JP2022048571A - Concrete repair material - Google Patents

Abstract

To provide a concrete protective material that has good thixotropy, is less malodorous, has good curability, and gives a coating layer having good wet adhesion and alkali resistance.SOLUTION: A concrete repair material contains a resin having polymerizable unsaturated groups at both terminals (A), an unsaturated polyester (B), a monofunctional (meth)acryl monomer with a flash point of 70°C or higher (C), a polyfunctional (meth)acryl monomer (D), a cyclodextrin derivative (E), and silica fine particles (F).SELECTED DRAWING: None

Description

The present invention relates to a concrete repair material.

Deterioration factors of concrete structures include corrosion of internal reinforcing bars caused by infiltration of rainwater and the like. As measures against this, a construction method that protects the concrete surface with a covering material and prevention of peeling by pasting fibers or the like are adopted. The materials used are required to have quick-curing properties that can complete construction in a short time, adhesion to concrete moistened by rainy weather, and environmentally friendly low odor properties. As such a material, a concrete protective material containing a urethane (meth) acrylate, a radically polymerizable monomer, a cyclodextrin and / or a derivative thereof, and an unsaturated polyester has been proposed (for example, Patent Document 1). reference.).

However, this material has insufficient alkali resistance, and when it is applied to the wall surface of a concrete structure, it has insufficient thixotropic property and has a problem of sagging. Therefore, there has been a demand for a material capable of obtaining a coating film having excellent thixotropic properties, low odor, excellent curability, and excellent wet adhesiveness and alkali resistance.

JP-A-2015-229707

An object to be solved by the present invention is to provide a concrete protective material capable of obtaining a coating film having excellent thixotropic properties, low odor, excellent curability, excellent wet adhesiveness and alkali resistance.

As a result of diligent research to solve the above problems, the present inventors have conducted a resin having a polymerizable unsaturated group at both ends, an unsaturated polyester, and a single amount of monofunctional (meth) acrylic having a flammability of 70 ° C. or higher. We have found that a concrete repair material containing a body, a polyfunctional (meth) acrylic monomer, a cyclodextrin derivative, and silica fine particles can solve the above-mentioned problems, and completed the present invention.

That is, the present invention comprises a resin (A) having a polymerizable unsaturated group at both ends, an unsaturated polyester (B), a monofunctional (meth) acrylic monomer (C) having a flammability of 70 ° C. or higher, and a polyfunctional resin. It is an object of the present invention to provide a concrete repair material containing a (meth) acrylic monomer (D), a cyclodextrin derivative (E), and silica fine particles (F).

Since the concrete repair material of the present invention can obtain a coating film having excellent thixotropic properties, low odor, excellent curability, excellent wet adhesiveness and alkali resistance, it is suitably used as a repair material for various concretes. Can be done.

The concrete protective material of the present invention includes a resin (A) having a polymerizable unsaturated group at both ends, an unsaturated polyester (B), a monofunctional (meth) acrylic monomer (C) having a ignition point of 70 ° C. or higher, and the like. It contains a polyfunctional (meth) acrylic monomer (D), a cyclodextrin derivative (E), and silica fine particles (F).

In the present invention, the "(meth) acrylic monomer" means one or both of the acrylic monomer and the methacrylic monomer, and the "(meth) acrylate" means one or both of the methacrylate and the acrylate. The term "(meth) acrylic loyl" refers to one or both of acryloyl and methacryloyl.

Examples of the resin (A) having a polymerizable unsaturated group at both ends include epoxy (meth) acrylate, polyester (meth) acrylate, and urethane (meth) acrylate. The resin (A) having a polymerizable unsaturated group at both ends thereof may be used alone or in combination of two or more.

The epoxy (meth) acrylate is obtained, for example, by reacting an epoxy compound obtained by mixing a bisphenol type epoxy compound or a bisphenol type epoxy compound with a novolak type epoxy compound with an unsaturated monobasic acid by a conventionally known method. Can be used.

