WO1999062977A1 - Radical polymerization-curing working material compositions, method for reinforcing concrete structures and reinforced concrete structures with the use of the same - Google Patents

Abstract

Radical polymerization-curing working material compositions having a prolonged working life which contain the following components (a) to (e): (a) a polymerizable unsaturated monomer; (b) a polymer being soluble of dispersible in the above component (a); (c) a radical polymerization initiator; (d) a transition metal soap; and (e) a compound capable of forming a complex or a chelate with the transition metal in the above component (d). These compositions are applicable at from low temperatures (about - 20 °C) in winter to high temperatures (about 70 °C), in particular, on the road surface in summer, etc.

Description

 Description Radical polymerization curable construction material composition, method for reinforcing concrete structure using the same, and reinforcement for concrete structure

 The present invention relates to a radical polymerization-curable construction material composition having an extended pot life, which is mainly used at a room temperature in the field of civil engineering, a method for reinforcing a concrete structure using the same, and a concrete structure It's about the captives. Background art

 Conventionally, pavement materials for roads, waterproofing materials for floor slabs of highways, etc., leveling agents for joints, concrete injecting agents, repair and reinforcement methods for steel plates wound around piers, etc. Epoxy resins have been used extensively in civil engineering-related fields.

 In recent years, in order to deal with the aging of concrete structures such as expressways and tunnels due to the occurrence of earthquakes and an increase in traffic volume, the above-mentioned repair and reinforcement work has been increasing, and the speed of construction work is expected. It is rare. However, the above epoxy resins require a long time to cure and have a difficulty in curing at low temperatures (especially in winter). Recently, acrylic resins, unsaturated polyester resins, and vinyl esters have been used. Resin-based radical polymerization Hard coating materials are attracting attention. These radical polymerization hardening materials are evaluated as having overcome the above-mentioned drawbacks of the epoxy resin.

Although the above-mentioned radical polymerization curable construction material can secure a sufficient pot life before gelling at a relatively low temperature, the working temperature must be as high as 15 ° C or more. As it has become increasingly difficult, the time until gelation (pot life) is rapidly reduced, and it is difficult to take sufficient working time. Also, once the gelation starts, the fluidity and coating workability deteriorate, and the material hardens rapidly due to heat generation, so there are many problems especially in the workability in summer. When the amount of the polymerization initiator is reduced for the purpose of extending the pot life at high temperatures, the coating surface strength and the uncured property may be left, stickiness may remain, or the physical properties of the coating film may deteriorate. Also However, it has also been proposed to add a polymerization inhibitor for the same purpose. The appropriate amount of addition is small, and the addition amount range is narrow, making it difficult to adjust the pot life. May not be hard.

 The present invention has been made in view of such circumstances, and a radical polymerization-curable construction material composition which can secure a sufficient pot life even at a high temperature (especially in summer), has excellent construction workability, and a concrete material using the same. It is an object of the present invention to provide a method for reinforcing a single-piece structure and a reinforcement for a concrete structure. Disclosure of the invention

 In order to achieve the above object, a first aspect of the present invention is a radial polymerizable and curable construction material composition containing the following components (a) to (e).

 (a) Polymerizable unsaturated monomers.

 (b) A polymer soluble or dispersible in the component (a).

 (c) radical polymerization initiator.

 (d) Transition metal stone II.

 (e) A compound which forms a complex or chelate with the transition metal in the component (d). Further, the present invention relates to a method for using the radical polymerizable dangling construction material composition,

Radical polymerization in which the above components (a), (b), (d) and (e). Are mixed in advance to prepare the main component, and the main component is mixed with the component (c) immediately before use. The second point is how to use the curable construction material composition.

 Further, the present invention provides a method for applying the radical polymerization-curable construction material composition to a surface of a concrete structure, and attaching a fiber base material thereon, and further applying the fiber base material on the fiber base material. A radical polymerization curable construction material composition is applied, and then the radical polymerization curable construction material composition is polymerized and cured, and a concrete layer is formed on the surface of the concrete structure to form a reinforcing layer made of the fibrous base material. The third point is how to reinforce the structure.

Further, the present invention relates to a concrete structure reinforcement obtained by the method for reinforcing a concrete structure, wherein the reinforcement structure is formed of a fibrous base material on a surface of the concrete structure. The summary of the The transition metal stone (d component) is usually used for the purpose of accelerating the radical curing reaction at a low temperature, but the effect of accelerating the radical polymerization reaction is remarkable even with a small amount of addition, and the reaction rate is suppressed. Is difficult. Therefore, in the past, a small amount of a polymerization inhibitor such as hydroquinone or phenol was added to suppress the reaction curing rate, but the polymerization curing reaction was completely stopped depending on the amount added and the curing conditions. There were many problems with the method of adjusting the reaction rate, for example, the physical properties after hardening did not appear due to incomplete hardening. The present inventors have conducted intensive studies on a method of adjusting the polymerization curing rate in the polymerization curing system. As a result, the polymerization hardening reaction system in the presence of the transition metal stone (d component) has the following effects. The present inventors have found that the use of a compound (e component) that forms a complex or a chelate with a transition metal can accurately and stably adjust the initiation of polymerization at ordinary temperature and the cure anti-ife, and arrived at the present invention.

 Then, after mixing the above components a, b, d, and e to form a main component, immediately before use, mixing the above main component (components a, b, d, and e) with the above radical polymerization initiator (component c). By doing so, it is possible to secure a sufficient pot life after mixing the component c, and it is possible to significantly improve workability.

 Further, according to the method for reinforcing a concrete structure of the present invention, the working efficiency can be remarkably improved. By using a specific fiber sheet as the fiber base material, the concrete structure can be more appropriately reinforced according to the purpose. BEST MODE FOR CARRYING OUT THE INVENTION

 Next, embodiments of the present invention will be described in detail.

 The radical polymerization curable construction material composition of the present invention comprises a polymerizable unsaturated monomer (a component), a polymer soluble or dispersible in the component a (b component), and a radical polymerization initiator ( c), a transition metal stone (d), and a compound (e) that forms a complex or chelate with the transition metal in the d).

The polymerizable unsaturated monomer (component (a)) constitutes the skeleton of the polymerized and cured product, and includes, for example, acrylate, methacrylate, styrene, and acrylic. Ronitrile and methacrylonitrile.

 Examples of the above acrylate ester include methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and isobornyl acrylate. Can be Examples of the above methacrylates include, for example, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethyl methacrylate, methacryloleic acid Lauryl, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. The styrene is mainly used when a vinyl ester resin or an unsaturated polyester resin is used as the component b, or when it is desired to improve water resistance, chemical resistance, and electrical properties.

 The above monomers are selected according to the construction purpose, and they can be used alone or in combination of two or more. For example, if the base material is a concrete floor coating, or if it is used for repair and reinforcement of concrete structures or for heat resistance, the glass transition temperature of the polymerized cured product will be 80 ° C or higher. Thus, a combination of monomers is selected. In addition, when directly applying to a moving substrate such as asphalt concrete, the combination of monomers is selected so that the glass transition temperature of the polymerized and cured product is 0 to 4 ° C. When imparting waterproofness to the cured coating film, a combination of monomers is selected so that the glass transition temperature of the polymerized cured product is 120 to 0 ° C.

 In addition, together with the above monomers, crosslinking monomers such as divinylbenzene, ethylene glycol dimethyl acrylate, and diaryl phthalate, and polymerizable unsaturated monomers having an air drying property (for example, dicyclopentadiene, tricyclodecane, etc.). Acrylic acid derivatives) can also be used in combination.

