JP7245054B2 - Resin composition for repairing concrete structures - Google Patents

Description

The present invention relates to a resin composition for repairing concrete structures.

Concrete structures have the advantages of high strength, excellent workability, and low cost. Concrete structures have excellent durability. In addition to the freezing and thawing of the water that is stored in the structure, chloride ions such as calcium chloride and sodium chloride used as snow melting agents permeate, causing corrosion expansion and cracking and other structural deterioration. As a result, there is a risk that part of the concrete structure will come off and human damage will occur.

One common method for repairing concrete structures is to recast concrete, but this method has the disadvantage that it takes time for the concrete to harden, and the concrete does not harden at low temperatures. There is Against this background, as a simpler repair method, a repair using a resin-based cross-section covering material or a fiber sheet in combination with an adhesive has been proposed (see, for example, Patent Documents 1 to 3).

International Publication No. 2016/133094 JP 2012-026238 A JP 2013-019146 A

However, in conventional repair methods that use a resin-based cross-section covering material or a fiber sheet in combination with an adhesive, the adhesive on the surface is inhibited by oxygen at low temperatures, resulting in insufficient curing, and the desired peeling prevention performance cannot be obtained. There was a fear that the construction period would be prolonged.
In addition, when used in combination with a fiber sheet, insufficient curing of the adhesive causes the fiber sheet to float or peel off, especially on uneven parts of concrete structures, and sufficient reinforcement strength such as adhesion strength and bending strength is required. There is a risk that the guarantee will not be possible, and there has been a strong demand for the development of adhesives and fiber sheets that can improve such defects.

The present invention has been made based on the above circumstances. The present invention relates to a resin composition and a concrete structure repair method using the composition.

As a result of repeated studies, the present inventors have found that a concrete structure having excellent low-temperature curing properties in the surface layer of the adhesive is obtained by using both an organic compound having a nitrogen-containing heterocyclic structure and an organic metal salt in a radically polymerizable composition. It was found that a resin composition for repairing items can be obtained. Further, the present inventors have found that by integrating this resin composition and a fiber sheet, it is possible to provide a concrete structure repair method that is excellent in adhesive strength and bending strength necessary for uneven workability and peeling performance, resulting in the present invention.

〔Ｃｌ：塩化物イオン透過度（ｇ／ｍ^２・ｄａｙ）、Ｖ：セル中の脱イオン水の量（ｍｌ）、Ｍ：測定した塩素イオン濃度（ｍｇ／ｌ）、Ａ：塩素イオン透過面積（ｃｍ^２）〕
（１７）土木学会規格 ＪＳＣＥ Ｋ－５３３「コンクリート片のはく落防止に適用する表面被覆材の押し抜き試験方法」に準拠した耐荷重性能（押し抜き性）の試験において、５℃雰囲気下、２４時間後の最大荷重が少なくとも１．０ｋＮを超える（１２）～（１６）の何れか一項に記載の積層体。
（１８）コンクリート構造物と、繊維シートと、（１）～（１１）の何れか一項に記載のコンクリート構造物補修用樹脂組成物とを使用するコンクリート構造物補修工法。 That is, the present invention is represented by the following (1) to (19).
(1) A resin composition for repairing concrete structures containing a radically polymerizable composition (A), an organometallic salt (B), an organic compound having a nitrogen heterocyclic structure (C), and an organic peroxide (D) is a thing,
The molar ratio between the organometallic salt (B) and the organic compound (C) having a nitrogen heterocyclic structure is (C)/(B) = 0.01 to 6.0, and the nitrogen heterocyclic structure is The amount of the organic compound (C) used is 0.1 to 5.0 parts by mass per 100 parts by mass of the radically polymerizable composition (A).
(2) The resin composition for repairing concrete structures according to (1), wherein the organic metal salt (B) is a cobalt metal salt.
(3) the organic compound (C) having a nitrogen heterocyclic structure is 2,2'-bipyridyl, 2,3'-bipyridyl, pyridine, 6-methyl-2,2'-bipyridyl, 6,6'-dimethyl -2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4,4 '-dimethoxy-2,2'-bipyridyl, 4,5-diazafluorene, 2,2':6',2″-terpyridine, 2-(2-pyridinyl)quinoline, 2-methylpyridine, 4-methylpyridine , 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridine, 4- Phlolopyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 5-methylpyridine-3-carbonitrile, 2,4-lutidine, pyridazine , pyrimidine, quinazoline, 2,2′-bipyrimidine, pyrazine, quinoxaline, phthalazine, cinnoline, quinazoline, 1,10-phenanthroline, 4,7-phenanthroline, 1,7-phenanthroline, quinoline, isoquinoline, benzoquinoline, acridine, naphthyridine The resin composition for repairing concrete structures according to (1) or (2), wherein at least one kind is selected from the above.
(4) The organic compound (C) having a nitrogen heterocyclic structure is at least one selected from 2,2′-bipyridyl, 2,3′-bipyridyl, pyridine, and 1,10-phenanthroline (1) to (3) ) The resin composition for repairing concrete structures according to any one of ).
(5) Organic peroxide (D) is at least dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate The resin composition for repairing a concrete structure according to any one of (1) to (4), which is selected from one type.
(6) Organic peroxide (D) is a mixture of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluoyl peroxide, a mixture of cumene hydroperoxide and t-butyl peroxybenzoate, cumene hydro The resin composition for repairing concrete structures according to any one of (1) to (5), wherein at least one kind is selected from a mixture of peroxide, t-butyl peroxybenzoate and methyl ethyl ketone peroxide.
(7) The organic compound (C) having a nitrogen heterocyclic structure is a complex in which the organometallic salt (B) is coordinated, and the amount of the complex used is such that the radically polymerizable composition (A) is The composition according to any one of (1) to (6), which is 0.1 to 5.0 parts by mass per 100 parts by mass.
(8) Viscosity at 20° C. and 2 rpm is 1,000 to 300,000 mPa·s, and thixotropic index value (viscosity at 2 rpm/20 rpm) is 1.5 to 10. The resin composition for repairing concrete structures according to any one of (1) to (7).
(9) Surface curability in an atmosphere of 5 ° C. is 24 hours in a test conforming to JIS K5600 3-3 "Paint general test method-Part 3: Coating film formation function-Section 3: Curing and drying property" The resin composition for repairing concrete structures according to any one of (1) to (8) below.
(10) The composition according to any one of (1) to (9), which further contains fiber.
(11) The resin composition for repairing concrete structures according to (10), wherein the fiber has a fiber length of 0.1 mm to 50 mm and a fineness of 100 to 5,000 dtex.
resin composition for
(12) A laminate comprising the composition according to any one of (1) to (11) and a fiber sheet.
(13) A laminate comprising a concrete structure, a fiber sheet, and the resin composition for repairing a concrete structure according to any one of (1) to (11).
(14) The fiber sheet is a laminate obtained by laminating at least two layers of sheet-like members,
When the first layer and the second layer are arranged from the concrete structure side, the first layer is a multiaxial mesh sheet combining multifilaments,
The laminate according to (13), wherein the second layer is a porous sheet.
(15) The laminate according to (14), wherein the multiaxial mesh sheet has a tensile strength of 0.2 kN/10 mm or more, and the porous sheet has a tear strength of 2.0 N or more.
(16) In a chloride ion permeability test in accordance with NEXCO Standard Test Method 425 "Durability test method for preventing flaking", the chloride ion concentration measured by the chloride ion analysis method of JIS K0101 is used, and the general formula The laminate according to any one of (12) to (15), wherein the chloride ion permeability obtained from (1) is 0.005 g/m ² ·day or less.

[Cl: chloride ion permeability (g / m ² day), V: amount of deionized water in the cell (ml), M: measured chloride ion concentration (mg / l), A: chloride ion permeation area (cm ² )]
(17) In a test of load-bearing performance (push-out property) in accordance with the Japan Society of Civil Engineers standard JSCE K-533 "Push-out test method for surface coating material applied to prevent concrete pieces from falling off", in an atmosphere of 5 ° C for 24 hours Laminate according to any one of (12) to (16), wherein the maximum subsequent load exceeds at least 1.0 kN.
(18) A concrete structure repair method using a concrete structure, a fiber sheet, and the concrete structure repair resin composition according to any one of (1) to (11).

According to the concrete structure repair resin composition of the present invention and the concrete structure repair method using the composition, an organic compound having a nitrogen-containing heterocyclic structure and an organic metal salt are used in combination in the radically polymerizable composition. As a result, a resin composition for repairing concrete structures having excellent low-temperature curing properties on the surface layer of the adhesive is obtained. It is possible to provide a repair method for concrete structures with excellent strength and bending strength.

The resin composition for repairing concrete structures of the present invention comprises at least a radically polymerizable composition (A), an organometallic salt (B), an organic compound having a nitrogen heterocyclic structure (C), and an organic peroxide (D ) is a resin composition containing.

<Radical polymerizable composition (A)>
Here, the radically polymerizable composition (A) contained in the resin composition for repairing concrete structures includes at least one (meth)acryloyl group-containing radically polymerizable unsaturated monomer in the molecule, urethane ( It is selected from at least one of meth)acrylate resins, polyester (meth)acrylate resins, and vinyl ester resins. Moreover, "(meth)acrylate" means "one or both of methacrylate and acrylate". In addition, the term "(meth)acryloyl group" as used herein means "one or both of an acryloyl group and a methacryloyl group".

<(Meth)acryloyl group-containing radically polymerizable unsaturated monomer>
Specific examples of (meth)acryloyl group-containing radically polymerizable unsaturated monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, and 2-ethylhexyl acrylate. , octyl acrylate, nonyl acrylate, decyl acrylate, alkyl acrylates such as dodecyl acrylate, aryl acrylates such as phenyl acrylate, benzyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, acrylic Alkoxyalkyl acrylates such as propoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, salts such as acrylic acid and alkali metal acrylate salts, salts such as methacrylic acid and alkali metal methacrylate salts, methyl methacrylate, Methacrylate alkyl esters such as ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, dodecyl methacrylate , phenyl methacrylate, methacrylate aryl esters such as benzyl methacrylate, alkoxyalkyl methacrylates such as methoxyethyl methacrylate, ethoxyethyl methacrylate, propoxyethyl methacrylate, butoxyethyl methacrylate, ethoxypropyl methacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, propylene glycol diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate (poly)alkylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, propylene glycol dimethacrylate, Dimethacrylates of (poly)alkylene glycols such as dimethacrylates of dipropylene glycol, dimethacrylates of tripropylene glycol, trimethylol proppant Polyvalent acrylic acid esters such as triacrylate, polyvalent methacrylic acid esters such as trimethylolpropane trimethacrylate, acrylonitrile, methacrylonitrile; vinyl acetate, vinylidene chloride, 2-chloroethyl acrylate, methacrylic acid Vinyl halide compounds such as 2-chloroethyl, acrylic acid esters of alicyclic alcohols such as cyclohexyl acrylate, methacrylic acid esters of alicyclic alcohols such as cyclohexyl methacrylate, 2-vinyl-2-oxazoline, 2 -Oxazoline group-containing polymerizable compounds such as vinyl-5-methyl-2-oxazoline and 2-isopropenyl-2-oxazoline, acryloylaziridine, methacryloylaziridine, 2-aziridinylethyl acrylate, 2-methacrylate Aziridine group-containing polymerizable compounds such as aziridinylethyl, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, glycidyl acrylate, 2-ethyl glycidyl acrylate, 2-ethyl glycidyl methacrylate Epoxy group-containing vinyl monomers such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, acrylic acid, or methacrylic acid and polypropylene glycol, or polyethylene glycol Hydroxyl group-containing vinyl compounds such as monoesters, adducts of lactones and 2-hydroxyethyl (meth)acrylate, fluorine-containing vinyl monomers such as fluorine-substituted methacrylic acid alkyl esters and fluorine-substituted acrylic acid alkyl esters , Unsaturated carboxylic acids such as itaconic acid, crotonic acid, maleic acid, fumaric acid, excluding (meth)acrylic acid, their salts, their (partial) ester compounds and acid anhydrides, 2-chloroethyl vinyl ether , reactive halogen-containing vinyl monomers such as vinyl monochloroacetate, amide group-containing vinyl monomers such as methacrylamide, N-methylol methacrylamide, N-methoxyethyl methacrylamide, N-butoxymethyl methacrylamide, vinyl organosilicon group-containing vinyls such as trimethoxysilane, γ-methacryloxypropyltrimethoxysilane, allyltrimethoxysilane, trimethoxysilylpropylallylamine, 2-methoxyethoxytrimethoxysilane; Examples include compound monomers, and macromonomers having a radically polymerizable vinyl group at the end of a monomer obtained by polymerizing a vinyl group (eg, fluorine-based monomers, silicone-containing monomers, macromonomers, styrene, silicone, etc.).
Moreover, from the viewpoint of strength and durability, a radically polymerizable unsaturated monomer having two or more (meth)acryloyl groups in the molecule can be used in combination. Specific examples of radically polymerizable unsaturated monomers having two or more (meth)acryloyl groups in the molecule include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth) Acrylates, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethoxylated bisphenol A di( meth)acrylate, tricyclodecane di(meth)acrylate, 1,10-decanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1 , 9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, ethoxylated polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, ε-caprolactone-modified tris-(2-acryloxyethyl)isocyanurate, pentaerythritol tri(meth)acrylate, dimethylolpropane tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate ) acrylate, dipentaesritol poly(meth)acrylate, dipentaesritol hexa(meth)acrylate, 2,2-bis[4-(methacryloxyethoxy)phenyl]propane, 2,2-bis[4- (Methacryloxy-diethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy-polyethoxy)phenyl]propane, 2,2-bis[4-(acryloxy-diethoxy)phenyl]propane, 2,2-bis[4 -(acryloxy-polyethoxy)phenyl]propane and the like.