Examples of the bisphenol type epoxy compound include a glycidyl ether type epoxy compound having two or more epoxy groups in one molecule obtained by a reaction between epichlorohydrin and bisphenol A or bisphenol F, and methyl epichlorohydrin and bisphenol A or bisphenol F. A dimethylglycidyl ether type epoxy compound obtained by reacting the above, an epoxy compound obtained by reacting an alkylene oxide adduct of bisphenol A with epichlorohydrin or methylepicrolhydrin, and the like can be used. These epoxy compounds may be used alone or in combination of two or more.

As the novolak type epoxy compound, for example, an epoxy compound obtained by reacting phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin can be used. These epoxy compounds may be used alone or in combination of two or more.

As the unsaturated monobasic acid, for example, (meth) acrylic acid, cinnamic acid, crotonic acid, monomethylmalate, monopropylmalate, monobutenemalate, sorbic acid, mono (2-ethylhexyl) malate and the like are used. be able to. These unsaturated monobasic acids may be used alone or in combination of two or more.

As the polyester (meth) acrylate, for example, a saturated polyester or an unsaturated polyester having two or more (meth) acryloyl groups in one molecule can be used. The saturated polyester is a condensation reaction of a saturated dibasic acid and a polyhydric alcohol, and the unsaturated polyester is a condensation reaction of an α, β-unsaturated dibasic acid and a polyhydric alcohol. All of them have a (meth) acryloyl group at the end.

As the saturated dibasic acid, α, β-unsaturated dibasic acid and the polyhydric alcohol, the same ones used for the synthesis of the unsaturated polyester (B) described later can be used.

Examples of the method for producing the polyester (meth) acrylate include a method of reacting a saturated polyester or an unsaturated polyester with a glycidyl (meth) acrylate by a known method.

As the urethane (meth) acrylate, for example, those obtained by reacting a polyol, a polyisocyanate, and a (meth) acrylic compound having a hydroxyl group or an isocyanate group by a conventionally known method can be used.

As the polyol, for example, polyester polyol, polycarbonate polyol, polyether polyol, acrylic polyol, caprolactone polyol, butadiene polyol and the like can be used. These polyols may be used alone or in combination of two or more.

Examples of the polyisocyanate include aromatic diisocyanates such as phenylenediocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and xylylene diisocyanate. Aliphatic or alicyclic diisocyanates such as isocyanates and tetramethylxylylene diisocyanates; formalin condensates of xylylene diisocyanates, tolylene diisocyanates, diphenylmethane diisocyanates, phenylenedi isocyanates, polyphenylene polymethylene polyisocyanates, methylene diphenyl disisocyanate, 4, 4 Aromatic polyisocyanates such as carbodiimide modified versions of'-diphenylmethane diisocyanate can be used. These polyisocyanates may be used alone or in combination of two or more.

Examples of the (meth) acrylic compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. (Meta) acrylic acid alkyl ester having a hydroxyl group of the above; polyethylene glycol monoacrylate, polypropylene glycol monoacrylate and the like can be used. These compounds may be used alone or in combination of two or more.

Examples of the (meth) acrylic compound having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 2- (2- (meth) acryloyloxyethyloxy) ethyl isocyanate, and 1,1-bis ((meth)). Acryloyloxymethyl) ethyl isocyanate or the like can be used. These compounds may be used alone or in combination of two or more.

The number average molecular weight of the resin (A) is preferably 500 to 4,000 because workability and curability can be further improved.

The content of the resin (A) in the concrete repair material is preferably 10 to 50% by mass, more preferably 20 to 40% by mass, because the curability can be further improved.

As the unsaturated polyester (B), for example, one obtained by reacting a dibasic acid containing α, β-unsaturated dibasic acid with a polyhydric alcohol by a conventionally known method can be used.

As the α, β-unsaturated dibasic acid, for example, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like can be used. These dibasic acids may be used alone or in combination of two or more.

As the dibasic acid that can be used in addition to the α, β-unsaturated dibasic acid, saturated dibasic acid can be used, for example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, and the like. Telephthalic acid, tetrahydrophthalic acid, tetrahydrohydrochloride phthalic acid, hexahydrophthalic acid, hexahydrohydrochloride phthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12 -Dodecane diic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid, and these. Dialkyl ester of the above can be used. These dibasic acids may be used alone or in combination of two or more.

