阅读说明：本技术 自由基聚合性树脂组合物及结构物修补材料 (Radical polymerizable resin composition and structural repair material ) 是由 海野笃 新林良太 于 2019-08-20 设计创作，主要内容包括：提供在用于混凝土结构物的修补的情况下,即使在低温环境下也能够施工,高强度,由固化引起的收缩率低,并且可以抑制裂缝的自由基聚合性树脂组合物以及结构物修补材料。一种自由基聚合性树脂组合物以及含有该自由基聚合性树脂组合物、有机过氧化物、和填充材料(Z)的结构物修补材料,上述自由基聚合性树脂组合物含有自由基聚合性树脂(A)、自由基聚合性单体(B)、以及通式(I)所示的含有羟基的芳香族叔胺(C),上述自由基聚合性树脂(A)包含选自乙烯基酯树脂、氨基甲酸酯(甲基)丙烯酸酯树脂、和聚酯(甲基)丙烯酸酯树脂中的至少1种,上述自由基聚合性单体(B)包含具有异冰片基的不饱和化合物(B1)；上述自由基聚合性树脂组合物含有合计75质量％以上的自由基聚合性树脂(A)和自由基聚合性单体(B)。(Provided are a radical polymerizable resin composition and a structural repair material which can be used for repairing a concrete structure, can be applied even in a low-temperature environment, has high strength and low shrinkage rate due to curing, and can suppress cracks. A radically polymerizable resin composition comprising a radically polymerizable resin (A) containing at least 1 selected from the group consisting of a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin, a radically polymerizable monomer (B) containing an unsaturated compound having an isobornyl group (B1), and a hydroxyl group-containing aromatic tertiary amine (C) represented by the general formula (I); the radical polymerizable resin composition contains 75% by mass or more of a radical polymerizable resin (A) and a radical polymerizable monomer (B) in total.)

1. A radically polymerizable resin composition comprising a radically polymerizable resin A, a radically polymerizable monomer B, and a hydroxyl-containing tertiary aromatic amine C represented by the following general formula (I),

the radical polymerizable resin A contains at least 1 selected from a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin,

the radically polymerizable monomer B comprises an unsaturated compound B1 having an isobornyl group,

the radical polymerizable resin composition contains 75 mass% or more of a radical polymerizable resin A and a radical polymerizable monomer B in total,

in the formula (I), R¹Representation H, CH₃Or OCH₃，R²Represents a hydroxyalkyl group having 1 to 10 carbon atoms, R³Represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms.

2. The radical polymerizable resin composition according to claim 1, wherein the unsaturated compound B1 having an isobornyl group contains an ethylenically unsaturated bond.

3. The radical polymerizable resin composition according to claim 2, wherein the isobornyl group-containing unsaturated compound B1 is isobornyl (meth) acrylate.

4. The radically polymerizable resin composition according to any one of claims 1 to 3, wherein the content of the isobornyl-containing unsaturated compound B1 is 10% by mass or more and 65% by mass or less relative to the total amount of the radically polymerizable resin A and the radically polymerizable monomer B.

5. The radically polymerizable resin composition according to any one of claims 1 to 4, wherein a content of the isobornyl-containing unsaturated compound B1 in the radically polymerizable monomer B is 30% by mass or more and 90% by mass or less.

6. The radically polymerizable resin composition according to any one of claims 1 to 5, wherein the radically polymerizable monomer B2 other than the unsaturated compound B1 having an isobornyl group in the radically polymerizable monomer B comprises at least 1 selected from the group consisting of a mono (meth) acrylate, a di (meth) acrylate and a tri (meth) acrylate.

7. The radically polymerizable resin composition according to any one of claims 1 to 6, wherein the radically polymerizable monomer B2 other than the isobornyl-containing unsaturated compound B1 in the radically polymerizable monomer B comprises at least 1 selected from the group consisting of tricyclodecenyloxyethyl (meth) acrylate, (meth) acryloylmorpholine, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.

8. The radically polymerizable resin composition according to any one of claims 1 to 7, wherein R in the formula (I)³A hydroxyalkyl group having 1 to 10 carbon atoms.

9. The radically polymerizable resin composition according to any one of claims 1 to 8, wherein the content of the hydroxyl group-containing aromatic tertiary amine C is 0.1 to 10% by mass.

10. The radically polymerizable resin composition according to any one of claims 1 to 9, wherein the radically polymerizable resin A comprises a vinyl ester resin.

11. The radically polymerizable resin composition according to any one of claims 1 to 10, further comprising at least 1 selected from the group consisting of a wax, an amine other than the hydroxyl group-containing aromatic tertiary amine C, a solvent, a polymerization inhibitor, a coupling agent, a curing accelerator, and an antioxidant as an additive component.

12. A structure repair material comprising: the radically polymerizable resin composition X according to any one of claims 1 to 11, an organic peroxide Y, and a filler Z.

13. The structure repair material according to claim 12, the filler material Z comprising at least 1 selected from the group consisting of an inorganic thixotropic agent, an organic compound fiber, calcium carbonate, cement, silica sand and silica.

14. The structure repair material according to claim 12 or 13, wherein the content of the filler Z is 100 to 700 parts by mass with respect to 100 parts by mass of the radical polymerizable resin composition X.

15. The structure repair material according to any one of claims 12 to 14, wherein the content of the organic peroxide Y is 0.1 parts by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the radical polymerizable resin composition X.

Technical Field

The present invention relates to a radical polymerizable resin composition and a structure repair material comprising the radical polymerizable resin composition.

Background

In recent years, concrete structures have been remarkably deteriorated by the influence of neutralization, salt damage, and the like, and thus, they have been in a state requiring repair. In particular, in cold regions, cracks and the like are likely to occur due to freeze-thawing of moisture contained in concrete, and deterioration of concrete is likely to further progress due to chlorides such as calcium chloride and sodium chloride used as snow-melting agents. Therefore, repair of concrete structures is frequently required in cold regions.

As one of methods for repairing a concrete structure, a method of injecting a filler into a crack of a concrete structure is known. As the injection material, generally, an injection material containing an epoxy resin is used.

However, epoxy resins tend to have a significantly reduced curing speed in a low-temperature environment. Further, since the viscosity of the injection material using the epoxy resin becomes very high in a low-temperature environment, workability when injecting the injection material up to the deep part of the crack has a problem.

As a repair material that cures at a low temperature, patent document 1 describes a composition containing a radical polymerizable resin composition, a hydroxyl group-containing aromatic tertiary amine, an organic peroxide, and an inorganic filler. The radical polymerizable resin composition comprises at least 1 radical polymerizable resin selected from a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin, and a radical polymerizable unsaturated monomer having 2 or more (meth) acryloyl groups in the molecule.

Patent document 2 describes a resin composition containing a resin component, an aromatic tertiary amine, and an organic peroxide. The resin component contains at least 1 kind of radical reactive resin selected from vinyl ester resin, urethane (meth) acrylate resin and polyester (meth) acrylate resin, and a radical polymerizable unsaturated monomer having a (meth) acryloyloxy group in the molecule.

