WO2015064191A1

WO2015064191A1 - Concrete repair material

Info

Publication number: WO2015064191A1
Application number: PCT/JP2014/072246
Authority: WO
Inventors: 博美入江; 松本　高志
Original assignee: Dic株式会社
Priority date: 2013-10-30
Filing date: 2014-08-26
Publication date: 2015-05-07
Also published as: CN105658602B; JP5743043B1; JPWO2015064191A1; TWI652301B; TW201518385A; CN105658602A

Abstract

The present invention addresses the issue of providing a concrete repair material having excellent adhesion not only to dried concrete but also to wet concrete. The present invention provides a concrete repair material characterized by containing: a radically polymerizable resin (A); a radically polymerizable monomer (B); and a cyclodextrin and/or a derivative thereof (C). This concrete repair material exhibits excellent adhesion not only to dried concrete but also to wet concrete. In addition, this concrete repair material has excellent workability, excellent tensile properties and other mechanical strength, and has very little odor. The amount of cyclodextrin and/or derivative thereof (C) is ideally within the range of 0.1-20 parts by mass relative to 100 parts by mass of the total content of radically polymerizable resin (A) and radically polymerizable monomer (B).

Description

Concrete repair material

The present invention relates to a concrete repair material having excellent adhesion to wet concrete.

In the civil engineering and building industry, such as repairing concrete structures, the degree of attention to infrastructure reinforcement is increasing against the background of the accident of the fall of the Isogo tunnel. Since concrete structures constructed after the period of high economic growth are 50 years old in the next 30 years, the demand for concrete repairs is increasing.

As the current concrete repair material, epoxy resin-based repair materials and (meth) acrylic-based repair materials occupy most (for example, see Patent Document 1). Although these concrete repair materials have excellent adhesion to dry concrete, there is a problem that the desired adhesion cannot be obtained when wet in the rain or when used in humid environments such as sewers. .

JP 2002-201802 A

The problem to be solved by the present invention is to provide a concrete repair material having excellent adhesion to not only dry concrete but also wet concrete.

The present invention provides a concrete repair material comprising a radical polymerizable resin (A), a radical polymerizable monomer (B), and cyclodextrin and / or a derivative thereof (C). is there.

The concrete repair material of the present invention has excellent adhesion to wet concrete (hereinafter referred to as “wet surface adhesion”) as well as adhesion to dry concrete (hereinafter abbreviated as “dry surface adhesion”). Abbreviated as “sex”.). In addition, the concrete repair material of the present invention is excellent in mechanical strength such as workability and tensile properties, and has very little odor.

The concrete repair material of the present invention contains a radical polymerizable resin (A), a radical polymerizable monomer (B), and cyclodextrin and / or a derivative thereof (C) as essential components.

As the radical polymerizable resin (A), for example, unsaturated polyester, epoxy (meth) acrylate, polyester (meth) acrylate, urethane (meth) acrylate, or the like can be used. These resins may be used alone or in combination of two or more.

As the unsaturated polyester, for example, those obtained by reacting a dibasic acid containing an 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, a saturated dibasic acid can be used. For example, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, Terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,12 -Dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4'-biphenyldicarboxylic acid, and these The dialkyl ester or the like can be used. These dibasic acids may be used alone or in combination of two or more.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and 2-methyl-1. 1,3-propanediol, 1,3-butanediol, neopentyl glycol, hydrogenated bisphenol A, 1,4-butanediol, alkylene oxide adduct of bisphenol A, 1,2 , 3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4, '- Geo - le, 2,6-decalin glycolate - le, 2,7-decalin glyco - can be used Le like. These polyhydric alcohols may be used alone or in combination of two or more.