The content of the polymerizable unsaturated monomer (component (a)) is not particularly limited, and is appropriately set according to the application of the radical polymerization-curable construction material composition of the present invention. For example, when the radical polymerization-curable construction material composition of the present invention is used as a paint or an adhesive, the content of the component a is 20 to 80% by weight of the entire radical polymerization-curable construction material composition (hereinafter, referred to as the “a”). (Abbreviated as “%”), and particularly preferably 30 to 70%. That is, the content of the component a is less than 20% In addition, the viscosity of the obtained radical polymerization-curable construction material composition tends to be too high, so that the apparent gel time (pot life) tends to be short, and the mixed solubility of other components in the construction material composition Also decrease. Conversely, if the content of the component a exceeds 80%, the viscosity becomes too low, and it becomes difficult to secure the coating thickness and the thickness of the adhesive layer. When the radical polymerization curable construction material composition of the present invention is used as a primer or an injecting agent, the content of the component a is 40 to 90% of the entire radical polymerization curable construction material composition. Is preferably set, and particularly preferably 60 to 80%. That is, if the content of the component a is less than 40%, the viscosity becomes too high, so that impregnation into the groundwork, cracks in concrete or the like, and appropriate fluidity for pouring into gaps cannot be obtained. %, The viscosity becomes so low that most of the primer is impregnated into the substrate and does not remain on the surface of the substrate, so not only repeated coating work is required, but also more primer is consumed than necessary. It is because it is.

A functional monomer having a functional group such as a glycidyl group, a carboxyl group, a silyl group, or a hydroxyl group may be used in combination with the polymerizable unsaturated monomer (component (a)) for the purpose of improving adhesiveness. . The content of these functional monomers is preferably set to about 0.5 to 10% of the entire component a. Examples of the positive monomer having a glycidyl group include glycidyl methacrylate and glycidyl acrylate. Examples of the functional monomer having a carboxyl group include acrylic acid, methacrylic acid, and oligoester acrylate (eg, Aronics M560, M650, manufactured by Toagosei Co., Ltd.). Can be Examples of the functional monomer having a silyl group include vinyl trimethoxy silane, vinyl triethoxy silane, vinyl tris (/ 3-methoxy ethoxy) silane, and 7-methacryloxy propyl trimethoxy silane. Examples of the above-mentioned hydroxyl-containing monomeric monomer include hydroxyl methacrylate, hydroxyethyl acrylate, and hydroxypropyl methyl acrylate. The component b used together with the polymerizable unsaturated monomer (component a) is a polymer that is soluble or dispersible in the polymerizable unsaturated monomer (component a). This polymer also includes a prepolymer. The specific polymer (component (b)) may be used in combination with the polymerizable unsaturated monomer (component (a)), particularly an acrylic monomer or styrene. With this, the mechanical strength, hardness, thermal deformation, acid resistance, alkali resistance, chemical resistance, weatherability, etc. of the cured product are improved, and the viscosity is improved by giving it a viscosity as compared with the monomer alone. Hard: plays a role in reducing the contraction rate.

 As the above-mentioned component b, a vinyl ester resin, an unsaturated polyester resin, and an acrylic resin are preferably used.When imparting the separated adhesive strength, flexibility, and toughness to the cured product, A polymer having rubber elasticity is preferably used. These may be used alone or in combination of two or more.

 The above vinyl ester resin is an epoxy acrylate resin having an acryl group or a methacryl group in one molecule. Due to the difference in the structure of the epoxy skeleton, bisphenol Α type vinyl ester resin, novolak type resin Vinylesters are classified into fatty acids and brominated vinylester resins. The vinyl ester resin is obtained, for example, by reacting an epoxy resin with an unsaturated monobasic acid in the presence of an esterification catalyst such as tetrabutyl zirconate, zirconium naphthenate, and tetrabutyl titanate. Can be. The epoxy resin preferably has an average epoxy equivalent set in the range of 150 to 450. As the epoxy resin and the unsaturated monobasic acid, for example, those described on pages 10 to 21 of “Vinyl ester resin” (published by Kagaku Kogyo Nippo, 1993) can be used. Commercially available vinyl ester resins include, for example, Lipoxy R-800 series, 1 ^ -600 series, S-500 series, manufactured by Showa Polymer Co., Ltd., and Dainippon Ink and Chemicals, Inc. Products such as the Dick Lay small series and the Diova series.

The unsaturated polyester resin is a polycondensate of an unsaturated polybasic acid and a saturated polybasic acid with a polyhydric alcohol, and is generally commercially available by dissolving this in a polymerizable vinyl monomer such as styrene. It is. Examples of the unsaturated polybasic acid include maleic anhydride, fumaric acid, citraconic acid, itaconic acid and the like. Examples of the saturated polybasic acids include phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic anhydride, tetrabromophthalic anhydride, endomethylenetetrahydrohydroanhydride, tetrahydrophthalic anhydride, and hexahydroanhydride. Examples include phthalic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, anthracene-maleic anhydride adduct, and rosin-maleic anhydride adduct. In addition, the above Examples of the dihydric alcohol include ethylene glycol, propylene glycol,

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1,4-butanediol, 1,3-butanediol, 2,3-butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol , 2,2,4-Trimethylpentanediol, Bisphenol hydride A, 2,2-Di (4-hydroquinpropoxyphenyl) propane, Penno erythritol diaryl ether, glycerin, trimethylene glycol, 2-ethylethyl 1 , 3-hexanediol, phenyldaricidyl ether, arylglycidyl ether and the like.

 The unsaturated polyester resin is usually prepared, for example, by subjecting the unsaturated polybasic acid and the saturated polybasic acid to a polyhydric alcohol to 100 to 2

By performing a dehydration condensation reaction in an oxygen-free inert gas under heating at 00 ° C., an unsaturated polyester resin having a molecular weight of about 100 to 300 can be produced. The method for producing such an unsaturated polyester resin is described in detail, for example, in Plastic Materials Course “Polyester Resin” (published by Nikkan Kogyo Shimbun, Showa 45), pp. 37-61. The unsaturated polyester resin thus obtained is usually sold in the form of a solution in a polymerizable vinyl monomer such as styrene. Commercial products of the above unsaturated polyester resins include, for example, Rigolac manufactured by Showa Polymer Co., Evolak manufactured by Nippon Shokubai Co., Ltd., Dick Light manufactured by Dainippon Ink and Chemicals, Polymer manufactured by Takeda Pharmaceutical, Hitachi, Ltd. Polyset manufactured by Kasei Co., Ltd. and Ester manufactured by Mitsui Toatsu Chemicals Co., Ltd. can be mentioned.

Examples of the acryl resin include methyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, iso-bonyl methacrylate, Monomers such as methyl acrylate, ethyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, isobornyl acrylate, acrylic acid, methacrylic acid, etc. Or a polymer obtained by polymerizing monomers such as styrene, acrylonitrile, methacrylonitrile, ethylene, vinyl acetate, and vinyl chloride. Coalescence and the like. Among them, methyl methacrylate polymer, 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, etc.). The acrylic resin preferably has a molecular weight in the range of 10,000 to 100,000. Commercially available acrylic resins include, for example, Paraloid B-60 (MMAZ BMA copolymer) and Paraloid A-21 (MM.A polymer) manufactured by ROHM 'and' Haas. Is received.