<Urethane (meth)acrylate resin>
The urethane (meth)acrylate resin is a radically polymerizable unsaturated group-containing oligomer obtainable by reacting a compound having at least one or more active hydrogen groups, an isocyanate compound, and a hydroxy group-containing (meth)acrylate compound. is.
The method for producing the urethane (meth)acrylate resin is not particularly limited, but a method of reacting an active hydrogen group-containing compound with an isocyanate compound, preparing an isocyanate-terminated prepolymer, and then reacting a hydroxy group-containing acrylate compound, or a method of reacting a hydroxy group-containing acrylate A method of reacting a compound with an isocyanate compound and then reacting it with an active hydrogen group-containing compound can be mentioned. In these production methods, from the viewpoint of production stability, etc., the (meth)acryloyl group-containing radically polymerizable unsaturated monomer and solvent excluding the hydroxy group-containing acrylate compound are appropriately selected and adjusted.

<Compound containing active hydrogen group>
Specific examples of the active hydrogen group-containing compound used in the urethane (meth)acrylate resin are not particularly limited as long as they have at least one or more active hydrogen groups and react with an isocyanate compound. At least one polymer or low-molecular-weight polyol having an active hydrogen group, such as polyester polyols, polyether polyols, polycarbonate polyols, (meth)acrylic polyols, silicone polyols, castor oil-based polyols, fluorine-based polyols, olefin polyols, and polythiol compounds Selected from types.

<Polyester polyol>
Specific examples of polyester polyols including dimer polyols include phthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, succinic acid, tartaric acid, oxalic acid, malonic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, glutaconic acid. , azelaic acid, sebacic acid, 1,4-cyclohexyldicarboxylic acid, α-hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α,β-diethylsuccinic acid, maleic acid, fumaric acid dicarboxylic acids such as oleic acid and linoleic acid, dicarboxylic acids having 36 carbon atoms obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, or one or more of these anhydrides, ethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8 -octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane- 1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. Mention may be made of those obtained from condensation polymerization reactions with one or more of the molecular polyols. Also included are lactone-based polyester polyols obtained by ring-opening polymerization of cyclic ester (so-called lactone) monomers such as ε-caprolactone, alkyl-substituted ε-caprolactone, δ-valerolactone, and alkyl-substituted δ-valerolactone. Furthermore, a polyester-amide polyol obtained by replacing part of the low-molecular-weight polyol with a low-molecular-weight polyamine such as hexamethylenediamine, isophoronediamine, or monoethanolamine or a low-molecular-weight aminoalcohol can also be used.

<Polyether polyol>
Specific examples of polyether polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5 - pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, Neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, bisphenol A, bis(β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc. or low-molecular-weight polyamines such as ethylenediamine, propylenediamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, and xylylenediamine. Polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide using compounds as initiators, alkyl glycidyl ethers such as methyl glycidyl ether, and aryls such as phenyl glycidyl ether Examples include polyether polyols obtained by ring-opening polymerization of cyclic ether monomers such as glycidyl ethers and tetrahydrofuran.

<Polycarbonate polyol>
Specific examples of polycarbonate polyols include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- Pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3,3-dimethylolheptane, diethylene glycol, dipropylene glycol, neo Pentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide or propylene oxide adduct of bisphenol A, bis(β-hydroxyethyl)benzene, One or more of low-molecular-weight polyols such as xylylene glycol, glycerin, trimethylolpropane, and pentaerythritol, dialkyl carbonates such as dimethyl carbonate and diethyl carbonate, alkylene carbonates such as ethylene carbonate and propylene carbonate, diphenyl carbonate, and dinaphthyl Those obtained from dealcoholization reaction and dephenolation reaction with diaryl carbonates such as carbonate, dianthryl carbonate, diphenanthryl carbonate, diindanyl carbonate, and tetrahydronaphthyl carbonate can be mentioned.
A polyol obtained by a transesterification reaction of a polycarbonate polyol, a polyester polyol and a low-molecular-weight polyol can also be used.

<(Meth) acrylic polyol>
The acrylic polyol contains at least one hydroxyl group-containing acrylate compound in the molecule that can serve as the reaction point, and a (meth)acryloyl group-containing radically polymerizable unsaturated monomer and a polymerization initiator are heated. Examples include those obtained by copolymerizing acrylic monomers using energy, ultraviolet rays, light energy such as electron beams, or the like.

<Silicone polyol>
Specific examples of silicone polyols include vinyl group-containing silicone compounds obtained by polymerizing γ-(meth)acryloxypropyltrimethoxysilane, etc., and α,ω-dihydroxypolydimethylsiloxanes having at least one terminal hydroxyl group in the molecule. , α,ω-dihydroxypolydiphenylsiloxane and the like.

<Castor oil-based polyol>
Specific examples of castor oil-based polyols include linear or branched polyester polyols obtained by reacting castor oil fatty acids with polyols. Dehydrated castor oil, partially dehydrated castor oil, and hydrogenated castor oil to which hydrogen is added can also be used.

<Fluorinated polyol>
A specific example of the fluorine-based polyol is a linear or branched polyol obtained by a copolymerization reaction of a fluorine-containing monomer and a monomer having a hydroxyl group as essential components. Here, the fluorine-containing monomer is preferably a fluoroolefin such as tetrafluoroethylene, chlorotrifluoroethylene, trichlorofluoroethylene, hexafluoropropylene, vinylidene fluoride, vinyl fluoride, trifluoromethyltrifluoroethylene. etc. Examples of monomers having a hydroxyl group include hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether and cyclohexanediol monovinyl ether, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, and vinyl hydroxyalkyl crotonates. Examples include hydroxyl group-containing vinyl carboxylates, or monomers having an allyl ester group and a hydroxyl group.

<Olefin polyol>
Specific examples of olefin polyols include diene compounds such as butadiene, isoprene, butene, and isobutene, and after polymerizing in the presence of anionic polymerization catalysts such as metallic lithium, metallic potassium, and metallic sodium, ethylene oxide, propylene oxide, and the like. Examples include polyols having a number average molecular weight of 1,000 to 8,000 obtained by addition polymerization of alkylene oxide, and hydrogenated polyols obtained by hydrogenating these. Specifically, polybutadiene polyol, polyisoprene polyol, polybutene Polyol, polyisobutylene polyol, hydrogenated polybutadiene polyol, hydrogenated polyisoprene polyol, hydrogenated polybutene polyol, and hydrogenated polyisobutylene polyol.

<Polythiol compound>
Specific examples of polythiol compounds include methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6- Hexanedithiol, 1,2,3-propanetrithiol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2 -dithiol, 2-methylcyclohexane-2,3-dithiol, bicyclo[2,2,1]pepta-exo-cis-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, bis(2-thiomalate) -mercaptoethyl ester), 2,3-dimercaptosuccinic acid (2-mercaptoethyl ester), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (3- mercaptoacetate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis ( mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane tris(2-mercapto acetate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), 1,2-bis (2-mercaptoethylthio) -3-mercaptopropane), 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl) ) benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2 - bis (mercapto methyleneoxy) benzene, 1,3-bis (mercapto methyleneoxy) benzene, 1,4-bis (meth) mercaptoethyleneoxy)benzene, 1,2-bis(mercaptoethyleneoxy)benzene, 1,3-bis(mercaptoethyleneoxy)benzene, 1,4-bis(mercaptoethyleneoxy)benzene, 1,2,3-tri Mercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene, 1 , 3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene , 1,2,3-tris(mercaptomethyleneoxy)benzene, 1,2,4-tris(mercaptomethyleneoxy)benzene, 1,3,5-tris(mercaptomethyleneoxy)benzene, 1,2,3-tris (mercaptoethyleneoxy)benzene, 1,2,4-tris(mercaptoethyleneoxy)benzene, 1,3,5-tris(mercaptoethyleneoxy)benzene, 1,2,3,4-tetramercaptobenzene, 1,2 , 3,5-tetramercaptobenzene, 1,2,4,5-tetramercaptobenzene, 1,2,3,4-tetrakis(mercaptomethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyl)benzene , 1,2,4,5-tetrakis(mercaptomethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptoethyl)benzene, 1,2, 4,5-tetrakis(mercaptoethyl)benzene, 1,2,3,4-tetrakis(mercaptoethyl)benzene, 1,2,3,5-tetrakis(mercaptomethyleneoxy)benzene, 1,2,4,5- Tetrakis(mercaptomethyleneoxy)benzene, 1,2,3,4-tetrakis(mercaptoethyleneoxy)benzene, 1,2,3,5-tetrakis(mercaptoethyleneoxy)benzene, 1,2,4,5-tetrakis( mercaptoethyleneoxy)benzene, 2,2′-dimercaptobiphenyl, 4,4′-dimercaptobiphenyl, 4,4′-dimercaptobibenzyl, 2,5-toluenedithiol 3,4-toluenedithiol, 1,4 - naphthalenedithiol, 1,5-naphthalenedithiol, 2,6-naphthalenedithiol, 2,7-naphthalenedithiol, 2,4-dimethylbenzene-1,3-dithiol, 4,5-dimethylbenzene-1,3-dithiol, 9,10-anthracenedimethanethiol, 1,3-di(p- methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, 2,4-di(p-mercaptophenyl)pentane, 2,5- Dichlorobenzene-1,3-dithiol, 1,3-di(p-chlorophenyl)propane-2,2-dithiol, 3,4,5-tribromo-1,2-dimercaptobenzene, 2,3,4,6 -tetrachloro-1,5-bis(mercaptomethyl)benzene, 2-methylamino-4,6-dithiol-sym-triazine, 2-ethylamino-4,6-dithiol-sym-triazine, 2-amino-4, 6-dithiol-sym-triazine, 2-morpholino-4,6-dithiol-sym-triazine, 2-cyclohexylamino-4,6-dithiol-sym-triazine, 2-methoxy-4,6-dithiol-sym-triazine , 2-phenoxy-4,6-dithiol-sym-triazine, 2-thiobenzeneoxy-4,6-dithiol-sym-triazine, 2-thiobutyloxy-4,6-dithiol-sym-triazine, 1,2 -bis(mercaptomethylthio)benzene, 1,3-bis(mercaptomethylthio)benzene, 1,4-bis(mercaptomethylthio)benzene, 1,2-bis(mercaptoethylthio)benzene 1,3-bis(mercaptoethylthio) ) benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mermercaptomethylthio)benzene, 1,2,4-tris(mermercaptomethylthio)benzene, 1,3,5-tris (mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, 1 , 2,3,4-tetrakis(mercaptomethylthio)benzene, 1,2,3,5-tetrakis(mercaptomethylthio)benzene, 1,2,4,5-tetrakis(mercaptomethylthio)benzene, 1,2,3, 4-tetrakis(mercaptoethylthio)benzene, 1,2,3,5-tetrakis(mercaptoethylthio)benzene e) Benzene, 1,2,4,5-tetrakis(mercaptoethylthio)benzene, bis(mercaptomethyl)sulfide, bis(mercaptoethyl)sulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis( 2-mercaptoethylthio)methane, bis(3-mercaptopropyl)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-(2-mercaptoethylthio)ethane, 1,2-(3-mercaptopropyl ) ethane, 1,3-bis(mercaptomethylthio)propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris ( mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercapto ethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-bis(mercaptomethyl) -1,4-dithiane, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)disulfide, hydroxymethylsulfide bis(2-mercaptoacetate), hydroxymethylsulfide bis(3-mercaptopropionate) ), hydroxyethylsulfide bis (2-mercaptoacetate), hydroxyethyl sulfide bis (3-mercaptopropionate), hydroxypropyl sulfide bis (2-mercaptoacetate), hydroxypropyl sulfide bis (3-mercaptopropionate), Hydroxymethyl disulfide bis (2-mercaptoacetate), Hydroxymethyl disulfide bis (3-mercaptopropionate), Hydroxyethyl disulfide bis (2-mercaptoacetate), Hydroxyethyl disulfide bis (3-mercaptopropionate), Hydroxypropyl disulfide bis (2-mercaptoacetate), hydroxypropyl disulfide bis (3-mercaptopropionate), 2-mercaptoethyl ether bis (2-mercaptoacetate), 2-mercaptoethyl ether -terbis(3-mercaptopropionate), 1,4-dithiane-2,5-diolbis(2-mercaptoacetate), 1,4-dithiane-2,5-diolbis(3-mercaptopropionate), thioglycol acid bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), 4,4-thiodibutyric acid bis(2-mercaptoethyl ester), dithiodiglycolic acid bis(2-mercaptoethyl ester) , bis(2-mercaptoethyl ester) dithiodipropionate, bis(2-mercaptoethyl ester) 4,4-dithiodibutyrate, bis(2,3-dimercaptopropyl ester) thiodiglycolate, thiodipropionic acid bis(2,3-dimercaptopropyl ester), dithioglycolic acid bis(2,3-dimercaptopropyl ester), dithiodipropionic acid (2,3-dimercaptopropyl ester), 3,4-thiophenedithiol, 2 ,5-dimercapto-1,3,4-thiadiazole and the like.

<Low-molecular-weight polyol>
The low-molecular-weight polyol is a polyol having a number average molecular weight of 500 or less. Specific examples include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3- butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 3-methyl-1,5-pentanediol, 3 , 3-dimethylolheptane, diethylene glycol, dipropylene glycol, neopentyl glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, dimer acid diol, ethylene oxide and propylene oxide adducts of bisphenol A, bis (β-hydroxyethyl)benzene, xylylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like.

