阅读说明：本技术 结构物的修补方法 (Method for repairing structure ) 是由 大谷和男 海野笃 黑木一博 于 2019-08-20 设计创作，主要内容包括：本发明提供一种在应用于混凝土结构物的情况、在大温度范围内能够确保短工期并且高可靠性的、结构物的修补方法。包含以下工序：将自由基聚合性树脂组合物(A)涂布在结构物上形成第1修复层的第1修复层形成工序；在使第1修复层固化前,在第1修复层上涂布含有自由基聚合性树脂组合物(Ax)和填充材料(B)的修复材料(X)而形成第2修复层的第2修复层形成工序；以及使自由基聚合性树脂组合物(A)和自由基聚合性树脂组合物(Ax)固化的修复层固化工序,所述(A)和所述(Ax)中都含有：自由基聚合性树脂(a1)、自由基聚合性不饱和单体(a2)、含有羟基的芳香族叔胺(a3)、以及有机过氧化物(a4),所述(A)和所述(Ax)中所述(a1)和(a2)的合计含有率为75质量％以上。(The invention provides a method for repairing a concrete structure, which can ensure a short period of time and high reliability in a large temperature range when applied to the concrete structure. Comprises the following steps: a1 st repair layer forming step of forming a1 st repair layer by applying the radical polymerizable resin composition (a) to the structure; a2 nd repair layer forming step of applying a repair material (X) containing a radical polymerizable resin composition (Ax) and a filler (B) on the 1 st repair layer to form a2 nd repair layer before curing the 1 st repair layer; and a repair layer curing step of curing a radical polymerizable resin composition (a) and a radical polymerizable resin composition (Ax), wherein both of (a) and (Ax) contain: a radically polymerizable resin (a1), a radically polymerizable unsaturated monomer (a2), a hydroxyl group-containing tertiary aromatic amine (a3), and an organic peroxide (a4), wherein the total content of the (a1) and the (a2) in the (A) and the (Ax) is 75 mass% or more.)

1. A method for repairing a structure, comprising the steps of:

a1 st repair layer forming step of forming a1 st repair layer by applying the radical polymerizable resin composition A to a structure;

a2 nd repair layer forming step of forming a2 nd repair layer by applying a repair material (X) containing a radical polymerizable resin composition Ax and a filler (B) on the 1 st repair layer before curing the 1 st repair layer; and

a repair layer curing step of curing the radical polymerizable resin composition A and the radical polymerizable resin composition Ax,

the radical polymerizable resin composition A and the radical polymerizable resin composition Ax both contain:

at least 1 radical polymerizable resin (a1) selected from the group consisting of vinyl ester resins, urethane (meth) acrylate resins and polyester (meth) acrylate resins,

At least 1 radical-polymerizable unsaturated monomer (a2) selected from the group consisting of mono (meth) acrylates, di (meth) acrylates and tri (meth) acrylates,

A hydroxyl group-containing aromatic tertiary amine (a3) represented by the following general formula (I), and

an organic peroxide (a4) and,

the total content of the radically polymerizable resin (a1) and the radically polymerizable unsaturated monomer (a2) in the radically polymerizable resin composition A and the radically polymerizable resin composition Ax is 75% by mass or more,

the radical polymerizable resin composition A and the radical polymerizable resin composition Ax do not contain a filler,

in the general formula (I), R¹Representation H, CH₃Or OCH₃，R²Represents hydroxyalkyl, R³Represents an alkyl group or a hydroxyalkyl group.

2. The method for repairing a structure according to claim 1, wherein said radically polymerizable resin composition A and said radically polymerizable resin composition Ax have the same composition.

3. The method for repairing a structure according to claim 1 or 2, wherein the radical polymerizable resin (a1) comprises a vinyl ester resin having an unsaturated group bonded to at least one terminal of an epoxy polymer via an ester bond.

4. The method for repairing a structure according to claim 3, wherein the unsaturated group is at least 1 selected from the group consisting of a vinyl group, an allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group.

5. The method for repairing a structure according to any one of claims 1 to 4, wherein the radical polymerizable resin (a1) contains a urethane (meth) acrylate resin having a (meth) acryloyl group at least at 1 end in the molecule and being a polyurethane obtained by polymerizing a diisocyanate and a linear diol.

6. The method for repairing a structure according to any one of claims 1 to 5, wherein the radical polymerizable resin (a1) contains a polyester (meth) acrylate resin obtained from a diol and at least one of an aromatic dicarboxylic acid and an aliphatic saturated dicarboxylic acid, and has a (meth) acryloyl group at least one end of a molecular chain.

7. The method for repairing a structure according to any one of claims 1 to 6, wherein a content of the radically polymerizable resin (a1) in the radically polymerizable resin composition A is 5 to 90% by mass based on a polymerization amount of the radically polymerizable resin (a1) and the radically polymerizable unsaturated monomer (a 2).

8. The method for repairing a structure according to any one of claims 1 to 7, wherein the radical polymerizable resin composition A contains 0.1 to 10 mass% of the hydroxyl group-containing tertiary aromatic amine (a3) and 0.1 to 10 mass% of the organic peroxide (a 4).

9. The method for repairing a structure according to any one of claims 1 to 8, wherein the repair material (X) contains 80 to 500 parts by mass of the filler (B) per 100 parts by mass of the radically polymerizable resin composition Ax.

10. The method for repairing a structure according to any one of claims 1 to 9, wherein the filler (B) is an inorganic filler.

11. The method for repairing a structure according to any one of claims 1 to 10, further comprising a reinforcing step of forming a reinforcing layer containing a curable resin composition (C) and a fiber material (D) on the 2 nd repair layer after the repair layer curing step.

12. The method for repairing a structure according to claim 11, wherein the reinforcing step comprises the steps of:

a1 st reinforcing layer forming step of forming a1 st reinforcing layer by applying a curable resin composition (C) to the 2 nd repair layer;

a reinforcing fiber layer forming step of forming a reinforcing fiber layer containing a fiber material (D) on the 1 st reinforcing layer;

a2 nd reinforcing layer forming step of forming a2 nd reinforcing layer by applying a curable resin composition (C) on the reinforcing fiber layer, and

and a reinforcing layer curing step of curing the curable resin composition (C) contained in the 1 st reinforcing layer and the 2 nd reinforcing layer.

13. The method for repairing a structure according to claim 11 or 12, wherein the curable resin composition (C) contains at least 1 selected from the group consisting of a vinyl compound and an epoxy compound.

14. Method for repairing a structure according to claim 12 or 13, said fibrous material (D) being a sheet of carbon fibres.

15. The method for repairing a structure according to any one of claims 1 to 14, wherein the structure is a concrete structure.

Technical Field

The present invention relates to a method for repairing a structure.

Background

As a repairing method and a reinforcing method for damaged or aged portions of a building or civil structure, a reinforced concrete crimping method, a steel plate crimping and overlaying method, a concrete filling method, a carbon fiber method (for example, patent documents 1 and 2) and the like are widely known.

In the civil engineering field in recent years, aging of social infrastructure required for a highly economical growth period is regarded as a problem, and particularly, in 2032 years, 65% of roads and bridges and 47% of tunnels of 2m or more become 50 years or more after construction, and the problem of aging due to aging is considered to be more serious than at present. In addition, almost all such aged articles are repaired articles that require repair for seismic reinforcement or the like. In the future, there is a fear that conventional repair methods cannot satisfy these requirements. Therefore, in order to meet such a demand, development of a rapid repair method having a short period of time is urgently required.

In addition, in the field of construction, buildings which were made before 1981 and which did not meet the standards for earthquake resistance are also in the period of time when they were to be modified. In the modification of these objects, seismic reinforcement and the like are also required, and particularly in urban spaces where buildings are close to each other without gaps, a reinforcement construction method capable of performing construction in a narrow place is required. Although the above-described carbon fiber process method meets such a requirement, no sufficient research has been conducted on a technique for shortening the construction period.

In addition, in the conventional repairing method, an epoxy resin is mainly used as a curable resin. However, since epoxy resins are difficult to cure in a low-temperature environment, Methyl Methacrylate (MMA) resins or Vinyl Ester (VE) resins have also been used in operations such as winter field work. MMA resins and VE resins can be cured by radical polymerization, and compared with epoxy resins, they are cured at a higher speed, contributing to shorter construction periods, but even when these resins are used, conventional repair methods have not sufficiently satisfied modern requirements for further shorter construction periods.

As an invention that can satisfy such a requirement for shortening the construction period, patent document 3 describes a composition containing a radical polymerizable resin composition, a hydroxyl-containing tertiary aromatic amine, an organic peroxide, and an inorganic filler, and a cross-section repairing method using the same. Here, the radical polymerizable resin composition includes: at least 1 kind of radical polymerization resin selected from vinyl ester resin, urethane (methyl) acrylate resin and polyester (methyl) acrylate resin, and radical polymerization unsaturated monomer with more than 2 methyl acryloyl in the molecule.