 Examples of the polymer having rubber elasticity include acrylonitrile-butadiene copolymer, styrene-butadiene copolymer, styrene-based block copolymer, isoprene rubber, chlorosulfonated polyethylene, epichlorohydrin rubber, and chloroprene rubber. And urethane resin, urethane prepolymer, acrylic urethane oligomer, ethylene-vinyl acetate resin, ethylene-vinyl acetate-vinyl chloride copolymer and the like.

 The content of the component b is preferably set to 5 to 75% of the entire radical polymerization-curable construction material composition, and particularly preferably 10 to 65%.

 The radical polymerization initiator (component c) used together with the component a and the component b is for polymerizing and curing the radical polymerization curable construction material composition of the present invention. As the above-mentioned radical polymerization initiator (component c), for example, various organic peroxides are suitably used. Specifically, ketone peroxide-based, peroxyketal-based, and hydroperoxide-based And dialkyl peroxysides, diacyl peroxysides, peroxyesters, and peroxydicarbonates. These are appropriately selected according to various conditions at the time of construction, and are used alone or in combination of two or more.

Examples of the above ketone peroxide-based compounds include, for example, methyl ethyl ketone oxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexyl peroxide, and methylcyclohexanone oxide. Oxide and the like. Examples of the above-mentioned alkoxy ketals include 1,1-di (t-butyloxy) 3,3,5-trimethylcyclohexanone, 1,1-di (t- P 9/00897 butyl peroxy) cyclohexane, n-butyl 1,4-di (t-butyl benzoquin) phosphate, 2,2-di (t-butyl peroxy) butane, 2,2-di (t Monobutylperoxy) octane and the like. Examples of the above-mentioned hydroperoxides include, for example, t-butyl hydroperoxide, cumene dropperoxide, diisopropylbenzene hydroperoxide, .p-menthane peroxide, 2,5-dimethylhexane 12 , 5-dihydroperoxide, 1,1,3,3-tetramethylbutylhydroxide, and the like. Examples of the above-mentioned dialkyl peroxides include di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, a, α-bis (t-butyl peroxide ρ-diisopropyl). Benzene, 2,5-dimethyl-2,5-di (t-butylpyroxy) hexane, and 2,5-dimethyl-2,5-di (t-butylvinyloxy) hexine-13. Examples of the above-mentioned diasylpoxides include, for example, acetilbaoxide, propionylpoxide, isoptyrylpoxide, octanoylpoxide, decanolpoxyd, lauroylpoxide, stearoylpoxide Monooxide, 3,5,5-trimethylhexanoyl baroxide, succinic acid peroxyde, benzoyl peroxide, 2,4-dichlorobenzyl peroxide, and the like. Examples of the above-mentioned peroxyesters include t-butylperoxyisobutyrate, t_butylperoxypivalate, t-butylperoxyneodecanoate, cumylperoxynedecanoate. T-butylperoxy-2-ethylhexanoate, t-butylperoxy-3-, 5,5-trimethylhexanoate, t-butylvinyloxylaurate, t-butylvinyloxybenzoate, tert-butyldioxyphthalate, 2,5-dimethyl-1,2,5-di (benzoylperoxy) hexane, t-butyl peroxymaleic acid, t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, etc. Can be Examples of the above-mentioned peroxydicarbonate type include diisopropyloxydicarbonate, di (2-ethylhexyl) peroxydicarbonate, and di (2-ethoxyquinethyl) peroxydicarbonate. Nath, di (methoxyisopropyl) peroxydicarb And sodium di-n-propylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, acetyl chloride and quinylsulfonyl peroxide.

 The content of the above component c is appropriately set depending on the working temperature, but is preferably set to 0.5 to 10%, particularly preferably 1 to 10%, of the whole radically polymerizable construction material composition. 8%. Generally, when the working temperature is low, it is preferable to set the content of the component c high, and when the working temperature is high, it is preferable to set the content of the component c low.

 In order to avoid danger in handling, for example, an inert liquid such as dibutyl phthalate, or an inert liquid such as magnesium carbonate or calcium phosphate is used as the radical polymerization initiator (component c). It is preferably used in the form of paste, emulsified, or powdered with a concentration of 30 to 50% using a powder such as aluminum hydroxide.

The transition metal stone (d component) mainly plays a role of accelerating the polymerization curing reaction at a low temperature when used in combination with the peroxide used as the radical polymerization initiator (c component). Depending on the structure of the peroxide, the presence of metal stones, tertiary amines, and quaternary ammonium salts coexist with each other. It is known to promote reactions. The above tertiary amines and quaternary ammonium salts have the disadvantage that it is difficult to control the polymerization reaction rate by the system of the present invention, and that the cured product changes over time to dark brown. Therefore, in the present invention, the transition metal stone (d component) is used as a polymerization curing reaction accelerator. The transition metal stone (d component) is preferably a carboxylate of a transition metal, specifically, cobalt naphthenate, copper naphthenate, nickel naphthenate, manganese naphthenate, calcium naphthenate, lithium naphthenate, Lead naphthenate, Zinc naphthenate, Zirconium naphthenate, Barium naphthenate, Ferric naphthenate, Cobalt octoate, Calcium octoate, Manganese octoate, Copper octoate, Lead octoate, Zinc octoate, Zirconium octoate, Nickel octoate, magnesium octoate, ferric octoate, tin octoate, cobalt octoate, octoate Examples thereof include acid conochlorte, vanadyl octoate, iron hexanoate, iron propionate, and copper oleate. These may be used alone or in combination of two or more. Commercial products of the above transition metal experiments (d component) include, for example, Shinto Paint, Dainippon Ink Chemical Industry, Nippon Chemical Industry, Harima Chemicals, Hope Pharmaceutical, Toei Chemical, Tokyo Fine Chemical, Takeda Pharmaceutical, Takeda Pharmaceutical, Mitsui East Commercially available products from manufacturers such as pressure chemistry, Showa High Polymer, and Johoku Chemical can be used.

 The radical polymerization-curable construction material composition of the present invention uses a compound (e component) that forms a complex or chelate with a transition metal in the transition metal stone (d component) together with the a to (! Components). The above transition metal stone (d component) is usually used for the purpose of accelerating the radical hardening reaction at a low temperature. Therefore, it is difficult to control the reaction rate, and in the past, a small amount of a polymerization inhibitor such as hydroquinone or phenols was added to suppress the reaction curing rate. The method of adjusting the reaction rate was problematic in that the polymerization curing reaction was completely stopped depending on the curing conditions, and physical properties after curing were not developed due to incomplete curing. For polymerization curing system As a result of intensive studies on the method of adjusting the polymerization curing rate, a compound which forms a complex or chelate with the transition metal in the d component in the polymerization reaction system in the presence of the above transition metal stone (d component). It has been found that the use of (component (e)) can accurately and stably adjust the initiation of polymerization at room temperature and the hardening reaction.