Next, the isocyanate compound will be explained. Isocyanate compounds used in urethane (meth)acrylate resins include aromatic diisocyanates, araliphatic diisocyanates, aliphatic diisocyanates, alicyclic diisocyanates, sulfur atom-containing diisocyanates, and these allophanate-modified polyisocyanates and isocyanurate-modified polyisocyanates. Isocyanates, uretdione-modified polyisocyanates, urethane-modified polyisocyanates, burette-modified polyisocyanates, uretonimine-modified polyisocyanates, acyl urea-modified polyisocyanates, and the like can be used alone or in combination of two or more.
A polyisothiocyanate compound may be used as the isocyanate compound.

<Aromatic diisocyanate>
Specific examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate/2,6-tolylene diisocyanate mixture, 4,4′-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate/4,4'-diphenylmethane diisocyanate mixture, m-xylylene diisocyanate, p-xylylene diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrodiphenyl- 4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate , p-phenylene diisocyanate, naphthylene-1,4-diisocyanate, naphthylene-1,5-diisocyanate, 3,3'-dimethoxydiphenyl-4,4'-diisocyanate, and the like.

<Aroliphatic Diisocyanate>
Specific examples of araliphatic diisocyanates include 1,3- or 1,4-xylylene diisocyanate or mixtures thereof, 1,3- or 1,4-bis(1-isocyanato-1-methylethyl)benzene or mixtures thereof , ω,ω'-diisocyanato-1,4-diethylbenzene and the like.

<Aliphatic Diisocyanate>
Specific examples of aliphatic diisocyanates include hexamethylene diisocyanate, tetramethylene diisocyanate, 2-methyl-pentane-1,5-diisocyanate, 3-methyl-pentane-1,5-diisocyanate, lysine diisocyanate, trioxyethylene diisocyanate, ethylene Diisocyanate, trimethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, 2,2′-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, decamethylene diisocyanate, butene diisocyanate, 1,3-butadiene-1,4- diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 1,6,11-undecane triisocyanate, 1,3,6-hexamethylene triisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 2,5, 7-trimethyl-1,8-diisocyanate-5-isocyanatomethyloctane, bis(isocyanatoethyl)carbonate, bis(isocyanatoethyl)ether, 1,4-butylene glycol dipropyl ether-α,α'-diisocyanate, lysine diisocyanatemethyl Ester, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2-isocyanatopropyl-2,6-diisocyanatohexanoate and the like can be mentioned.

<Alicyclic diisocyanate>
Specific examples of alicyclic diisocyanates include isophorone diisocyanate, cyclohexyl diisocyanate, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, dicyclohexyldimethylmethane diisocyanate, 2,2′-dimethyldicyclohexylmethane diisocyanate, bis(4- isocyanate-n-butylidene) pentaerythritol, hydrogenated dimer acid diisocyanate, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl- 3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2,2, 1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-5 -(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2, 1]-heptane, 2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2-isocyanatomethyl-2-(3- isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo-[2,2,1]-heptane, 2,5-bis(isocyanatomethyl)-bicyclo[2,2,1]-heptane hydrogenated diphenylmethane diisocyanate, Norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated xylene diisocyanate, hydrogenated tetramethylxylene diisocyanate and the like can be mentioned.
In particular, isophorone diisocyanate or dicyclohexylmethane diisocyanate can be preferably used from the viewpoint of flexibility and compatibility.

<Sulfur atom-containing diisocyanate>
Specific examples of sulfur atom-containing diisocyanates include thiodiethylene diisocyanate, thiodipropyl diisocyanate, thiodihexyl diisocyanate, dimethylsulfone diisocyanate, dithiodimethyl diisocyanate, dithiodiethyl diisocyanate, dithiodipropyl diisocyanate, diphenylsulfide-2,4'-diisocyanate, diphenyl sulfide-4,4'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanatodibenzylthioether, bis(4-isocyanatomethylphenyl) sulfide, 4,4'-methoxyphenylthioethylene glycol-3, 3'-diisocyanate, diphenyl disulfide-4,4'-diisocyanate, 2,2'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3 '-dimethyldiphenyl disulfide-6,6'-diisocyanate, 4,4'-dimethyldiphenyl disulfide-5,5'-diisocyanate, 3,3'-dimethoxydiphenyl disulfide-4,4'-diisocyanate, 4,4'- Dimethoxydiphenyldisulfide-3,3'-diisocyanate, diphenylsulfone-4,4'-diisocyanate, diphenylsulfone-3,3'-diisocyanate, benzidinesulfone-4,4'-diisocyanate, diphenylmethanesulfone-4,4'- diisocyanate, 4-methyldiphenylsulfone-2,4'-diisocyanate, 4,4'-dimethoxydiphenylsulfone-3,3'-diisocyanate, 3,3'-dimethoxy-4,4'-diisocyanate benzyldisulfone, 4,4 '-dimethyldiphenylsulfone-3,3'-diisocyanate, 4,4'-di-tert-butyldiphenylsulfone-3,3'-diisocyanate, 4,4'-methoxyphenylethylenesulfone-3,3'-diisocyanate, 4,4'-dicyclodiphenylsulfone-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester, 4-methoxy-3-isocyanatophenylsulfonyl-4'-isocyanatophenol ester , 4-methyl-3-isocyanate phenylsulfonylanilide-3′-methyl-4′-isocyanate diphenylsulfonyl-ethylenediamine-4,4'-diisocyanate, 4,4'-methoxyphenylsulfonyl-ethylenediamine-3,3'-diisocyanate, 4-methyl-3-isocyanatophenylsulfonylanilide-4-methyl-3 ′-isocyanate, thiophene-2,5-diisocyanate, 1,4-dithiane-2,5-diisocyanate and the like.

<Polyisothiocyanate compound>
Specific examples of polyisothiocyanate compounds include 1,2-diisothiocyanatoethane, 1,3-diisothiocyanatopropane, 1,4-diisothiocyanatobutane, 1,6-diisothiocyanatohexane, p-phenylenedi isopropylidene diisothiocyanate, cyclohexane diisothiocyanate, 1,2-diisothiocyanatobenzene, 1,3-diisothiocyanatobenzene, 1,4-diisothiocyanatobenzene, 2,4-diisothiocyanatotoluene, 2,5 -diisothiocyanate-m-xylene, 4,4-diisothiocyanate-1,1'-biphenyl, 1,1'-methylenebis(4-isothiocyanatobenzene), 1,1'-methylenebis(4-isothiocyanate- 2-methylbenzene), 1,1′-methylenebis(4-isothiocyanato-3-methylbenzene), 1,1′-(1,2-ethanediyl)bis(4-isothiocyanatobenzene), 4,4′- diisothiocyanate benzophenone, 4,4'-diisothiocyanate-3,3'-dimethylbenzophenone, benzanilide-3,4'-diisothiocyanate, diphenyl ether-4,4'-diisothiocyanate, diphenylamine-4,4' -diisocyanate, 2,4,6-triisothiocyanate-3,5-triazine, hexanedioyl diisothiocyanate, nonanedioil diisothiocyanate, carbonic diisothiocyanate, 1,3-benzenecarbonyldiisothiocyanate, 1,4 -benzenecarbonyldiisothiocyanate, (2,2'-bipyridine)-4,4'-dicarbonyldiisothiocyanate, thiobis(3-isothiocyanatopropane), thiobis(2-isothiocyanatoethane), dithiobis(2-iso thiocyanatoethane), 1-isothiocyanato-4-[(2-isocyanate)sulfonyl]benzene, thiobis(4-isothiocyanatobenzene), sulfonylbis(4-isothiocyanatobenzene), sulfinylbis(4-isothiocyanatobenzene), dithiobis(4-isothiocyanatobenzene), 4-isothiocyanato-1-[(4-isocyanatophenyl)sulfonyl]-2-methoxy-benzene, 4-methyl-3-isothiocyanatobenzenesulfonyl-4'-isocyanatophenyl ester, 4-methyl-3-isothi Ocyanatobenzenesulfonylanilide-3′-methyl-4′-isocyanate, thiophenone-2,5-diisothiocyanate, 1,4-dithiane-2,5-diisothiocyanate, 1-isocyanate-3-isothiocyanatopropane, 1-isocyanato-5-isothiocyanatopentane, 1-isocyanato-6-isothiocyanatohexane, isothiocyanatocarbonyl isocyanate, 1-isocyanato-4-isothiocyanatocyclohexane, 1-isocyanato-4-isothiocyanatobenzene, 4-methyl-3 -isothiocyanate-1-isothiocyanatobenzene, 2-isothiocyanate-4,6-diisothiocyanate-1,3,5-triazine, 4-isothiocyanate-4'-isothiocyanatodiphenyl sulfide, 2-isothiocyanate-2' - isothiocyanate diethyl disulfide and the like.

<Polyester (meth)acrylate resin>
Specific examples of the polyester (meth)acrylate resin include (1) a dicarboxylic acid having 36 carbon atoms obtained by dimerizing the unsaturated fatty acid having 18 carbon atoms, or one or more of these anhydrides and a molecular weight A polyester (meth) obtained by reacting an epoxy compound containing an α,β-unsaturated carboxylic acid ester group with a carboxyl group-terminated polyester obtained by a condensation polymerization reaction with one or more of low-molecular-weight polyols of 500 or less. Acrylate resin, (2) dicarboxylic acid having 36 carbon atoms obtained by dimerizing the unsaturated fatty acid having 18 carbon atoms, or one or more of these anhydrides and low molecular weight polyols having a molecular weight of 500 or less A polyester (meth)acrylate resin obtained by reacting (meth)acrylic acid with a polyester polyol obtained from a condensation polymerization reaction with one or more kinds, and (3) dimerizing the unsaturated fatty acid having 18 carbon atoms. A carboxyl group-terminated polyester obtained from a polycondensation reaction of one or more types of dicarboxylic acids having 36 carbon atoms obtained by or anhydrides thereof and one or more types of low-molecular-weight polyols having a molecular weight of 500 or less, Examples include polyester (meth)acrylate resins obtained by reacting one or more hydroxy group-containing acrylate compounds.

<Vinyl ester resin>
A specific example of the vinyl ester resin is an epoxy (meth)acrylate resin, and a conventionally known one obtained by an esterification reaction of an epoxy compound and an unsaturated monobasic acid (saturated dibasic acid if necessary) is used. be able to. Such known vinyl ester resins are described, for example, in "Polyester Resin Handbook", Nikkan Kogyo Shimbun, 1988, and "Paint Glossary", edited by Shikizai Kyokai, 1993.

<Epoxy compound>
Specific examples of epoxy compounds used in vinyl ester resins include a reaction product of bisphenol A and epichlorohydrin, a reaction product of hydrogenated bisphenol A and epichlorohydrin, a reaction product of cyclohexanedimethanol and epichlorohydrin, norbornane dialcohol and epichlorohydrin. reaction product of tetrabromobisphenol A and epichlorohydrin, reaction product of tricyclodecanedimethanol and epichlorohydrin, alicyclic diepoxycarbonate, alicyclic diepoxyacetal, alicyclic diepoxycarboxylate, Bisphenol A-type glycidyl ethers such as novolak-type glycidyl ethers and cresol novolac-type glycidyl ethers, novolak-type glycidyl ethers, and other epoxy compounds can be mentioned.

<Unsaturated basic acid>
Specific examples of unsaturated basic acids used in vinyl ester resins include unsaturated monobasic acids such as acrylic acid and methacrylic acid. Saturated dibasic acids include adipic acid, sebacic acid, dimer acid and the like.

Next, the organometallic salt (B) contained in the resin composition for repairing concrete structures will be described. The organic metal salt (B) has a role of a reaction accelerator that generates radicals from the organic peroxide (D) by oxidation-reduction reaction with the organic peroxide (D) as a radical reaction initiator, and a reaction with oxygen. The reaction has the effect of suppressing curing inhibition.

<Organometallic salt (B)>
Specific examples of the organic metal salt (B) are not particularly limited as long as they undergo a redox reaction with the organic peroxide (D) of the radical reaction initiator, but are scandium, titanium, vanadium, chromium, manganese, iron, It is an organic transition metal salt selected from at least one of cobalt, nickel, and copper, and from the viewpoint of a reaction accelerator and suppression of curing inhibition, a cobalt metal salt is preferred, and cobalt naphthenate or cobalt octylate is particularly preferred.

Next, the organic compound (C) having a nitrogen heterocyclic structure contained in the resin composition for repairing concrete structures will be described. The organic compound (C) having a nitrogen heterocyclic structure is coordinated with the organometallic salt (B) such as a cobalt metal salt to raise the energy level of one electron in the 3d orbital of the organometallic salt, thereby Since it becomes easy to emit one electron from the organic peroxide (D), it becomes easy to reduce the organic peroxide (D), so that the reaction can be promoted particularly at low temperatures. In addition, the role of a reaction accelerator that generates radicals from the organic peroxide (D) by redox reaction with the organic peroxide (D) as a radical reaction initiator and the reaction with oxygen prevent curing inhibition. It has a suppressive effect.

<Organic Compound (C) Having Heterocyclic Structure of Nitrogen>
Specific examples of the organic compound (C) having a nitrogen heterocyclic structure include 2,2'-bipyridyl, 2,3'-bipyridyl, pyridine, 6-methyl-2,2'-bipyridyl, 6,6'- dimethyl-2,2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4, 4′-dimethoxy-2,2′-bipyridyl, 4,5-diazafluorene, 2,2′:6′,2″-terpyridine, 2-(2-pyridinyl)quinoline, 2-methylpyridine, 4-methyl pyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridine, 4 - phlolopyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 5-methylpyridine-3-carbonitrile, 2,4-lutidine, pyridazine, pyrimidine, quinazoline, 2,2′-bipyrimidine, pyrazine, quinoxaline, phthalazine, cinnoline, quinazoline, 1,10-phenanthroline, 4,7-phenanthroline, 1,7-phenanthroline, quinoline, isoquinoline, benzoquinoline, acridine, It is an organic compound (C) having at least one nitrogen heterocyclic structure selected from naphthyridine, and from the viewpoint of surface curability at low temperatures, 2,2'-bipyridyl, 2,3'-bipyridyl, pyridine, 1, 10-phenanthroline is particularly preferred.