Documents of the prior art

Patent document

Patent document 1 Japanese patent laid-open publication No. 2002-235444

Patent document 2 Japanese laid-open patent application No. 2005-336952

Patent document 3 International publication No. WO2016/133094

Disclosure of Invention

Problems to be solved by the invention

In the cross-section repair method described in patent document 3, a composition containing an inorganic filler (low-temperature-curing cross-section repair material) is directly applied to a material to be repaired, but as is clear from comparative examples 1 and 5 described below, there is still room for improvement in adhesive strength.

Accordingly, an object of the present invention is to provide a method for repairing a structure, which can ensure a short period of time and high reliability in a wide temperature range when applied to a concrete structure.

Means for solving the problems

To achieve the above object, the present invention has the following aspects.

[1] A method for repairing a structure, comprising the steps of:

a1 st repair layer forming step of forming a1 st repair layer by applying the radical polymerizable resin composition A to a structure;

a2 nd repair layer forming step of forming a2 nd repair layer by applying a repair material (X) containing a radical polymerizable resin composition Ax and a filler (B) on the 1 st repair layer before curing the 1 st repair layer; and

a repair layer curing step of curing the radical polymerizable resin composition A and the radical polymerizable resin composition Ax,

the radical polymerizable resin composition A and the radical polymerizable resin composition Ax both contain:

at least 1 radical polymerizable resin (a1) selected from the group consisting of vinyl ester resins, urethane (meth) acrylate resins and polyester (meth) acrylate resins,

At least 1 radical-polymerizable unsaturated monomer (a2) selected from the group consisting of mono (meth) acrylates, di (meth) acrylates and tri (meth) acrylates,

A hydroxyl group-containing aromatic tertiary amine (a3) represented by the following general formula (I), and

an organic peroxide (a4) and,

the total content of the radically polymerizable resin (a1) and the radically polymerizable unsaturated monomer (a2) in the radically polymerizable resin composition A and the radically polymerizable resin composition Ax is 75% by mass or more,

the radical polymerizable resin composition A and the radical polymerizable resin composition Ax do not contain a filler,

in the general formula (I), R¹Representation H, CH₃Or OCH₃，R²Represents hydroxyalkyl, R³Represents an alkyl group or a hydroxyalkyl group.

[2] The method for repairing a structure according to [1], wherein the composition of the radical polymerizable resin composition A is the same as that of the radical polymerizable resin composition Ax.

[3] The method for repairing a structure according to [1] or [2], wherein the radically polymerizable resin (a1) contains a vinyl ester resin having an unsaturated group bonded to at least one terminal of an epoxy polymer via an ester bond.

[4] The method for repairing a structure according to [3], wherein the unsaturated group is at least 1 selected from the group consisting of a vinyl group, an allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group.

[5] The method for repairing a structure according to any one of [1] to [4], wherein the radical polymerizable resin (a1) contains a urethane (meth) acrylate resin having a (meth) acryloyl group at least at 1 end in the molecule, and is a polyurethane obtained by polymerizing a diisocyanate and a linear diol.

[6] The method for repairing a structure according to any one of [1] to [5], wherein the radical polymerizable resin (a1) contains a polyester (meth) acrylate resin obtained from a diol and at least one of an aromatic dicarboxylic acid and an aliphatic saturated dicarboxylic acid, and has a (meth) acryloyl group at least one end of a molecular chain.

[7] The method for repairing a structure according to any one of [1] to [6], wherein a content of the radically polymerizable resin (a1) is 5 to 90% by mass based on a polymerization amount of the radically polymerizable resin (a1) and the radically polymerizable unsaturated monomer (a 2).

[8] The method for repairing a structure according to any one of [1] to [7], wherein the radically polymerizable resin composition A contains 0.1 to 10 mass% of the hydroxyl group-containing aromatic tertiary amine (a3) and 0.1 to 10 mass% of the organic peroxide (a 4).

[9] The method for repairing a structure according to any one of [1] to [8], wherein the repair material (X) contains 80 to 500 parts by mass of the filler (B) per 100 parts by mass of the radically polymerizable resin composition Ax.

[10] The method for repairing a structure according to any one of [1] to [9], wherein the filler (B) is an inorganic filler.

[11] The method for repairing a structure according to any one of [1] to [10], further comprising a reinforcement step of forming a reinforcement layer containing a curable resin composition (C) and a fiber material (D) on the 2 nd repair layer after the repair layer curing step.

[12] The method for repairing a structure according to [11], wherein the reinforcement step comprises the steps of:

a1 st reinforcing layer forming step of forming a1 st reinforcing layer by applying a curable resin composition (C) to the 2 nd repair layer;

a reinforcing fiber layer forming step of forming a reinforcing fiber layer containing a fiber material (D) on the 1 st reinforcing layer;

a2 nd reinforcing layer forming step of forming a2 nd reinforcing layer by applying a curable resin composition (C) on the reinforcing fiber layer, and

and a reinforcing layer curing step of curing the curable resin composition (C) contained in the 1 st reinforcing layer and the 2 nd reinforcing layer.

[13] The method for repairing a structure according to [11] or [12], wherein the curable resin composition (C) contains at least 1 selected from a vinyl compound and an epoxy compound.

[14] The method for repairing a structure according to [12] or [13], wherein the fibrous material (D) is a carbon fiber sheet.

[15] The method for repairing a structure according to any one of [1] to [14], wherein the structure is a concrete structure.

Effects of the invention

The present invention can provide a method for repairing a structure, which can ensure a short period of time and high reliability in a wide temperature range when applied to a concrete structure.

Drawings

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

Fig. 2 is a flowchart showing an example of the method for repairing a structure according to embodiment 2 of the present invention.

Fig. 3 is a flowchart showing an example of the method for repairing a structure according to embodiment 3 of the present invention.

Fig. 4 is a diagram showing a concrete adhesion test method.

Detailed Description

The following specifically describes an embodiment of the method for repairing a structure according to the present invention. The repairing method of the following embodiment is preferably applied to a concrete structure, but can also be applied to a construction surface made of asphalt concrete other than concrete, mortar, wood, metal, and the like. The structure is preferably a building or a civil structure, and examples thereof include, but are not limited to, a bridge pier, a projected floor, a column, a beam, a floor, a covering section of a tunnel, and an outer wall of a chimney. Here, "repair" refers to not only trimming and repairing of aged and damaged portions, but also reinforcement of structures that have not been aged or damaged.

"cured" refers to a polymer in which molecules contained in raw materials are bonded to each other by a chemical reaction to form a network structure. "drying" means that no chemical reaction occurs but a part of the components contained in the mixture, composition, etc. volatilize. Further, curing and drying may be performed simultaneously, and for example, while curing is performed, components that do not undergo a chemical reaction or components generated by a chemical reaction may volatilize.

"(meth) acrylate" means acrylate or methacrylate, "(meth) acrylic acid" means acrylic acid or methacrylic acid, "(meth) acryloyl" means acryloyl or methacryloyl.

The term "radical polymerizability" refers to a property that components contained in a composition are cured by radical polymerization under certain conditions, and examples of the curing conditions include heating and light irradiation.

"unsaturated bond" refers to double and triple bonds between carbon atoms other than those forming aromatic rings.

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 concrete.

"workability" means ease of application when the radical polymerizable resin composition (a) or the repair material (X) is applied to a work surface.

< 1. embodiment 1 >

< 1-1. method for repairing structure

Fig. 1 is a flowchart showing an example of a method for repairing a structure according to embodiment 1 of the present invention. The repairing method according to the present embodiment includes a1 st repair layer forming step S1, a2 nd repair layer forming step S2, a repair layer curing step S3, a1 st reinforcement layer forming step S4, a reinforcing fiber layer forming step S5, a2 nd reinforcement layer forming step S6, and a reinforcement layer curing step S7. Here, the 1 st reinforcing layer forming step S4, the reinforcing fiber layer forming step S5, the 2 nd reinforcing layer forming step S6, and the reinforcing layer curing step S7 are collectively referred to as a reinforcing step. These steps will be described below. Specific examples of the radical polymerizable resin composition (a), the radical polymerizable resin composition (Ax), the filler (B), the repair material (X), the curable resin composition (C), and the fiber material (D) used in the present embodiment are not described here, but will be described later.

In the 1 st repair layer forming step S1, the radical polymerizable resin composition (a) is applied to the application surface of the structure to form the 1 st repair layer. Preferably, a fragile layer such as dirt, an attached matter, and a laitance layer is removed from the construction surface of the structure in advance. Before this step, it is preferable to perform a foundation treatment for adjusting the working surface. Examples of the base treatment include grinding the surface of a rough or stained structure by a disc sander, sandblasting, water spraying, or the like. This treatment can improve the adhesion strength of the repair layer cured after curing to the construction surface.