Examples of the polyvalent alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and 2-methyl-1. , 3-Propanediol, 1,3-Butanjiol, Neopentyl Glico, Hydrogenated Bisphenol A, 1,4-Butanjiol, Bisphenol A alkylene oxide adduct, 1,2 , 3,4-Tetrahydroxybutane, glycerin, trimetyl propane, 1,3-propanediol, 1,2-cyclohexaneglycol, 1,3-cyclohexaneglycol, 1,4-cyclohexaneglycol , 1,4-Cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-geol, 2,6-decalinglycol, 2,7-decalinglycol, etc. Can be done. These polyhydric alcohols may be used alone or in combination of two or more.

The content of the unsaturated polyester (B) in the concrete repair material is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, because the curability can be further improved.

Examples of the monofunctional (meth) acrylic monomer (C) having a ignition point of 70 ° C. or higher include isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, and dicyclopentanyl (meth). ) Acrylate (meth) acrylic monomer having an alicyclic structure such as acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate; 2-ethylbutyl (meth) acrylate, n-pentyl (meth) acrylate , N-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, 3-methylbutyl (meth) acrylate , Isooctyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, neopentyl (meth) acrylate, hexadecyl (meth) acrylate, isoamyl (meth) acrylate and other aliphatic (meth) acrylics. Monomer; 3-methoxybutyl (meth) acrylate), 2-methoxyethyl (meth) acrylate, 3-methoxypropyl (meth) acrylate, 2-methoxybutyl (meth) acrylate, and oxyethylene with an additional molar number of 1 to 1 to For example, methoxypolyethylene glycol (meth) acrylate in the range of 15, methoxypolyethylene glycol (meth) acrylate in the range of 1 to 15 added moles of oxypropylene, ethoxy-diethylene glycol (meth) acrylate, ethyl carbitol (meth) acrylate and the like. (Meta) acrylic monomer having ethylene oxide and / or propylene oxide; having hydroxyl group such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate (meth) ) Acrylic monomer; benzyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol acrylate, phenyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, etc. Aromatic (meth) acrylic monomer; (meth) acrylamide, dimethyl (meth) acrylamide, acryloylmorpholin, dimethylaminopropyl (me) (Ta) Acrylamide, isopropyl (meth) acrylamide, diethyl (meth) acrylamide, diacetone (meth) acrylamide, hydroxyethyl acrylamide and other (meth) acrylic monomers having a nitrogen atom can be used. , A (meth) acrylic monomer having a nitrogen atom, a (meth) acrylic monomer having a hydroxyl group, an ethylene oxide and / or a (meth) acrylic monomer having a propylene oxide is preferable because the odor can be further suppressed. These (meth) acrylic monomers may be used alone or in combination of two or more.

The flash point in the present invention is a value measured by a seta closed flash point measurement.

The content of the (meth) acrylic monomer (C) in the concrete repair material is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, because it can exhibit better curability at low viscosity. , 30-50% by mass is more preferable.

Examples of the polyfunctional (meth) acrylic monomer (D) include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, and 1,3-. Butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol di (meth) acrylate, 1,4-cyclohexanedimethanol di (meth) acrylate, tri Di (meth) acrylate compounds such as methylol propanedi (meth) acrylate; trifunctional or higher polyfunctional (meth) acrylates such as trimethyl propantriacrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate. However, a di (meth) acrylate compound is preferable because excellent wet surface adhesion can be obtained.

The content of the polyfunctional (meth) acrylic monomer (D) in the concrete repair material is preferably 3 to 50% by mass, preferably 5 to 40% by mass, because it can exhibit better curability at low viscosity. More preferably, 10 to 30% by mass is further preferable.

The mass ratio (C / D) of the (meth) acrylic monomer (C) to the polyfunctional (meth) acrylic monomer (D) is such that the balance between curability and wet surface adhesion is further improved. Therefore, 100/0 to 30/70 is preferable, and 90/10 to 50/50 is more preferable.