The molar ratio of the organometallic salt (B) contained in such a concrete structure repair resin composition to the organic compound (C) having a nitrogen heterocyclic structure is (C)/(B)=0.01. to 6.0 and the amount of the organic compound (C) having a nitrogen heterocyclic structure is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the radically polymerizable composition (A). there has to be When the molar ratio and the amount of the organometallic salt (B) and the organic compound (C) having a nitrogen heterocyclic structure are equal to or higher than the lower limit, low-temperature curability can be obtained, and the displacement of the fiber sheet to be used and the does not cause falls. When the molar ratio and amount of the organometallic salt (B) and the organic compound (C) having a nitrogen heterocyclic structure are equal to or lower than the upper limit, the surface curability and curability are improved, and the peeling performance is improved. Necessary adhesion strength and bending strength can be obtained.

Further, the organic metal salt (B) contained in the resin composition for repairing concrete structures and the organic compound (C) having a nitrogen heterocyclic structure are preliminarily adjusted to have a molar ratio of (C)/(B)=0. The same effect can be obtained by adding 0.1 to 5.0 parts by mass of a complex formed by coordinating to 01 to 6.0 with respect to 100 parts by mass of the radically polymerizable composition (A). is obtained.

The organic peroxide (D) contained in the resin composition for repairing a concrete structure is a reaction initiator that generates radicals in an oxidation-reduction reaction when used in combination with the organometallic salt (B). Organic peroxides (D) include those classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates and azo compounds. Specific examples include benzoyl peroxide, dibenzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, 1,1-bis(t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3,3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl peroxide , Dicumyl Hydroperoxide, Acetyl Peroxide, Bis(4-t-Butylcyclohexyl) Peroxydicarbonate, Diisopropyl Peroxydicarbonate, Isobutyl Peroxide, 3,3,5-Trimethylhexanoyl Peroxide, Lauryl Peroxide , azobisisobutyronitrile, azobiscarbonamide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate and the like. Among these, at least one selected from the group consisting of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide and t-butyl peroxybenzoate Organic peroxides are preferred. From the viewpoint of reactivity, a mixture of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluoyl peroxide, a mixture of cumene hydroperoxide and t-butyl peroxybenzoate, cumene hydroperoxide and t-butyl One or more mixtures of peroxybenzoate and methyl ethyl ketone peroxide are preferred.

The amount of the organic peroxide (D) used is preferably 0.1 to 10 parts by mass, more preferably 2 to 8 parts by mass, per 100 parts by mass of the radically polymerizable resin composition (A). When the amount of the organic peroxide (D) used is at least the above range, curing proceeds sufficiently. On the other hand, if the blending ratio of the organic peroxide (D) is equal to or less than the above range, it is economically preferable and the physical properties of the cured product are improved.

The thus obtained resin composition for repairing concrete structures has a viscosity of 1,000 to 300,000 mPa·s at 20° C. and a rotation speed of 2 rpm, and a thixotropic index value (viscosity at a rotation speed of 2 rpm /viscosity at 20 rpm) is preferably 1.5-10. When the viscosity is equal to or higher than the lower limit, there is no risk of dripping of the resin composition or dropping of the fiber sheet. Further, when the thixotropic index value is at least the lower limit, there is no fear of dripping of the resin or the fiber sheet falling, and when it is at most the upper limit, the workability is improved and the fiber sheet is sufficiently impregnated with the resin composition. However, the adhesion strength and bending strength required for peeling performance can be obtained.

In addition, the resin composition for repairing concrete structures of the present invention may contain inorganic fillers, photopolymerization initiators, photosensitizers, polymerization inhibitors, waxes, tackifiers, silane cups, as long as the performance is not deteriorated. Ring materials, antioxidants, organic solvents, etc. can also be used.

<Inorganic filler>
By using an inorganic filler in combination with a resin composition for repairing concrete structures, it is expected that the reinforcement effect, barrier effect, and workability will be improved. Specific examples of inorganic fillers include, but are not limited to, silica sand, silica, talc, alumina, aluminum hydroxide, calcium carbonate, aluminum, titanium, and the like. Also, the inorganic filler having a particle size of 1 nm to 5000 μm can be used.

<Photoinitiator>
Further improvements in surface curability and physical properties can be expected by using a photopolymerization initiator in combination with the resin composition for repairing concrete structures. Specific examples of the photopolymerization initiator include, but are not limited to, benzoin ether-based photopolymerization initiators, acetophenone-based photopolymerization initiators, α-ketol-based photopolymerization initiators, aromatic sulfonyl chloride-based photopolymerization initiators, and photopolymerization initiators. Active oxime photoinitiators, benzoin photoinitiators, benzyl photoinitiators, benzophenone photoinitiators, ketal photoinitiators, thioxanthone photoinitiators, acylphosphine oxide photoinitiators An initiator or the like can be used.

<Benzoin ether-based photopolymerization initiator>
Specific examples of benzoin ether photopolymerization initiators include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 2,2-dimethoxy-1,2-diphenylethan-1-one ( trade name: Irgacure 651, manufactured by BASF), anisole methyl ether, and the like.

<Acetophenone-based photopolymerization initiator>
Specific examples of acetophenone-based photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone (trade name: Irgacure 184, manufactured by BASF), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 1-[4- (2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (trade name: Irgacure 2959, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propane -1-one (trade name: Irgacure 1173, manufactured by BASF), methoxyacetophenone, and the like.

<α-ketol photopolymerization initiator>
Specific examples of α-ketol photopolymerization initiators include 2-methyl-2-hydroxypropiophenone, 1-[4-(2-hydroxyethyl)-phenyl]-2-hydroxy-2-methylpropane-1 -on and the like.

<Aromatic sulfonyl chloride-based photopolymerization initiator>
Specific examples of aromatic sulfonyl chloride photopolymerization initiators include 2-naphthalenesulfonyl chloride.

<Photoactive oxime photopolymerization initiator>
Specific examples of photoactive oxime-based photopolymerization initiators include 1-phenyl-1,1-propanedione-2-(o-ethoxycarbonyl)-oxime.

<Benzoin-based photopolymerization initiator>
Benzoin etc. are mentioned as a specific example of a benzoin-type photoinitiator.

<Benzyl-based photopolymerization initiator>
Specific examples of the benzyl-based photopolymerization initiator include benzyl and the like.

<Benzophenone-based photopolymerization initiator>
Specific examples of benzophenone-based photopolymerization initiators include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio) Phenylphenylmethane, methyl-2-benzophenone, 1-[4-(4-benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis (dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4-methoxy-4'-dimethylaminobenzophenone and the like.

<Ketal photopolymerization initiator>
Specific examples of ketal-based photopolymerization initiators include benzyl dimethyl ketal and the like.

<Thioxanthone-based photopolymerization initiator>
Specific examples of thioxanthone-based photopolymerization initiators include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and isopropylthioxanthone. , 2,4-diisopropylthioxanthone, dodecylthioxanthone, and the like.

<Acylphosphine-based photopolymerization initiator>
Specific examples of acylphosphine-based photopolymerization initiators include bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)(2,4,4-trimethylpentyl)phosphine oxide, bis (2,6-dimethoxybenzoyl)-n-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)-(2-methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-(1 -methylpropan-1-yl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-t-butylphosphine oxide, bis(2,6-dimethoxybenzoyl)cyclohexylphosphine oxide, bis(2,6-dimethoxybenzoyl)octyl Phosphine oxide, bis(2-methoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2-methoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-di ethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,6-diethoxybenzoyl)(1-methylpropan-1-yl)phosphine oxide, bis(2,6-dibutoxybenzoyl)( 2-methylpropan-1-yl)phosphine oxide, bis(2,4-dimethoxybenzoyl)(2-methylpropan-1-yl)phosphine oxide, bis(2,4,6-trimethylbenzoyl)(2,4- dipentoxyphenyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2- Phenylethylphosphine oxide, bis(2,6-dimethoxybenzoyl)benzylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylpropylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2-phenylethylphosphine oxide, 2,6-dimethoxybenzoylbenzylbutylphosphine oxide, 2,6-dimethoxybenzoylbenzyloctylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diisopropylphenylphosphine oxide, bis(2,4 ,6-trimethylbenzoyl)-2-methylphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl)-4-methylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,5-diethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl) -2,3,5,6-tetramethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-di-n-butoxyphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)isobutylphosphine oxide, 2,6-dimethoxybenzoyl-2,4, 6-trimethylbenzoyl-n-butylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-2,4-dibutoxyphenylphosphine oxide, 1, 10-bis[bis(2,4,6-trimethylbenzoyl)phosphine oxide]decane, tri(2-methylbenzoyl)phosphine oxide and the like.
The amount of the photopolymerization initiator used is preferably 0.1 to 10 parts by mass, more preferably 2 to 8 parts by mass, per 100 parts by mass of the radically polymerizable resin composition (A). When the amount of the photopolymerization initiator used is at least the above range, curing proceeds sufficiently. On the other hand, when the amount of the photopolymerization initiator used is not more than the above range, it is economically preferable and the physical properties of the cured product are improved.

<Photosensitizer>
Moreover, a photopolymerization initiator and a photosensitizer can be used in combination in order to enhance the photopolymerizability. The photosensitizer is not particularly limited and known ones can be used. Specific examples include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- isoamyl dimethylaminobenzoate, 4,4-dimethylaminobenzophenone, 4,4-diethylaminobenzophenone and the like.

<Polymerization inhibitor>
In addition, a polymerization inhibitor can be used in combination to suppress self-polymerization of the radically polymerizable composition contained in the resin composition for repairing concrete structures. Specific examples of polymerization inhibitors include 4-tert-butylpyrocatechol, tert-butylhydroquinone, 1,4-benzoquinone, 2,6-di-tert-butyl-p-cresol, 1,1-diphenyl-2- Mention may be made of picrylhydrazyl free radical, hydroquinone, hydroquinone monomethyl ether, phenothiazine, ammonium-N-nitrosophenylhydroxylamine, N-nitrosophenylhydroxylamine aluminum salt. These polymerization inhibitors can be used alone or in combination of two or more, and are preferably added at 100 ppm to 5,000 ppm to the radical polymerization composition.

<Waxes>
In the resin composition for repairing concrete structures, waxes such as natural waxes, synthetic waxes, and mixed natural and synthetic waxes can be used in combination in order to improve the surface curability. A surface hardening aid may also be used in combination to improve solubility of waxes and segregation of waxes on the surface of the cured product.

<Natural wax>
Specific examples of natural waxes include plant waxes such as candelilla wax, carnauba wax, rice wax, Japan wax and jojoba oil, animal waxes such as beeswax, lanolin and spermaceti, montan wax, ozokerite, ceresin and the like. mineral waxes, paraffin waxes, microcrystalline waxes, petroleum waxes such as petrolactam;

<Synthetic wax>
Specific examples of synthetic waxes include synthetic hydrocarbons such as Fischer-Tropsch wax and polyethylene wax, montan wax derivatives, NPS-9125 (manufactured by Nippon Seiro Co., Ltd.), NPS-9210 (manufactured by Nippon Seiro Co., Ltd.), and NPS-6010. (manufactured by Nippon Seiro Co., Ltd.), HAD-5080 (manufactured by Nippon Seiro Co., Ltd.), NSP-8070 (manufactured by Nippon Seiro Co., Ltd.), OX-020 (manufactured by Nippon Seiro Co., Ltd.) T, OX-1949 (manufactured by Nippon Seiro Co., Ltd.) ), modified waxes such as paraffin wax derivatives and microcrystalline wax derivatives, animal and vegetable oil derivatives such as diamond wax (manufactured by Shin Nippon Rika Co., Ltd.), Ceramer 67 (manufactured by Toyo Petrolite Co., Ltd.), Ceramer 1608 (Toyo Petrolite Co., Ltd.) ), hydrogenated waxes such as hydrogenated castor oil and hydrogenated castor oil derivatives, fatty acids with 12 or more carbon atoms such as stearic acid, dodecanoic acid and octadecyl stearate, and their Alcohols obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to alkylphenols and higher alcohols such as derivatives, Nonipol 160 (manufactured by Sanyo Chemical Industries Co., Ltd.) and Emalmine 200 (manufactured by Sanyo Chemical Industries Co., Ltd.).

The wax preferably has a melting point of 40 to 100°C. If it is at least the lower limit, the wax precipitates on the surface when the resin composition is cured, thereby improving the surface curability. If it is less than the upper limit, the wax dissolves in the resin composition and the physical properties are improved. The melting points of waxes are values measured according to JIS K 2235-1991. The amount of wax used is preferably 0.1 to 30 parts by mass per 100 parts by mass of the radically polymerizable composition (A). When it is at least the lower limit, the surface curability is improved. If it is less than the upper limit, the wax dissolves in the resin composition and the physical properties are improved.

<Surface hardening aid>
Saturated fatty acids, unsaturated fatty acids such as monounsaturated fatty acids and polyunsaturated fatty acids, and mixtures thereof can be used together as a surface hardening aid for segregating waxes on the surface of the cured product. A surface hardening aid alone does not exhibit surface curability, and the surface curability can be improved only when it is used in combination with waxes. The amount of the surface hardening aid used is preferably surface hardening aid/wax=0.1 to 20, more preferably 1 to 10, in terms of mass ratio of wax to surface hardening aid.