The repairing method according to the present embodiment may include a step of coating the working surface with another material before the 1 st repair layer forming step S1. In this case, the repair layer is formed on the application surface in a grounded manner via the coating layer made of the other material. However, from the viewpoint of shortening the construction period, it is preferable not to include a step of coating the construction surface with another material. That is, the repair layer is preferably formed directly on the construction surface. With the repairing method according to the present embodiment, even if the repair face is repaired without using another material, that is, the repair layer is directly formed on the repair face, the adhesion strength between the repair face and the repair layer can be sufficiently ensured.

Examples of the method for applying the radical polymerizable resin composition (a) include spraying, coating using a device such as a roller, a brush, or a doctor blade, and dipping. However, in order to sufficiently increase the adhesive strength of the 2 nd repair layer to be described later, it is preferable that the basis weight (weight per unit area) of the 1 st repair layer is 50g/m²Above, more preferably 100g/m²The above. In order to prevent the 1 st repair layer from sagging or drooling before curing, the basis weight of the 1 st repair layer is preferably 500g/m²Below, more preferably 400g/m²The amount of the surfactant is preferably 300g/m²The following.

In the 2 nd repair layer forming step S2, the repair material (X) containing the radical polymerizable resin composition (Ax) and the filler (B) is applied to the 1 st repair layer to form the 2 nd repair layer. Hereinafter, the 1 st repair layer and the 2 nd repair layer are collectively referred to as a repair layer in some cases. The 2 nd repair layer forming step S2 is performed before the radical polymerizable resin composition (a) applied in the 1 st repair layer forming step S1 is cured. This is because the adhesion between the repair layer 1 and the repair layer 2 can be improved, and the adhesion strength of the cured repair layer can be increased. In addition, due to the 1 st modificationThe multiple layer and the No. 2 repair layer are cured at the same time, so that the time required for curing can be shortened. The mesh weight of the 2 nd repairing layer is preferably 5-30 Kg/m²More preferably 10 to 25Kg/m²And further preferably 13 to 23Kg/m²。

When the radical polymerizable resin composition (a) contained in the 1 st repair layer contains a volatile monomer, the 2 nd repair layer is preferably formed immediately after the 1 st repair layer forming step S1, for example, within 30 minutes after the 1 st repair layer forming step S1 is completed, and more preferably within 10 minutes.

When the construction surface of the structure having the irregularities on the surface is to be flattened in the 2 nd repair layer forming step S2, the 2 nd repair layer forming step S2 is also referred to as irregularity adjustment. 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 spatula, and a spraying method and a dipping method.

In the repair layer curing step S3, the radical polymerizable resin compositions (a) and (Ax) contained in the repair layer are cured. The curing method is not particularly limited, and there are methods such as covering the application surface with a protective sheet or the like and leaving it for a sufficiently long time for curing. The time and suitable temperature for leaving the composition vary depending on the components and combinations contained in the radically polymerizable resin compositions (A) and (Ax). In addition, for example, in the case where the radical polymerizable resin composition (a) and/or (Ax) contains a photopolymerization initiator, curing is efficiently performed by light irradiation. In this case, the wavelength region of the irradiated light is appropriately determined depending on the components of the radical polymerizable resin composition (a) and/or (Ax), particularly the kind of the photopolymerization initiator. As a method for confirming the curing of the repair layer, there is a method of confirming that no trace is left by touching with a finger, that is, the repair layer is not plastically deformed by touching with a finger.

In the 1 st reinforcing layer forming step S4, the curable resin composition (C) is applied to the cured repair layer to form a1 st reinforcing layer. Examples of the coating method in this step include spraying, coating using a tool such as a roller, a brush, or a doctor blade, and dippingAnd is not limited to these. In order to ensure sufficient bonding strength of the reinforcing fiber layer formed in the subsequent step, the basis weight of the 1 st reinforcing layer is preferably 50g/m²Above, more preferably 100g/m²The above. In order to prevent the 1 st reinforcing layer from sagging or running before curing, the basis weight of the 1 st reinforcing layer is preferably 500g/m²Hereinafter, it is more preferably 400g/m²The lower, more preferably 300g/m²The following.

A reinforcing fiber layer is formed on the 1 st reinforcing layer through the reinforcing fiber layer forming process S5. As a typical example of the method for forming the reinforcing fiber layer, a fiber sheet containing the fiber material (D) is attached to the 1 st reinforcing layer, but the method is not limited thereto. This may be, for example, a method of placing or bonding one fiber or a plurality of fibers gathered in a bundle on or to the 1 st reinforcing layer, etc. The material and form of the fiber material (D) will be specifically described later. When a fiber sheet is used as the fiber material (D) contained in the reinforcing fiber layer, the number of sheets to be attached is not limited to 1, and a plurality of sheets may be stacked.

In the 2 nd reinforcing layer forming step S6, the curable resin composition (C) is applied to the reinforcing fiber layer to form the 2 nd reinforcing layer. The coating method in this step and the range of the preferred basis weight of the 2 nd reinforcing layer are the same as those in the 1 st reinforcing layer forming step S4. Hereinafter, the 1 st reinforcing layer, the reinforcing fiber layer, and the 2 nd reinforcing layer may be collectively referred to as a reinforcing layer.

The curable resin composition (C) contained in the reinforcing layer is cured in the reinforcing layer curing step S7. The curing method is not particularly limited, and examples thereof include covering the construction surface with a protective sheet or the like, and leaving the construction surface for a sufficiently long time for curing. The time and the appropriate temperature for leaving the curable resin composition (C) may vary depending on the components and the composition contained therein. In addition, for example, when the curable resin composition (C) contains a photopolymerization initiator, curing is efficiently performed by light irradiation. In this case, the wavelength range of the irradiated light may be appropriately determined depending on the components of the curable resin composition (C), particularly the kind of photopolymerization initiator. As a method for confirming that the reinforcing layer is cured, there is no trace after confirming that the reinforcing layer is touched with a finger, that is, the reinforcing layer is not plastically deformed by the finger touch.

< 1-2. radical polymerizable resin composition (A) >

The radical polymerizable resin composition (A) contains a radical polymerizable resin (a1), a radical polymerizable unsaturated monomer (a2), a hydroxyl group-containing aromatic tertiary amine (a3) represented by the following general formula (I), and an organic peroxide (a 4).

In the above formula (I), R¹Representation H, CH₃Or OCH₃，R²Represents hydroxyalkyl, R³Represents an alkyl group or a hydroxyalkyl group.

In order to ensure sufficient strength of the radically polymerizable resin composition (a) after curing, the total content of the radically polymerizable resin (a1) and the radically polymerizable unsaturated monomer (a2) in the radically polymerizable resin composition (a) is preferably 75% by mass or more, preferably 82% by mass or more, and more preferably 90% by mass or more. The radical polymerizable resin composition (a) does not contain a component corresponding to a filler (B) described later.

[ 1-2-1. radically polymerizable resin (a1) ]

The radical polymerizable resin (a1) 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 radical polymerizable resin (a1) is preferably composed of 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 vinyl ester resin, the urethane (meth) acrylate resin, and the polyester (meth) acrylate resin are described below.

(vinyl ester resin)

Vinyl ester resins are sometimes referred to as epoxy (meth) acrylate resins and are, for example, esterified with an epoxy polymer and a carboxylic acid having 1 or more unsaturated groups or a derivative thereof. Examples of the carboxylic acid derivative include a carboxylic acid halide and a carboxylic acid anhydride. That is, the vinyl ester resin is a polymer of an epoxy compound having an unsaturated group bonded to at least one terminal of the epoxy polymer via an ester bond. The unsaturated group here is preferably located at the end of the molecule, and more preferably is 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 (manufactured by news agency in the japanese journal industry, published 1988)", and "dictionary for coating material (compiled by color and Material association, published 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 linear glycidyl ether. More specifically, the epoxy compound includes bisphenol a diglycidyl ether, hydrogenated bisphenol a diglycidyl ether, tetrabromobisphenol a diglycidyl ether, linear diglycidyl ether, cresol linear 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 in a mixture of 2 or more kinds, but it is preferable to use a mixture of bisphenol A diglycidyl ether and linear diglycidyl ether. This is because flexibility and toughness of the cured repair layer can be improved. From such a viewpoint, it is more preferable that the epoxy compound is a mixture of bisphenol A diglycidyl ether and 1, 6-hexanediol diglycidyl ether.

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

Examples of the monocarboxylic acid having 1 unsaturated group include acrylic acid and methacrylic acid. Examples of the monocarboxylic acid having a plurality of unsaturated groups include a half-ester carboxylic acid obtained by reacting trimethylolpropane diallyl ether with phthalic anhydride or a derivative thereof. Examples of the phthalic anhydride derivative include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and endomethylenetetrahydrophthalic anhydride, with tetrahydrophthalic anhydride being preferred. These carboxylic acids may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

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

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

The vinyl ester resin may be prepared by reacting a part of epoxy groups at the terminal of an epoxy polymer as a raw material with a carboxylic acid having no unsaturated group for the purpose of adjusting the degree of crosslinking of a cured product. Examples of the carboxylic acid having no unsaturated group include adipic acid, sebacic acid, phthalic anhydride, and the like.