As the epoxy (meth) acrylate, a bisphenol type epoxy compound or an epoxy compound obtained by mixing a bisphenol type epoxy compound and a novolac type epoxy compound with an unsaturated monobasic acid by a conventionally known method is used. 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 reaction of epichlorohydrin and bisphenol A or bisphenol F, methyl epichlorohydrin and bisphenol A or bisphenol F, and the like. A dimethyl glycidyl ether type epoxy compound obtained by reacting bisphenol A, an epoxy compound obtained by reacting an alkylene oxide adduct of bisphenol A with epichlorohydrin or methyl epichlorohydrin, and the like can be used. These epoxy compounds may be used alone or in combination of two or more.

As the novolac 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.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, cinnamic acid, crotonic acid, monomethylmalate, monopropylmalate, monobutenemalate, sorbic acid, mono (2-ethylhexyl) malate, and the like. 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. Each of them has a (meth) acryloyl group at the terminal.

The saturated dibasic acid, α, β-unsaturated dibasic acid and polyhydric alcohol can be the same as those used for the synthesis of the unsaturated polyester.

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

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

As the polyol, for example, polyether polyol, polycarbonate polyol, polyester polyol, acrylic polyol, caprolactone polyol, polybutadiene polyol, polyisoprene 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 phenylene diisocyanate, diphenylmethane diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, xylylene Aliphatic or cycloaliphatic diisocyanates such as diisocyanate and tetramethylxylylene diisocyanate; formalin condensation of xylylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, polyphenylene polymethylene polyisocyanate, methylene diphenyl disissocyanate Body, and aromatic polyisocyanates carbodiimide-modified products such as 4,4'-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. (Meth) acrylic acid alkyl esters having the following hydroxyl groups; 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)). An acryloyloxymethyl) ethyl isocyanate etc. can be used. These compounds may be used alone or in combination of two or more.

In the present invention, “(meth) acrylate” refers to one or both of methacrylate and acrylate, and “(meth) acryloyl group” refers to one or both of methacryloyl group and acryloyl group. “Acrylic acid” refers to one or both of methacrylic acid and acrylic acid, and “(meth) acrylic compound” refers to one or both of an acrylic compound and a methacrylic compound.

The number average molecular weight of the radical polymerizable resin (A) is preferably in the range of 500 to 10,000, more preferably in the range of 800 to 5,000, from the viewpoint of further improving the tensile properties and wet surface adhesion. Is more preferable, and the range of 1,000 to 3,000 is even more preferable. In addition, the number average molecular weight of the said radical polymerizable resin (A) shows the value measured on condition of the following by the gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"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 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(Standard polystyrene)
"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

Examples of the radical polymerizable monomer (B) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, and hexyl. (Meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, decyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-ethoxyethyl ( (Meth) acrylate, 2-cyanoethyl (meth) acrylate, cyclohexyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, polycaprolactone (meth) acrylate (Meth) acrylic such as relate, diethylene glycol monomethyl ether mono (meth) acrylate, dipropylene glycol monomethyl ether mono (meth) acrylate, 2-ethylhexyl carbitol (meth) acrylate, tris (2-hydroxyethyl) isocyanur (meth) acrylate Monomer: (Meth) acrylic monomers having a boiling point of 100 ° C. or higher, such as dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, phenoxyethyl (meth) acrylate, and the like can be used. These monomers may be used alone or in combination of two or more. As the radical polymerizable monomer (B), it is preferable to use methyl (meth) acrylate and / or a (meth) acrylic monomer having a boiling point of 100 ° C. or higher from the viewpoint that the room temperature drying property can be further improved. Furthermore, it is more preferable to use a (meth) acrylic monomer having a boiling point of 100 ° C. or higher from the viewpoint that the odor during construction can be further improved.

The mass ratio [(A) / (B)] between the radical polymerizable resin (A) and the radical polymerizable monomer (B) is 10/90 to 10 from the viewpoint of tensile properties and wet surface adhesion. A range of 90/10 is preferable, and a range of 20/80 to 80/20 is more preferable.

The cyclodextrin and / or derivative (C) is an essential component for imparting wet surface adhesion.