The cyclodextrin derivative (E) includes, for example, cyclodextrin; the hydrogen atom of the hydroxyl group of the glucose unit of cyclodextrin such as alkylated cyclodextrin, acetylated cyclodextrin, and hydroxyalkylated cyclodextrin is substituted with another functional group. Things can be used. The cyclodextrin skeleton in cyclodextrin and cyclodextrin derivatives includes α-cyclodextrin consisting of 6 glucose units, β-cyclodextrin consisting of 7 glucose units, and γ-cyclodextrin consisting of 8 glucose units. Any of these can be used. These cyclodextrin derivatives (E) may be used alone or in combination of two or more. Among these, methylated β-cyclodextrin is preferable because it has excellent solubility in a resin.

The content of the cyclodextrin derivative (E) in the concrete repair material is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, because the wet surface adhesion is improved.

Examples of the silica fine particles (F) include dry silica and wet silica, but dry silica is preferable because thixotropic properties are further improved.

Further, the average primary particle diameter of the silica fine particles (F) is preferably 5 to 50 nm because the thixotropic property is further improved.

The silica fine particles (F) preferably have a hydrophobic surface because thixotropic properties are further improved.

The content of the silica particles (F) in the concrete repair material is preferably 0.1 to 10% by mass, preferably 0.5 to 5% by mass, because it is excellent in workability.

The concrete repair material of the present invention includes the resin (A), the unsaturated polyester (B), the monofunctional (meth) acrylic monomer (C), and the polyfunctional (meth) acrylic monomer (D). The cyclodextrin derivative (E) and the silica fine particles (F) are contained as essential components, but other additives and the like may be contained if necessary.

Examples of the other additives include polymerization inhibitors, antioxidants, light stabilizers, solvents, rust inhibitors, sensitizers, leveling agents, rhology control agents, tackifiers, antistatic agents, and flame retardant curing agents. Examples thereof include agents, curing accelerators, pigments, fillers, reinforcing materials, aggregates, petroleum waxes and the like.

The active energy rays that cure the concrete repair material of the present invention are ionized radiation such as ultraviolet rays, electron beams, α rays, β rays, and γ rays, but specific energy sources or curing devices include, for example. Bactericidal lamps, fluorescent lamps for ultraviolet rays, carbon arcs, xenon lamps, high-pressure mercury lamps for copying, medium-pressure or high-pressure mercury lamps, ultra-high pressure mercury lamps, electrodeless lamps, metal halide lamps, fluorescent chemical lamps, ultraviolet rays using natural light as a light source, or scanning. Examples include a mold and an electron beam using a curtain type electron beam accelerator.

The concrete repair material of the present invention can be used as a protective material for concrete such as cement concrete, asphalt concrete, mortar concrete, resin concrete, permeable concrete, and ALC (Autoclaved Lightweight Aerated Concrete) board.

Since the concrete protective material of the present invention can obtain a coating film having excellent thixotropic properties, low odor, excellent curability, excellent wet adhesiveness and alkali resistance, it is suitably used as a repair material for various concretes. Can be done.

Hereinafter, the present invention will be described in more detail with reference to specific examples. The acid value was measured in accordance with JIS-K-6901, and the average molecular weight was measured under the following GPC measurement conditions.

[GPC measurement conditions]
Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series and used.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 This "TSKgel G2000" (7.8 mm ID x 30 cm) x 1 Detector: RI (Differential Refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (sample concentration 4 mg / mL tetrahydrofuran solution)
Standard sample: A calibration curve was prepared using the following monodisperse polystyrene.

(Polystyrene monodisperse)
"TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation
"TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

(Synthesis Example 1: Synthesis of resin (A-1) having polymerizable unsaturated groups at both ends)
Epicron 850 (manufactured by DIC Co., Ltd.) 1850 parts by mass, acrylic, which is an epoxy equivalent obtained by the reaction of bisphenol A and epichlorohydrin in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux cooler. 860 parts by mass of acid, 1.36 parts by mass of hydroquinone and 10.8 parts by mass of triethylamine were charged, heated to 120 ° C. and reacted for 10 hours at the same time to obtain epoxy acrylate having a molecular weight of 512 and an acid value of 3.5. A resin (A-1) having a polymerizable unsaturated group at the terminal was obtained.