(urethane (meth) acrylate resin)

The urethane (meth) acrylate resin can be obtained, for example, by reacting a polyol with a polyisocyanate to produce a polyurethane having an isocyanate group at the end, and reacting the polyurethane with a hydroxyl group-containing (meth) acrylate. In the reaction of the hydroxyl group-containing (meth) acrylate, 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 one end in the molecule.

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

The polyisocyanate used as a raw material of the urethane (meth) acrylate resin includes, for example, 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 commercially available products thereof 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 Kabushiki Kaisha), デスモジュール L (manufactured by Suzuki Kaisha 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.

< 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 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 repair layer after curing.

(content of radical polymerizable resin (a 1))

The content of the radical polymerizable resin (a1) is preferably 5 to 90% by mass, more preferably 8 to 70% by mass, even more preferably 15 to 70% by mass, and particularly preferably 30 to 50% by mass, based on the total amount of the radical polymerizable resin (a1) and the radical polymerizable unsaturated monomer (a 2). By setting the content of the radical polymerizable resin (a1) in the radical polymerizable resin composition (a) to the above range, good workability can be ensured.

[ 1-2-2 ] radically polymerizable unsaturated monomer (a2) ]

The radical polymerizable unsaturated monomer (a2) is at least 1 selected from the group consisting of mono (meth) acrylate, di (meth) acrylate and tri (meth) acrylate. The inclusion of the radical polymerizable unsaturated monomer (a2) can reduce the viscosity of the radical polymerizable resin composition (a) to a suitable degree. In addition, the viscosity of the repairing material (X) can be appropriately reduced under the conditions of the radical polymerizable resin composition (Ax) described later, as in the case of the radical polymerizable resin composition (a). Further, the cured repair layer can be improved in hardness, strength, chemical resistance, water resistance, and the like.

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, isobornyl (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, it is preferable that the radical polymerizable unsaturated monomer (a2) is a methacrylate. From the same viewpoint, it is particularly preferable that the composition 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, 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.

(content of radical polymerizable unsaturated monomer (a 2))

The content of the radical polymerizable unsaturated monomer (a2) is preferably 10% by mass or more relative to the total amount of the radical polymerizable resin (a1) and the radical polymerizable unsaturated monomer (a 2). This is because the viscosity of the radically polymerizable resin composition (A) is suitable for good workability in a low-temperature (e.g., -25 ℃) environment, and the compatibility with the filler (B) described later is good. From such a viewpoint, the content of the radical polymerizable unsaturated monomer (a2) is more preferably 30% by mass or more, and still more preferably 50% by mass or more. The content of the radical polymerizable unsaturated monomer (a2) is preferably 95% by mass or less with respect to the total amount of the radical polymerizable resin (a1) and the radical polymerizable unsaturated monomer (a 2). This is because the repair layer after curing can maintain high strength and water resistance. From such a viewpoint, the content of the radical polymerizable unsaturated monomer (a2) is more preferably 85% by mass or less, and still more preferably 70% by mass or less.

[ 1-2-3 ] hydroxy-containing aromatic tertiary amine (a3) ]

The hydroxyl group-containing aromatic tertiary amine (a3) is represented by the following formula (I).

In the formula (I), R¹Is H, CH₃Or OCH₃Preferably CH₃More preferably CH in para position₃。R²Is a hydroxyalkyl group, preferably a hydroxyalkyl group having 1 to 10 carbon atoms, more preferably a hydroxyalkyl group having 3 or less carbon atoms. R³Is an alkyl group or a hydroxyalkyl group, preferably an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 4 or less carbon atoms or a hydroxyalkyl group having 4 or less carbon atoms, and still more preferably a hydroxyalkyl group having 4 or less carbon atoms.

The hydroxyl-containing aromatic tertiary amine (a3) 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-di (β -hydroxyethyl) aniline, N-di (β -hydroxypropyl) aniline, N-di (β -hydroxyethyl) -p-toluidine, N-di (β -hydroxyethyl) p-toluidine, N-di, N, N-bis (β -hydroxypropyl) -p-toluidine, N-diisopropyl-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 (a3) may be used alone in 1 kind or in combination of 2 or more kinds.

(content of hydroxyl group-containing aromatic Tertiary amine (a 3))

The content of the hydroxyl group-containing aromatic tertiary amine (a3) in the radical polymerizable resin composition (a) is preferably 0.1 to 10% by mass, more preferably 0.1 to 8.0% by mass, and still more preferably 0.2 to 5.0% by mass. The aromatic tertiary amine (a3) containing a hydroxyl group can accelerate the curing reaction of the radically polymerizable resin composition (a) and improve workability.

[ 1-2-4. organic peroxide (a4) ]

The organic peroxide (a4) can act as a radical polymerization initiator at room temperature by using an amine such as a hydroxyl group-containing aromatic tertiary amine (a3) or by using a combination of an amine and a metal soap as an optional component described later.

The organic peroxide (a4) 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, and the like, 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.

These organic peroxides (a4) may be used alone in 1 kind, or 2 or more kinds may be mixed and used. Examples of the mixture of 2 or more species include a mixture of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide and m-toluoyl peroxide, a mixture of cumene hydroperoxide and t-butyl peroxybenzoate and methyl ethyl ketone, and the like.

(content of organic peroxide (a 4))

The content of the organic peroxide (a4) in the radical polymerizable resin composition (a) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 1.0% by mass or more. In order to reduce the cost and improve the strength of the repair layer after curing, the content of the organic peroxide (a4) is preferably 10.0% by mass or less, more preferably 8.0% by mass or less, and still more preferably 6.0% by mass or less.

[ 1-2-5. optional Components ]

The radical polymerizable resin composition (a) may contain other components as optional components within a range not to impair the effects of the present invention. Examples of the optional components include monomers other than those described above (hereinafter, sometimes referred to as "other monomers"), amines, azo compounds, metal soaps, photopolymerization initiators, reinforcing materials, and various additives.

Examples of the other monomer include styrene-based monomers such as (meth) acrylic acid, (meth) acryloylmorpholine, styrene, derivatives of styrene in which at least one hydrogen atom in the α -position, o-position, m-position or p-position is substituted with an alkyl group, a nitro group, a cyano group, a substituent having an amide bond or a substituent having an ester bond, chlorostyrene, vinyltoluene, divinylbenzene, etc.; diene compounds such as butadiene, 2, 3-dimethylbutadiene, isoprene and chloroprene, but not limited thereto. As the other monomer, a condensate of an unsaturated fatty acid such as maleic acid, fumaric acid, itaconic acid, and the like, and an alcohol, or the like can be used. These can be used alone, or more than 2 kinds can be mixed and used. The other monomer preferably has a (meth) acryloyl group, and more preferably has an acryloyl group.

Examples of the amine as an optional component include an aromatic tertiary amine other than the aromatic tertiary amine (a3) having a hydroxyl group, and examples thereof include an aromatic tertiary amine having no hydroxyl group. Examples of the optional component include dimethylaniline and dimethyl-p-toluidine. These may be used alone in 1 kind, or 2 or more kinds may be mixed and used.

When the radical polymerizable resin composition (a) contains an amine as an optional component, the content of the amine as an optional component in the radical polymerizable resin composition (a) is preferably 0.01 to 5.0% by mass, and more preferably 0.1 to 3.0% by mass. By the decomposition reaction of the peroxide due to the contact of the organic peroxide (a4) with the amine of an arbitrary component, the polymerization of the components contained in the radical polymerizable resin composition (a) is accelerated, and the surface drying property and curability of the repair layer are further improved.

Examples of the azo compound include azobisisobutyronitrile and azobisformamide. These may be used alone in 1 kind, or 2 or more kinds may be mixed and used. When the radical polymerizable resin composition (a) contains an azo compound, the content of the azo compound in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.1 to 5.0% by mass, and more preferably 0.5 to 3.0% by mass. By containing the azo compound, the surface of the repair layer is efficiently cured. When azobisisobutyronitrile, azobisformamide, or the like is used as the azo compound, the polymerization of the components contained in the radical polymerizable resin composition (a) can be accelerated.

Examples of the metal soap include cobalt octylate, manganese octylate, zinc octylate, vanadium octylate, cobalt naphthenate, copper naphthenate, and barium naphthenate, among which cobalt octylate, manganese octylate, and cobalt naphthenate are preferable, and cobalt octylate is more preferable. When the radical polymerizable resin composition (a) contains a metal soap, the content of the metal soap in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.1 to 10.0% by mass, more preferably 0.3 to 5.0% by mass. By containing the metal soap, polymerization of the components contained in the radical polymerizable resin composition (a) is promoted by the decomposition reaction of the organic peroxide caused by contact of the organic peroxide (a4) with the metal salt, and the curability of the repair layer is further improved.