<Saturated Fatty Acid>
Specific examples of saturated fatty acids used as surface hardening aids include butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid, and margaric acid. , stearic acid, arachidic acid, henicosyl acid, behenic acid, lignoceric acid, cerotic acid, montanic acid, melissic acid, and derivatives thereof.

<Unsaturated fatty acid>
Specific examples of unsaturated fatty acids used as surface hardening aids include crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, eicosenoic acid, erucic acid, and nervonic acid. , linoleic acid, eicosadienoic acid, docosadienoic acid, linolenic acid, pinolenic acid, eleostellaric acid, mead acid, dihomo-γ-linolenic acid, eicosatrilenic acid, stearidonic acid, arachidonic acid, eicosatetraenoic acid, adrenic acid, boseopentaenoic acid, eicosapentaenoic acid, osponded acid, sardine acid, tetracosapentaenoic acid, docosahexaenoic acid, nisinic acid, derivatives thereof, and the like.

<Mixture>
Specific examples of mixtures of saturated and unsaturated fatty acids used as surface hardening aids include cottonseed oil, corn oil, coconut oil, olive oil, palm oil, rapeseed oil, safflower oil, sesame oil, soybean oil, sunflower oil, turpentine oil. , almond oil, avocado oil, bergamot oil, castor oil, zedel oil, chlorophyll oil, clove oil, mustard oil, eucalyptus oil, fennel oil, fusel oil, grape seed oil, jojoba oil, kukui nut oil, lavender oil, lemon oil, linseed oil, macadamia nut oil, meadowfoam oil, orange oil, origanum oil, persic oil, rosehip, and derivatives including hydrogenated products thereof.

<Tackifier>
Resin compositions for repairing concrete structures include hydrogenated rosin, hydrogenated rosin derivatives of rosin derivatives, hydrogenated terpene resins, aromatic modified terpene resins, and terpene phenols to improve adhesiveness. Hydrogenated terpene derivatives of resin, hydrogenated C5 petroleum resin obtained by copolymerizing C5 fraction, hydrogenated C9 petroleum resin obtained by copolymerizing C9 fraction, C5 fraction A hydrogenated C5/C9 petroleum resin obtained by copolymerizing a C9 fraction, or a tackifier such as an alicyclic (meth)acrylate oligomer can be used in combination. The softening point of these tackifiers is preferably 80 to 140° C., more preferably 90 to 120° C., from the viewpoint of adhesion and heat resistance. If it is less than the lower limit, there is a possibility that sufficient heat resistance may not be obtained. On the other hand, when the upper limit is exceeded, there is a possibility that a precipitate may be formed or the adhesiveness may be lowered, which is not preferable.

<Hydrogenated rosin derivatives>
Specific examples of hydrogenated rosin derivatives include unmodified rosin resins such as gum rosin, wood rosin and tall oil rosin; rosin ester resins obtained by esterifying unmodified rosin resins with alcohols; Examples thereof include hydrogenated phenol-modified rosin resins modified with phenols such as cresol, 3,5-xylenol, p-alkylphenol, and resorcinol. These hydrogenated rosin derivatives can be used alone or in combination of two or more.

<Hydrogenated terpene resin>
Specific examples of hydrogenated terpene resins (hereinafter sometimes referred to as hydrogenated terpene derivatives) include unmodified terpene resins such as α-pinene polymer, β-pinene polymer, and dipentene polymer, and unmodified Hydrogenated products of aromatic modified terpene resins obtained by modifying terpene resins with aromatic compounds such as styrene, unmodified terpene resins modified with phenol compounds such as phenol, m-cresol, 3,5-xylenol, p-alkylphenol and resorcinol and hydrogenated phenol-modified terpene resins. These hydrogenated terpene derivatives can be used alone or in combination of two or more.

<Hydrogenated product of C5/C9/C5/C9 petroleum resin>
Specific examples of hydrogenated products of C5-based petroleum resin include, for example, copolymerization of unsaturated hydrocarbons having 5 carbon atoms such as pentene, isoprene, piperine, and 1,3-pentadiene produced by thermal decomposition of petroleum naphtha. Hydrogenated products of C5 petroleum resins such as dicyclopentadiene can be mentioned.
Specific examples of hydrogenated products of C9 petroleum resins include indene, vinyltoluene, α-methylstyrene, β-methylstyrene, etc., which are produced by thermal decomposition of petroleum naphtha in the same manner as C5 petroleum resins. Hydrogenated products of C9 petroleum resins obtained by copolymerizing unsaturated hydrocarbons having 9 carbon atoms are exemplified.
Specific examples of the hydrogenated C5/C9 petroleum resin include, for example, the hydrogenated C5/C9 petroleum resin obtained by copolymerizing the C5 fraction and the C9 fraction. These hydrogenated petroleum resins can be used alone or in combination of two or more.

<Alicyclic (meth)acrylate oligomer>
Specific examples of alicyclic (meth)acrylate oligomers include cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate, and dicyclopentenyl (meth)acrylate. , dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, and at least one alicyclic (meth)acrylate, and an aliphatic alicyclic (meth)acrylic acid ester oligomers obtained by copolymerizing with a (meth)acrylic acid ester.

<Silane coupling agent>
A silane coupling agent can be used in combination with the resin composition for repairing concrete structures from the viewpoint of improving adhesion to concrete and fiber sheets and improving moisture resistance. The silane coupling agent is not particularly limited, but preferably has a functional group (reactive group) such as an amino group, an epoxy group, a vinyl group, an allyl group, a (meth)acrylic group, or a sulfide group. A silane coupling agent having an epoxy group is preferably used.
Specific examples of silane coupling agents include amino group-containing alkoxysilanes [for example, 3-aminopropyltrimethoxysilane, 3-aminopropylethoxysilane, 3-(2-aminoethyl)aminopropyltrimethoxysilane, 3-( 2-aminoethyl)aminopropylmethyldimethoxysilane, 3-phenylaminopropyltrimethoxysilane, etc.], epoxy group-containing alkoxysilanes [e.g., 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, etc.], sulfide group-containing alkoxysilanes [e.g., bis(3 -(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, etc.], vinyl group-containing alkoxysilanes (e.g., vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, etc.) , allyl group-containing alkoxysilanes (e.g., allyltrimethoxysilane, etc.), (meth)acrylic group-containing alkoxysilanes (e.g., 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, etc.), mercapto group-containing Alkoxysilanes (e.g., 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, etc.) and the like, preferably epoxy group-containing alkoxysilanes, can be used alone or in combination of two or more. .
Moreover, the amount of the silane coupling agent used is preferably 0.01 to 6 parts by mass with respect to 100 parts by mass of the radically polymerizable composition (A). When it is at least the lower limit, the adhesiveness and the resistance to moist heat are improved. When it is equal to or less than the upper limit, the silane coupling agent does not precipitate in the resin composition.

<Antioxidant>
In order to impart weather resistance to the resin composition for repairing concrete structures, an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant are added. It can be used alone or in combination of two or more.

<Aromatic amine antioxidant>
Specific examples of aromatic amine antioxidants include phenylnaphthylamine, 4,4'-dimethoxydiphenylamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine, and 4-isopropoxydiphenylamine. However, among these, the use of diphenylamine compounds is preferred.

<Hindered Phenolic Antioxidant>
Specific examples of hindered phenol antioxidants include 2,4-dimethyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, hydroxy methyl-2,6-di-t-butylphenol, 2,6-di-t-butyl-α-dimethylamino-p-cresol, 2,5-di-t-butyl-4-ethylphenol, 4,4' -bis(2,6-di-t-butylphenol), 2,2'-methylene-bis-4-methyl-6-t-butylphenol, 2,2'-methylene-bis(4-ethyl-6-t- butylphenol), 4,4'-methylene-bis(6-t-butyl-o-cresol), 4,4'-methylene-bis(2,6-di-t-butylphenol), 2,2'-methylene- Bis(4-methyl-6-cyclohexylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), 4,4'-thiobis(6-t-butyl-3-methylphenol) , bis(3-methyl-4-hydroxy-5-t-butylbenzyl)sulfide, 4,4′-thiobis(6-t-butyl-o-cresol), 2,2′-thiobis(4-methyl-6 -t-butylphenol), 2,6-bis(2'-hydroxy-3'-t-butyl-5'-methylbenzyl)-4-methylphenol, 3,5-di-t-butyl-4-hydroxybenzene diethyl ester of sulfonic acid, 2,2′-dihydroxy-3,3′-di(α-methylcyclohexyl)-5,5′-dimethyl-diphenylmethane, α-octadecyl-3(3′,5′-di-t -butyl-4′-hydroxyphenyl)propionate, 6-(hydroxy-3,5-di-t-butylanilino)-2,4-bis-octyl-thio-1,3,5-triazine, hexamethylene glycol-bis [β-(3,5-di-t-butyl-4-hydroxyphenol)propionate], N,N′-hexamethylene-bis(3,5-di-t-butyl-4-hydroxyhydrocinnamic acid amide) , 2,2-thio[diethyl-bis-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate], dioctadecyl of 3,5-di-t-butyl-4-hydroxybenzenephosphonic acid ester, tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, 1,3,5-trimethyl-2,4,6- tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, 1,1,3-tris(2-methyl-4-hydroxy-5-di-t-butylphenyl)butane, tris(3, 5-di-t-butyl-4-hydroxyphenyl)isocyanurate, tris[β-(3,5-di-t-butyl-4hydroxyphenyl)propionyl-oxyethyl]isocyanurate and the like. Among these, those having a molecular weight of 500 daltons or more, such as tetrakis[methylene-3(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, are particularly preferred.

<Sulfur-based antioxidant>
Sulfur-based antioxidants are compounds containing sulfur such as thioether-based, dithioate-based, mercaptobenzimidazole-based, thiocarbanilide-based, and thiodipropionate-based antioxidants. Among these, use of thiodipropionate-based compounds is particularly preferred.

<Phosphorus antioxidant>
Phosphorus-based antioxidants are compounds containing phosphorus such as phosphoric acid, phosphorous acid, hypophosphorous acid derivatives, phenylphosphonic acid, polyphosphonates, dialkylpentaerythritol diphosphites, and dialkylbisphenol A diphosphites. Among these, it is preferable to use a compound having both a phosphorus atom and a sulfur atom in the molecule, or a compound having two or more phosphorus atoms in the molecule.

<Organic solvent>
The resin composition for repairing concrete structures may contain an organic solvent as an auxiliary agent in order to quickly form the waxes on the surface during curing. Specific examples of organic solvents include aliphatic hydrocarbons such as hexane, octane, decane, nonane, and undecane; Hydrogens, aromatic hydrocarbons such as toluene, styrene, ethylbenzene, cumene, and anisole, ketones such as methyl isobutyl ketone and cyclohexanone, esters such as butyl acetate and isobutyl acetate, ethylene glycol ethyl ether acetate, propylene glycol monomethyl ether Glycol ether esters such as acetate, 3-methyl-3-methoxybutyl acetate and ethyl-3-ethoxypropionate, ethers such as dioxane, halogenated hydrocarbons such as methylene iodide and monochlorobenzene, N-methyl Polar aprotic solvents such as pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphonylamide, and the like. These solvents can be used alone or in combination of two or more.
The boiling point of the organic solvent is preferably 90°C or less, and particularly preferably 30 to 90°C. If it is at least the lower limit, the volatilization speed from the surface of the resin composition during curing is not too fast, so that the wax does not precipitate rapidly, and a uniform continuous wax film is formed on the surface, resulting in uneven floating. There is no drying failure caused by If it is less than the upper limit, it does not remain inside the resin as a residual solvent, and the physical properties do not deteriorate.

The resin composition for repairing a concrete structure obtained in this manner was measured at 20°C with an E-type viscometer (JIS Z8803, conical plate rotational viscometer, 3 degree cone, cone angle 20°). The viscosity is 1,000 to 100,000 mPa s at a rotation speed of 20 rpm, and the thixotropic index value (viscosity at a rotation speed of 2 rpm/viscosity at a rotation speed of 20 rpm) is adjusted to a range of 1.5 to 10 with a thixotropic agent. is preferred. When the viscosity of the resin composition for repairing a concrete structure is equal to or higher than the lower limit, the resin composition tends to be thickened. If it is equal to or less than the upper limit, integration with the fiber sheet is easy, and the repair performance of the concrete structure is ensured. Further, when the thixotropic index value is equal to or higher than the lower limit, the resin composition tends to be thickened. If it is less than the upper limit, the fiber sheet is easily impregnated with the resin, the resin composition and the fiber sheet are easily integrated, the anchor effect with the concrete is obtained, and the repair performance of the concrete structure is guaranteed. be done.

The thixotropic agent used for imparting thixotropic properties to the resin composition for repairing concrete structures is not particularly limited, and includes inorganic thixotropic agent fumed silica and organic thixotropic agent polyether. Compounds, fatty acid amides, hydrogenated castor oil, urethane/urea resins, etc. can be used alone or in combination of two or more.

<Inorganic thixotropic agent: fumed silica>
Fumed silica used to impart thixotropic properties to the resin composition for repairing concrete structures includes hydrophilic silica and hydrophobic silica. Hydrophilic silica is hydrophilic fumed silica obtained by flame hydrolysis of silicon tetrachloride, has hydrophilic silanol groups on the surface, has a primary particle size of 5 to 20 nm, and has a specific surface area (BET method) of is 40 to 400 m ² /g. Commercial products of such hydrophilic fumed silica include Aerosil #300 (manufactured by Nippon Aerosil Co., Ltd.), #200 (manufactured by Nippon Aerosil Co., Ltd.), #380 (manufactured by Nippon Aerosil Co., Ltd.), and the like. Hydrophobic silica is fumed silica obtained by chemically treating the above hydrophilic fumed silica with organic silane, organic siloxane, etc. to make it hydrophobic, and has a primary particle diameter of 7 to 25 nm and a specific surface area ( BET method) is 50 to 500 m ² /g. Commercial products of such hydrophobic fumed silica include R805 (manufactured by Nippon Aerosil Co., Ltd.), R972 (manufactured by Nippon Aerosil Co., Ltd.), R974 (manufactured by Nippon Aerosil Co., Ltd.), RY200S (manufactured by Nippon Aerosil Co., Ltd.), and the like. The primary particle sizes of the hydrophilic silica and the hydrophobic silica can be measured, for example, by a dynamic light scattering method. The amount of these fumed silicas to be used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the radically polymerizable composition. When it is at least the lower limit, the thixotropic property is sufficient and the film thickness of the resin composition can be easily increased. Below the upper limit, the fiber sheet is easily impregnated with the resin, the resin composition and the fiber sheet are easily integrated, an anchor effect with the concrete structure is obtained, and the repair performance of the concrete structure is ensured. .

