WO2022224989A1

WO2022224989A1 - Recess filling material kit, cured product thereof, and method for filling recess

Info

Publication number: WO2022224989A1
Application number: PCT/JP2022/018288
Authority: WO
Inventors: 陽一郎坂口; 広平斉藤
Original assignee: 昭和電工株式会社
Priority date: 2021-04-23
Filing date: 2022-04-20
Publication date: 2022-10-27
Also published as: JPWO2022224989A1; CN117136175A

Abstract

Provided are: a recess filling material kit which is capable of providing a construction method and the like that eliminates construction defects such as initial adhesion to a concrete material or a steel material used in a recess; a cured product thereof; and a method for filling a recess using the recess filling material kit. The recess filling material kit according to the present invention has first and second radical polymerizable resin compositions. The first radical polymerizable resin composition contains a first radical polymerizable compound (A-1), a first radical polymerizable unsaturated monomer (B-1), an acidic compound (C), and a first radical polymerization initiator (D-1). The second radical polymerizable resin composition contains a second radical polymerizable compound (A-2), a second radical polymerizable unsaturated monomer (B-2), a second radical polymerization initiator (D-2), an expansion material (J), cement (P), and aggregate (K).

Description

Recess filling material kit, its hardened product and recess filling method

TECHNICAL FIELD The present invention relates to a recess filling material kit, its cured product, and a recess filling method. In addition, the present invention provides a recess for connecting bolts, which is opened at the periphery of a segment used as a material in constructing a subway passage, a sewer pipe, a collecting pipe such as an electric wire or a gas pipe, etc., which are underground pipes. The present invention relates to a resin mortar filling method for filling recesses including inner or worn/worn or damaged reinforcing steel structures.
This application claims priority based on Japanese Patent Application No. 2021-073532 filed in Japan on April 23, 2021, the content of which is incorporated herein.

When constructing underground underground pipelines such as subway passages, sewage pipelines, collection pipelines for electric wires and gas pipes, etc., a vertical hole is excavated to a predetermined depth and a device is brought in to form a predetermined horizontal hole. While forming a horizontal hole by operating this device, the segments are sequentially connected to construct a pipeline having a predetermined diameter. The larger the diameter of the pipe, the deeper the excavation depth, and the weaker the ground, the stronger the segment. A concave portion (bolt box, box cut portion) is formed, and the segments are arranged so that the concave portions are adjacent to each other, and are joined by bolts and nuts or PC steel materials. There are an enormous number of these recesses and bolts and nuts in proportion to the size of the diameter of the pipe and the length of the pipe.

If the pipeline is used with this recess exposed, the bolt and nut will corrode due to various environmental factors. A mortar filling method has been used to prevent the corrosion of joints and, as a result, prevent the deterioration of joint strength.
However, the mortar filling method used at the time of construction has deteriorated due to long-term use, and various materials used at the time of construction are missing or completely damaged (falling off, etc.). It has also come to be seen here and there that the bolts and nuts are corroding.

If corroded bolts and nuts are left as they are, the joints of the connected pipelines will become weak, causing problems such as the infiltration of groundwater from the gaps between the segments, or the outflow of fluid flowing through the pipelines. becomes more frequent. In addition, bolt boxes in which the materials used in the mortar filling method are missing or completely damaged lead to an increase in the resistance of the fluid flowing in the pipeline, so immediate countermeasures are required.
In addition, the same problem as the repair of these recesses is aging deterioration of collection pipes such as subway roads, sewer pipes, electric wires, gas pipes, etc., including reinforced structures constructed underground in urban areas. Due to this deterioration over time, there are countless cracks and damages in the collection pipes, exposing the reinforcing bars, causing various problems such as the seepage of groundwater and river water into the pipes, or the outflow of sewage from the pipes. provoke. Therefore, immediate countermeasures are required. However, there were many problems with existing materials, such as adhesion to reinforcing bars and concrete structures, and the limited construction time, which is a problem unique to underground structures.