As the photopolymerization initiator, a photopolymerization initiator having photosensitivity in the visible light to near infrared light region is preferably used, and more specifically, イルガキュア (registered trademark) 1800 (manufactured by BASF) and the like are exemplified.

When the radical polymerizable resin composition (a) has a photopolymerization initiator, the content of the photopolymerization initiator in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass. The photopolymerization initiator can suppress the deterioration of other physical properties and shorten the curing time.

Examples of the reinforcing material include short fibers such as polyester, vinylon, carbon, ceramics, and stainless steel. These reinforcing materials may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When the radical polymerizable resin composition (a) contains a reinforcing material, the content of the reinforcing material in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.01 to 2.0% by mass. By containing the reinforcing material, the strength and durability of the repaired structure can be improved.

Examples of the various additives include waxes, polymerization inhibitors, coupling agents, curing accelerators, thixotropic agents, and solvents.

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 thereof 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) -LP-S6665, manufactured by ビックケミー · ジャパン. 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 radical polymerizable resin composition (a) contains a wax, the content of the wax in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.1 to 5.0% by mass, more preferably 0.1 to 2.0% by mass. By containing wax, the drying time can be shortened.

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

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

Silane coupling agents such as aminosilane, vinylsilane, epoxysilane, and acrylic silane are preferable as the coupling agent. These coupling agents may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the radical polymerizable resin composition (a) contains a coupling agent, the content of the coupling agent in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5.0% by mass. The strength of the cured repair layer 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 radically polymerizable resin composition (a) contains a curing accelerator, the content of the curing accelerator in the radically polymerizable resin composition (a) 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 repair layer.

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 the radical polymerizable resin composition (a) contains a thixotropic agent, the content of the thixotropic agent in the radical polymerizable resin composition (a) is not particularly limited, but is preferably 0.1 to 10% by mass, more preferably 0.2 to 5.0% by mass. The thixotropic agent imparts excellent thixotropic properties and improves workability.

Examples of the solvent include, but are not particularly limited to, alkyl 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. In particular, when a hydrocarbon solvent described in Japanese patent application laid-open No. 2002-97233, for example, n-hexane, cyclohexane, pentane, trimethylbenzene, butylbenzene, pentylbenzene, or the like is used in combination with a wax, a film of the wax can be rapidly formed during curing of the radical polymerizable resin composition (A), and the drying property can be improved.

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

[ 1-2-6 ] preparation method and viscosity of radically polymerizable resin composition (A) ]

The method for preparing the radical polymerizable resin composition (a) is not particularly limited, and examples thereof include weighing each component and mixing by a homomixer, a hand mixer, or the like, but mixing by a homomixer is preferable. From the viewpoint of carrying out the homogeneous curing reaction, it is preferable that the radical polymerizable resin (a1) and the radical polymerizable unsaturated monomer (a2) are mixed in advance before adding other components. After the hydroxyl group-containing aromatic tertiary amine (a3) and the organic peroxide (a4) are blended, it is preferable to use the radical polymerizable resin composition (a) quickly before the curing is performed.

The viscosity of the radical polymerizable resin composition (A) is preferably 25 ℃ and 150 mPas or less. Similarly to the radical polymerizable resin composition (a), the viscosity of the radical polymerizable resin composition (Ax) is set to the above range under the conditions of the radical polymerizable resin composition (Ax) described later, whereby a decrease in workability in producing the repairing material (X) at a low temperature (for example, 5 ℃ or lower), kneading of the filler (B), or coating of the radical polymerizable resin composition (a) and the repairing material (X) can be suppressed. From this viewpoint, the viscosity of the radical polymerizable resin composition (A) is more preferably 25 ℃ and 100 mPas or less. The viscosity of the radical polymerizable resin composition (A) is preferably 25 ℃ and 10 mPas or more. This is because the flow of the radical polymerizable resin composition (a) before curing can be suppressed when it is applied to a slant surface or a vertical surface.

< 1-3. repair Material (X) >

The repair material (X) contains a radical polymerizable resin composition (Ax) and a filler (B). The conditions of the radical polymerizable resin composition (Ax) are the same as those of the radical polymerizable resin composition (A), as described above. The radical polymerizable resin composition (Ax) may be the same as or different from the radical polymerizable resin composition (a), but it is preferable that the radical polymerizable resin composition (Ax) and the radical polymerizable resin composition (a) have the same composition. This is because the increase in cost due to the increase in the number of types of materials can be suppressed, and the radical polymerizable resin composition (a) as the 1 st repair layer and the repair material (X) as the 2 nd repair layer are easily combined, and the adhesive strength is increased. The radical polymerizable resin composition (Ax) does not contain a component corresponding to the filler (B) described below.

[ 1-3-1. filling Material (B) ]

The filler (B) functions as an aggregate. The filler (B) is preferably an inorganic filler. Examples of the inorganic filler include talc, calcium carbonate, alumina, aluminum hydroxide, aluminum, titanium, silica sand, silica and the like. Among these, at least 1 selected from talc, calcium carbonate, silica sand and silica is preferably contained, and at least 1 selected from calcium carbonate, silica sand and silica is more preferably contained from the viewpoint of cost and material availability, and among them, at least 1 selected from calcium carbonate and silica sand is particularly preferably contained. These inorganic fillers may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The average particle diameter D of the filler (B) is preferably 1nm to 5000. mu.m, more preferably 10nm to 2000. mu.m, and still more preferably 100nm to 2000. mu.m. Within the above range, the workability and physical properties of the repair material (X) can be improved. Here, the average particle diameter D (. mu.m) is a ratio of particles obtained by the air permeation methodSurface area S (cm)²G) and true density of the particles rho (g/cm)³) D ═ k/(ρ S) } × 10⁴And (4) showing. Where κ is the shape factor, as where the particles are spheres, i.e., calculated as κ ═ 6.

The content of the filler (B) in the repair material (X) is preferably 80 to 500 parts by mass with respect to 100 parts by mass of the radical polymerizable resin composition (Ax). This is because the radical polymerizable resin composition (Ax) contained in the repair material (X) is sufficiently cured and good workability can be obtained. From such a viewpoint, the content of the filler (B) is more preferably 120 to 450 parts by mass, and still more preferably 150 to 450 parts by mass, based on 100 parts by mass of the radical polymerizable resin composition (Ax).

The total content of the filler (B) and the radical polymerizable resin composition (Ax) in the repair material (X) is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more, for example, 100% by mass.

[ 1-3-2. optional Components ]

The repair material (X) may contain any component other than the radical polymerizable resin composition (Ax) and the filler (B) within a range not to impair the effects of the present invention. Any components are the same as those described in items 1 to 2 to 5.

[ 1-3-3. method for preparing repair Material (X) ]

The method for preparing the repair material (X) is not particularly limited, and the above-mentioned components may be weighed, appropriately mixed and mixed to prepare the repair material (X). In order to accelerate the curing speed of the radical polymerizable resin composition (Ax), it is preferable to mix the filler (B) quickly after the production of the radical polymerizable resin composition (Ax) for a predetermined use.

The cured product (cured 2 nd repair layer) of the repair material (X) has a compressive strength after 24 hours of preferably 20MPa or more, more preferably 30MPa or more, and even more preferably 60MPa or more, as measured in accordance with JIS K6911 "general test methods for thermosetting plastics". If the compressive strength of the cured product after 24 hours is within the above range, the cured product can maintain good performance as a repair layer after curing even if frozen and thawed after the construction by the present method.

Further, the repair material (X) can be cured in a short time even in a low-temperature environment of-25 ℃ or lower. Therefore, the repair material (X) is excellent in workability, and the cured repair layer formed by the repair material (X) is excellent in strength expression.

< 1-4. curable resin composition (C) >

The curable resin composition (C) contains a curable compound. The curable compound preferably contains at least one of a vinyl compound and an epoxy compound. Among these, it is more preferable to contain a vinyl compound as the curable compound from the viewpoints of shortening the curing time and improving the adhesive strength between the repair layer after curing and the reinforcing layer after curing.

When the curable resin composition (C) contains a vinyl compound, the vinyl compound is a radical polymerizable resin and a radical polymerizable unsaturated monomer. In this case, as a preferable component of the radical polymerizable resin in the vinyl compound, the same as the radical polymerizable resin (a1) in the radical polymerizable resin composition (a) and as a preferable component of the radical polymerizable unsaturated monomer, the same as the radical polymerizable unsaturated monomer (a2) in the radical polymerizable resin composition (a) are preferable. The preferable range of the composition ratio of the radical polymerizable resin and the radical polymerizable unsaturated monomer in the vinyl compound is the same as the composition ratio of the radical polymerizable resin (a1) and the radical polymerizable unsaturated monomer (a2) in the radical polymerizable resin composition (a).

