measured. And mixed uniformly to form a radical polymerizable primer composition according to Examples 1 to 3.
Example 12 was prepared. The curing agent "BPO powder" containing the polymerization initiator component (c) was added and mixed immediately before the application of the primer. Next, these primer compositions were subjected to JIS.
-On the surface of a concrete plate specified in A-5304,
The coating was performed at a rate of 0.2 kg / m ² using a brush at 5 ° C., and the cured state of the primer film surface after 2 hours was observed. The evaluation results were indicated by x when the tackiness was remarkable by finger touch, Δ when the tackiness was slight, and ○ when there was no tackiness.

After curing at 5 ° C. for one day, the adhesive strength (tensile force) between the concrete surface and the primer one day after coating was measured by the Kenken-type tensile test method (JIS-A-6909). (Strength), and the breaking mode at the time of breaking was also observed. On the other hand, 20 g of a part of the primer composition was added to 100 parts.
The sample was collected in a polypropylene container having a capacity of cc, and the time from the addition and mixing of “BPO powder” in a 5 ° C. atmosphere to the gelling of the primer composition (the time until the fluidity was lost) was measured. The gelation time was 80% of the time from the addition of the "BPO powder" to the peak of the heat generation. The results are shown in the lower part of Table 1. In addition, the destruction mode was displayed as follows. A: Concrete interface destruction C: Cohesive destruction of primer layer or matrix layer M: Concrete material destruction

(Comparative Examples 1-2) Commercially available epoxy resin-based primer (two-solvent mixed type, evaporation residue after mixing: 25)
%) And a urethane-based primer (solvent-type one-part moisture-curing type, evaporation residue: 35%) in the same manner as in Example 1. Surface curing state after 2 hours, adhesive strength after 5 ° C. × 1 day, breaking mode, gel time at 5 ° C. (In the case of the comparative example, the primer was occasionally stirred with a glass rod to flow Table 1 also shows the measurement results.

[0067]

[Table 1]

(Examples 11 to 19, Comparative Example 3) Example 1
Using the components prepared in the above, the radical polymerization curable resin-forming composition compositions of Examples 11 to 19 and Comparative Example 3 were blended and prepared. The curing agent “BPO powder” was added and mixed immediately before applying the radical polymerization curable resin-forming composition. First, the primer composition of Example 1 was coated on a concrete plate in the same manner as in Example 1, and left at 5 ° C. for 1 hour. Next, on the dried and cured primer composition of Example 1, Examples 11 to 11 of the radical polymerizable resin-forming composition were formed.
Using Example 19 and Comparative Example 3, a carbon fiber sheet (Folkatoshite FTS-C1-20 manufactured by Tonen Co., Ltd.) was attached to two layers in the vertical and horizontal directions to form a radical polymerization-curable resin. It was constructed so that the total thickness of the composite layer of the composition and the carbon fiber sheet was 1 mm. In the laminating operation, various test pieces were prepared using a degassing roller so that air bubbles did not enter the composite layer and carbon fiber sheets did not float on the surface. After the test specimen was cured at 5 ° C. for one day, the concrete and the carbon fiber sheet / radical polymerization-curable resin-forming composition composite layer were subjected to the Kenken-type tensile test in the same manner as in Example 1. Measure the adhesive strength,
Was observed. Further, the gelation time at 5 ° C. of each radical polymerization curable resin-forming composition was measured in the same manner as in Example 1. The above-mentioned carbon fiber bonding work
In a 0 ° C. atmosphere, a concrete flat plate was placed upright so that the bonding surface was vertical, and the dripping condition until the radical polymerization-curable resin-forming composition was cured and the uniformity of the coating thickness were checked. The evaluation results of the dripping state were indicated as ○: no dripping, Δ: slight dripping, ×: dripping.

On the other hand, a radical polymerization-curable resin-forming composition,
Using Examples 11 to 19 and Comparative Example 3, JIS-
A No. 1 type test piece having a thickness of 2 mm specified in K-7113 was prepared, cured at 5 ° C. for one week, and then the tensile strength was measured. (Measurement conditions: 20 ° C., pulling speed: 50 mm / mi
n) (Comparative Examples 4 and 5) As Comparative Example 4, a commercially available epoxy-based adhesive composition (two-part cold curing type, main agent / curing agent = 2/1 blend), and as Comparative Example 5 a urethane-based adhesive composition (2
The same evaluation and measurement as in Examples 11 to 19 and Comparative Example 3 were carried out for a liquid room-temperature fast-curing type, and a main agent / curing agent = 1/1 mixture). (The gelation time at 5 ° C.
It measured similarly to 2. Table 2 shows the results of Examples 11 to 19 and Comparative Examples 3 to 5.

[0070]

[Table 2]

(Examples 20 and 21) JIS-A-113
In accordance with 2 above, a square pillar-shaped concrete bending strength measurement specimen having a size of 40 mm × 40 mm × 160 mm was prepared.
Cured for a week. The radical polymerizable primer composition prepared as described above (Example 1) was applied at a rate of 0.2 kg / m ² to one side of the square pillar, which was not a small edge, at a rate of 0.2 kg / m ² , and left at 5 ° C. for 1 hour. Using the radical polymerization-curable resin-forming composition Examples 11 and 17, two carbon fiber sheet layers were adhered by the methods described in Examples 11 to 19 and Comparative Example 3, and further heated at 5 ° C. Cured for a week. After removing these specimens from the curing room at 5 ° C,
Immediately, as shown in FIG. 1, the span width was set to 100 mm, and the three-point bending strength was measured. (Measurement temperature: 20 ° C., head speed of indenter 2 mm / min). The results are shown in Table 3.