Documents of the prior art

Patent document

Patent document 1: international publication WO2016/133094

Patent document 2: japanese patent laid-open publication No. 2017-214441

Disclosure of Invention

Problems to be solved by the invention

As described above, the radical polymerizable resin composition described in patent document 1 uses a radical polymerizable unsaturated monomer having 2 or more (meth) acryloyl groups in the molecule, and high compressive strength is obtained. However, VE5 and VE6 in examples described later in the present application contain diethylene glycol dimethacrylate as the radical polymerizable monomer (B) in a large amount, but it is clear from comparative examples 5 and 6 using the same that there is room for improvement in linear shrinkage, that is, shrinkage due to curing.

With respect to the resin composition described in patent document 2, for example, a mixture of the resin component of example 1 of patent document 2, the aromatic tertiary amine (C), and the organic peroxide (D) corresponds to a mixture of the resin composition (X) and the organic peroxide of comparative examples 1 and 3 described later in the present application, and with respect to example 2 of patent document 2, it also corresponds to comparative examples 2 and 4 described later in the present application. In addition, in the present application, comparative examples 1 to 4 have room for improvement in compressive strength at-10 ℃ as described later.

Accordingly, an object of the present invention is to provide a radical polymerizable resin composition and a structural repair material which can be applied even under a low-temperature environment, have high strength, have a low shrinkage rate due to curing, and can suppress cracks when used for repairing a concrete structure.

Means for solving the problems

In order to achieve the above object, the present invention is configured as follows.

[1] A radically polymerizable resin composition comprising a radically polymerizable resin (A), a radically polymerizable monomer (B), and a hydroxyl-containing tertiary aromatic amine (C) represented by the following general formula (I),

the radical polymerizable resin (A) contains at least 1 selected from the group consisting of a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin,

the radically polymerizable monomer (B) contains an unsaturated compound (B1) having an isobornyl group,

the radical polymerizable resin composition contains 75% by mass or more of a radical polymerizable resin (A) and a radical polymerizable monomer (B) in total.

(in the above formula (I), R¹Representation H, CH₃Or OCH₃，R²Represents a hydroxyalkyl group having 1 to 10 carbon atoms, R³Represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms)

[2] The radical polymerizable resin composition according to the above [1], wherein the isobornyl group-containing unsaturated compound (B1) contains an ethylenically unsaturated bond.

[3] The radical polymerizable resin composition according to the above [2], wherein the isobornyl group-containing unsaturated compound (B1) is isobornyl (meth) acrylate.

[4] The radically polymerizable resin composition according to any one of [1] to [3], wherein the content of the isobornyl-containing unsaturated compound (B1) is 10% by mass or more and 65% by mass or less relative to the total amount of the radically polymerizable resin (A) and the radically polymerizable monomer (B).

[5] The radically polymerizable resin composition according to any one of the above [1] to [4], wherein the content of the isobornyl-containing unsaturated compound (B1) in the radically polymerizable monomer (B) is 30% by mass or more and 90% by mass or less.

[6] The radically polymerizable resin composition according to any one of the above [1] to [5], wherein the radically polymerizable monomer (B2) other than the unsaturated compound (B1) having an isobornyl group in the radically polymerizable monomer (B) contains at least 1 selected from the group consisting of a mono (meth) acrylate, a di (meth) acrylate and a tri (meth) acrylate.

[7] The radically polymerizable resin composition according to any one of the above [1] to [6], wherein the radically polymerizable monomer (B2) other than the unsaturated compound (B1) having an isobornyl group in the radically polymerizable monomer (B) comprises at least 1 selected from the group consisting of tricyclodecenyloxyethyl (meth) acrylate, (meth) acryloylmorpholine, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.

[8]According to the above [1]～[7]The radically polymerizable resin composition according to any one of the above formulas (I), wherein R is³A hydroxyalkyl group having 1 to 10 carbon atoms.

[9] The radically polymerizable resin composition according to any one of the above [1] to [8], wherein the content of the hydroxyl group-containing aromatic tertiary amine (C) is 0.1 to 10% by mass.

[10] The radically polymerizable resin composition according to any one of the above [1] to [9], wherein the radically polymerizable resin (A) comprises a vinyl ester resin.

[11] The radically polymerizable resin composition according to any one of the above [1] to [10], further comprising at least 1 selected from the group consisting of a wax, an amine other than the hydroxyl group-containing aromatic tertiary amine (C), a solvent, a polymerization inhibitor, a coupling agent, a curing accelerator, and an antioxidant as an additive component.

[12] A structure repair material comprising: the radically polymerizable resin composition (X) according to any one of the above [1] to [11], the organic peroxide (Y), and the filler (Z).

[13] The structure repairing material according to the above [12], wherein the filler (Z) comprises at least 1 selected from the group consisting of inorganic thixotropic agents, organic compound fibers, calcium carbonate, cement, silica sand and silica.

[14] The structure repair material according to the above [12] or [13], wherein the content of the filler (Z) is 100 to 700 parts by mass per 100 parts by mass of the radical polymerizable resin composition (X).

[15] The structure repair material according to any one of the above [12] to [14], wherein the content of the organic peroxide (Y) is 0.1 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the radical polymerizable resin composition (X).

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a radical polymerizable resin composition and a structural material repair material can be provided which can be used for repairing a concrete structure, can be applied even in a low-temperature environment, has high strength and low shrinkage rate due to curing, and can suppress cracks.

Drawings

Fig. 1 is a flowchart showing an example of a method for repairing a structure using the structure repairing material according to the present invention.

Detailed Description

The embodiments of the present invention are described in detail below.

The term "cured" refers to a polymer in which molecules contained in raw materials are chemically bonded to each other to form a network structure. The term "dry" means that a part of components contained in a mixture, a composition, and the like volatilizes without accompanying a chemical reaction. In addition, curing and drying may be performed simultaneously, and for example, a component that does not undergo a chemical reaction or a component generated by a chemical reaction may volatilize while curing is performed.

The term "(meth) acrylate" means acrylate or methacrylate, "(meth) acrylic acid" means acrylic acid or methacrylic acid, and the term "(meth) acryloyl" means acryloyl or methacryloyl.

The "radical polymerizability" is a property that components contained in the composition are cured by radical polymerization under certain conditions, and examples of the conditions for curing include heating and irradiation with light. The "radically polymerizable component" refers to, for example, a component having radical polymerizability, which is composed of the radically polymerizable resin (a) and the radically polymerizable monomer (B) described below. That is, the amount of the "radical polymerizable component" refers to the total amount of the radical polymerizable resin (a) and the radical polymerizable monomer (B).

The term "ethylenically unsaturated bond" refers to a double bond between carbon atoms other than the carbon atoms forming the aromatic ring.

The term "laitance layer" refers to a porous and brittle mud film layer formed by precipitation of components contained in concrete on the surface of the concrete.

< 1. Structure repair Material

The structure repair material according to the present embodiment includes a radical polymerizable resin composition (X), an organic peroxide (Y), and a filler (Z). Hereinafter, these components contained in the structure repair material according to the present embodiment will be described.