Examples of the cyclodextrin and / or its derivative (C) include, 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. Those substituted with a group 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 compounds may be used alone or in combination of two or more. Among these, a cyclodextrin derivative is used from the viewpoint that compatibility with the radical polymerizable resin (A) and the radical polymerizable monomer (B) can be further improved and wet surface adhesion can be further improved. It is preferable to use an alkylated cyclodextrin.

The degree of substitution of other functional groups in the cyclodextrin derivative is 0.3 from the viewpoint of compatibility with the radical polymerizable resin (A) and the radical polymerizable monomer (B) and wet surface adhesion. It is preferably in the range of ˜14 / glucose, more preferably in the range of 0.5 to 8 / glucose.

As the alkylated cyclodextrin, for example, methyl-α-cyclodextrin, methyl-β-cyclodextrin, methyl-γ-cyclodextrin and the like can be used. These compounds may be used alone or in combination of two or more.

As the acetylated cyclodextrin, for example, monoacetyl-α-cyclodextrin, monoacetyl-β-cyclodextrin, monoacetyl-γ-cyclodextrin and the like can be used. These compounds may be used alone or in combination of two or more.

As the hydroxyalkylated cyclodextrin, for example, hydroxypropyl-α-cyclodextrin, hydroxypropyl-β-cyclodextrin, hydroxypropyl-γ-cyclodextrin and the like can be used. These compounds may be used alone or in combination of two or more.

As content of the said cyclodextrin and / or its derivative (C), compatibility with the said radical polymerizable resin (A) and the said radical polymerizable monomer (B), tensile physical property, and wet surface adhesiveness are more. From the viewpoint of further improvement, the content is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass in total of the radical polymerizable resin (A) and the radical polymerizable monomer (B). The range of 0.5 to 10 parts by mass is more preferred, and the range of 1.5 to 8 parts by mass is even more preferred.

The concrete repair material used in the present invention contains the radical polymerizable resin (A), the radical polymerizable monomer (B), and the cyclodextrin and / or its derivative (C) as essential components. You may contain another additive as needed.

Examples of the other additive include a curing agent, a curing accelerator, a polymerization inhibitor, a pigment, a thixotropic agent, an antioxidant, a solvent, a filler, a reinforcing material, an aggregate, a flame retardant, and petroleum wax. be able to.

As the curing agent, an organic peroxide is preferably used from the viewpoint of surface dryness at room temperature. For example, a diacyl peroxide compound, a peroxy ester compound, a hydroperoxide compound, a dialkyl peroxide compound, a ketone peroxide. A compound, a peroxyketal compound, an alkyl perester compound, a carbonate compound, or the like can be used. These curing agents may be used alone or in combination of two or more. Among these, it is preferable to use a hydroperoxide compound from the viewpoint of storage stability.

The amount of the curing agent used is preferably in the range of 0.001 to 10% by mass in the concrete repair material from the viewpoint of curability.

The curing accelerator is a substance having an action of decomposing an organic peroxide of the curing agent by a redox reaction and facilitating generation of active radicals. For example, a cobalt organic acid such as cobalt naphthenate and cobalt octylate is used. Salts, metal soaps such as zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, metal chelates such as vanadium acetyl acetate, cobalt acetyl acetate, iron acetylacetonate; aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-dimethyl-p-toluidine ethylene oxide adduct, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bi (2-hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, N, N-substituted anilines such as triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline; N, N-substituted-p-toluidine, An amine compound such as 4- (N, N-substituted amino) benzaldehyde can be used. These curing accelerators may be used alone or in combination of two or more.

The amount of the curing accelerator used is preferably in the range of 0.001 to 10% by mass in the concrete repair material from the viewpoint of curability.

Hereinafter, the present invention will be described in more detail with reference to examples.