The content of the above component d is preferably set to 0.05 to 2%, particularly preferably 0.1 to 0.5%, of the entire radical polymerization curable construction material composition. As the compound (e component) which forms a complex or a chelate with the transition metal in the transition metal stone (d component), a compound having at least one secondary amino group in one molecule (secondary amine) ), Oxime compounds, imine compounds and the like are preferably used. Compounds that form complexes or chelates with the transition metals in the transition metal stones described above include, for example, primary amines, secondary amines, tertiary amines, imines, substituted imines, and oximes. Compounds containing a nitrogen atom, thioethers, thiols: compounds containing a sulfur atom such as thioketone, compounds containing a ketone or alkoxy, compounds containing an oxygen atom of a carboxylic acid estero! ^, Compounds, phosphonates, sulfonates, etc. Are known. However On the other hand, compounds containing a sulfur atom such as the thioether have an effect of inhibiting a polymerization reaction, and there is a problem that the resin is in an unhardened state. It was also confirmed by experiments that compounds containing oxygen atoms, such as ethylenediaminetetraacetic acid (EDTA), did not inhibit the curing reaction but did not retard the polymerization reaction. Among the above compounds having a nitrogen atom, primary amines and tertiary amines undergo a redox reaction with a peroxide which is a radical polymerization initiator (component c), and conversely promote the polymerization reaction to be usable. It is not suitable for the purpose of the present invention because of the reduced time. As a result of repeated experiments, the present inventors have found that a compound having at least one secondary amino group in one molecule (secondary amine), an oxime compound, and an imine compound are suitable for the purpose of the present invention. Found o

 The amount of the e-component to be added depends on its structure, molecular weight, transition metal species in the d-component and the content of the d-component, etc., and the sum of the components a, b, and (hereinafter referred to as “base resin solution”). The amount is preferably in the range of 0.01 to 20 parts, more preferably 0.05 to 10 parts, per 100 parts by weight (hereinafter abbreviated as "part"). That is, if the addition amount of the above-mentioned component e is less than 0.01 part, the effect of delaying the polymerization initiation reaction is reduced. Conversely, if the amount of the component e exceeds 20 parts, the initiation reaction is significantly delayed, the viscosity of the radical-polymerization-curable construction material composition increases, the workability becomes poor, and the radical-polymerization curing occurs. This is because the physical properties (eg, tensile strength, compressive strength, compressive elasticity, etc.) of the non-conductive construction material composition may be reduced. When the above-mentioned component e has a low molecular weight (molecular weight of 100 or less), it is appropriate to add a small amount thereof. Specifically, the base resin solution (components a, b and d). The range of 0.05 to 1 part relative to 0 part is preferred. When the component e has a high molecular weight (the molecular weight exceeds 100,000), it is appropriate to add a relatively large amount. Specifically, the base resin solution (components a, b, and d) 10 The range of 0.5 to 10 parts relative to 0 parts is preferred. In general, a polymer (polymer) has a milder delay effect, and it is easier to adjust the time until gelation (pot life).

Specific examples of the above-mentioned component e include dimethylamine, getylamine, dipropylamine, diisopropylpropylamine, N-ethyl-1,2-dimethylpropylamine, as secondary amines having a relatively low molecular weight. Dibutylamine, diisobutylamine, 7 Diamylamine, N-methylhexylamine, dioctylamine, getyl-N- (2-ethylhexyl) -11-hexaneamine, diarylamine, methylaniline, ethyleniline, propylaniline, butylylaniline, dibenzylamine, N- Methylbenzylamine, diphenylamine, zinclohexylamine, diethanolamine, diisopropanolamine, n-butylmonoethanolamine, ethylmonoethanolamine, monomethylaniline, N-mono-n-butylaniline , N-monoamylamine, 4-benzylpiperidine, 1-piperidinemethanol, 1-piperidineethanol, pipecoline, pipecolic acid, lupetidine, 4—hydroxypiperidine, 4—piperidino piperidine, 2— Aminome Rubi peridine, 1,3-di (4-piperidyl) propane, phenyl-α-naphthylamine, phenyl-2-9-naphthylamine, octylated diphenylamine, 4,4 ′-((, α-dimethylbenzyl) diphenylamine, ρ— (ρ—toluenesulfonylamide) diphenylamine, Ν, Ν'-di- (2-naphthyl) -one ρ-phenylene-diamine, Ν, Ν'-diphenylamine ρ-phenyleneamine, Ν— Phenyl-Ν'-isopropyl-1-ρ-phenylenediamine, Ν-phenyl N '-(1,3-dimethylbutyl) _ρ—phenylenediamine, pyrrolidine, hydroxypyrrolidine, pyrrole, indole, indolin, Imidazole, 2-methylimidazole, ethylimidazole, 2-ethyl-41-methylimidazole, 2-mercaptobe Mentuimidazole, 2-mercaptomethylbenzimidazole, triazole, benzotriazole, tolyltriazole, hydroxyxetoxysylpiperazine, homopyrazine, Ν-methylhomopirazine, Ν-acylhomopirazine , Ν-Methylbiperazine, Ν-Carboethoxypiperazine, Ν-Formyl piperazine, 1- (ο-Chlorophenyl) pirazine, I- (m-Chlorophenyl) pirazine, 1- (p —Chlorophenyl) pidazine, 1- (2-pyrimidylyl) pidazine, 1-cyclopentylbiperazine, 2-methylbiperazine, 2,6-dimethylbiperazine, 2,5—dimethylbipera Gin, N— (2-pyridyl) piperazine, monomethylol urea, dimethylol urea, trimethyl thiourea, N, Ν'-diethyl thiourea , Tributylthiourea, Ν, N'-diphenylthiourea, guanidine, tetramethylguanidine, butyrylguanidine, 1,3-diph Enylguanidine, di-1 0—triluguanidine, 1-10—trilubiguanide, m

 > Rufolin, N-tert-butyl-12-benzothiazolylsulfenamide, N-cyclohexyl-12-benzothiazolylsulfenamide, 6-ethoxy-11,2-dihydro2,2 , 4-—trimethylquinoline, dihydrazide, diacetone acrylamide, etc. These may be used alone or in combination of two or more.

 As the high molecular weight (polymer) secondary amine, a thermoplastic urethane resin soluble or dispersible in a polymerizable unsaturated monomer (a component) (for example, Pandex T by Dainippon Ink and Chemicals, Inc.). Series, DISMOCO manufactured by Sumitomo Bayer Perethane Co., Ltd.), Perethane Prepolymers (for example, Takeda Pharmaceutical Co., Ltd. Joule series), urea resin, urea urethane resin, epoxy-modified urethane resin, acrylic urethane oligomer, polyamide resin, polyamide imide, hydroxam, acid group polymer, imidazole group polymer, Polyamine Z thiourea condensate and the like. When these polymers are solid or have a high viscosity, it is desirable to dissolve or disperse them in the above-mentioned polymerizable unsaturated monomer (component (a)) before adding them to the composition.

 As the component e, an imine compound may be used. The imine compound is a compound in which two hydrogen atoms of ammonia have been substituted with a divalent hydrocarbon residue (cyclic second amine). Specific examples of the imine compound include those having a relatively low molecular weight such as piperidine, pentamethylenimine and hexamethyleneimine, and those having a high molecular weight such as polyethyleneimine.

An oxime compound can also be used as the component e. Oxime produces secondary amines upon contact with a force reducing substance that has no cure retarding effect by itself, and retards cure. Specific examples of the above-mentioned oxime compounds include those having relatively low molecular weights, such as acetate aldoxime, propion aldoxime, acrylaldoxime, benzaldoxime, phenylacetoaldoxime, salicylaldoxime, and tolualdoxime. , Glyoxime, acetoxime, diisopropylketoxime, cyclopentone nonoxime, cyclohexanonoxime, carboxy Acetophenoxime, benzoinoxime, dimethyldalioxime, quinone dioxime, benzyldioxime, butoxycarboxime, pyridoxime, dibenzoyldioxime, methylethylketone oxime, dimethylglyoxime

, 8-quinolinol and the like. These may be used alone or in combination of two or more.