Examples of possible applications for this mortar filling method include a quick-setting mortar method in which a quick-setting mortar containing a quick-setting agent is manually filled or sprayed as described in Patent Document 1, and a lightweight mortar with a reduced specific gravity described in Patent Document 2. A lightweight mortar construction method in which mortar is hand-filled, a cured foaming urethane construction method in which a two-liquid curing and foaming type urethane composition is injected and filled as described in Patent Document 3, and the like are known. A case where an epoxy resin mortar is used to fill the recessed portions, or a case where an epoxy resin is mixed with water and emulsified as in Patent Document 5 is also conceivable.
However, none of the materials can simultaneously solve all problems such as adhesion to reinforcing bars, bolts, and concrete structures, and material shrinkage due to aging. .

On the other hand, radically polymerizable resin compositions are often used in resin mortar filling methods. For example, considerable shrinkage occurs when polymerization is carried out using common liquid vinyl monomers. Due to this shrinkage, problems such as insufficient strength occur when a vinyl monomer is used as the recess filling material. Therefore, it is industrially very significant to create a resin having a small shrinkage rate during polymerization.

Radically polymerizable resin compositions such as unsaturated polyester resins and vinyl ester resins (epoxy acrylate) usually also undergo shrinkage during curing. Since "styrene" and "methyl methacrylate", which are the monomers shown in Table 1 of Non-Patent Document 1, are often used as monomers, the unsaturated polyester resin in a general formulation is 8 to 12%, and the vinyl Ester resins are accompanied by volumetric shrinkage of about 8-10%.
This numerical value is a considerably large numerical value even when compared with the volumetric shrinkage of 3 to 6% for general epoxy resins. Therefore, it has prevented the use of unsaturated polyester resins or vinyl ester resins for industrial purposes, or their advancement into other industries and applications.

As a method for solving this problem, in Patent Document 6, by using polystyrene beads as a low-shrinkage material, it is possible to reduce the number of manufacturing steps or shorten the manufacturing time, and to achieve excellent low-shrinkage, dimensional stability, and surface smoothness. It is possible to produce a low-shrinkage unsaturated polyester resin composition having

Further, in Patent Document 7, by blending an AB type block copolymer into an unsaturated polyester resin composition, shrinkage at the time of curing is low, and a molded article having excellent heat resistance can be produced. It is stated that a shrinkable unsaturated polyester resin composition can be obtained.

Furthermore, in Patent Document 8, by mixing an AB type block copolymer (vinyl acetate-styrene type) consisting of segments A and B with an unsaturated polyester resin and fine particles of silicic acid, It is stated that it is possible to obtain a low-shrinkage unsaturated polyester resin composition that has a large low-shrinkage effect when molded at moderate temperatures and has a high degree of water resistance.

Japanese Patent No. 2700609 Japanese Patent Application Laid-Open No. 2001-270765 Japanese Patent No. 3479819 JP 2020-94192 A JP 2019-52203 A JP-A-11-315198 Japanese Patent No. 2794802 JP-A-05-222282

The present invention has been made in view of the above-mentioned conventional circumstances, and is compatible with materials for various mortar filling methods, such as cement concrete materials, polymer cement mortar materials, two-component curing/foaming urethane compositions, and epoxy resin mortar materials. It is possible to provide a construction method that eliminates construction defects such as initial adhesion, initial adhesion to concrete materials and steel materials used in recesses, and falling off due to shrinkage during hardening of resin materials.
Further, in conventional radically polymerizable resin compositions, thermoplastic resins such as polystyrene are blended alone or block copolymers of two or more types are used in order to create resins with low shrinkage. Most of them functioned as "anti-shrinkage materials".
These resin compositions are based on the idea of offsetting the thermal expansion of thermoplastic resins due to the heat generated by curing and the curing shrinkage of unsaturated polyester resins. BMC), etc., are often limited to applications where heat molding is performed in the medium temperature range or higher.

The present invention has been made in view of the above-mentioned conventional circumstances, and by incorporating an expanding material instead of an anti-shrinking material, the curing of the resin composition is not limited to the molding method, temperature of use, application, etc. It is intended to provide a recess filling material kit containing a radically polymerizable resin composition whose shrinkage rate is small when the whole expands at a constant ratio and then stabilizes, a cured product thereof, and a recess filling method using the same. In addition to the purpose, by using a primer for metal adhesion, it is possible to ensure adhesion to reinforcing steel structures, bolts, etc. existing in the recess.