[Synthesis Example 1] Synthesis of urethane methacrylate (A-1) Polybutadiene diol having a number average molecular weight of 1,400 in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser. Was added in an amount of 500 parts by mass and 114 parts by mass of tolylene diisocyanate were reacted at 80 ° C. for 4 hours under a nitrogen stream. It was confirmed that the isocyanate group equivalent was 600, which was almost the theoretical value, and then cooled to 50 ° C. Next, 0.07 parts by mass of hydroquinone and 89 parts by mass of 2-hydroxyethyl methacrylate were added under an air stream and reacted at 90 ° C. for 5 hours. When the isocyanate% became 0.1% or less, 0.07 part by mass of tertiary butyl catechol was added to obtain urethane methacrylate (A-1) having a number average molecular weight of 2607.

[Synthesis Example 2] Synthesis of urethane methacrylate (A-2) Polypropylene glycol having a number average molecular weight of 1,000 in a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, an air inlet and a reflux condenser. Of 500 parts by mass and 174 parts by mass of tolylene diisocyanate were charged and reacted at 80 ° C. for 4 hours under a nitrogen stream. It was confirmed that the isocyanate group equivalent was 600, which was almost the theoretical value, and then cooled to 50 ° C. Next, 0.07 parts by mass of hydroquinone and 131 parts by mass of 2-hydroxyethyl methacrylate were added under an air stream and reacted at 90 ° C. for 5 hours. When the isocyanate percentage became 0.1% or less, 0.07 part by mass of tertiary butylcatechol was added to obtain urethane methacrylate (A-2) having a number average molecular weight of 1584.

[Example 1]
30 parts by mass of urethane methacrylate (A-1) obtained in Synthesis Example 1, 70 parts by mass of dicyclopentenyloxyethyl methacrylate, and 1 part by mass of “methyl-β-cyclodextrin” (manufactured by Junsei Chemical Co., Ltd.) By mixing and stirring, a radical polymerizable resin composition was obtained. Next, 20 parts by mass of the radical polymerizable resin composition was weighed and adjusted to 25 ° C., and then 1 part by mass of cumene hydroperoxide was added to obtain a concrete repair material.

[Examples 2 to 3 and Comparative Examples 1 to 3]
A concrete repair material was obtained in the same manner as in Example 1 except that the type and / or amount of the radical polymerizable resin, radical polymerizable monomer and cyclodextrin and / or derivative thereof were changed as shown in Table 1. It was.

[Adhesion evaluation method]
Two 40 mm × 40 mm × 80 mm mortar plates were faced to create a 1 mm gap and fixed with tape. The concrete repair materials obtained in the examples and comparative examples were poured into the gaps thus produced and cured for one week in an environment of 23 ° C. and humidity of 50%. After curing, an adhesion test was performed in accordance with JIS A6024: 2008, the adhesive strength (MPa) and the fracture state were observed, and the dry surface adhesion was evaluated. In addition, using a mortar plate soaked purely for 24 hours, injecting a concrete repair material in the same manner and curing for one week in an environment of 23 ° C. and 50% humidity, the adhesive strength (MPa) is similarly applied. And the destruction state was observed and wet surface dryness was evaluated.

Examples 1 to 3 which are concrete repair materials of the present invention are not only dry surface adhesive. It was found that the wet surface dryness was also excellent.

On the other hand, Comparative Examples 1 to 3 did not contain cyclodextrin and / or its derivative (C), but wet surface drying was poor.

Claims

A concrete repair material comprising a radical polymerizable resin (A), a radical polymerizable monomer (B), and cyclodextrin and / or a derivative thereof (C).
The content of the cyclodextrin and / or its derivative (C) is 0.1 to 20 masses with respect to 100 mass parts in total of the radical polymerizable resin (A) and the radical polymerizable monomer (B). The concrete repair material according to claim 1, which is in the range of a part.
The concrete repair material according to claim 1, wherein the cyclodextrin and / or its derivative (C) is an alkylated cyclodextrin.