 The radical polymerization-curable construction material composition of the present invention can contain various polymers for the purpose of adjusting the viscosity of the composition and improving the toughness and durability of the cured product. Examples of the above polymers include acrylic polymers, polyvinyl acetate resins, ethylene vinyl acetate resins, ethylene monoacetate-vinyl chloride copolymers, reactive epoxy resins, acrylic nitrile-butadiene rubber, and styrene rubber. Examples include gen rubber, styrene block copolymer, isoprene rubber, chlorosulfonated polyethylene, epichlorohydrin rubber, chloroprene rubber, and urethane resin. These may be used alone or in combination of two or more.

Further, the radical polymerization-curable construction material composition of the present invention can contain inorganic powders, inorganic viscosity improvers, polymer viscosity improvers, pigments, and the like. Examples of the inorganic powders include calcium carbonate, clay, alumina powder, silica powder, talc, barium sulfate, myriki, aluminum hydroxide, silica sand, cement, blast furnace nest rug, and gypsum. Examples of the inorganic viscosity improver include finely divided silica such as aerosil and sepiolite. Examples of the polymer viscosity improver include acrylic polymer-based, fatty acid amide wax-based, hydrogenated castor oil-based, and urea urethane-based improvers. Examples of the above-mentioned pigments include titanium oxide, black carbon black, red iron oxide, ultramarine blue, koval blue, phthalocyanine blue, yellow bell and the like. The radical polymerization-curable construction material composition of the present invention includes an antifoaming agent, a pigment dispersant, an anti-settling agent, an ultraviolet absorber, a polymerization inhibitor, and a polymerization accelerator such as primary amine and tertiary amine. Can be contained as necessary. The polymerization inhibitor is used to maintain the seal life of the product, and a polymerization accelerator such as a tertiary amine is used to initiate radical polymerization at room temperature. In addition, in order to eliminate stickiness on the surface of the cured product, waxes, compounds containing aryl ether groups, compounds containing dicyclopentadiene, drying oils, etc. May be appropriately added.

 The above additives are appropriately selected and used depending on conditions such as the purpose of construction, the place of construction, and the temperature during construction.

 The radical polymerization-curable construction material composition of the present invention can be used (constructed) as follows, for example. First, the polymerizable unsaturated monomer (a component), a specific polymer (b component), a transition metal stone (d component), and a specific compound (e component) are uniformly mixed to form a main agent ( a, b, d, and e components). Immediately before use (construction) of the radical polymerization curable construction material composition, by mixing the above-mentioned filler (a, b, d, and e components) with the radical polymerization initiator (c component) Can be used. That is, when the radical polymerization initiator (c component) and the main agent (a, b, d, and e components) are mixed, the polymerization curing reaction is immediately started. It is preferable that the polymerization initiator (.component) is added and mixed immediately before performing a coating operation or a bonding operation of the radical polymerization curable construction material composition.

 The radical polymerization-curable construction material composition of the present invention can be used, for example, for repair and injection of paints, adhesives, primers, mortars, concretes, etc .; Installation of members with large area, floor slab waterproofing material, material for correcting unevenness at the joint of expressway, material for repairing rutted roads, non-slip pavement material near expressway tollgates and bus lanes, drainage pavement material, factory It can be suitably used as an office flooring material, a pavement material for a parking lot, a pavement material for a sidewalk, a carbon fiber for a concrete structure, and an impregnating adhesive for reinforcing with an aramide fiber.

Next, a method for reinforcing a concrete structure using the radical polymerization-curable construction material composition of the present invention will be described. First, the above-mentioned radial polymerization curable construction material composition is applied to the surface of the concrete structure, and a fiber base material is adhered thereon. Next, the radical polymerization-curable composition material composition is applied and impregnated on the fiber base material. Then, the radically polymerizable construction material composition is polymerized and the fiber base material is adhered to the surface of the concrete structure. In this way, the concrete structure is reinforced by producing a concrete structure reinforcement body in which the reinforcing layer made of the fiber base material is formed on the surface of the concrete structure. It can be carried out.

 The fibrous base material is not particularly limited, and a carbon fiber sheet, a polyaramid fiber sheet, a glass fiber sheet and the like are preferably used. When these fiber base materials are used, the surface of the concrete structure is provided with a fiber-reinforced plastic (

The reinforcing layer made of FRP) can be formed, and the reinforcement of the concrete structure can be performed more firmly.

 In the present invention, the reinforcing layer formed on the surface of the concrete structure is not limited to a single-layer structure, and may have a multilayer structure.

 Further, in the present invention, the following steps may be performed prior to the implementation of the method for capturing a concrete structure. That is, first, at least one primer selected from the group consisting of the radically polymerizable curable construction material composition of the present invention, an epoxy resin and a urethane resin is applied to the surface of the concrete structure and cured. Then, a putty material for preparing an undercoat containing the composition of the present invention may be applied and cured, and then the above-described method for reinforcing a concrete structure may be carried out.

 In the method for reinforcing a concrete structure according to the present invention, there is no particular limitation on the concrete structure to be used. For example, floor slabs of highways and elevated railways, piers, tunnels, underpasses, water and sewage systems, Chimneys and the like. There is no particular limitation on the shape of the concrete structure, and the concrete structure may be formed on various parts of the concrete structure such as an outer corner, a corner, a flat surface, a curved surface, a vertical wall surface, a ceiling surface, and a floor surface.で き る You can.

According to the method for consolidating a concrete structure of the present invention, there are the following advantages. Concrete reinforcement works are often performed in narrow places or high places where mechanical power cannot be brought in.Generally, construction work is done manually, and the resin material used for construction can be made of resin. In consideration of time, it is customary to mix the limit amount in each batch in a batch system and transport it to the construction site for use. In this case, if a conventional radical polymerization curable construction material is used, the pot life is too short, so there is a problem that the construction material hardens during the construction work and coating becomes impossible. In addition, when an epoxy resin is used, the pot life is long, so that the time required to reach the dangling is long, and the working efficiency is poor. In addition, the lower the working temperature, the longer the curing time, and if the temperature is below 5 ° C, the curing becomes impossible. On the other hand, the radical polymerization-curable material composition of the present invention is a construction material that can be applied from a low temperature in winter of about 120 ° C to a high temperature of about 70 ° C. The conventional pot life is short. 欠 点 It can eliminate the drawbacks of the radical polymerizable and curable construction material and the epoxy resin. The radical polymerizable curable construction material composition of the present invention can be designed for a material having a pot life of 30 to 70 minutes and a curing time of 1 to 3 hours at room temperature. Οο: Materials that are most suitable for reinforcing structures can be prepared. Therefore, when the conventional epoxy resin is used, for example, it takes three days for the construction work to obtain a three-layered reinforcing layer, but according to the present invention, the construction work is completed in one day Work efficiency can be dramatically increased by fS].

 Next, examples will be described together with comparative examples.