(Synthesis Example 2: Synthesis of resin (A-2) having polymerizable unsaturated groups at both ends)
A four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet and a reflux condenser was charged with 250 parts by mass of neopentyl glycol, 100 parts by mass of propylene glycol, 390 parts by mass of adipic acid, and 100 parts by mass of maleic anhydride. 0.5 part by mass of monobutyltin oxide was added as an esterification catalyst, and the mixture was reacted at 205 ° C. for 11 hours. Then, the mixture was cooled to 140 ° C., then 25 parts by mass of glycidyl methacrylate was added and reacted for 10 hours to obtain a polyester (meth) acrylate having a number average molecular weight of 4,150, which was a resin having polymerizable unsaturated groups at both ends (A). -2) was obtained.

(Synthesis Example 3: Synthesis of resin (A-3) having polymerizable unsaturated groups at both ends)
A reaction vessel equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser is charged with 500 parts by mass of polypropylene glycol having a number average molecular weight of 1000 and 172 parts by mass of tolylene diisocyanate at 80 ° C. under a nitrogen stream. The reaction was carried out for 2 hours. Since the NCO equivalent was 600, which was almost the theoretical equivalent value, the mixture was cooled to 50 ° C. Under air flow, 0.07 parts by mass of hydroquinone was added, 135 parts by mass of 2-hydroxyethyl methacrylate was added, and the mixture was reacted at 90 ° C. for 4 hours. When NCO% becomes 0.1% or less, 0.07 parts by mass of tertiary butylcatechol is added to form urethane methacrylate having a number average molecular weight of 1,580, which is a resin having a polymerizable unsaturated group at both ends (A). -3) was obtained.

(Synthesis Example 4: Synthesis of unsaturated polyester (B-1))
In a reaction vessel equipped with a thermometer, agitator, an inert gas inlet and a reflux cooler, 231 parts by mass of triethylene glycol, 80 parts by mass of diethylene glycol, 102 parts by mass of phthalic anhydride, and 3-methyltetrahydrophthalic acid. 210 parts by mass, 0.3 part by mass of dibutyl acid hydride and 0.1 part by mass of methylhydroquinone were charged, and the mixture was reacted at 205 ° C. for 4 hours. The mixture was cooled to 150 ° C., 34 parts by mass of maleic anhydride was charged, and the mixture was reacted under 190 ° C. conditions for 4 hours to obtain an unsaturated polyester (B-1) having an acid value of 12.0.

(Example 1: Preparation and evaluation of concrete repair material (1))
In a light-shielding container equipped with a stirrer, a reflux cooling tube, and a thermometer, 30 parts by mass of a resin (A-1) having a polymerizable unsaturated group at both ends, 10 parts by mass of an unsaturated polyester (B-1), and methylated β. 0.5 parts by mass of cyclodextrin, 30 parts by mass of dicyclopentenyloxyethyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 20 parts by mass of diethylene glycol dimethacrylate, silica fine particles ("Leorosea QS-102" manufactured by Tokuyama Co., Ltd., dry silica) Hereinafter, it is abbreviated as silica fine particles (F-1).) 3 parts by mass and 1.5 parts by mass of a rheology control agent (“BYK R-605” manufactured by BYK) are stirred and mixed to prepare a concrete repair material (1). Obtained.

[Evaluation of thixotropic property]
The viscosity of the concrete repair material (1) obtained above was measured with a type i, BM viscometer in Table 7 in accordance with JIS K6901: 2008 "When using the 5.5.1 Brookfield viscometer method". , TI value (viscosity value at 6 rpm / viscosity value at 60 rpm) was calculated, and thixotropic property was evaluated according to the following criteria.
◯: TI value is 4 or more ×: TI value is less than 4

[Preparation of sample for evaluation]
To 50 parts by mass of the concrete repair material (1) obtained above, 0.25 parts by mass of 8% by mass cobalt octylate and 0.5 parts of a toluidin compound isopropanol solution (“RP-191” manufactured by DH Material Co., Ltd.). 1 part by mass and 1 part by mass of a 40% by mass benzoyl peroxide solution were added and mixed to obtain an evaluation sample (1).