(Comparative Examples 6 to 8) The same as Examples 20 to 21 except that the epoxy-based primers and adhesives and the urethane-based primers and adhesives used in Comparative Examples 1-2 and 4-5 were used. , And the three-point bending strength was measured. The results are shown in Table 3. The flexural strength of the concrete specimen without any reinforcement was measured as a blank.

[0073]

[Table 3]

From the results in Table 3, it can be seen that in Examples 20 to 21, the reinforcing effect was large and cracks were generated at a relatively large angle with respect to the load direction. Small and cracks are generated parallel to the load direction. When a test as shown in FIG. 1 is performed, it is generally known that the larger the reinforcing effect is, the more the crack occurs at a larger angle with respect to the load direction, which corresponds to this result.

[Brief description of the drawings]

FIG. 1 is a view showing a bending test of a concrete structure reinforced by integrally integrating a radical polymerization-curable resin-forming composition / carbon fiber sheet composite layer.

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 Indenter 3 Crack 5 Concrete specimen 7 Radical polymerization curable resin forming composition / carbon fiber sheet composite layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08F 2/00 C08F 2/00 C 4J011 290/06 290/06 4J027 C08J 5/24 CFC C08J 5/24 CFC 4J038 C09D 4/00 C09D 4/00 5/00 5/00 D 163/10 163/10 E01D 19/02 E01D 19/02 E04G 23/02 E04G 23/02 DF term (reference) 2D059 AA03 GG40 2E176 AA01 BB29 4D075 AE17 BB26Y BB26Z CA02 CA03 CA12 CA13 CA18 CA32. AF06 AF29 AG03 AG16 AH02 AH25 AK05 AL17 4G028 FA03 FA06 4J011 CA02 CA03 CA08 CB02 CC04 4J027 AE02 AE07 BA07 BA20 CA14 CA18 CA25 CA32 CA38 CB03 CC01 CD08 4J038 DB061 DB062 DB071 DB072 DB211 DB212 FA121 FA122 FA141 FA142 FA201 FA202 GA03 GA06 GA07 GA15 JA66 JB01 KA03 KA04 PA12 PB05 PC04

Claims (5)

[Claims] 1. A method of applying a radically polymerizable primer composition to the surface of a concrete structure, and then impregnating and constructing a fibrous base material and a radically polymerizable curable resin-forming composition, polymerizing and curing the fibrous base material. A method for reinforcing a concrete structure wherein a composite material layer of a material and the curable composition is formed on the surface of the concrete structure, wherein the radical polymerizable primer composition comprises: (a) a polymerizable unsaturated monomer; and (b) a vinyl ester resin. (C) benzoyl peroxide as a radical polymerization initiator,
And a tertiary amine as a curing accelerator, wherein the radical polymerization curable resin-forming composition comprises (a) a polymerizable unsaturated monomer, (b) a vinyl ester resin, and (c) radical polymerization initiation. A method for reinforcing a concrete structure which is a composition containing benzoyl peroxide (f) a thixotropy-imparting component as an agent and a tertiary amine as a curing accelerator. 2. A radical polymerizable primer composition is applied to the surface of a concrete structure and cured, and then the radical polymerizable resin-forming composition is applied to the cured surface of the radical polymerizable primer composition. After adhering the fibrous base material, a radical polymerization curable resin-forming composition is further applied thereon, impregnated in the fibrous base material, polymerized and cured to cure the fibrous base material and the curable resin. A method for reinforcing a concrete structure wherein a composite material layer of the composition is formed on the surface of the concrete structure, wherein the radical polymerizable primer composition comprises: (a) a polymerizable unsaturated monomer; (b) a vinyl ester resin; Benzoyl peroxide as a polymerization initiator,
And a tertiary amine as a curing accelerator, wherein the radical polymerization curable resin-forming composition comprises (a) a polymerizable unsaturated monomer, (b) a vinyl ester resin, and (c) radical polymerization initiation. A method for reinforcing a concrete structure which is a composition containing benzoyl peroxide as an agent, (f) a thixotropic agent component, and a tertiary amine as a curing accelerator. 3. A radical polymerizable primer composition comprising: (a) a polymerizable unsaturated monomer: 40 to 80% by weight, (b) a vinyl ester resin: 5 to 50% by weight, and (c) a radical polymerization initiator. Benzoyl peroxide:
A composition containing 0.1 to 10% by weight and a tertiary amine as a curing accelerator, wherein the radically polymerizable resin-forming composition comprises: (a) a polymerizable unsaturated monomer: 20 to 70% by weight (B) vinyl ester resin: 10 to 60% by weight, (c) benzoyl peroxide as a radical polymerization initiator:
A composition containing 0.1 to 10% by weight, (f) finely divided silica as a thixotropic agent component: 0.5 to 5% by weight, and a tertiary amine as a curing accelerator. 3. The method for reinforcing a concrete structure according to item 2. 4. The radical polymerizable primer composition and the radical polymerizable resin-forming composition, wherein (a) the polymerizable unsaturated monomer contains at least one selected from alkyl acrylates and methacrylates. The method for reinforcing a concrete structure according to any one of claims 1 to 3. 5. The method for reinforcing a concrete structure according to claim 1, wherein the fiber base is a carbon fiber base.