 First, prior to Examples and Comparative Examples, base resin solutions shown below were prepared. (Base resin liquid 1)

 In a vessel equipped with a stirrer, thermometer, heater and cooler, add 166 parts of isophthalic acid as a saturated polybasic acid, 96.8 parts of 1,2-propylene glycol as a polyhydric alcohol, and tetrahydrochloride as an esterification catalyst. Butyl titanate. Q. 3 parts were charged, and a heating dehydration condensation reaction was performed at 220 ° C. for 10 hours in an inert gas atmosphere. At this time, the excess amount of 1,2-propylene glycol was distilled off under reduced pressure to obtain a condensate having an acid value of 6 mgKOHZg of the solid component. Then, after cooling the condensate to 100 ° C, 49 parts of maleic anhydride as an unsaturated polybasic acid was added, and the mixture was heated again to 220 ° C and subjected to a heat dehydration condensation reaction for 5 hours. Thus, a condensate having an acid value of 25 mgK0Hg of the solid content was obtained. Hydroquinone (50 ppm) was added to the condensate, the temperature was adjusted to 140 ° C, glycidyl methacrylate (284 parts) was added, and the mixture was reacted at 140 ° C for 10 hours. Then, an unsaturated polyester acrylate (component b) having an acid value of 10 mg KOHZg was obtained. While cooling the unsaturated polyester acrylate (component b) to room temperature, an equivalent amount of styrene (component a) and 0.5% of cobalt octylate relative to the total amount

(d component), 0.3% vanadyl octoate (d component) is added, and the base resin solution is added.

Got one. (Base resin liquid 2)

 In a four-neck flask equipped with a stirrer, thermometer, cooling condenser, and gas inlet tube, 135 parts of bisphenol epoxy resin (Epicoat 834, Epoxy Equivalent 250) manufactured by Yuka Shell Epoxy Co., Ltd., methacrylic acid 45 parts, 0.25 parts of hydroquinone monomethyl ether, and 1.7 parts of triethylmethylammonium chloride as an esterification catalyst were charged and reacted at 110 ° C for 5 hours in air to obtain a viscosity of 5 parts. A 2-poise liquid epoxyacrylate (component b) was obtained. While cooling this liquid epoxy acrylate (component b) to room temperature, 100 parts of the above liquid epoxy acrylate (component b) was added with 40 parts of methyl methacrylate (component a) and 30 parts of methyl methacrylate (component a). Petriacrylate (component a), 30 parts of styrene (component a), 0.5 parts of paraffin wax (melting point 70-75 ° C), 0.5 parts of paraffin wax (melting point 60-6) At 5 ° C), 0.3 parts of cobalt naphthenate (d component) and 0.5 parts of manganese naphthenate (d component) were added and uniformly dissolved to obtain a base resin solution 2.

 (Base resin liquid 3)

 In a four-neck flask equipped with a stirrer, thermometer and condenser, 40 parts of methyl methacrylate (component a), 20 parts of 2-ethylhexyl acrylate (component a), 20 parts of ethylene glycol dimethacrylate (component a) 15 Parts, 0.5 parts of paraffin wax (melting point: 70 to 75 ° C) and 0.5 parts of paraffin wax (melting point: 60 to 65 ° C) were added, and while stirring, methyl methacrylate was added as component b. 24 parts of a polymer (Paraloid A-21, manufactured by Rohm and Haas) was added little by little and dissolved. Then, the content was heated to 75 ° C while stirring, and after confirming that the methyl methacrylate copolymer (b component) and paraffin wax were completely and completely dissolved, the content was cooled to room temperature. Add 0.2 part of N, N'-dimethyl-p-toluidine and 0.1 part of copper naphthenate (d-component) to completely dissolve completely, and to obtain a viscosity of 350 cps / 20 ° C. Resin liquid 3 was obtained.

 (Base resin liquid 4)

Methyl methacrylate (component a) 43 parts, styrene (component a) 10 parts, butyl acrylate (component a) 20 parts, ethylene glycol dim Evening acrylate (component a) 5 parts, methacrylic acid 4 parts, epoxy 0.5 parts of T / JP99 / 00897 orchid (A-189, manufactured by Nippon Tunicer) and paraffin wax (melting point: 60 to 65 ° C) were uniformly dissolved to obtain a mixture. Then, 2 parts of a styrene-based block polymer (Sorprene T-406, manufactured by Asahi Kasei Corporation) was added as a b component to the mixture and dissolved, and then N, N'-di (2-hydroxypropyl) -P — Toluidine (0.5 part) and copper naphthenate (d component) (0.2 part) were added and completely dissolved to obtain a base resin solution 4 having a viscosity of 550 cps / 20.

 (Base resin liquid: 5)

 Methyl methacrylate (component a) 4 parts, 2-ethylhexyl acrylate (component a) 34 parts, vinylsilane (A-172, manufactured by Nippon Unicar) 2 parts, 3 parts of methacrylic acid, 1 part of ethyleneglycol dimethacrylate (component a) and 0.5 part of paraffin wax (melting point: 70 to 75 ° C) were uniformly dissolved to obtain a mixture. Then, 16 parts of a styrene-based block polymer (Sorprene T-406, manufactured by Asahi Kasei Corporation) was gradually added to this mixture as a component b, and the mixture was completely dissolved. Then, N, Ν'-dimethyl-ρ-toluidine was added. Five parts and 0.2 part of copper naphthenate (d component) were added and uniformly dissolved to obtain a base resin liquid 5 having a viscosity of 1500 cpsZ 20 ° C.

 (Examples 1-1 to 6, Comparative Examples 1 to 6)

 First, as shown in Table 1 below, component e is added to each base resin solution at the ratio shown in the table, mixed uniformly, and the main ingredient of the radical polymerization hardening construction material composition ( a, b, d, e components) were prepared. The addition amount of the e component indicates parts by weight based on 100 parts of the base resin liquid (a, b, and d components). Then, 100 g of the above main ingredients (a, b, d, and e components) were weighed into a 200 cc plastic container at 30 ° C. in a fan atmosphere, and this was used as a radical polymerization initiator (.component). Benzyl peroxyside (Nipa BO, manufactured by Nippon Yushi Co., Ltd.) was added 2 g and mixed quickly and uniformly. And radical polymerization

After adding (.component), the system was stirred occasionally with a spatula, and while checking, the pot life (gel time) until the system reached gelation was measured. The results are shown in Table 2 below. 897

Example Main agent (a, b, d, e components)

 Base 榭 e component (low molecular weight) e component addition amount Fatty liquid (parts by weight) 榭 Fat liquid 1 dibutylamine 0.5 榭 Fat liquid 1 dibutylamine

 Resin liquid 1 dibutylamine

 Resin liquid 2 dibutylamine

 Resin liquid 2 dimethylbenzylamine

 Resin liquid 2 piperidine

 Resin liquid 2 N, N'-di-2-naphthyl-p-0.05

 Two Range

 Resin solution 2 N, N '—Jetylthiourea 0.05 Resin solution 2 1,3-Diphenylguanidine. 0.1

10 Resin liquid 2 2-Ethyl-4-methylimidazole

 11 Resin liquid 2 Morpholine

 12 Resin liquid 2 N-methylethanolamine 0.3

13 Resin liquid 3 Dibutylamine

 14 Resin liquid 4 Dimethylbenzylamine

 15 Resin liquid 5 Amino alcohol MMA 0.3

16 Resin liquid 2 Methyl ethyl ketone

 Resin liquid 1

Ratio

 Resin liquid 2

 Resin liquid 2 urea

An example

 Resin liquid 2 Tetraacetic acid (EDTA)

 Resin liquid 2 N-methylpyrrolidone

Resin liquid 2 Dimethyl para-toluidine 0.5 Table 2 Yes J ambassador ", interval 1 (\ minute J)

(Gel time) [30 ° C] 丄 1 1 6 Actual

 0 2 5 Out

 0 Q 4 0 Example

 A 4 4 3

 U 3 o p u. 2 2

7 3 0 o P 2 1

Q Ό 4 o i 丄 nJ 0

1 丄 1 丄

 丄 1 ώ 9 2 7

1 top << 3 3 3 8

1 A 4 o 丄 ί) 4 5

 I fi 4 4

1 1 n ratio

 2 1 2 Comparison

 3. 9 examples

 4 1 2

5 1 2

6 7 From the results in Table 2 above, in each Example, since a low molecular weight secondary amine and an oxime compound were used as the e component, it was clearly usable compared to Comparative Examples 1 and 2 without the e component. You can see that the time has been extended. On the other hand, in Comparative Examples 3 to 6, since the primary amine, the tertiary amine and the chelating agent were used as the e component, the effect of prolonging the pot life was not recognized, but the pot life was conversely increased. You can see that some are shortened.