< 1-1. radical polymerizable resin composition (X) >

The radical polymerizable resin composition (X) (hereinafter, may be simply referred to as resin composition (X)) contains a radical polymerizable resin (a), a radical polymerizable monomer (B) containing an unsaturated compound (B1) having an isobornyl group, and a hydroxyl group-containing aromatic tertiary amine (C) represented by the following general formula (I).

In the above formula (I), R¹Representation H, CH₃Or OCH₃，R²Represents a hydroxyalkyl group having 1 to 10 carbon atoms, R³Represents an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms.

In the resin composition (X), the total content of the radically polymerizable resin (a) and the radically polymerizable monomer (B) (content of the radically polymerizable component) is 75% by mass or more, preferably 85% by mass or more, and more preferably 95% by mass or more. The resin composition (X) preferably does not contain a component corresponding to the filler (Z) described later.

< 1-1-1. radical polymerizable resin (A) >

The radical polymerizable resin (a) contains at least 1 selected from a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin. The radical polymerizable resin (a) preferably contains a vinyl ester resin, and more preferably a vinyl ester resin. Hereinafter, a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin, which are used as the radical polymerizable resin (a), will be described.

< 1-1-1(a) vinyl ester resin

The vinyl ester resin is also sometimes referred to as an epoxy (meth) acrylate resin, and is, for example, a product obtained by esterifying an epoxy compound with a carboxylic acid having 1 or more ethylenically unsaturated bonds or a derivative thereof. Examples of the carboxylic acid derivative include carboxylic acid halides and carboxylic acid anhydrides. That is, the vinyl ester resin is a polymer of an epoxy compound having an ethylenically unsaturated bond bonded to at least one terminal of an epoxy polymer via an ester bond. Here, the ethylenically unsaturated bond is preferably located at the end of the molecule, and more preferably a vinyl group, an allyl group, (meth) acryloyl group, or (meth) acryloyloxy group. Such a vinyl ester resin is described in, for example, "ポリエステル colophony ハンドブック (japanese industrial new , published in 1988)", and "paint dictionary (compiled by kyowa, published in 1993)".

The epoxy compound used as a raw material of the vinyl ester resin is preferably a diepoxy compound, and examples thereof include bisphenol a type glycidyl ether and novolac type glycidyl ether. More specifically, the epoxy compound includes bisphenol a diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, tetrabromobisphenol a diglycidyl ether, novolac-type diglycidyl ether, cresol novolac-type diglycidyl ether, and the like. Examples of the other epoxy compounds include 1, 6-hexanediol diglycidyl ether, 1, 4-cyclohexanedimethanol diglycidyl ether, 5-norbornane-2, 3-dimethanol diglycidyl ether, tricyclodecanedimethanol diglycidyl ether, alicyclic diepoxy carbonate, alicyclic diepoxy acetal, and alicyclic diepoxy carboxylate.

These epoxy compounds may be used alone in 1 kind, or may be used in combination in 2 or more kinds, but it is preferable to use bisphenol a diglycidyl ether in combination with a linear diglycidyl ether. Because the flexibility and toughness of the cured structure repair material are improved. From this viewpoint, the epoxy compound is more preferably a mixture of bisphenol a diglycidyl ether and 1, 6-hexanediol diglycidyl ether.

The carboxylic acid having an ethylenically unsaturated bond used as a raw material of the vinyl ester resin is preferably one in which 2 hydrogen atoms are bonded to a carbon atom forming the ethylenically unsaturated bond, that is, the ethylenically unsaturated bond is located at a molecular terminal, and more preferably the ethylenically unsaturated bond forms a vinyl group or an allyl group.

Examples of the monocarboxylic acid having 1 ethylenically unsaturated bond include acrylic acid and methacrylic acid. Examples of monocarboxylic acids having a plurality of ethylenically unsaturated bonds include half ester carboxylic acids obtained by the reaction of trimethylolpropane diallyl ether with phthalic anhydride or a derivative thereof. Examples of the derivatives of phthalic anhydride include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, etc., and tetrahydrophthalic anhydride is preferred. These carboxylic acids may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Further, the carboxylic acid having an ethylenically unsaturated bond may be a dicarboxylic acid. Examples of the dicarboxylic acid having an ethylenically unsaturated bond include those esterified by reacting 1 carboxyl group in a 3-membered carboxylic acid such as citric acid with a compound having an ethylenically unsaturated bond and a hydroxyl group such as trimethylolpropane diallyl ether.

When a derivative of a carboxylic acid having an ethylenically unsaturated bond is used instead of the carboxylic acid having an ethylenically unsaturated bond, a halide such as a chloride or a bromide of the above carboxylic acid, or the above carboxylic anhydride may be used.

Vinyl ester resins can be obtained by reacting a carboxylic acid having no ethylenically unsaturated bond with a part of epoxy groups at the terminal of an epoxy polymer as a raw material for the purpose of adjusting the degree of crosslinking of a cured product or the like. Examples of the carboxylic acid having no ethylenically unsaturated bond include adipic acid, sebacic acid, and phthalic anhydride.

< 1-1-1(b) > urethane (meth) acrylate resin

The urethane (meth) acrylate resin can be obtained, for example, by reacting a polyisocyanate with a polyol to produce a polyurethane having an isocyanate group at the end, and reacting a hydroxyl group-containing (meth) acrylate with the polyurethane. When the hydroxyl group-containing (meth) acrylate is reacted, a hydroxyl group-containing allyl ether compound may be further added. That is, the urethane (meth) acrylate resin is a polyurethane having a (meth) acryloyl group at least at either end of the molecule.

The method for synthesizing the urethane (meth) acrylate resin is not limited to this, and for example, the urethane resin can be obtained by reacting a polyisocyanate with a polyol to produce a polyurethane having a hydroxyl group at the end, and reacting a (meth) acrylate containing an isocyanate group with the polyurethane.

Examples of the polyisocyanate used as a raw material of the urethane (meth) acrylate resin include 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 4' -diphenylmethane diisocyanate, 1, 6-hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate, and examples of commercially available polyisocyanates include ミリオネート MT (manufactured by Nippon ポリウレタン Co., Ltd.), バーノック D-750 (manufactured by DIC Co., Ltd.), クリスボン NK (manufactured by DIC Co., Ltd.), デスモジュール L (manufactured by Suzuki コベストロウレタン Co., Ltd.), コロネート L (manufactured by Chilo ソー Co., Ltd.), and the like, タケネート D102 (manufactured by Mitsui chemical Co., Ltd.), イソネート 143L (manufactured by Mitsubishi ケミカル Co., Ltd.), デュラネート (registered trademark) series (manufactured by Asahi Kasei corporation) and the like. These polyisocyanates may be used alone in 1 kind, or may be used in combination in 2 or more kinds. The polyisocyanate used herein is preferably a diisocyanate, and among them, from the viewpoint of cost, 4' -diphenylmethane diisocyanate is more preferable.