That is, the present invention is represented by the following [1] to [13].
[1] A recess filling material kit comprising a first radically polymerizable resin composition and a second radically polymerizable resin composition,
The first radically polymerizable resin composition comprises a first radically polymerizable compound (A-1), a first radically polymerizable unsaturated monomer (B-1), an acidic compound (C), and a first containing a radical polymerization initiator (D-1),
The second radically polymerizable resin composition comprises a second radically polymerizable compound (A-2), a second radically polymerizable unsaturated monomer (B-2), and a second radical polymerization initiator (D- 2), a cement (P), an expanding material (J), and an aggregate (K).
[2] The recess filler kit according to [1], wherein the first radically polymerizable compound (A-1) and the second radically polymerizable compound (A-2) each independently contain a vinyl ester resin. .
[3] The recess filling material kit according to [1] or [2], wherein the expanding material (J) contains at least one selected from the group consisting of quicklime and calcium sulfoaluminate.
[4] Any one of [1] to [3], wherein the first radical polymerization initiator (D-1) and the second radical polymerization initiator (D-2) are each independently hydroperoxides A recess filler kit as described.
[5] The first radically polymerizable resin composition further contains a first metal-containing compound (E-1) and a first thiol compound (F-1),
The recess according to any one of [1] to [4], wherein the second radically polymerizable resin composition further contains a second metal-containing compound (E-2) and a second thiol compound (F-2). filler kit.
[6] The expansion agent (J) is 0.3 parts per 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). Parts by mass to 30 parts by mass,
20 parts by mass to 200 parts by mass of the cement (P) with respect to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) and
200 parts by mass to 800 parts by mass of the aggregate (K) with respect to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) The recess filling material kit according to any one of [1] to [5], which is a part.
[7] The first radical polymerization initiator (D- 1) is 0.1 parts by mass to 10 parts by mass,
The second radical polymerization initiator (D-2) is added to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). The recess filling material kit according to any one of [1] to [6], which is 0.1 to 10 parts by mass.
[8] In the first radically polymerizable resin composition, with respect to a total of 100 parts by mass of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1), The recess filling material kit according to any one of [1] to [7], wherein the acidic compound (C) is 1 to 20 parts by mass.
[9] The recess filling material kit according to any one of [1] to [8], wherein the acidic compound (C) is an unsaturated monobasic acid.
[10] The recess filling material according to any one of [1] to [9], wherein the first radical polymerization initiator (D-1) is a photoradical polymerization initiator having photosensitivity from ultraviolet light to visible light region. kit.
[11] A cured product of the recess filling material kit according to any one of [1] to [10], wherein the first cured product, which is a cured product of the first radically polymerizable resin composition, is applied to the surfaces of the recesses. is formed, and a second cured product of the second radically polymerizable resin composition is formed on the first cured product.
[12] A recess filling method for filling recesses using the recess filling material kit according to any one of [1] to [10],
a base layer forming step of applying the first radically polymerizable resin composition to the surface of the recess to form a base layer;
and a filling step of filling the surface of the underlayer formed on the surface of the recess with the second radically polymerizable resin composition.
[13] The recess filling method according to [12], wherein the recess is a bolt box.

According to the present invention, initial adhesion to concrete substrates, steel jigs (bolts), reinforcing steel structures, etc., falling off due to shrinkage during hardening of organic resin materials, and inside the box during pipe line operation The structure itself can be protected from corrosion and abrasion caused by fluid flowing through the pipe, vibration from cars and trains, wind pressure, etc., and the long-term operation of the pipeline itself becomes possible.
According to the present invention, the addition of an acidic compound to the first radically polymerizable resin composition can achieve initial adhesion not only to concrete substrates but also to steel jigs and reinforcing steel structures. In addition, according to one embodiment of the present invention, the first radically polymerizable resin composition has the effect of complexing a metal soap with a thiol having a specific structure, and the addition of an acidic compound. Initial adhesion with jigs, rebar structures, etc. can be achieved. As the second radically polymerizable resin composition, an appropriate amount of expansion material is added to a radically polymerizable resin composition that causes cure shrinkage due to a decrease in the free volume of the liquid component during curing. , a recess filling material kit having a radically polymerizable resin composition that expands at a constant rate when the resin composition is cured and then stabilizes, so that the shrinkage rate is small, without being limited to the application, and A cured product thereof can be provided.
In addition, it is possible to provide a recess filling method that combines these methods.