<Organic thixotropic agent>
Commercially available polyether compounds used for imparting thixotropic properties to resin compositions for repairing concrete structures include DISPARLON3600N (manufactured by Kusumoto Kasei Co., Ltd.), SN970 (manufactured by San Nopco Co., Ltd.), and SN984 (manufactured by San Nopco Co., Ltd.). ). Commercially available fatty acid amides include DISPARLON 6900-20X (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON 6900-10X (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON A603-20X (manufactured by Kusumoto Kasei Co., Ltd.), and DISPARLON A603-10X (manufactured by Kusumoto Kasei Co., Ltd.). , DISPARLONA670-20M (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON 6810-20X (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON 6850-20X (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON6820-20M (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON 6820-10M (Kusumoto Kasei Co., Ltd.) DISPARLON FS-6010 (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON PFA-131 (manufactured by Kusumoto Kasei Co., Ltd.), DISPARLON PFA-231 (manufactured by Kusumoto Kasei Co., Ltd.), and BYK-405 (manufactured by BYK Chemie Japan Co., Ltd.). Commercially available hydrogenated castor oils include DISPARLON 308 (manufactured by Kusumoto Kasei Co., Ltd.) and ASA T-20SF (manufactured by Ito Seiyu Co., Ltd.). Commercially available urethane/urea resins include BYK-410 (manufactured by BYK-Chemie Japan), BYK-411 (manufactured by BYK-Chemie Japan), and BYK-420 (manufactured by BYK-Chemie Japan). The amount of these organic thixotropic agents to be used is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the radically polymerizable composition. When it is at least the lower limit, the thixotropic property is sufficient and the film thickness of the resin composition can be easily increased. Below the upper limit, the fiber sheet is easily impregnated with the resin, the resin composition and the fiber sheet are easily integrated, an anchor effect with concrete is obtained, and the repair performance of the concrete structure is ensured.
<Elastomer component>
In the present invention, it is preferred to use an elastomer component in order to improve adhesion strength. As the elastomer component, it is preferable to exclude organic thixotropic agents.
Elastomer components used in the present invention include (meth)acrylonitrile-butadiene-(meth)acrylic acid copolymer, (meth)acrylonitrile-butadiene-methyl(meth)acrylate copolymer, methyl(meth)acrylate-butadiene- Styrene copolymer (MBS), (meth)acrylonitrile-styrene-butadiene copolymer, and various synthetic rubbers such as (meth)acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, chloroprene rubber and butadiene rubber, Styrenic thermoplastic elastomers such as natural rubber, styrene-polybutadiene-styrene synthetic rubber, olefinic thermoplastic elastomers such as polyethylene-EPDM synthetic rubber, urethane thermoplastic elastomers such as caprolactone type, adipate type and PTMG type, polybutylene terephthalate - Polyester thermoplastic elastomers such as polytetramethylene glycol multi-block polymers, polyamide thermoplastic elastomers such as nylon-polyol block copolymers and nylon-polyester block copolymers, 1,2-polybutadiene thermoplastic elastomers, and PVC system thermoplastic elastomers, and the like. One or more of these elastomer components may be used as long as they have good compatibility.
Terminal (meth)acrylic-modified polybutadiene can also be used.
Among these, methyl (meth) acrylate-butadiene-styrene copolymer and/or (meth) acrylonitrile-butadiene rubber are preferable in terms of solubility and adhesion strength to the radically polymerizable composition (A), and methyl ( A meth)acrylate-butadiene-styrene copolymer is more preferred.
The amount of these elastomer components used is preferably 3 to 40 parts by mass, more preferably 10 to 20 parts by mass, per 100 parts by mass of the radically polymerizable composition. When it is at least the lower limit, the thixotropic property is sufficient and the film thickness of the resin composition can be easily increased. Below the upper limit, the fiber sheet is easily impregnated with the resin, the resin composition and the fiber sheet are easily integrated, an anchor effect with concrete is obtained, and the repair performance of the concrete structure is ensured.

The surface curing time of the resin composition for repairing concrete structures obtained in this way in an atmosphere of 5 ° C. is determined according to JIS K5600 3-3 "General test method for paint - Part 3: Coating film formation function - Section 3: Curing and drying property", curing in 24 hours or less will shorten the construction period and ensure early flaking prevention performance.

In addition, the cured product prepared using the resin composition for repairing concrete structures has a compressive strength of 20 MPa or more after 24 hours in an atmosphere of 5 ° C in a test conforming to JIS K6911 "General test method for thermosetting plastics". and more preferably 60 MPa or more. When the compressive strength of the cured product after 24 hours is within the above range, it is possible to sufficiently ensure the anti-stripping performance after construction.

Next, a method for repairing a concrete structure composed of the resin composition for repairing a concrete structure of the present invention and a fiber sheet or a fiber fiber will be described.

The concrete structure repair method of the present invention includes (1) a step of applying a surface treatment to the surface of the concrete structure (surface treatment step) as necessary, and (2) a step of applying a primer to the concrete structure as necessary (primer treatment). step), (3) step of adjusting unevenness as necessary (step of adjusting unevenness), (4) step of applying the resin composition for repairing concrete structures of the present invention, or concrete structure mixed with fiber The step of applying a repair resin composition (step of applying a repair resin composition), (5) the step of attaching a fiber sheet (except when fiber is mixed), and (6) the step of applying a protective coating as necessary to the concrete structure. It is possible to impart properties such as peeling prevention performance to objects.

<Surface treatment process>
The surface treatment process, which is carried out as necessary, is performed to remove laitance, surface stains, and deteriorated substrates of concrete structures in order to stably ensure the anti-stripping performance and adhesion. , and known techniques such as water jet treatment and cleaning treatment using a wire brush can be used.

<Primer treatment step>
In addition, as a primer treatment step that is performed as necessary, not only does it improve the adhesiveness between the concrete structure and the resin composition, but it also impregnates the concrete structure that has deteriorated such as cracks to restore the soundness of the structure. known acrylic resin-based primers and epoxy resin-based Primers, vinyl ester resin primers, silicone resin primers, and inorganic primers can be used as appropriate. The amount of primer to be applied varies depending on the state of the concrete structure, but in general, it can be appropriately applied in the range of 0.05 to 1.0 kg/m ² using a known method such as roller or spray coating. can be done.

<Unevenness adjustment process>
As an unevenness adjustment process that is carried out as necessary, if the surface roughness of the concrete structure exceeds 2 mm due to the surface treatment, resin and bone It is preferable to adjust unevenness with resin mortar, polymer cement mortar, or the like that uses a combination of materials.

<Repair resin composition application step>
In the step of applying the resin composition for repairing concrete structures of the present invention, it is possible to sufficiently secure the performance of the peeling prevention performance by integrating with the fiber sheet in addition to the adhesiveness with the concrete structure. Become. The coating amount of the resin composition for repairing concrete structures varies depending on the condition of the concrete structure, the basis weight of the fiber sheet, etc., but it is in the range of 0.3 to 5.0 kg/m ² , and is known as a brush, spatula, or trowel. can be applied as appropriate using the method of In addition, when the fiber sheet is not used in the next step, fiber can be mixed in order to ensure the anti-flaking performance.

<Textile fiber>
By using fiber fibers in combination with the resin composition for repairing concrete structures, the reinforcing effect of the fiber fibers develops shear resistance during tension, and the ability to prevent concrete pieces from falling off can be enhanced. The types of fibers used in combination here include glass fiber, carbon fiber fiber, acrylic resin fiber, polyethylene fiber, nylon 6 fiber, nylon 6,6 fiber, polyester fiber, polypropylene fiber, vinylon fiber, aramid fiber, BPO (polyparaphenylene benzoxazole) fibers, surface treated products thereof, and the like, which can be used singly or in combination of two or more. Preferably, the energy difference is 10 mJ/m ² or less. When it is 10 mJ/m ² or less, the fibers are uniformly dispersed in the resin composition, and the shear resistance during tension is exhibited. The fiber fineness is preferably in the range of 100 to 5,000 dtex. When it is at least the lower limit, the desired anti-flake performance can be obtained. If it is less than the upper limit, flexibility and uneven workability can be obtained. Moreover, the fiber length of the fiber is preferably in the range of 0.1 to 50 mm. When it is at least the lower limit, the desired anti-flake performance can be obtained. If it is less than the upper limit, the flexibility, workability on irregularities, and workability are improved.
The amount of such fibers used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the resin composition for repairing concrete structures. At the lower limit or more, the desired anti-flake performance can be obtained. If it is below the upper limit, flexibility, uneven workability, and workability can be obtained.

<Process of pasting the fiber sheet>
After applying the resin composition for repairing a concrete structure of the present invention, a step of attaching a fiber sheet is carried out by continuous construction. By continuously applying the resin composition for repairing concrete structures within the pot life, the fiber sheet can be impregnated with the resin composition to form an FRP, and excellent peeling performance and bending strength can be ensured. Here, the pot life is the time in which the reaction rate of the (meth)acryloyl group is 30 mol% or less. It can be expressed by 0.5 times the time at the exothermic peak temperature. The pot life is preferably 10 to 180 minutes, more preferably 20 to 60 minutes. When it is at least the lower limit, the fiber sheet can be easily attached, the fiber sheet can be easily impregnated with the resin composition, and the desired peeling performance and bending strength can be obtained. If it is equal to or less than the upper limit, the workability is improved and the fiber sheet does not shift or the like.

<Fiber sheet>
The fiber sheet used in the concrete structure repair method is a laminate in which at least two layers of sheet-like members are laminated, and when the first layer and the second layer are arranged from the concrete structure side, the first layer is multifilament. wherein the second layer is composed of a laminate containing a porous sheet. The concrete structure of the present invention coated in the repair resin composition coating step by ensuring the peeling prevention performance by configuring the first layer multifilament and by making the second layer porous sheet the outermost layer The resin composition for repair is impregnated, and excellent flexural strength can be secured by making the porous sheet and the resin composition FRP.

<Multi-axis mesh sheet>
Here, the multiaxial mesh sheet combining multifilaments of the first layer is an at least biaxial fiber sheet woven from long fibers such as yarns and rovings by plain weave, twill weave, leno weave, etc., and has a tensile strength of at least 0.2 kN/10 mm fiber sheet, specifically glass fiber sheet, carbon fiber sheet, acrylic resin fiber sheet, polyethylene fiber sheet, nylon 6 fiber sheet, nylon 6,6 fiber sheet, polyester fiber sheet, polypropylene Fiber sheets, vinylon fiber sheets, aramid fiber sheets, BPO (polyparaphenylenebenzoxazole) fiber sheets, surface-treated products thereof, and the like can be mentioned, and fiber sheets can be used alone or in combination of two or more. In particular, it is preferable to select a fiber sheet having a surface free energy difference of 10 mJ/m ² or less between the resin composition for repairing a concrete structure and the fiber sheet. From the viewpoint of strength, a glass fiber sheet is most preferable. When the surface free energy is 10 mJ/m ² or less, the fiber sheet is easily impregnated with the resin composition, and excellent peeling performance and bending strength can be ensured.

The fineness of the multiaxial mesh sheet is preferably 100 to 5,000 dtex, and the basis weight is preferably 100 to 1,000 g/m ² . When it is at least the lower limit value, the desired anti-flake performance can be obtained. If it is less than the upper limit, flexibility and uneven workability can be obtained.
Moreover, the opening of the mesh sheet is preferably 1 to 25 mm, more preferably 3 to 10 mm. By using a mesh sheet with an opening within the range, excellent adhesion to concrete structures can be obtained, and performance such as fire spreadability can be achieved at the same time.

<Porous sheet>
The porous sheet used in the second layer is a porous sheet having a tear strength of at least 2.0 N, and is made of glass fiber, carbon fiber, acrylic resin fiber, polyethylene fiber, nylon 6 fiber, nylon 6,6 fiber. , polyester fiber, polypropylene fiber, vinylon fiber, aramid fiber, BPO (polyparaphenylene benzoxazole) fiber, and surface-treated products thereof, etc., alone or in combination of two or more thereof. In particular, nonwoven fabrics of polyethylene fiber, nylon 6 fiber, nylon 6,6 fiber, polyester fiber, and polypropylene fiber are preferred, and polyester fiber is most preferred, from the viewpoint of conformability to irregularities and workability.
Further, the porous sheet preferably has a basis weight in the range of 5 to 50 g/m ² at which the porosity becomes at least 90% or more. As a result, the concrete structure repair resin composition of the present invention applied in the repair resin composition coating step is impregnated, and excellent bending strength can be secured by converting the porous sheet and the resin composition into FRP. .
Moreover, it is preferable that the porous sheet and the multiaxial mesh sheet are integrated in advance as a laminate with a thermosetting adhesive, a thermoplastic adhesive, or the like. By integrating the sheets, it is possible to prevent the sheet from slipping during the coating and impregnation, and to shorten the work process.