Examples of the polyhydric alcohol used as a raw material of the urethane (meth) acrylate resin include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1, 3-propanediol, 1, 3-butanediol, bisphenol a-propylene oxide adduct, bisphenol a-ethylene oxide adduct, 1,2,3, 4-tetrahydroxybutane, glycerol, trimethylolpropane, 1, 3-butanediol, 1, 2-cyclohexanediol, 1, 3-cyclohexanediol, 1, 4-cyclohexanediol, p-xylylene glycol, dicyclohexyl-4, 4-diol, 2, 6-decahydronaphthalene diol, 2, 7-decahydronaphthalene diol, and the like. Further, examples of the polyol include polyester polyol and polyether polyol. More specifically, there may be mentioned glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene oxide adduct, and the like. These polyhydroxy compounds may be used alone in 1 kind, or may be used in combination of 2 or more kinds. The polyol used here is preferably a linear diol, and more preferably polypropylene glycol.

Examples of the hydroxyl group-containing (meth) acrylate used as a raw material of the urethane (meth) acrylate resin include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, di (meth) acrylate of tris (hydroxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, and glycerol (mono) (meth) acrylate, and commercially available products include ブレンマー (registered trademark) series (manufactured by Nichikoku corporation). Among these (meth) acrylates, the (meth) acrylates having 1 hydroxyl group and 1 (meth) acryloyl group each in the molecule, that is, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 3-hydroxybutyl (meth) acrylate are more preferable, and 2-hydroxypropyl (meth) acrylate is particularly preferable. These hydroxyl group-containing (meth) acrylates may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Specific examples of the hydroxyl group-containing allyl ether compound used as a raw material of the urethane (meth) acrylate resin include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1, 2-butanediol monoallyl ether, 1, 3-butanediol monoallyl ether, hexanediol monoallyl ether, octanediol monoallyl ether, trimethylolpropane diallyl ether, glycerol diallyl ether, pentaerythritol triallyl ether, and the like. These hydroxyl group-containing allyl ether compounds may be used alone in an amount of 1 kind, or may be used in combination in an amount of 2 or more kinds.

< 1-1-1 (c.) polyester (meth) acrylate resin

The polyester (meth) acrylate resin is obtained, for example, by reacting a (meth) acrylate having a hydroxyl group or an epoxy group with a polyester having a carboxyl group at the terminal, which is obtained from a polycarboxylic acid and a polyhydric alcohol. The polyester (meth) acrylate resin may be obtained by reacting (meth) acrylic acid with a polyester having a hydroxyl group at the end, which is obtained from a polycarboxylic acid and a polyhydric alcohol, for example. That is, the polyester (meth) acrylate resin is a polyester having a (meth) acryloyl group at least either end of the molecular chain.

The polycarboxylic acid used as a raw material of the polyester (meth) acrylate resin preferably contains at least one of an aromatic dicarboxylic acid and an aliphatic saturated dicarboxylic acid, and more preferably contains an aromatic dicarboxylic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, and anhydrides thereof. Examples of the aliphatic dicarboxylic acid include adipic acid, sebacic acid, and anhydrides thereof. These polycarboxylic acids may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The polycarboxylic acid used as a raw material of the polyester (meth) acrylate resin may include an aliphatic unsaturated dicarboxylic acid, and examples of the aliphatic unsaturated dicarboxylic acid include fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, and the like, and anhydrides thereof. These aliphatic unsaturated dicarboxylic acids may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The polycarboxylic acid used as a raw material of the polyester (meth) acrylate resin may include a polycarboxylic acid other than the above-mentioned dicarboxylic acid, or may be used in combination with the above-mentioned dicarboxylic acid and a polycarboxylic acid other than the above-mentioned dicarboxylic acid.

The polyhydric alcohol used as a raw material of the polyester (meth) acrylate resin is preferably a diol, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1, 2-butanediol, 1, 3-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 2-methyl-1, 3-propanediol, 2-dimethyl-1, 3-propanediol, cyclohexane-1, 4-dimethanol, an ethylene oxide adduct of bisphenol a, and a propylene oxide adduct of bisphenol a. These polyols may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The (meth) acrylate having an epoxy group used as a raw material of the polyester (meth) acrylate resin is preferably a (meth) acrylate having no unsaturated bond other than an α, β -unsaturated bond, more preferably having 1 epoxy group in the molecule, and examples thereof include glycidyl methacrylate and the like.

The hydroxyl group-containing (meth) acrylate used as a raw material of the polyester (meth) acrylate resin may be the same compound as the compound exemplified as the hydroxyl group-containing (meth) acrylate used as a raw material of the urethane (meth) acrylate resin, and only 1 kind may be used alone, or 2 or more kinds may be used in combination.

Examples of the (meth) acrylic acid used as a raw material of the polyester (meth) acrylate resin include acrylic acid, methacrylic acid, and itaconic acid. These (meth) acrylic acids may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

Among the polyester (meth) acrylate resins obtained from the above-mentioned raw materials, a bisphenol a type polyester (meth) acrylate resin is preferable from the viewpoint of improving the mechanical strength (compressive strength, hardness, etc.) of the cured structure repair material.

< 1-1-2. radically polymerizable monomer (B) >

The radical polymerizable monomer (B) can suitably reduce the viscosity of the resin composition (X) and the structure repair material, and can improve the strength, chemical resistance, water resistance, and the like of the cured structure repair material. The radical polymerizable monomer (B) includes an unsaturated compound (B1) (hereinafter, also referred to as an unsaturated compound (B1)) having an isobornyl group. The radical polymerizable monomer (B) does not contain a component corresponding to the radical polymerizable resin (a).

The content of the radical polymerizable monomer (B) in the resin composition (X) is preferably 40% by mass or more. The resin composition (X) has a viscosity suitable for good workability even in a low-temperature (e.g., -25 ℃) atmosphere, and has good wettability with respect to a filler (Z) described later. From this viewpoint, the content of the radical polymerizable monomer (B) is more preferably 50% by mass or more, and still more preferably 55% by mass or more.

The content of the radical polymerizable monomer (B) in the resin composition (X) is preferably 90% by mass or less. Since the high strength and water resistance of the cured structural repair material can be maintained. From this viewpoint, the content of the radical polymerizable monomer (B) is more preferably 80% by mass or less, and still more preferably 70% by mass or less.

< 1-1-2(a) >. unsaturated compound having isobornyl group (B1) >

The unsaturated compound (B1) is a compound having an isobornyl group and an ethylenically unsaturated bond. The unsaturated compound (B1) can improve the strength of the resin composition (X) after curing without greatly increasing the shrinkage of the resin composition (X) due to curing. The unsaturated compound (B1) is preferably a (meth) acrylate having an isobornyl group, and more preferably isobornyl (meth) acrylate. Isobornyl refers to a residue obtained by removing a hydroxyl group from isoborneol.

The content of the unsaturated compound (B1) in the radically polymerizable components (a) + (B) is preferably 10% by mass or more. Because the strength of the cured repair material is increased. From this viewpoint, the content of the unsaturated compound (B1) in the radically polymerizable components (a) + (B) is more preferably 20% by mass or more, and still more preferably 30% by mass or more.

The content of the unsaturated compound (B1) in the radically polymerizable components (a) + (B) is preferably 65% by mass or less. Since the shrinkage of the repair material caused by curing becomes small. From this viewpoint, the content of the unsaturated compound (B1) in the radically polymerizable components (a) + (B) is more preferably 55% by mass or less, and still more preferably 45% by mass or less.