When the curable resin composition (C) contains a vinyl compound, the curable resin composition (C) preferably further contains an organic peroxide. In this case, the preferable range of the content of the organic peroxide (a4) in the radical polymerizable resin composition (a) is the same as that of the radical polymerizable resin composition (a).

When the curable resin composition (C) contains a vinyl compound, the curable resin composition (C) may contain a hydroxyl group-containing aromatic tertiary amine represented by the above general formula (I). The preferred component of the hydroxyl group-containing aromatic tertiary amine is the same as that of the radical polymerizable resin composition (a). The curable resin composition (C) may further contain, as necessary, any component that can be contained in the radical polymerizable resin composition (A), that is, the component described in the item 1-2 to 5. The curable resin composition (C) may be blended in the same manner as the radical polymerizable resin composition (a) used for forming the repair layer.

When the curable resin composition (C) contains an epoxy compound, the curable resin composition (C) contains a curing agent in addition to the epoxy compound. Further, a diluent may be contained as necessary.

When the curable resin composition (C) contains an epoxy compound, the epoxy compound is a compound having at least 2 or more epoxy groups in the molecule. Examples of such epoxy compounds include ether-type bisphenol epoxy resins, novolak epoxy resins, polyphenol epoxy resins, aliphatic epoxy resins, ester-type aromatic epoxy resins, cycloaliphatic epoxy resins, ether-ester epoxy resins, and the like. These epoxy resins may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

When the curable resin composition (C) contains an epoxy compound, an amine, imidazole, an imidazole derivative, an imine, a polyamide, or the like having 2 or more amino groups in the molecule can be used as the curing agent. Among them, aliphatic amines are preferable for curing at room temperature. Examples of the aliphatic amine having 2 or more amino groups in the molecule include ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-diaminobutane, 1, 6-hexamethylenediamine, 2, 5-dimethyl-2, 5-hexamethylenediamine, 2, 4-trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, 4-aminomethyloctamethylenediamine, 3 '-iminobis (propylamine), 3' -methyliminobis (propylamine), bis (3-aminopropyl) ether, 1, 2-bis (3-aminopropoxy) ethane, menthanediamine, isophoronediamine, bisaminomethylnorbornane, bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, and mixtures thereof, 1, 3-diaminocyclohexane, 3, 9-bis (3-aminopropyl) -2,4,8, 10-tetraoxaspiro [5,5] undecene, and the like. These curing agents may be used alone in 1 kind, or 2 or more kinds may be mixed and used. The amount of the curing agent added is preferably in accordance with the epoxy equivalent of the epoxy resin of the main agent. That is, the amount of the curing agent to be added is preferably adjusted so as to provide an amine equivalent corresponding to the epoxy equivalent of the main agent.

When the curable resin composition (C) contains an epoxy compound, a low-viscosity compound having an epoxy group may be used as a diluent in order to adjust the viscosity of the curable resin composition (C). The diluent that can be used is not particularly limited, and examples thereof include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolethane triglycidyl ether, and neopentyl glycol diglycidyl ether. These diluents may be used alone in 1 kind or in a mixture of 2 or more kinds.

< 1-4. fiber Material (D) >

The fibers contained in the fiber material (D) are preferably carbon fibers such as carbon fibers, graphite fibers, and graphite whiskers, glass fibers, aramid fibers, and polyester fibers, and preferably carbon fibers. Examples of the carbon fibers include polyacrylonitrile-based fibers, cellulose-based fibers, and carbon fibers produced from pitch, aromatic hydrocarbons, carbon black, and the like as raw materials. These fiber materials may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Examples of the fiber material (D) include, but are not limited to, nonwoven fabrics, tapes, sheets, felts, and woven fabrics in which fibers are oriented in a predetermined direction. The fiber material (D) may be impregnated with a thermosetting resin such as a prepreg, for example, in addition to the above-described fibers.

< 2 > embodiment 2

Fig. 2 is a flowchart illustrating an example of a method for repairing a structure according to embodiment 2 of the present invention. The repairing method according to the present embodiment includes a1 st repair layer forming step S1, a2 nd repair layer forming step S2, a repair layer curing step S3, a reinforcing layer forming step S8, and a reinforcing layer curing step S9. Here, the reinforcing layer forming step S8 and the reinforcing layer curing step S9 are collectively referred to as a reinforcing step. The 1 st repair layer forming step S1, the 2 nd repair layer forming step S2, and the repair layer curing step S3 are the same as those in embodiment 1, and therefore, description thereof is omitted here. The specific cases of the radical polymerizable resin composition (a), the filler (B), and the repair material (X) are the same as those described in embodiment 1.

In the reinforcing layer forming step S8, a reinforcing sheet is attached to the cured repair layer to form a reinforcing layer. Examples of the reinforcing sheet include fibers such as woven fabric and nonwoven fabric of the fiber material (D) impregnated with a thermosetting resin or a photocurable resin, but the reinforcing sheet is not limited to this as long as it contains the fiber material and the curable resin.

The reinforcing layer curing step S9 is a step of curing the resin contained in the reinforcing sheet forming the reinforcing layer. The curing conditions vary depending on the resin contained in the reinforcing sheet. Examples thereof include a thermosetting resin which is maintained at an appropriate temperature for efficient curing, and a photocurable resin which is irradiated with light in a wavelength range for a sufficient time for efficient curing. As a method for confirming that the reinforcing sheet is cured, there is no trace after touching with a finger, that is, the reinforcing sheet is not plastically deformed by touching with a finger.

<3 > embodiment 3

Fig. 3 is a flowchart showing an example of the method for repairing a structure according to embodiment 3 of the present invention. The repairing method according to the present embodiment includes a1 st repair layer forming step S1, a2 nd repair layer forming step S2, and a repair layer curing step S3. The 1 st repair layer forming step S1, the 2 nd repair layer forming step S2, and the repair layer curing step S3 are the same as those in embodiment 1 and embodiment 2.

Examples

The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

< 1. Synthesis of radically polymerizable resin (a1) >

The vinyl ester resin (a1-1), urethane methacrylate resin (a1-2), and polyester methacrylate resin (a1-3) were synthesized as follows, respectively.

< 1-1. vinyl ester resin (a1-1) >

Bisphenol a epoxy resin (product name "エポミック (trademark) R140P", manufactured by mitsui chemical co., ltd., epoxy equivalent 189) was charged into a reaction apparatus equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer: 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, 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 (a2-1) (product name "ファンクリル FA-512 MT" available from Hitachi chemical Co., Ltd.): 145g, 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" available from Seiko chemical Co., Ltd.) was added: 1.0g of methylhydroquinone (manufactured by Tokyo chemical Co., Ltd.): 0.3g, the reaction was carried out by raising the temperature to 110 ℃ while passing air. 1 hour after the start of the reaction, the acid value became 25 mgKOH/g. Then, methacrylic acid (manufactured by Kabushiki Kaisha クラレ): 120g, 2,4, 6-tris (dimethylaminomethyl) phenol: 1.0g of the mixture was heated to 130 ℃. The acid value was measured in accordance with JIS K0070: 1992, the neutralization titration method described in section 3.1 (hereinafter, the same applies to the measurement of the acid value) was carried out by taking a small amount (about 0.1 mL) from the reaction solution, and therefore the amount taken out for the measurement did not affect the total amount (hereinafter, the same applies to the measurement of the acid value). The reaction was carried out while keeping the temperature, and the acid value was 14mgKOH/g after 4 hours at 130 ℃. Then, the reaction was terminated to obtain a mixture containing 679g of the vinyl ester resin (a1-1) and 145g of tricyclodecenyloxyethyl methacrylate (a 2-1).

< 1-2. urethane methacrylate resin (a1-2) >

4, 4' -diphenylmethane diisocyanate (product name "ミリオネート MT" manufactured by Nippon ポリウレタン Co., Ltd.) was charged into a reaction apparatus equipped with a stirrer, a reflux condenser, a gas introduction pipe, and a thermometer: 226g of polypropylene glycol (number average molecular weight 1000 available from Showa Kagaku Co., Ltd.): 610g, acryloyl morpholine (a 2-2): 320g of methoxyethyl methacrylate (a2-3) (product name "アクリ ester MT" manufactured by Mitsubishi ケミカル Co.): 576g, hydroquinone: 0.3g, the temperature was raised to 60 ℃ while introducing air. Dibutyltin dilaurate (product name "KS-1260", manufactured by co-products corporation) was added as a polymerization catalyst while maintaining the temperature: 0.02 g. Then, the temperature was raised to 70 ℃ to carry out the reaction. Wave number of 2270cm from isocyanate group in the result of infrared absorption spectrometry (IR measurement)^-1And a wave number derived from a urethane bond of 1730cm^-1When the peak intensity ratio was not changed, 2-hydroxypropyl methacrylate (product name "ライトエステル HOP", Co., Ltd.) was added: 91g, dibutyltin dilaurate as catalyst were subsequently added: 0.06g, and the temperature was raised to 75 ℃ to carry out the reaction. As a result of IR measurement, it was confirmed that the wave number of the isocyanate group-derived material was 2270cm^-1The reaction was terminated by disappearance of the peak (b) to obtain 927g of a urethane methacrylate resin (a1-2), 320g of acryloylmorpholine (a2-2) and 576g of methoxyethyl methacrylate (a 2-3).