The concrete structure repair method using the concrete structure repair resin composition obtained in this way is JIS The chloride ion permeability determined from the general formula (1) for the chloride ion concentration measured by the chloride ion analysis method of K0101 is preferably 0.005 g/m ² ·day or less. When it is below the upper limit, the effect of suppressing the deterioration of the concrete structure can be obtained.

〔Ｃｌ：塩化物イオン透過度（ｇ／ｍ^２・ｄａｙ）、Ｖ：セル中の脱イオン水の量（ｍｌ）、Ｍ：測定した塩素イオン濃度（ｍｇ／ｌ）、Ａ：塩素イオン透過面積（ｃｍ^２）〕

[Cl: chloride ion permeability (g / m ² day), V: amount of deionized water in the cell (ml), M: measured chloride ion concentration (mg / l), A: chloride ion permeation area (cm ² )]

In addition, the concrete structure repair method was tested for load-bearing performance (push-out property) in accordance with the Japan Society of Civil Engineers standard JSCE K-533 "Push-out test method for surface coating material applied to prevent concrete pieces from falling off". The maximum load after 24 hours in an atmosphere of °C is preferably 1.5 kN or more, and more preferably exceeds 1.5 kN. When it is at least the lower limit, sufficient anti-flake performance can be obtained.

The concrete structure repair method using the concrete structure repair resin composition of the present invention includes concrete floor slabs, walls, balustrades, inner walls of underpasses at road grade intersections of expressway bridges and railway bridges, It can be applied to concrete structures with various uses and forms such as tunnel lining walls, concrete chimneys, buildings, cultural assets, etc., and prevents concrete pieces from falling off from them, ensuring soundness and safety. It can be widely used when necessary.

Examples of the present invention will be described below, but the present invention is not limited to these examples. In the resin composition for repairing concrete structures of the present invention, the reaction is initiated by mixing the two liquids, so in the examples, the two liquids are separately described as agent A and agent B.

<Adjustment of resin composition for repairing concrete structures>
<Example 1: Agent A>
In a stirring device equipped with a stirrer, a thermometer, and a heating device, 43 parts by mass of bisphenol A (EO) 4 dimethacrylate (trade name: Miramer M241, manufactured by Miwon Specialty Chemical Co., Ltd., hereinafter referred to as M241) and dicyclopentenyl 33 parts by mass of oxyethyl methacrylate (trade name: DH-500, manufactured by Hitachi Chemical Co., Ltd., hereinafter referred to as DH-500) and 2-hydroxyethyl methacrylate (trade name: BISOMER HEMA, manufactured by Japan Chemtech, hereinafter referred to as 2 -HEMA) and 10 parts by mass of bisphenol A-type diglycidyl ether acrylic acid adduct (trade name: Viscoat #540, manufactured by Osaka Organic Chemical Industry Co., Ltd., hereinafter referred to as Viscoat #540), and dry air. The mixture was stirred and mixed at 60° C. for 30 minutes under air flow. After that, 14.3 parts by mass of MBS-based polymer (trade name: KANE ACE B-513, manufactured by Kaneka Corporation, hereinafter referred to as B-513) was added and dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of paraffin wax (trade name: P-47, manufactured by Nippon Seiro Co., Ltd., melting point: 47 ° C., hereinafter referred to as P-47) melted by heating to 60 ° C., and linseed oil ( Product name: Non-break linseed oil Composition: 6.8% palmitic acid, 4.1% stearic acid, 16.2% oleic acid, 15.3% linoleic acid, 57.6% linolenic acid, Sanwa Yushi Kogyosha 5 parts by mass of linseed oil), hydrophobic fumed silica (trade name: Aerosil R972, manufactured by Nippon Aerosil Co., Ltd., primary particle size 16 nm, specific surface area (BET method) 110 m ² /g, hereinafter , R972) was mixed and stirred at 60°C for 3 hours. After that, it was cooled to room temperature, and 1.4 parts by mass of a cumene hydroperoxide mixture (trade name: Kayakumene H, manufactured by Kayaku Akzo Co., Ltd., hereinafter referred to as Kayakumene H) and 2,2'-bipyridyl (trade name: 2 , 2′-bipyridyl, manufactured by Tokyo Kasei Kogyo Co., Ltd., hereinafter referred to as BPY) was added and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 1-A.

<Example 1: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, cool to room temperature, add 40 parts by mass of cobalt octylate mineral spirit solution (trade name: CO-8, manufactured by Tokyo Fine Chemicals Co., Ltd., hereinafter referred to as CO-8 (50%)), and stir at room temperature for 30 minutes. Then, a resin composition 1-B for repairing concrete structures was obtained.

<Example 2: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. After that, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H and 4.2 parts by mass of BPY were added, and stirred at room temperature for 30 minutes to obtain a resin composition for repairing concrete structures 2-A.

<Example 2: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 2.8 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 2-B.

<Example 3: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 3-A.

<Example 3: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. After that, it is cooled to room temperature, and 7 parts by mass of a reactant prepared in advance by adjusting the molar ratio of BPY and CO-8 (50%) to BPY/CO-8 (50%) = 3.0 is added, and the mixture is cooled at room temperature. After stirring for 30 minutes, a concrete structure repair resin composition 3-B was obtained.

<Example 4: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. After that, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H and 9.6 parts by mass of BPY were added, and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 4-A.

<Example 4: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 3.2 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 4-B.

<Example 5: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. Then, cool to room temperature, add 1.4 parts by mass of Kayakumen H and 4.2 parts by mass of 1,10-phenanthroline (trade name: 1,10-phenanthroline, manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as phenanthroline). and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 5-A.

<Example 5: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 2.8 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 5-B.

<Example 6: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. After that, it is cooled to room temperature, 1.4 parts by mass of Kayakumen H, 0.2 parts by mass of BPY, and bis (2,4,6-trimethylbenzoyl)-phenylphosphine oxide (trade name: Irgacure 819, BASF) (hereinafter referred to as Irgacure 819) was added and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 6-A.

<Example 6: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to normal temperature, 0.07 part by mass of CO-8 (50%) was added, and the mixture was stirred at normal temperature for 30 minutes to obtain a concrete structure repair resin composition 6-B.

<Example 7: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C. and 5 parts by mass of linseed oil were mixed with this mixed solution, and the mixture was stirred at 60° C. for 3 hours. After that, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H and 0.2 parts by mass of BPY were added, and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 7-A.

<Example 7: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C. and 5 parts by mass of linseed oil were mixed with this mixed solution, and the mixture was stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 40 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 7-B.

<Example 8: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 25 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. After that, the mixture was cooled to normal temperature, 1.4 parts by mass of Kayakumen H and 0.2 parts by mass of BPY were added and stirred at normal temperature for 30 minutes to obtain a resin composition for repairing concrete structures 8-A.

<Example 8: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 25 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. After cooling to room temperature, vanadium naphthenate/naphthenic acid solution (trade name: 35% vanadium naphthenate/naphthenic acid solution, manufactured by Fuji Film Wako Pure Chemical Industries, Ltd., hereinafter referred to as vanadium naphthenate (35%)) was added to 57. 2 parts by mass were added and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 8-B.

<Example 9: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 6 parts by mass of R972 was mixed with this mixed solution and stirred at 60° C. for 3 hours. After that, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H and 4.2 parts by mass of BPY were added and stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 9-A.

<Example 9: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 6 parts by mass of R972 was mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 8.4 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 9-B.

<Synthesis of comparative resin>
<Comparative Example 1: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H was added, and the mixture was stirred for 30 minutes at room temperature to obtain a resin composition 10-A for repairing concrete structures.

<Comparative Example 1: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 2.8 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 10-B.

<Comparative Example 2: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. After that, the mixture was cooled to room temperature, 1.4 parts by mass of Kayakumen H and 14 parts by mass of BPY were added and stirred at room temperature for 30 minutes to obtain a resin composition for repairing concrete structures 11-A.

<Comparative Example 2: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 28 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 11-B.

<Comparative Example 3: Agent A>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. To this mixed solution, 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil and 6 parts by mass of R972 were mixed and stirred at 60° C. for 3 hours. Then, it is cooled to room temperature, and 1.4 parts by mass of Kayakumen H, N,N-di(β-hydroxyethyl)-p-toluidine (trade name: PT-2HE, manufactured by Morin Chemical Industry Co., Ltd., hereinafter referred to as PT- 2HE) was added and stirred for 30 minutes at room temperature to obtain a resin composition 12-A for repairing concrete structures.

<Comparative Example 3: Agent B>
43 parts by mass of M241, 33 parts by mass of DH-500, 14 parts by mass of 2-HEMA, and 10 parts by mass of Viscoat #540 are charged into a stirring device equipped with a stirrer, a thermometer, and a heating device, and dried. The mixture was stirred and mixed at 60° C. for 30 minutes under an air stream. After that, 14.3 parts by mass of B-513 was charged and further dissolved with stirring at 60° C. for 1 hour. 0.5 parts by mass of P-47 heated and melted at 60° C., 5 parts by mass of linseed oil, and 6 parts by mass of R972 were mixed with this mixed solution and stirred at 60° C. for 3 hours. Then, the mixture was cooled to room temperature, 2.8 parts by mass of CO-8 (50%) was added, and the mixture was stirred at room temperature for 30 minutes to obtain a concrete structure repair resin composition 12-B.

The abbreviations of raw materials used in Tables 1 to 4 are as follows.
(1) M241: bisphenol A type (EO) 4 dimethacrylate (2) DH-500: dicyclopentenyloxyethyl methacrylate (3) 2-HEMA: 2-hydroxyethyl methacrylate (4) Viscoat #540: bisphenol A type dimethacrylate Glycidyl ether acrylic acid adduct (5) CO-8 (50%): cobalt octylate mineral spirit solution (6) BPY: 2,2'-bipyridyl (7) phenanthroline: 1,10-phenanthroline (8) PT-2HE : N,N-di(β-hydroxyethyl)-p-toluidine (9) Kayakumene H: cumene hydroperoxide mixture (10) P-47: paraffin wax, melting point 47°C
(11) B-513: MBS-based polymer (12) R972: Hydrophobic fumed silica (13) Irgacure819: Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

<Evaluation of Resin Composition for Repairing Concrete Structure>
The A and B agents of Examples 1 to 9 and Comparative Examples 1 to 3 were mixed and stirred, and surface curability was evaluated after coating to a thickness of 1 mm. In addition, Example 6 was evaluated using UV irradiation (365 nm, 3 mW/cm ² ) in combination after coating.

<Appearance after mixing>
The color of the resin composition for repairing a concrete structure in which agent A and agent B were mixed was visually confirmed.

<Viscosity>
Regarding the resin composition for repairing concrete structures, an E-type viscometer (JIS Z8803, conical plate rotary viscometer, 3 degree cone, 20 degree cone angle) was used. Viscosity was measured at a predetermined number of revolutions under the condition of 20°C.

<Surface Curability>
A resin composition for repairing a concrete structure prepared by mixing agent A and agent B adjusted to 5° C. was applied to a PET film to a thickness of 1 mm using a coater. After that, leave it in a constant temperature bath at 5°C, and evaluate the curability of the surface according to JIS K5600 3-3 "General test method for paint - Part 3: Coating film formation function - Section 3: Curing and drying property". bottom.
<Evaluation Criteria>
・ 12 hours or less: Pass (Evaluation: ○)
・ 13 to 24 hours: Passed (Evaluation: △)
・ 25 hours or more: failed (evaluation: ×)

<Compressive strength>
In accordance with JIS K6911 "General test method for thermosetting plastics" in an atmosphere of 5°C, a resin composition for repairing a concrete structure prepared by mixing agents A and B adjusted to 5°C was measured in a length of 25.4 mm and a width of 12.5°C. It was formed into a mold of 7 mm and 12.7 mm in thickness, and the compressive strength was evaluated after 24 hours.
<Evaluation Criteria>
・ Less than 20 MPa: failed (evaluation: ×)
・ 20 to 59 MPa: Passed (Evaluation: △)
・60 MPa or more: pass (evaluation: ○)

Tables 5 and 6 show the properties of the resin composition for repairing concrete structures.

As shown in Tables 5 and 6, the resin compositions for repairing concrete structures prepared in Examples 1 to 9 were excellent in surface curability and compressive strength at low temperatures. In contrast, Comparative Examples 1 to 3 were inferior in performance.

<Evaluation of concrete structure repair method using fiber sheet>
Using the A agent and the B agent obtained in Examples and Comparative Examples, evaluation as a concrete structure repair method was carried out.

<Pushability (maximum push-out load, displacement)>
The surface of the U-shaped lid ((central part: φ100 mm drilled with a core cutter, leaving 5 mm), name 1 type 300 (400 mm × 600 mm × 60 mm)) specified in JIS A5372 (precast reinforced concrete product) is scraped with a disk sander. bottom. After equal amounts of A and B at 5°C were mixed, 1 kg/m ² of the mixture was applied to the concrete surface at 5°C. After that, a fiber sheet was pasted together, and the specimen was cured at 5°C for 24 hours and 168 hours, and the specimen conformed to the Japan Society of Civil Engineers standard JSCE K-533 "Push-out test method for surface coating material applied to prevent concrete pieces from falling off". and tested. The maximum load at a displacement of 10 mm or more and the displacement at the maximum load were measured.
<Evaluation criteria (maximum push-out load)>
・ Less than 1.0 kN: Failed (Evaluation: ×)
・ 1.0 to 2.0 kN: pass (evaluation: △)
・2.1 kN or more: pass (evaluation: ○)
<Evaluation criteria (displacement)>
・Less than 5 mm: Failed (Evaluation: ×)
・ 6 to 10 mm: pass (evaluation: △)
・ 10 mm or more: pass (evaluation: ○)

<Adhesion>
The surface of a concrete flat plate (300 mm x 300 mm) defined in JIS A 5371 was subjected to shaving with a disk sander. After equal amounts of A and B at 5°C were mixed, 1 kg/m ² of the mixture was applied to the concrete surface at 5°C. After that, the fiber sheets were pasted together, and the specimens cured at 5° C. for 24 hours and 168 hours were pasted on a jig using an epoxy resin (manufactured by Konishi Co., Ltd., Quick Mender). The test was carried out using a Kenken type adhesion tester.
<Evaluation Criteria>
・ Less than 1.5 N / mm ² : failed (evaluation: ×)
・1.5 to 2.0 N/mm ² : Passed (Evaluation: △)
· 2.1 N / mm ² or more: pass (evaluation: ○)

<Evaluation of concrete structure repair method using fiber fiber>
Using the A agent and the B agent obtained in Examples and Comparative Examples, evaluation as a concrete structure repair method was carried out.