The content of the unsaturated compound (B1) in the radically polymerizable monomer (B) is preferably 30% by mass or more. Because the strength of the cured repair material is increased. From this viewpoint, the content of the unsaturated compound (B1) in the radical polymerizable monomer (B) is more preferably 40% by mass or more, and still more preferably 50% by mass or more.

The content of the unsaturated compound (B1) in the radically polymerizable monomer (B) is preferably 90% by mass or less. Since the shrinkage of the repair material caused by curing becomes small. From this viewpoint, the content of the unsaturated compound (B1) in the radical polymerizable monomer (B) is more preferably 80% by mass or less, and still more preferably 70% by mass or less.

< 1-1-2(B) other radically polymerizable monomer (B2) >

The radically polymerizable monomer (B) may contain another radically polymerizable monomer (B2) in addition to the unsaturated compound (B1). The other radical polymerizable monomer (B2) contains an ethylenically unsaturated bond. Examples of the other radically polymerizable monomer (B2) include unsaturated carboxylic acid esters, unsaturated dicarboxylic acid monoesters, styrene, α -methylstyrene, aromatic vinyl compounds, glycidyl (meth) acrylate, and the like. The other radically polymerizable monomer (B2) preferably contains a (meth) acrylate, and more preferably contains at least 1 selected from the group consisting of a mono (meth) acrylate, a di (meth) acrylate, and a tri (meth) acrylate.

The mono (meth) acrylate is not particularly limited, and examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, n-lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like, Cyclopentyl (meth) acrylate, benzyl (meth) acrylate, tricyclodecenyl oxyethyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. These (meth) acrylate monomers may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The di (meth) acrylate is not particularly limited, and examples thereof include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 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, glycerol di (meth) acrylate, and mixtures thereof, Ethoxylated polypropylene glycol di (meth) acrylate, 2-bis [4- (methacryloyloxyethoxy) phenyl ] propane, 2-bis [4- (methacryloyloxy-diethoxy) phenyl ] propane, 2-bis [4- (methacryloyloxy-polyethoxy) phenyl ] propane, 2-bis [4- (acryloyloxy-diethoxy) phenyl ] propane, 2-bis [4- (acryloyloxy-polyethoxy) phenyl ] propane, and the like.

The tri (meth) acrylate is not particularly limited, and examples thereof include trimethylolpropane tri (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, epsilon-caprolactone-modified tris- (2-acryloyloxyethyl) isocyanurate, pentaerythritol tri (meth) acrylate, and the like.

From the viewpoint of workability and compressive strength, the other radical polymerizable monomer (B2) more preferably contains at least 1 selected from the group consisting of tricyclodecenyloxyethyl (meth) acrylate, (meth) acryloylmorpholine, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate.

In addition to the above, as the other radically polymerizable monomer (B2), dimethylolpropane tetra (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, dipentaerythritol poly (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like may be used within a range in which the object of the present invention can be achieved.

< 1-1-3 > aromatic tertiary amine (C) containing hydroxyl group

The hydroxyl group-containing aromatic tertiary amine (C) is represented by the following formula (I).

In the formula (I), R¹Is H, CH₃Or OCH₃Is preferably CH₃More preferably CH in para position₃。R²A hydroxyalkyl group having 1 to 10 carbon atoms, preferably a hydroxyalkyl group having 3 or less carbon atoms. R³Is an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms, preferably an alkyl group or hydroxyalkyl group having 4 or less carbon atoms, more preferably a hydroxyalkyl group having 4 or less carbon atoms. Further preferred is R²And R³Are the same hydroxyalkyl groups.

The hydroxyl group-containing aromatic tertiary amine (C) represented by the general formula (I) is not particularly limited, and examples thereof include N-methyl-N- β -hydroxyethylaniline, N-butyl-N- β -hydroxyethylaniline, N-methyl-N- β -hydroxyethyl-p-toluidine, N-butyl-N- β -hydroxyethyl-p-toluidine, N-methyl-N- β -hydroxypropylaniline, N-methyl-N- β -hydroxypropyl-p-toluidine, N-bis (β -hydroxyethyl) aniline, N-bis (β -hydroxypropyl) aniline, N-bis (β -hydroxyethyl) -p-toluidine, N-bis (β -hydroxyethyl) p-toluidine, N-, N, N-bis (β -hydroxypropyl) -p-toluidine, N-diisopropanol-p-toluidine, N-bis (β -hydroxyethyl) -p-anisidine, and the like. Among them, N-bis (β -hydroxyethyl) -p-toluidine and N, N-bis (β -hydroxypropyl) -p-toluidine are preferable from the viewpoint of low-temperature curability.

These hydroxyl group-containing aromatic tertiary amines (C) may be used alone in 1 kind or in combination of 2 or more kinds.

The content of the hydroxyl group-containing aromatic tertiary amine (C) in the resin composition (X) is preferably 0.1 to 10% by mass, more preferably 0.1 to 5.0% by mass, and still more preferably 0.2 to 3.0% by mass. By including the hydroxyl group-containing aromatic tertiary amine (C), the curing reaction of the resin composition (X) is promoted, and workability is improved.

< 1-1-4 > additional component in resin composition (X)

Examples of the additive component contained in the resin composition (X) include a wax, an amine other than the hydroxyl group-containing aromatic tertiary amine (C) (hereinafter, may be referred to as "an amine of any component"), a solvent, a polymerization inhibitor, a coupling agent, a curing accelerator, an antioxidant, and the like, and can be used as long as the object of the present invention can be achieved.

Examples of the wax include, but are not limited to, petroleum wax (paraffin wax, microcrystalline wax, and the like), vegetable wax (candelilla wax, rice wax, wood wax, and the like), animal wax (beeswax, spermaceti, and the like), mineral wax (montan wax, and the like), and synthetic wax (polyethylene wax, amide wax, and the like). More specifically, paraffin wax having a melting point of about 20 to 80 ℃ is exemplified as the wax, and commercially available products include 115 ° F paraffin wax, 125 ° F paraffin wax, manufactured by japan ceresin co., ltd, and BYK (registered trademark) -S-750, BYK (registered trademark) -S-740, BYK (registered trademark) -S-780, manufactured by ビックケミー · ジャパン co. These waxes may be used alone in 1 kind, or may be used in combination in 2 or more kinds, and for example, waxes having different melting points may be used in combination.

When the resin composition (X) contains a wax, the content of the wax in the resin composition (X) is not particularly limited, but is preferably 0.01 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass. By adding the wax to the resin composition (X), the drying time of the structure repair material can be shortened.

Examples of the optional amine include aromatic tertiary amines other than the aromatic tertiary amine (C) having a hydroxyl group, and examples thereof include aromatic tertiary amines having no hydroxyl group. Examples of the amine as an optional component include dimethylaniline and dimethyl-p-toluidine. These may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the resin composition (X) contains an amine as an optional component, the content of the amine as an optional component in the resin composition (X) is preferably 0.01 to 5.0% by mass, and more preferably 0.1 to 3.0% by mass. By containing the amine as an optional component, the polymerization of the radically polymerizable component contained in the resin composition (X) is promoted by the decomposition reaction of the peroxide caused by the contact between the organic peroxide (Y) and the amine as an optional component, which will be described later, and the surface drying property and curability of the structure repair material are further improved.