< 1-3 polyester methacrylate resin (a1-3) >

Dipropylene glycol (manufactured by tokyo chemical co., ltd.) was added to a reaction apparatus equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer: 604g, isophthalic acid (manufactured by Tokyo Kaisha): 1080g, heated to 205 ℃ in a nitrogen atmosphere, reacted for 3 hours, and then cooled to 100 ℃. Next, methyl hydroquinone was added thereto in air: 0.6G of glycidyl methacrylate (product name "ブレンマー G" available from Nichikoku K.K.): 498g were reacted at 120 ℃ to 130 ℃ for 2 hours to obtain 2182g of a mixture containing a polyester methacrylate resin (a 1-3).

< 2. mixing of radically polymerizable resin (a1) and radically polymerizable unsaturated monomer (a2) >

The components were mixed in the amounts shown in Table 1 to obtain a mixture VE1 containing a vinyl ester resin (a1-1), VE2, VE3, a mixture UA1 containing a urethane methacrylate resin (a1-2), and a mixture PMA1 containing a polyester methacrylate resin (a 1-3). The amount of the "onium" component added to the radically polymerizable unsaturated monomer (a2) includes the amount of the component added during the synthesis of the radically polymerizable resin (a 1).

TABLE 1

*: this component is added when the radical polymerizable resin (a1) is synthesized.

Tricyclodecenyloxyethyl methacrylate (a 2-1): フアンクリル FA-512MT manufactured by Hitachi Kabushiki Kaisha

Methoxyethyl methacrylate (a 2-2): mitsubishi ケミカル, アクリ エ ス テ ル MT

Phenoxyethyl methacrylate (a 2-3): eikebana chemical co-products ライトエステル PO

Diethylene glycol dimethacrylate (a 2-4): eikebana chemical products ライトエステル 2EG

Isobornyl methacrylate (a 2-5): eikebana chemical products ライトエステル IB-X

N-lauryl methacrylate (a 2-6): product of Eikezi chemical Co Ltd ライトエステル L

Methyl methacrylate (a 2-7): アクリ エ ス テ ル M manufactured by Mitsubishi ケミカル K.K

Trimethylolpropane trimethacrylate (a 2-8): eikebana chemical co-product ライトエステル TMP

Acryloyl morpholine: ACMO manufactured by KJ ケミカル K.K

Paraffin wax 125 ° F: manufactured by Nippon Kogyo K.K

Paraffin wax 115 ° F: manufactured by Nippon Kogyo K.K

2,4, 6-tris (dimethylaminomethyl) phenol: セイクオール TDMP manufactured by Seiko chemical Co., Ltd

Dibutyltin dilaurate: KS-1260, a product for medical applications

Methyl hydroquinone: manufactured by Beijing chemical industry of imperial envrionment Kabushiki Kaisha

Hydroquinone: manufactured by Beijing chemical industry of imperial envrionment Kabushiki Kaisha

<3. example >

<3-1 > examples 1 to 5>

(preparation of Material for repair)

The components shown in table 2 were left to stand at 20 ± 5 ℃ for 24 hours, and after keeping the temperature constant, they were mixed to prepare radical polymerizable resin compositions a1 to a5, repair materials X1 to X5, and curable resin composition C1, respectively. Using the prepared radical polymerizable resin compositions a1 to a5, repair materials X1 to X5, and curable resin composition C1, concrete panels were repaired in an environment of 20 ± 5 ℃ by the following steps in each example.

(repair of concrete slab)

The repairing methods in examples 1 to 5 were all performed based on embodiment 1 (fig. 1). Table 2 shows the radically polymerizable resin compositions A1 to A5 and the repair materials X1 to X5 used in the respective steps of examples 1 to 5. The curable resin composition C1 and the carbon fiber sheet D1 used in the reinforcing step were used in common in examples 1 to 5.

On the surface of the concrete slab from which the laitance layer was removed, the basis weight was 200g/m²A radical polymerizable resin composition A1-A5 was coated with a brush to form a1 st repair layer, and then immediately before curing, repair materials X1-X5 were coated with a trowel to form a release coatThe amount is 18kg/m²The repair layer 2 of (1). Then, the 1 st repair layer and the 2 nd repair layer were placed at 20 ± 5 ℃ to be cured. The thickness of the cured repair layer was 10 mm. Shown in Table 2 is the time T1[ h ] required for the repair layer to cure]. The determination of curing is performed by touching with a finger and confirming that no trace of the finger is left on the repair layer, that is, the repair layer is not plastically deformed by the finger touch (the same applies to the determination of curing below).

The surface of the cured repair layer was polished to a basis weight of 400g/m²The curable resin composition C1 was coated with a brush to form a1 st reinforcing layer. The carbon fiber sheet D1 was adhered to the 1 st reinforcing layer to form a reinforcing fiber layer. The weight of the reinforcing fiber layer is 300g/m²The curable resin composition C1 was coated using a roll to form a2 nd reinforcing layer. Then, the curable resin composition C1 contained in the 1 st reinforcing layer and the 2 nd reinforcing layer was cured. Curing is carried out by standing at 20. + -. 5 ℃. Table 2 shows the time T2[ h ] required for curing of the reinforcing layer]。

< 3-2 > comparative examples 1 to 2

A concrete panel was repaired in the same manner as in example 1, except that the 1 st repair layer forming step S1 was not performed in comparative example 1. Table 2 shows the cure time T1[ h ] for the repair layer and the cure time T2[ h ] for the reinforcement layer.

In comparative example 2, a concrete panel was repaired in the same manner as in example 1 except that the 1 st repair layer was left at 20 ± 5 ℃ for 12 hours (longer than the measured curing time of the radical polymerizable resin composition (a) in this comparative example) after the 1 st repair layer forming step and before the 2 nd repair layer forming step. Further, the 1 st repair layer after the placement was confirmed to have been cured by finger touch. The standing time T0[ h ] of the 1 st repair layer, the time T1[ h ] required for curing of the 2 nd repair layer, and the time T2[ h ] required for curing of the reinforcing layer are shown in table 2.

< 3-3 > comparative examples 3 to 4

In comparative example 3, the main agent and the curing agent were left in an atmosphere of 20. + -. 5 ℃ for 24 hours for each of an epoxy primer P (エポキシプライマー P, manufactured by Mitsubishi ケミカル イ ン フ ラ テ ッ ク corporation, product name "エポサーム (registered trademark) プライマー XPS-100"), an epoxy putty Q (エポキシパテ Q, manufactured by Mitsubishi ケミカル イ ン フ ラ テ ッ ク corporation, product name "エポサーム (registered trademark) パテ L-200"), and an epoxy resin R (エポキシレジン R, manufactured by Mitsubishi ケミカル イ ン フ ラ テ ッ ク corporation, product name "エポサーム (registered trademark) レジン XL-300"), a resin for impregnation by CFRP for seismic reinforcement. Then, the concrete panel was repaired in an environment of 20 ± 5 ℃ by the following procedure.

On the surface of the concrete slab from which the floating layer was removed, an epoxy primer P obtained by mixing a main agent and a curing agent was applied in an amount of 200g/m²Coating was performed using a brush to form a1 st repair layer (primer layer). The 1 st repair layer is then left to cure at 20 ± 5 ℃. Table 2 shows the time T0[ h ] required for the curing of the 1 st repair layer]。

The surface of the cured first repair layer 1 is mixed with an epoxy putty Q formed by mixing a main agent and a curing agent in a weight per mesh of 18Kg/m²The coating was performed using a rubber roller (ゴムベラ) to form a2 nd repair layer. The repair layer 2 is then left to cure at 20 + -5 deg.C. Table 2 shows the time T1[ h ] required for the curing of the 2 nd repair layer]。

An epoxy resin R mixed by a main agent and a curing agent is arranged on the surface of the cured 2 nd repairing layer in a way that the eye weight is 400g/m²Coating was performed using a roller to form the 1 st reinforcing layer. The carbon fiber sheets used in examples 1 to 5 were bonded to the 1 st reinforcing layer to form a reinforcing fiber layer. The epoxy resin R was applied to the reinforcing fiber layer by a roll at a basis weight of 300g/m²Coating is performed to form a2 nd reinforcing layer. Then, the epoxy resin R contained in the 1 st reinforcing layer and the 2 nd reinforcing layer is cured. Curing is carried out by standing at 20. + -. 5 ℃. Table 2 shows the time T2[ h ] required for curing of the reinforcing layer]。

A concrete slab was repaired in the same manner as in comparative example 1 except that the first repair layer 1 of comparative example 3 was not formed in comparative example 4. Table 2 shows the time T1[ h ] required for curing of the repair layer, and the time T2[ h ] required for curing of the reinforcement layer.