<Pushability (maximum push-out load, displacement)>
The U-shaped lid specified in JIS A5372 (precast reinforced concrete product) ((central part: φ100mm drilled with a core cutter, leaving 5mm), name 1 type 300 (400mm x 600mm x 60mm)) surface is scraped with a disk sander. bottom. After mixing equal amounts of A and B at 5°C, nylon 6 cut fiber (fiber length: 5 mm, fineness: 1,000 dtex, amount used: 4 parts by weight per 100 parts by weight of the resin composition) was added. After weighing and mixing, 1 kg/m ² of the mixture was applied to the concrete surface at 5°C. After that, the test specimens cured for 24 hours and 168 hours at 5 ° C. were tested in accordance with the Japan Society of Civil Engineers standard JSCE K-533 "Push-out test method for surface coating material applied to prevent concrete pieces from falling off". . The maximum load at a displacement of 10 mm or more and the displacement at the maximum load were measured.
<Evaluation criteria (maximum push-out load)>
・ Less than 1.0 kN: Failed (Evaluation: ×)
・ 1.0 to 2.0 kN: pass (evaluation: △)
・2.1 kN or more: pass (evaluation: ○)
<Evaluation criteria (displacement)>
・ Less than 5 mm: Failed (Evaluation: ×)
・ 6 to 10 mm: pass (evaluation: △)
・ 10 mm or more: pass (evaluation: ○)

<Adhesion>
The surface of a concrete flat plate (300 mm x 300 mm) defined in JIS A 5371 was subjected to keren treatment with a disk sander. After mixing equal amounts of A and B at 5°C, nylon 6 cut fiber (fiber length: 5 mm, fineness: 1,000 dtex, amount used: 4 parts by weight per 100 parts by weight of the resin composition) was added. After weighing and mixing, 1 kg/m ² of the mixture was applied to the concrete surface at 5°C. After that, a jig was attached to the specimens cured at 5° C. for 24 hours and 168 hours using an epoxy resin (manufactured by Konishi Co., Ltd., Quick Mender). The test was carried out using a Kenken type adhesion tester.
<Evaluation Criteria>
・ Less than 1.5 N / mm ² : failed (evaluation: ×)
・1.5 to 2.0 N/mm ² : Passed (Evaluation: △)
· 2.1 N / mm ² or more: pass (evaluation: ○)

<Chloride ion permeability>
The surface of a mortar specimen specified in JIS R5201 was sandblasted. After mixing equal amounts of A and B at 5°C, nylon 6 cut fiber (fiber length: 5 mm, fineness: 1,000 dtex, amount used: 4 parts by weight per 100 parts by weight of the resin composition) was added. After weighing and mixing, 1 kg/m ² of the mixture was applied to the concrete surface at 5°C. After that, the specimen cured for 168 hours at 5° C. was cut into a size of Φ60 mm and subjected to the chlorine ion permeability test shown in NEXCO Standard Test Method 425 “Durability Test Method for Preventing Flaking”. In order to know the chloride ion permeability of sodium chloride (3% solution), the specimen was allowed to stand at 40° C. for 30 days. After that, using the chloride ion concentration measured by the chloride ion analysis method of JIS K0101, the chloride ion permeability was calculated from the general formula (1).

〔Ｃｌ：塩化物イオン透過度（ｇ／ｍ^２・ｄａｙ）、Ｖ：セル中の脱イオン水の量（ｍｌ）、Ｍ：測定した塩素イオン濃度（ｍｇ／ｌ）、Ａ：塩素イオン透過面積（ｃｍ^２）〕

[Cl: chloride ion permeability (g / m ² · day), V: amount of deionized water in the cell (ml), M: measured chloride ion concentration (mg / l), A: chloride ion permeation area (cm ² )]

<Evaluation Criteria>
・ Less than 0.002 g / m ² · day: pass (evaluation: ○)
・ 0.002 to 0.005 g / m ² · day: pass (evaluation: △)
・0.006 g/m ² ·day or more: failed (evaluation: x)

<Neutralization prevention>
After mixing equal amounts of A and B at 23° C., nylon 6 cut fiber (fiber length: 5 mm, fineness: 1,000 dtex, amount used: 4 parts by weight per 100 parts by weight of the resin composition) was added. 1 kg/m ² of the weighed and mixed resin was applied to five opposing surfaces of a mortar specimen (100 mm×100 mm×100 mm) defined in JIS A1153. After that, the test specimen cured for 168 hours at 23 ° C. is specified in JIS K5664, or an epoxy resin (manufactured by Konishi Co., Ltd., E2500) having the same performance as this. ) and cured for 14 days at 23°C. The sample was placed in an environmental chamber with a temperature of 30° C., a relative humidity of 60% and a carbon dioxide concentration of 5% for 28 days, and then cured under conditions of a temperature of 20° C. and a relative humidity of 60% for 24 hours. after that. A 1% alcohol solution of phenolphthalein was sprayed on the cross section of the specimen which was divided into two by splitting the specimen, and the portion which did not turn red was measured as the neutralized region.
<Evaluation Criteria>
· 0.0 mm: pass (evaluation: ○)
・ 0.1 to 1.0 mm: pass (evaluation: △)
・ 1.1 mm or more: disqualified (evaluation: ×)

Table 7 shows the characteristics of the concrete structure repair method.

The fiber sheets and fiber fibers used in Table 7 are as follows.
(1) Vinylon sheet: material polyvinyl alcohol, biaxial, plain weave, basis weight 91 g/m ² , opening 5 mm, tensile strength MD 76 MPa, TD 69 MPa, thickness 0.39 mm, fineness: 1,000 dtex
(2) Nylon sheet: material nylon 6, biaxial, plain weave, basis weight 160 g/m ² , opening 1 mm, tensile strength: 65 MPa, thickness 0.2 mm, fineness: 1,200 dtex
(3) Glass sheet: material ARG (alkali-resistant glass), biaxial, twist weave, basis weight 210 g/m ² , opening 5 mm, tensile strength 1,500 MPa, thickness 0.2 mm, fineness: 800 dtex
(4) Glass/non-woven mesh sheet:
・Multifilament: Material ARG (alkali-resistant glass), biaxial, twist weave, weight per unit area: 210 g/m ² , opening: 5 mm, tensile strength: 1500 MPa, thickness: 0.2 mm, fineness: 800 dtex
・Porous sheet: material polyester, non-woven fabric, basis weight 12 g/m ² , tear strength 3.0 N
(5) Nylon fiber: material: nylon 6, fiber length: 5 mm, fineness: 1,000 dtex

As shown in Table 7, the concrete structure repair methods according to Examples 10 to 12 provide excellent anti-flaking performance after 24 hours even at 5°C, whereas Comparative Example 4 is inferior in performance. Met.

Claims (18)

A resin composition for repairing concrete structures containing a radically polymerizable composition (A), an organic metal salt (B), an organic compound having a nitrogen heterocyclic structure (C), and an organic peroxide (D). ,
The molar ratio between the organometallic salt (B) and the organic compound (C) having a nitrogen heterocyclic structure is (C)/(B) = 0.01 to 6.0, and the nitrogen heterocyclic structure is The amount of the organic compound (C) used is 0.1 to 5.0 parts by mass with respect to 100 parts by mass of the radically polymerizable composition (A).
The radically polymerizable composition (A) contains at least one (meth)acryloyl group-containing radically polymerizable unsaturated monomer in the molecule, a urethane (meth)acrylate resin, a polyester (meth)acrylate resin, and a vinyl ester resin. is selected from at least one type from
The organic compound (C) having a nitrogen heterocyclic structure is 2,2'-bipyridyl, 2,3'-bipyridyl, pyridine, 6-methyl-2,2'-bipyridyl, 6,6'-dimethyl-2, 2'-bipyridyl, 5,5'-dimethyl-2,2'-bipyridyl, 4,4'-dimethyl-2,2'-bipyridyl, 6-bromo-2,2'-bipyridyl, 4,4'-dimethoxy -2,2′-bipyridyl, 4,5-diazafluorene, 2,2′:6′,2″-terpyridine, 2-(2-pyridinyl)quinoline, 2-methylpyridine, 4-methylpyridine, 2- methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2,6-dimethoxypyridine, 2-chloropyridine, 3-chloropyridine, 4-chloropyridine, 2-fluoropyridine, 3-fluoropyridine, 4-fluoropyridine, 2-bromopyridine, 3-bromopyridine, 4-bromopyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, 5-methylpyridine-3-carbonitrile, 2,4-lutidine, pyridazine, pyrimidine, at least one selected from quinazoline, 2,2′-bipyrimidine, pyrazine, quinoxaline, phthalazine, cinnoline, quinazoline, 1,10-phenanthroline, 4,7-phenanthroline, 1,7-phenanthroline, quinoline, isoquinoline, benzoquinoline, acridine, naphthyridine type selected,
A resin composition for repairing a concrete structure, wherein the organic peroxide (D) is a reaction initiator that generates radicals in a redox reaction when used in combination with the organic metal salt (B). The resin composition for repairing concrete structures according to claim 1, wherein the organic metal salt (B) is a cobalt metal salt. The radically polymerizable composition (A) contains a radically polymerizable unsaturated monomer having two or more (meth)acryloyl groups in the molecule, and the amount of the organic peroxide (D) used is The resin composition for repairing a concrete structure according to claim 1 or 2, which is 0.1 to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable resin composition (A). Any one of claims 1 to 3, wherein the organic compound (C) having a nitrogen heterocyclic structure is at least one selected from 2,2'-bipyridyl, 2,3'-bipyridyl, pyridine and 1,10-phenanthroline. The resin composition for repairing concrete structures according to claim 1. The organic peroxide (D) is at least one selected from dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate. The resin composition for repairing concrete structures according to any one of claims 1 to 4. The organic peroxide (D) is a mixture of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluoyl peroxide, a mixture of cumene hydroperoxide and t-butyl peroxybenzoate, cumene hydroperoxide and The resin composition for repairing concrete structures according to any one of claims 1 to 5, wherein at least one kind is selected from a mixture of t-butyl peroxybenzoate and methyl ethyl ketone peroxide. The amount of the complex in which the organic compound (C) having a nitrogen heterocyclic structure and the organometallic salt (B) are coordinated is 0.1 per 100 parts by mass of the radically polymerizable composition (A). 7. The resin composition for repairing concrete structures according to any one of claims 1 to 6, wherein the content is up to 5.0 parts by mass. The viscosity at 20° C. and a rotation speed of 2 rpm is 1,000 to 300,000 mPa·s, and the thixotropic index value (viscosity at a rotation speed of 2 rpm/viscosity at a rotation speed of 20 rpm) is 1.5 to 10. The resin composition for repairing a concrete structure according to any one of claims 7 to 7. Surface curability in an atmosphere of 5 ° C. is 24 hours or less in a test conforming to JIS K5600 3-3 "Paint general test method-Part 3: Coating film formation function-Section 3: Curing and drying property" The resin composition for repairing concrete structures according to any one of claims 1 to 8. The resin composition for repairing a concrete structure according to any one of claims 1 to 9, further comprising fiber. The resin composition for repairing concrete structures according to claim 10, wherein the fiber has a fiber length of 0.1 mm to 50 mm and a fineness of 100 to 5,000 dtex. A laminate comprising the resin composition for repairing a concrete structure according to any one of claims 1 to 11 and a fiber sheet. A laminate comprising a concrete structure, a fiber sheet, and the resin composition for repairing a concrete structure according to any one of claims 1 to 11. The fiber sheet is a laminate obtained by laminating at least two layers of sheet-like members,
When the first layer and the second layer are arranged from the concrete structure side, the first layer is a multiaxial mesh sheet combining multifilaments,
14. The laminate of Claim 13, wherein the second layer is a porous sheet. 15. The laminate according to claim 14, wherein the multiaxial mesh sheet has a tensile strength of 0.2 kN/10 mm or more, and the porous sheet has a tear strength of 2.0 N or more. In the chloride ion permeability test in accordance with NEXCO Standard Test Method 425 "Durability Test Method for Preventing Flaking", the chloride ion concentration measured by the chloride ion analysis method of JIS K0101 is used, and the general formula (1) 16. The laminate according to any one of claims 12 to 15, which has a chloride ion permeability of 0.005 g/m ² ·day or less obtained from

[Cl: chloride ion permeability (g / m ² · day), V: amount of deionized water in the cell (ml), M: measured chloride ion concentration (mg / l), A: chloride ion permeation area (cm ² )] In the load-bearing performance (push-out performance) test in accordance with the Japan Society of Civil Engineers standard JSCE K-533 "Push-out test method for surface coating materials applied to prevent concrete fragments from falling off", the maximum Laminate according to any one of claims 12 to 16, wherein the load exceeds at least 1.0 kN. A concrete structure repairing method using a concrete structure, a fiber sheet, and the concrete structure repairing resin composition according to any one of claims 1 to 11.