The solvent is not particularly limited, and examples thereof include alkyl ether acetates such as ethyl acetate, ethers such as tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, hydrocarbons such as benzene, toluene, xylene, octane, decane and dodecane, petroleum solvents such as petroleum ether, naphtha, hydrogenated naphtha and solvent naphtha, lactic acid esters such as methyl lactate, ethyl lactate and butyl lactate, dimethylformamide and N-methylpyrrolidone. These solvents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the resin composition (X) contains a solvent, the content of the solvent in the resin composition (X) is not particularly limited, but is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5.0% by mass. The viscosity of the resin composition (X) can be adjusted to a range suitable for the operation by the solvent, and when the resin composition (X) is used in combination with a wax, particularly paraffin wax, the solubility and dispersibility of the wax can be improved.

Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylcatechol, 2, 6-di-t-butyl-4-methylphenol, and the like.

When the resin composition (X) contains a polymerization inhibitor, the content of the polymerization inhibitor in the resin composition (X) is not particularly limited, but is preferably 0.001 to 1.0% by mass, and more preferably 0.005 to 0.5% by mass. The polymerization inhibitor can inhibit the progress of curing of the structure repair material and ensure the working time.

The coupling agent is preferably a silane coupling agent. Examples of the silane coupling agent include aminosilane, vinylsilane, epoxysilane, and acrylic silane. These coupling agents may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

When the resin composition (X) contains a coupling agent, the content of the coupling agent in the resin composition (X) is not particularly limited, and may be preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass. The strength of the structure repair material is improved by the coupling agent.

The curing accelerator is not particularly limited, and examples thereof include β -diketone compounds such as acetylacetone, ethyl acetoacetate, α -acetyl- γ -butyrolactone, N-pyrrolidinylacetoacetamide (N- ピロジニノアセトアセタミド), and N, N-dimethylacetoacetamide. These curing accelerators may be used alone in an amount of 1 kind, or may be used in combination in an amount of 2 or more kinds.

When the resin composition (X) contains a curing accelerator, the content of the curing accelerator in the resin composition (X) is not particularly limited, but is preferably 0.01 to 10% by mass, and more preferably 0.1 to 5.0% by mass. The curing accelerator can shorten the curing time of the resin composition (X).

The resin composition (X) may contain a polymerization catalyst used for the synthesis of the radical polymerizable resin (a) after the synthesis of the radical polymerizable resin (a), as long as the performance of the resin composition (X) and the repair material is not significantly impaired. Examples of the polymerization catalyst include 2,4, 6-tris (dimethylaminomethyl) phenol, triphenylphosphine and the like.

< 1-2. organic peroxide (Y) >

The organic peroxide (Y) functions as a room-temperature radical polymerization initiator by being used in combination with the hydroxyl group-containing aromatic tertiary amine (C). The organic peroxide (Y) is preferably mixed with the resin composition (X) immediately before the repair process of the structure. Because the curing of the resin composition (X) is suppressed before the use of the structure repair material.

The organic peroxide (Y) is not particularly limited, and examples thereof include those classified into ketone peroxides, peroxyketals, hydroperoxides, diallyl peroxides, diacyl peroxides, peroxyesters, and peroxydicarbonates. More specific examples of the organic peroxide include dibenzoyl peroxide, dicumyl peroxide, diisopropyl peroxide, di-t-butyl peroxide, 1-bis (t-butylperoxy) -3,3, 5-trimethylcyclohexane, 2, 5-dimethyl-2, 5-bis (t-butylperoxy) hexyl-3, 3-isopropyl hydroperoxide, t-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3, 5-trimethylhexanoyl peroxide, lauryl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, isopropyl benzene hydroperoxide, and isopropyl benzene hydroperoxide, T-butyl peroxybenzoate, and the like. Among them, at least 1 selected from dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide and t-butyl peroxybenzoate is preferable.

The 1-minute half-life temperature of the organic peroxide (Y) according to the present embodiment is preferably 80 ℃ or higher. The organic peroxide (Y) has good storage stability at room temperature. From this viewpoint, the 1-minute half-life temperature of the organic peroxide (Y) is more preferably 100 ℃ or higher, and still more preferably 110 ℃ or higher. The 1-minute half-life temperature of the organic peroxide (Y) according to the present embodiment is preferably 250 ℃. Since the low-temperature curability of the structure repair material becomes good. From this viewpoint, the 1-minute half-life temperature of the organic peroxide (Y) is more preferably 200 ℃ or less, and still more preferably 170 ℃ or less.

These organic peroxides (Y) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. Examples of the mixture of 2 or more species include a mixture of dibenzoyl peroxide, benzoyl peroxide-m-methylbenzoyl peroxide and m-toluyl peroxide, a mixture of cumene hydroperoxide and t-butyl peroxybenzoate and methyl ethyl ketone peroxide, and the like.

In order to sufficiently cure the resin composition (X), the amount of the organic peroxide (Y) added is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, and still more preferably 1.0 part by mass or more, per 100 parts by mass of the resin composition (X). In order to reduce the cost and to increase the strength of the cured structure repair material, the content of the organic peroxide (Y) is preferably 10 parts by mass or less, more preferably 8.0 parts by mass or less, and still more preferably 6.0 parts by mass or less.

< 1-3. filling Material (Z) >

The filler (Z) may contain a substance that functions as a thixotropic agent, a reinforcing material, or the like, in addition to a substance that functions as an aggregate. Examples of the filler (Z) include inorganic thixotropic agents, organic compound fibers, calcium carbonate, cement, silica sand, silica and the like. Among them, at least 1 selected from the group consisting of inorganic thixotropic agents, calcium carbonate, cement, silica sand and silica is preferably contained, and from the viewpoint of cost and material availability, at least 1 selected from the group consisting of calcium carbonate, cement and silica sand is more preferably contained, and among them, at least any one of calcium carbonate and silica sand is particularly preferably contained. These fillers (Z) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

The content of the filler (Z) in the structure repair material is preferably 100 parts by mass or more per 100 parts by mass of the resin composition (X). The flow of the structure repair material can be suppressed, and deformation and drop of liquid droplets due to the weight of the structure repair material when applied to a wall surface or a ceiling surface can be suppressed. From this viewpoint, the content of the filler (Z) is more preferably 200 parts by mass or more, and still more preferably 300 parts by mass or more, per 100 parts by mass of the resin composition (X). Here, when 2 or more components are contained as the filler (Z), the content of the filler (Z) is the total content of all components corresponding to the filler (Z) (the same applies to the following description of the upper limit).