The radically polymerizable curable construction material composition of Example 4 cured in about 50 minutes at 30 °. Molding the cured product film shape having a thickness of 2 mm, was subjected to a tensile test according to JIS- K- 7 1 1 3, the tensile strength has been made by 3 1 ² kg / cm 2. Next, 75 parts of Silica Sand No. 6 and 7.5 parts of Silica Sand No. 8 "and 2 parts of a coloring agent (Bell Road Toner 104, manufactured by NSC) were quickly mixed with the above composition, and the construction materials were mixed. Then, the construction material was applied to a concrete floor surface that had been primed with Bellroad Primer FP (manufactured by Nippon NS Co., Ltd.). The application material has a pot life of about 35 minutes, during which time it can be applied with good workability (iron handling and leveling), and after about an hour Finished with a walkable finish.

The radical polymerization-curable construction material composition of Example 9 exhibited a pot life of about 65 minutes at 15 ° C. This composition was placed in an automatic low-pressure resin injection container (KBK Cap II, manufactured by Nippon NS Co., Ltd.) and the concrete column inside the building was adjusted to about 0.5 mm in accordance with the specified method. When injected into the width crack, injection suitability and workability were good, and when observed after about 2 hours, curability was also good. Separately, this composition was prepared and tested according to JIS-A-624. The bond strength was 8.2 N / mm ² (standard conditions) and 8. ON / mm ² (low temperature). , 5.5 NZm m ² (wet), 7.5 N / mm ² (during dry and wet cycles), tensile strength 21.5 N / mm ² , tensile elongation at break 8.1% Was. Thus, the radical polymerization-curable construction material composition of Example 9 can be suitably used as a repair injection agent for mortar, concrete and the like.

 (Examples 17 to 30, Comparative Examples 7 to 11)

Same as the above example, except that the components shown in Table 3 below were used in the proportions shown in the table. In the same manner, the main components (a, b, d, and e components) of the radical polymerization curing material composition were prepared. Then, the pot life (gel time) was measured in a 15 ° C. atmosphere in the same manner as in the above example. The results are shown in Table 4 below.

Table 3

 * 1: 40% MMA solution of Pandex T-5201 manufactured by Dainippon Ink and Chemicals, Inc.

* 2: Takeda Pharmaceutical Co., Ltd., Takenate L-1028

 * 3: BYK-Japan Co., Ltd., BYK—410

 * 4: Asahi Denka Kogyo KK, EPU_16A

 * 5: Lufazole F G, manufactured by BAS F Japan

 * 6: Fuji Chemical Co., Ltd.

 * 7: Pekkamin P 1 3 8 manufactured by Dainippon Ink & Chemicals, Inc.

 * 8: Duo Light C—4 6 7 manufactured by Sumitomo Chemical Co., Ltd.

 * 9: Duolight C—43 3 3 manufactured by Sumitomo Chemical Co., Ltd.

(Note): e The value in parentheses of the amount of component added indicates the value when converted to 100% _c Table 4 Pot life (min) (gel time)

[15]

17 2 0

18 5 3 out

 19 2 4 Example

 20 5 7

21 1 9

22 5 0

23 2 3

24 6 5

25 2 0

26 2 8

27 3 5

28 3 0

29 4 3

30 6 0

7 1 6 ratio

 8 1 0 comparison

 9 1 4 Example

 .10 1 4

11 1 5

From the results in Table 4 above, in each Example, since a high molecular weight secondary amine or imine compound was used as the e component, it was clearly usable compared to the comparative example 7 without the e component. You can see that the time has been extended. On the other hand, in the ratios 8 to 11, the primary and tertiary amines were used as the e component, so that the effect of extending the pot life was not recognized. You can see that there is something. The content of the e component shown in Table 3 is relatively large compared to the content of the e component shown in Table 1, but the higher molecular weight has a milder delay effect. It is.

 Example 2 The radically polymerized hardening construction material composition of Example 5 showed a pot life of 2 (TC: about 60 minutes. 100 parts of this composition contained calcium carbonate (SL-300, Takehara Chemical Co., Ltd.) 15 parts were added and mixed evenly to obtain a construction material.The construction material was used for surface treatment with the above-mentioned Bellroad Primer FP (manufactured by NNS Corporation). A porcelain tile cut into about 5 cm square was pasted on the concrete sidewalk board and left for 8 hours at 20. After that, the adhesive strength was measured using a Kenken-type adhesive strength tester. However, the foundation concrete was broken and showed extremely good adhesive strength.

However, radical polymerization-curable adhesives were not suitable for bonding over a relatively large area because the curing speed was high and the pot life was not sufficient, but the present invention can solve this problem. . In addition to construction materials in the civil engineering field, advantages such as the ability to adjust the speed of the adhesive assembly line in factories and the temporary suspension of adhesive coating machines during lunch breaks are also expected.

 Next, the concrete structure was reinforced by using the radical polymerization hardening construction material composition of the above example. First, in order to measure the rupture load of the reinforcing layer formed on the surface of the concrete structure, the following two types of test specimens were prepared and their rupture loads were measured.

 (Preparation of specimen ①)

The radical polymerization-curable construction material composition of Example 20 above was applied on a release film, and a 250-mm-long carbon fiber sheet (Tonensha Co., Ltd., FTS—C 1—30 W) was applied thereon. And then apply the radical polymerization hardening material composition of Example 20 thereon, then cover it with a release film, and use a spatula, a defoaming roller, or the like. The bubble polymerization force in the carbon fiber sheet <the radical polymerization Impregnated with a functional construction material composition. Next, when it was in a semi-cured state, it was cut in the fiber direction to a width of 12.5 mm to prepare a test specimen having a thickness of about 1 mm.

 (Preparation of specimen ②)

 The radical polymerization-curable construction material composition of Example 20 above was applied on a release film, and a carbon fiber sheet having a length of 200 mm (FTS-C1-30W manufactured by Tonensha Co., Ltd.) was placed thereon. Is pressed uniformly, and the composition is further applied thereon, and is evenly impregnated using a spatula, a defoaming roller or the like so that no air bubbles remain in the carbon fiber sheet. The carbon fiber sheet of O mm was stuck to the carbon fiber sheet already impregnated and in an uncured state with a force <100 mm in length and overlapping so as to overlap. Next, the radical polymerization-curable construction material composition of Example 20 was applied and impregnated thereon. A release film was placed on top of it, and cured with a roller or the like to a uniform thickness. When it was in a semi-cured state, it was cut in the fiber direction to a width of 12.5.5 mm to prepare a lap strength measuring test specimen 約 having a thickness of about 1 mm and a length of 300 mm.

 (Breaking load)

 Using each of the test pieces thus obtained, the breaking load was measured as described below. That is, each specimen was cured at 20 ° C. for 1 day, and then pulled at a tensile speed of 2 mmZmin using an Instron according to JIS-K-7073 to measure the breaking load. As a result, the breaking load of the test piece ① was 832 kgf (average value of n = 10), and the breaking load of the test piece 7 was 785 kgf (average value of n = 10).