[Evaluation of odor]
In an environment of 23 ° C., the odor of the evaluation sample (1) 0.2 kg / m ² obtained above when coated on a slate plate with a brush was sensorially determined, and the odor was evaluated according to the following criteria.
〇: No odor or slight odor ×: Odor

[Evaluation of curability]
The evaluation sample (1) obtained above was spread on a slate plate at an amount of 0.2 kg / m ² with a brush, and under the condition of 23 ° C., the time for tack-free by touch was measured and described below. The curability was evaluated according to the criteria of.
〇: Less than 90 minutes ×: 90 minutes or more

[Evaluation of wet surface adhesion]
The evaluation sample (1) obtained above was soaked in water for one day, then taken out and spread on a pavement plate from which water droplets were wiped off with a brush at an amount of 0.2 kg / m ² . After curing the coating film for one day, it is pulled vertically using a Kenken type tensile tester ("TechnoStar RT-3000LD" manufactured by Sanko Techno Co., Ltd.), the peel strength is measured, and it is wetted according to the following criteria. The surface adhesiveness was evaluated.
〇 1.5N / mm ² or more x 1.5N / mm less than ²

[Evaluation of alkali resistance]
The specimen obtained by applying 0.2 kg / m ² of the evaluation sample (1) obtained above to a 70 × 70 × 20 mm mortar with a brush was semi-immersed in a saturated calcium hydroxide aqueous solution, and 40. It was cured for 30 days in a ℃ environment. After 30 days, the appearance of the specimen was visually observed, and the alkali resistance was evaluated according to the following criteria.
〇: No change ×: Swelling or cracking

(Examples 2 and 3: Preparation and evaluation of concrete repair materials (2) and (3))
Except for changing the resin (A-1) having a polymerizable unsaturated group at both ends used in Example 1 to the resin (A-2) or (A-3) having a polymerizable unsaturated group at both ends. After preparing the concrete repair materials (2) and (3) in the same manner as in Example 1, each physical property was evaluated.

(Comparative Examples 1 and 2: Preparation and evaluation of concrete repair materials (R1) and (R2))
The concrete repair materials (R1) and (R2) were prepared and then each physical property was evaluated in the same manner as in Example 1 except that the formulation of Example 1 was the one shown in Table 1.

Table 1 shows the compositions and evaluation results of the concrete repair materials (1) to (3) and (R1) to (R2) obtained above.

It was confirmed that the concrete repair materials of the present invention of Examples 1 to 3 have excellent thixotropic properties, low odor, excellent curability, and excellent wet adhesiveness and alkali resistance.

Comparative Example 1 is an example in which the unsaturated polyester (B) and the (meth) acrylic monomer are not contained, but the viscosity is high, the thixotropic property is insufficient, and the workability is inferior.

Comparative Example 2 is an example in which the polyfunctional (meth) acrylic monomer (D) is not contained, but the alkali resistance of the obtained coating film is insufficient.

Claims (4)

Resin (A) having a polymerizable unsaturated group at both ends, unsaturated polyester (B), monofunctional (meth) acrylic monomer (C) having a ignition point of 70 ° C. or higher, polyfunctional (meth) acrylic single amount. A concrete repair material containing a body (D), a cyclodextrin derivative (E), and silica fine particles (F). The concrete repair material according to claim 1, wherein the resin (A) is one or more resins selected from the group consisting of epoxy (meth) acrylate, polyester (meth) acrylate, and urethane (meth) acrylate. The concrete repair material according to claim 1 or 2, wherein the content of the polyfunctional (meth) acrylic monomer (D) is 3 to 50% by mass. The concrete repair material according to any one of claims 1 to 3, wherein the content of the silica fine particles (F) is 0.5 to 30% by mass.