The content of the filler (Z) in the structure repair material is preferably 700 parts by mass or less with respect to 100 parts by mass of the resin composition (X). The ease of handling of the structure repair material and the workability in coating can be ensured, and the filler (Z) and the object to be repaired can be sufficiently bonded by curing the resin composition (X). From this viewpoint, the content of the filler (Z) is more preferably 600 parts by mass or less, and still more preferably 500 parts by mass or less, per 100 parts by mass of the resin composition (X).

Hereinafter, an example of a component corresponding to the filler (Z) will be described, but the filler (Z) is not limited to the following.

Examples of the inorganic thixotropic agent include hydrophobic fumed silica (キャボジール TS-720, manufactured by キャボット Co., Ltd.), and hydrophilic fumed silica (AEROSIL (registered trademark) 200, manufactured by Nippon アエロジル Co., Ltd.), and the like. Examples of the organic thixotropic agent include polyethylene cotton fibers ("ケミベスト" made by Mitsui chemical Co., Ltd.), hydrogenated castor oil, and the like. Among them, hydrophobic silica and hydrophilic silica, ケミベスト, are preferable. These thixotropic agents may be used alone in an amount of 1 kind, or may be used in combination of 2 or more kinds. In particular, the hydrophilic silica can be used in combination with a thixotropic aid such as BYK (registered trademark) R605 (manufactured by ビックケミー & ジャパン).

When a thixotropic agent is added as the filler (Z), the amount of the thixotropic agent added is not particularly limited, but is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5.0 parts by mass, based on 100 parts by mass of the resin composition (X). By containing the thixotropic agent, the structure repairing material is imparted with good thixotropy, and workability is improved.

The calcium carbonate improves the viscosity of the structure repair material and improves the coating workability by using a trowel. The number average particle diameter of calcium carbonate is preferably 10 μm or less.

When calcium carbonate is added as the filler (Z), the amount of calcium carbonate added is not particularly limited, but is preferably 10 to 100 parts by mass, and more preferably 15 to 70 parts by mass, based on 100 parts by mass of the resin composition (X).

Examples of the organic compound fiber include a polyethylene cotton-like fiber (manufactured by mitsui chemical corporation, ケミベスト) and the like. From the viewpoint of workability, it is desirable that the length of the organic compound fiber in the short side direction is 100nm or more. The organic compound fiber imparts thixotropy to the resin, thereby improving workability of application of the structure repair material and suppressing dripping.

When the organic compound fiber is added as the filler (Z), the amount of the organic compound fiber added is not particularly limited, but is preferably 0.1 to 10 parts by mass, and more preferably 0.2 to 5.0 parts by mass, based on 100 parts by mass of the resin composition (X).

The cement improves the workability of a trowel made of the structure repair material. The cement preferably contains portland cement.

When cement is added as the filler (Z), the amount of cement added to 100 parts by mass of the resin composition (X) is not particularly limited, but is preferably 10 to 100 parts by mass, and more preferably 40 to 80 parts by mass.

Silica sand imparts heat resistance to the structure repair material and improves the compressive strength. As the silica sand, at least any one of silica sand nos. 4 to 8 is preferably used, and at least any one of silica sand nos. 5 to 7 is more preferably used. In addition, silica sand having different 2 size distributions can be used, and silica sand No. 5 and silica sand No. 7 are particularly preferably used.

When silica sand is added as the filler (Z), the amount of silica sand added to 100 parts by mass of the resin composition (X) is not particularly limited, but is preferably 100 to 500 parts by mass, and more preferably 200 to 400 parts by mass. When 2 or more types of silica sand having different size distributions are used as the silica sand, it is preferable to use the same amount on a mass basis.

The filler (Z) is not limited to the above-mentioned materials, and alumina, aluminum hydroxide, aluminum, titanium, or the like may be added. The amount of each component contained in the filler (Z) can be appropriately adjusted according to the specification of the structure repair material, the required performance, the effect of each component added, and the like.

< 1-4. other Components >

The structure repair material may contain components other than those described above as optional components within a range not to impair the effects of the present invention. Examples of the optional components include, but are not limited to, a photopolymerization initiator, a reinforcing material, and various additives.

< 2. method for repairing structure (method for using structure repairing material) >

Fig. 1 is a flowchart showing an example of the structure repairing method according to the present embodiment. The structure repairing method according to the present embodiment includes a preparation step S1 of the structure repairing material, a coating step S2 of coating the structure with the structure repairing material, and a curing step S3 of curing the structure repairing material. The atmospheric temperature in these steps is not particularly limited, and the structure repair material according to the present embodiment is suitable for use in a low-temperature environment of-10 ℃.

In the preparation step S1, the resin composition (X), the organic peroxide (Y), and the filler (Z) are mixed to prepare a structure repair material. The order of addition of each is not particularly limited within the range in which the effects of the present invention can be obtained. For example, the filler (Z) may be mixed with the resin composition (X) before the organic peroxide (Y) is added. The filler (Z) may be added to the mixture after the resin composition (X) and the organic peroxide (Y) are mixed. The resin composition (X), the organic peroxide (Y), and the filler (Z) may be mixed at the same time. The order of mixing these components may be determined as appropriate in consideration of the reactivity of the resin composition (X) and the organic peroxide (Y), the physical properties such as the viscosity of the resin composition (X), the organic peroxide (Y), and the filler (Z), and the like. However, before the structure repair material is used, it is preferable to mix the resin composition (X) with the filler (Z) before adding the organic peroxide (Y) in order to suppress the progress of curing.

In the coating step S2, the structure repair material is coated on the surface of the structure. The construction surface of the structure is preferably previously subjected to removal of a fragile layer such as a stain, an adhering substance, and a laitance layer. Further, it is preferable to perform a foundation treatment for finishing the working surface before this step. Examples of the base treatment include a treatment in which the surface of a rough or contaminated structure is shaved by a disc sander, sandblasting, water jetting, or the like. By this treatment, the adhesion strength of the cured structure repair material to the construction surface can be improved.

The basis weight (weight per unit area) of the structure repair material in the present embodiment is preferably 5 to 30kg/m²More preferably 10 to 25kg/m²More preferably 13 to 23kg/m². Examples of the coating method in this step include, but are not limited to, a coating method using a tool such as a trowel, a roller, a brush, and a doctor blade, and spraying and dipping.

In the curing step S3, the structure repair material applied to the structure is cured. The curing method is not particularly limited, and there are a method in which the construction surface is covered with a curing sheet or the like and left for a sufficient time for curing. Here, the time and suitable temperature at the time of standing differ depending on the components and composition contained in the resin composition (X). In addition, for example, in the case where the resin composition (X) contains a photopolymerization initiator, curing is efficiently performed by irradiation with light. In this case, the wavelength range of the irradiated light can be determined as appropriate depending on the components of the resin composition (X) and the kind of photopolymerization initiator. As a method for confirming the solidification of the structure repairing material, there is a method of confirming that the structure repairing material is not plastically deformed by finger contact without leaving any trace.

Examples

The present invention will be described in further detail below with reference to examples, but the present invention is not limited thereto.