 Next, a primer and a putty material for preparing a base material to be coated on the surface of the concrete structure were prepared.

 (Preparation of primer)

 To the radical polymerization curable construction material composition of Example 4 above, a 1 Z1 mixed solution of MMA monomer / styrene monomer was added to adjust the viscosity to 100 cp SZ 20 ° C, and the primer was prepared. Obtained.

 (Preparation of base material for putty)

28 parts of the radical polymerization-curable construction material composition of Example 4 above, light carbonic acid rubber (Calfine 200, manufactured by Maruo Calcium Co., Ltd.) '14, and heavy carbonic acid calcium ( Maruo Calcium Co., Ltd., Super 2000) 36 parts, Silica Sand No. 8 18 parts, After mixing with 4 parts of titanium oxide (manufactured by Fuji Titanium Co., Ltd., TR700) in a mixer, the mixture was vacuum degassed, and the viscosity was 15,000 cps. C, T. Putty material for base preparation with a value of 6.5 was obtained.

 (Preparation of concrete structure reinforcement)

Prepare a JIS standard concrete slab of 30 O mm square, sand it on its surface, then add 2% of benzoyl peroxyside liquid (Nyper-NS) to the above primer and mix it uniformly Was applied at a rate of 150 g / m ^{2 and} the mixture was hardened. Thereon, the base adjustment putty material base Nzoiruba one Okisai de liquid material a mixture added (Na Ipa NS) 1% homogeneity, at a rate of 4 0 0 g / m ^z using trowel to苹滑Coated and cured. Further, a reinforcing layer was formed thereon in the same manner as in Test Specimen (1), to produce a concrete structure reinforcing body.

 (Tensile breaking strength)

Using the concrete structure reinforcement thus obtained, the tensile soil strength was measured as follows. That is, an iron attachment (40 mm square) is adhered on the concrete structure reinforcing body using an epoxy resin (Nippon Ciba-Geigy Corporation, Araldite), and after the epoxy resin is cured, A layer was completely cut along the evening until it reached the underlying concrete layer, and a Kenken-type adhesion test was performed. As a result, the tensile fracture strength of the concrete structure reinforcement was 2.55.5 kgf / cm ² (average value of n = 5). In addition, the rupture code was the destruction of the concrete foundation.

 From the above, it can be seen that the radial polymerization curable construction material composition of the present invention can strongly reinforce a concrete structure.

 The radical polymerization-curable construction material composition of Example 28 contains a rubber-elastic polymer (styrene-based block polymer) as the component b, so that the obtained cured product has high toughness and durability. Excellent, with moderate pot life. Therefore, it is useful for mounting members having a relatively large bonding area in civil engineering work, building work, and the like.

The radically polymerizable construction material composition of Example 29 exhibited a pot life of about 50 minutes at 10 ° C. Using this composition, the Japan Road Association concrete floor slab After conducting tests according to the quality standard of the water layer, it must be able to meet the standard values such as waterproofness test, low temperature flexibility test, bow I tension adhesion test, etc. Therefore, it is expected that good workability and floor slab waterproofing material can be provided. Industrial applicability

 As described above, the radical polymerization curable construction material composition of the present invention comprises a polymerizable unsaturated monomer (a component), a specific polymer (b component), a radical polymerization initiator (c component), and a transition metal stone. A compound (e component) that forms a complex or chelate with the transition metal in the above d component is used together with (d component). Therefore, in the past, the pot life was about 5 to 15 minutes at room temperature, but according to the present invention, the pot life was extended to about 20 to 90 minutes, and the high temperature (especially in summer) However, sufficient pot life can be secured, and the physical properties after curing are not affected. Therefore, the radical polymerization hardening construction material composition of the present invention can be applied from a low temperature in winter of −20 ° C.¾ to a high temperature of about 70 ° C. (particularly, applicable to construction of road surface temperature such as roads in summer. Construction materials.

 Then, the radical polymerization-curable construction material composition of the present invention is prepared by mixing the above components a, b, d, and e in advance to prepare a main component, and immediately before using the main component (a, b, d, e components). ) And the above radical polymerization initiator (component (c)). Therefore, a sufficient pot life can be ensured after mixing the radical polymerization initiator (component c), and workability can be significantly improved.

 Further, according to the concrete structure capturing method of the present invention, the working efficiency can be remarkably improved. By using a specific fiber sheet as the fiber base material, the concrete structure can be more appropriately reinforced according to the purpose.

Claims

The scope of the claims 1. A radical polymerization-curable construction material composition comprising the following components (a) to (e):  (a) Polymerizable unsaturated monomers.  (b) A polymer soluble or dispersible in the component (a).  (c) radical polymerization initiator.  (d) Transition metal stone II.  (e) A compound which forms a complex or chelate with the transition metal in the component (d). 2. The radical polymerization-curable construction material composition according to claim 1, wherein the component (e) is a compound having at least one secondary amino group in one molecule.  3. The radical polymerization curable construction material composition according to claim 1, wherein the component (e) is an imine compound or an oxime compound.  4. The amount of component (e) to be added is 0.01 to 20 parts by weight based on 100 parts by weight of component (a), component (b) and component (d) in total. Item 4. The radical polymerization hardening construction material composition according to any one of Items 1 to 3.  5. The method according to claim 1, wherein the component (b) is at least one selected from the group consisting of a vinyl ester resin, an unsaturated polyester resin, an acryl resin, and a polymer having rubber elasticity. Radical polymerization curable construction material composition. 6. The component (d) is at least one transition metal selected from the group consisting of copper, cobalt, manganese, iron, nickel, zinc, chromium, vanadium, titanium, scandium, calcium, zirconium and lead, and carboxylic acid. The radical polymerization-curable construction material composition according to any one of claims 1 to 5, which is a salt with:  7. A method for using the radical polymerization curable construction material composition according to any one of claims 1 to 6, wherein the component (a), the component (b), the component (d), and the component (e) are used in advance. A method of using a radical polymerization-curable construction material composition, comprising mixing the main agent and the component (c) immediately after use to prepare the main agent after mixing. 8. Applying the radical polymerization curable construction material composition according to any one of claims 1 to 6 to the surface of the concrete structure, and after attaching a fiber base material thereon, The above-mentioned radical polymerization-curable construction material composition is applied on the fiber base material, and then the radical polymerization-curable construction material composition is polymerized and hardened, and the fiber base material is coated on the surface of the concrete structure. A method for reinforcing a concrete structure, characterized by forming a reinforcing layer made of:  9. Prior to the implementation of the method for reinforcing a concrete structure, the radical-polymerized construction material composition according to any one of claims 1 to 6, an epoxy resin and a polyurethane, on the surface of the concrete structure. After applying and curing at least one polymer selected from the group consisting of resin, a base material-preparing putty material containing the radical polymerization-curable construction material composition is applied thereon and cured. 9. The method for capturing a concrete structure according to claim 8, wherein the step is performed.  10. The concrete structure according to claim 8 or 9, wherein the fiber base material is at least one selected from the group consisting of a carbon fiber sheet, a polyaramide fiber sheet, and a glass fiber sheet. Reinforcement method.  11. A concrete structure obtained by the method for reinforcing a concrete structure according to any one of claims 8 to 10, wherein a reinforcing layer made of the fibrous base material is formed on a surface of the concrete structure. A catcher.