< 3-4 > examples 6 to 10 >

In examples 6 to 10, the components shown in Table 2 were left at-25. + -. 5 ℃ for 24 hours and mixed after keeping the temperature constant to produce radical polymerizable resin compositions A6 to A10, repair materials X6 to X10, and curable resin composition C2, respectively.

The procedure of examples 6 to 10 was the same as that of example 1 except that the temperatures of the repair layer curing step and the reinforcing layer curing step were-25 ± 5 ℃. Table 2 shows the radically polymerizable resin compositions A6 to A10 and the repair materials X6 to X10 used in the respective steps of examples 6 to 10. The curable resin composition C2 and the carbon fiber sheet D1 used in the reinforcing step were used in common in examples 6 to 10. Table 2 shows the times T1[ h ], T2[ h ] required for curing of the repair layer and the repair layer in each example.

< 3-5 > comparative examples 5 to 6

A concrete panel was repaired in the same manner as in example 6 except that the 1 st repair layer forming step S1 was not performed in comparative example 5. The cure time of the repair layer T1[ h ] and the cure time of the reinforcement layer T2[ h ] are shown in Table 2.

In comparative example 6, a concrete panel was repaired in the same manner as in example 6 except that the 1 st repair layer was left at-25. + -. 5 ℃ for 24 hours (in this comparative example, left to stand longer than the measured curing time of the radical polymerizable resin composition (A)) after the 1 st repair layer forming step and before the 2 nd repair layer forming step. Further, the 1 st repair layer after the placement was confirmed to have been cured by finger touch. Table 2 shows the time T0[ h ] for the 1 st repair layer to be left, the time T1[ h ] required for the 2 nd repair layer to cure, and the time T2[ h ] required for the reinforcement layer to cure.

< 3-6 > comparative example 7

In comparative example 7, an epoxy primer P (the same as that used in comparative example 3) comprising a mixture of a main agent and a curing agent was applied to the surface of the concrete slab from which the laitance layer was removed in an amount of 200g/m²Coating with a hairbrush to form a1 st repair layer. Then, the 1 st repair layer is cured at-25 +/-5 ℃, but even after 7 days, the coating film is not cured,so that the subsequent steps are not performed.

< 4. evaluation method >

< 4-1. Total curing time >

The total curing time was calculated as T1+ T2, which is the total of the repair layer curing time T1 and the reinforcement layer curing time T2, for each of the examples and comparative examples other than comparative examples 2 to 3 and comparative example 7, and as the total curing time, calculated as T0+ T1+ T2, which is the total of the repair layer leaving or curing time T0, the repair layer curing time T1, and the reinforcement layer curing time T2, for comparative examples 2 to 3. Table 2 shows the calculated total cure times. In comparative example 7, since no curing was performed, the total curing time could not be calculated.

< 4-2. test for adhesion of concrete >

Fig. 4 is a diagram showing a method of a concrete adhesion test. In each of examples 1 to 10 and comparative examples 1 to 6, a concrete adhesion test was performed on a cured repair layer 2 and a cured reinforcing layer 3 (hereinafter, referred to as "repair layer 2" and "reinforcing layer 3" in this project) formed on a concrete slab 1 according to the adhesive force test method of the national institute of research and development. The following description will be specifically made.

An additive 5 made of metal (bottom surface 4 cm. times.4 cm, attached area 1600 mm) was adhered to the surface of the reinforcing layer 3 with an adhesive 4²). As the adhesive 4, a quick-setting adhesive (クイックメンダー, manufactured by コニシ K.K.) was used in examples 1 to 5 and comparative examples 1 to 2, and the curing time of the adhesive 4 was 1 hour. In comparative examples 3 to 4, the curing time of the adhesive 4 was set to 24 hours using the same epoxy resin R as that used when the reinforcing layer 3 was integrated with the carbon fiber sheet. In examples 6 to 10 and comparative examples 5 to 6, the same curable resin composition C2 as used in the case of integrating the reinforcing layer 3 with the carbon fiber sheet was used, and the curing time of the binder 4 was 3 hours as long as the time T2 required for curing in the formation of the reinforcing layer 3.

After curing of the adhesive 4, a cut 6 is made along the periphery of the attachment 5 using a cutter to reach the depth of the concrete slab 1. The additive 5 is then applied perpendicularly (in the direction of arrow F in fig. 4) with respect to the surface of the reinforcement layer 3Pulling the steel sheet to pass through the maximum load [ N ] at the time of breaking]Divided by the area of attachment 5 of 1600mm²]Calculate the adhesive strength [ N/mm ]²]。

Further, the area of the broken portion of the concrete plate 1 in the portion of the concrete plate 1 to which the additive 5 was fixed was measured to determine the fixing area 1600[ mm ] to the additive 5²]As the base material (concrete) destruction ratio [% ]]. The area of the broken portion of the concrete panel 1 is determined by dividing the fixed portion of the additive 5 into a10 mm × 10mm mesh, approximating the portion of each mesh occupied by the broken portion of the concrete panel 1 to a triangle, a quadrangle, or a combination pattern thereof, and is the sum of the areas determined for each mesh. Table 2 shows the adhesive strength [ N/mm ] in each of examples and comparative examples except comparative example 7²]And base material destruction ratio [% ]]。

< 5. evaluation result >

As is clear from Table 2, in examples 1 to 5, the range of 20. + -. 5 ℃ and in examples 6 to 10, the range of-25. + -. 5 ℃ both gave high adhesive strength and base material failure ratio in a short total curing time. As the value of the adhesive strength is larger and the base material failure ratio is higher, it can be said that the concrete and the cured repair layer are more firmly bonded to each other and the cured repair layer and the cured reinforcing layer are more firmly bonded to each other.

In contrast, comparative example 3, in which the epoxy primer P was used in the 1 st repair layer forming step and the respective layers were cured at 20 ± 4 ℃ using the epoxy putty Q in the 2 nd repair layer forming step, had a long total curing time. In contrast, comparative example 4, in which the 1 st repair layer was not formed, had a longer total curing time and a lower adhesive strength and base material breakage ratio than comparative example 3. In addition, in comparative example 7 in which the epoxy primer P as the 1 st repair layer was to be cured at-25 ± 5 ℃, the epoxy primer P was not cured due to the low temperature.

Comparative example 1, in which the 1 st repair layer was not formed, had a lower adhesive strength and a lower base material breakage ratio than those of examples 1 to 5. This situation can be said to be the same when comparing comparative example 5 in which the 1 st repair layer is not formed with examples 6 to 10. From this, it is understood that the application of the radical polymerizable resin composition (a) before the application of the repair material (X) in the 2 nd repair layer forming step enables the concrete and the repair layer to be firmly joined.

In comparative example 2 in which the 1 st repair layer was cured before the 2 nd repair layer forming step S2, the adhesive strength and the base material breakage ratio were lower than those in examples 1 to 5. In this case, the same can be said in the case of comparing comparative example 6 in which the 1 st repair layer is cured with examples 6 to 10. Therefore, by forming the 2 nd repair layer before the 1 st repair layer is cured, the construction period can be shortened, and concrete can be firmly bonded to the cured repair layer.

As described above, when the following repairing method is applied to a concrete structure, a short period of time and high reliability can be ensured in a wide temperature range.

The repairing method comprises the following steps: a first repairing layer forming step of applying a radical polymerizable resin composition (A) to a structure to form a first repairing layer, a second repairing layer forming step of applying a repairing material (X) containing a radical polymerizable resin composition (Ax) and a filler (B) to the first repairing layer before the first repairing layer is cured to form a second repairing layer, and a repairing layer curing step of curing the radical polymerizable resin composition (A) and the radical polymerizable resin composition (Ax), wherein the radical polymerizable resin composition (A) and the radical polymerizable resin composition (Ax) contain at least 1 kind of radical polymerizable resin (a1) selected from a vinyl ester resin, a urethane (meth) acrylate resin, and a polyester (meth) acrylate resin, and at least 1 kind of radical polymerizable unsaturated monomer (a2) selected from a mono (meth) acrylate, a di (meth) acrylate, and a tri (meth) acrylate And a hydroxyl-containing tertiary aromatic amine (a3) represented by the general formula (I), and an organic peroxide (a4), wherein the content of the radical polymerizable resin (a1) and the radical polymerizable unsaturated monomer (a2) in the radical polymerizable resin compositions (A) and (Ax) is 75% by mass or more, and neither of the radical polymerizable resin compositions (A) and (Ax) contains a filler.

Description of the figures

1: concrete slab

2: repair layer

3: enhancement layer

4: adhesive agent

4: additive

6: incision