< 1. Synthesis of radical polymerizable resin (A) >

A reaction apparatus equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer was charged with bisphenol A epoxy resin (product name "エポミック (trade name) R140P", available from Mitsui chemical Co., Ltd., epoxy equivalent 189): 151g of 1, 6-hexanediol diglycidyl ether (product name "SR-16" manufactured by Kagaku Kogyo Co., Ltd., epoxy equivalent 157): 188g, trimethylolpropane diallyl ether (manufactured by Osaka ソー ダ Co., Ltd., product name "ネオアリル (trade mark) T-20"): 129g, tetrahydrophthalic anhydride (product name "リカシッド TH" available from Nissan chemical Co., Ltd.): 91g of tricyclodecenyloxyethyl methacrylate (B2-1) (product name "ファンクリル FA-512 MT" from Hitachi chemical Co., Ltd.): 145g, and the temperature was raised to 90 ℃. While maintaining this temperature, 2,4, 6-tris (dimethylaminomethyl) phenol (product name "セイクオール TDMP" from Seiko chemical Co., Ltd.) was added: 1.0g of methylhydroquinone (manufactured by Tokyo chemical Co., Ltd.): 0.3g, the temperature was raised to 110 ℃ while circulating air, and the reaction was carried out. After 1 hour from the start of the reaction, the acid value became 25 mgKOH/g. Here, methacrylic acid (manufactured by Kokai corporation クラレ) was added: 120g, 2,4, 6-tris (dimethylaminomethyl) phenol: after 1.0g, the reaction was carried out at 130 ℃ with increasing the temperature. The acid value was measured in accordance with JIS K0070: 1992, the neutralization titration method described in section 3.1 (the same applies to the measurement of the acid value described below) is performed by taking out a small amount (about 0.1 mL) from the reaction solution, and therefore the amount taken out for the measurement does not affect the entire amount (the same applies to the measurement of the acid value described below). After 4 hours from the temperature reached 130 ℃, the acid value became 14 mgKOH/g. Here, the reaction was terminated to obtain a mixture (. alpha.) containing 679g of the vinyl ester resin (A-1), 145g of tricyclodecenyloxyethyl methacrylate (B2-1), 2.0g of 2,4, 6-tris (dimethylaminomethyl) phenol and 0.3g of methylhydroquinone.

< 2. preparation of a radically polymerizable mixture

The mixture (α) synthesized as described above was mixed with each component shown in table 1 to prepare radically polymerizable mixtures VE1 to VE 6.

< 3. examples and comparative examples >

After the radical polymerizable mixtures VE1 to VE6 were left at-10 ℃ for 24 hours and the temperature of the mixtures was set to-10 ℃, the components and amounts shown in table 2 were mixed in examples 1 to 4 and comparative examples 1 to 6 at-10 ℃ to prepare a structure prosthesis.

< 4. evaluation method >

The structural repair materials produced in examples 1 to 4 and comparative examples 1 to 6 were evaluated as follows.

Curing at-10 ℃ of < 4-1 >

The concrete slab from which the laitance layer was removed was cured in an atmosphere of-10 c for 24 hours. Then, the compounded structure repair material shown in table 2 was applied to the concrete slab at a thickness of 10mm using a metal trowel under the temperature condition. Then, the concrete slab coated with the structure repairing material was left at-10 ℃ and after 6 hours and 12 hours from the completion of the coating of the structure repairing material, the curing of the structure repairing material was judged. In addition, when it is determined that the structure repair material is cured after 6 hours, the determination of curing after 12 hours is not necessary, and therefore, it is not performed. The determination of the curing is performed by confirming that no trace of the finger remains on the structure repair material by the finger contact, that is, the structure repair material is not plastically deformed by the finger contact. The case where the structural repair material was judged to have cured after 6 hours from the completion of the application of the structural repair material was regarded as o, the case where the curing was judged to have started after 12 hours had elapsed was regarded as Δ, and the case where the curing was not judged to have been cured after 12 hours had elapsed was regarded as x. The results of evaluation of the-10 ℃ curability of the structure repair materials according to the examples and comparative examples are shown in table 2.

Compressive strength of < 4-2 > -10 ℃

By JIS a 1181: method 2005 "レジンコンクリート" test (method for testing resin concrete) "section 7.1" what is described in "intensity, static elasticity, and absorbency for the sample for test" for molding the sample for testing the thermally conductive properties and the absorbency for the sample test produces samples for evaluation of compressive strength at-10 ℃. Specifically, the structure repair material was filled in a stainless steel mold at-10 ℃ atmosphere, the mold filled with the structure repair material was cured at-10 ℃ atmosphere for 24 hours, and then the mold was released to prepare a cylindrical test piece having a diameter of 75mm and a height of 150 mm. The compressive strength [ MPa ] at-10 ℃ was measured using the sample in accordance with "Yen column supply specimen による intensity strain test (based on the compressive strength test of a cylindrical sample)" item 8.1 of the above test method. The evaluation results of the-10 ℃ compressive strength of the structural repair materials according to the examples and comparative examples are shown in table 2.

< 4-3. Linear shrinkage >

The structure repair materials according to the examples and comparative examples were each prepared by mixing a mixture of: 60mm, height: 60mm, length: pouring in a mold with a 240mm cuboid mold cavity at-10 ℃, curing for 24 hours in an atmosphere of-10 ℃, demolding, and measuring the size of the cured structure repairing material. The linear shrinkage rate was calculated from the length of the cured molded article with respect to the size of the cavity of the mold (mold size) 240mm by the following calculation formula.

Linear shrinkage rate [% ] × (length [ mm ] -mold size [ mm ] of cured molded article/mold size [ mm ]

The results of evaluating the linear shrinkage rates of the structural repair materials according to the examples and comparative examples are shown in table 2.

< 4-4 crack evaluation >

From JIS a 5371: 2016, and the resulting concrete slab 60mm X300 mm was cured at-10 ℃ for 24 hours after removing the floating layer. Then, the structure repair materials according to the respective examples and comparative examples were applied to the concrete slab with a metal trowel having a thickness of 30mm under the temperature condition. The case where no crack was generated on the surface of the concrete slab opposite to the surface to which the structure repair material was applied 24 hours after the application was referred to as "none", and the case where a crack was generated as "present". The crack evaluation results are shown in table 2.

< 5. evaluation result >

Referring to Table 2, the structural repair materials of examples 1 to 4 all had good curability at-10 ℃ and high compressive strength at-10 ℃, and had low linear shrinkage due to curing and no cracks.

In comparative examples 1 and 3, which contained isobornyl methacrylate (B1-1) but phenoxyethyl methacrylate (B2-2) and acryloylmorpholine (B2-3), as the radical polymerizable monomer (B), the compressive strength at-10 ℃ was low.

The radical polymerizable monomer (B) contained not isobornyl methacrylate (B1-1) but phenoxyethyl methacrylate (B2-2) and diethylene glycol dimethacrylate (B2-4), and the linear shrinkage rate due to curing was high in comparative examples 2 and 4 to 6. Further, cracks caused by curing were generated in comparative examples 5 and 6 containing diethylene glycol dimethacrylate (B2-4) in a large amount.

As described above, according to the structure repair material of the present invention, when used for repairing a concrete structure, it can be applied even in a low-temperature environment, has high strength and low shrinkage rate due to curing, and can suppress cracks.