It is a figure which shows the manufacturing method of a test piece. (a) before casting, (b) during casting, (c) during curing.

The present invention will be described in detail below.
[Recess filling material kit]
The recess filling material kit of the present embodiment basically consists of the first radically polymerizable resin composition and the second radically polymerizable resin composition. However, other members, compositions, and the like may be included. The first radically polymerizable resin composition comprises a first radically polymerizable compound (A-1), a first radically polymerizable unsaturated monomer (B-1), an acidic compound (C), and a first and a radical polymerization initiator (D-1). The second radically polymerizable resin composition comprises a second radically polymerizable compound (A-2), a second radically polymerizable unsaturated monomer (B-2), and a second radical polymerization initiator (D- 2), expansive material (J), cement (P), and aggregate (K). In the recess to be filled, the first radically polymerizable resin composition and the second radically polymerizable resin composition are arranged independently of each other.
The reason why the recess filling material kit of the present embodiment includes the first radically polymerizable resin composition and the second radically polymerizable resin composition is that, with respect to the filling (repairing) portion of the recess, Both radically polymerizable compositions are arranged independently. It is not intended to mix both radically polymerizable compositions and use them as one recess filler mixture. Also, the meaning of "arranged independently" means that they are not mixed with each other before use. For example, a form of storing in each container or a form of storing in one container having a structure that is not mixed can be mentioned.

(First radically polymerizable resin composition)
The first radically polymerizable resin composition of the present embodiment comprises a first radically polymerizable compound (A-1), a first radically polymerizable unsaturated monomer (B-1), and an acidic compound (C). , and a first radical polymerization initiator (D-1). The first radically polymerizable resin composition of the present embodiment comprises, if necessary, a first metal-containing compound (E-1), a first thiol compound (F-1), a first polymerization inhibitor (H-1), A first curing retarder (I-1) or the like may be contained.

<First Radically Polymerizable Compound (A-1)>
The first radically polymerizable compound (A-1) of the present embodiment does not contain a first radically polymerizable unsaturated monomer (B-1) and an acidic compound (C) described below, and does not contain an ethylenic unsaturated monomer in the molecule. It refers to a resin or polymeric compound that has one or more saturated groups and undergoes a polymerization reaction by means of radicals.
The first radically polymerizable compound (A-1) of the present embodiment uses a radically polymerizable compound described below for the second radically polymerizable compound (A-2) of the present embodiment or preferred examples thereof. be able to. The first radically polymerizable compound (A-1) is preferably the same radically polymerizable compound as the second radically polymerizable compound (A-2), and the first radically polymerizable compound (A-1) is , it is more preferable to use the same radically polymerizable compound as the second radically polymerizable compound (A-2).
A radically polymerizable compound different from the second radically polymerizable compound (A-2) may be used as the first radically polymerizable compound (A-1).
For example, as the first radically polymerizable compound (A-1), it is preferable to use one or more selected from vinyl ester resins (epoxy (meth)acrylate resins), unsaturated polyester resins, and urethane (meth)acrylate resins. , it is more preferable to use a vinyl ester resin.

<First Radically Polymerizable Unsaturated Monomer (B-1)>
The first radically polymerizable unsaturated monomer (B-1) of the present embodiment is not particularly limited as long as it is a monomer that does not contain an acidic compound (C) described later and has a radically polymerizable unsaturated group. do not have. Preferred are monomers having a vinyl group, an allyl group, or a (meth)acryloyl group.
The first radically polymerizable unsaturated monomer (B-1) of the present embodiment is a radically polymerizable unsaturated monomer (B-2) described later in the second radically polymerizable unsaturated monomer of the present embodiment. Unsaturated monomers or preferred examples thereof can be used. The first radically polymerizable unsaturated monomer (B-1) is preferably the same radically polymerizable unsaturated monomer as the second radically polymerizable unsaturated monomer (B-2), More preferably, the first radically polymerizable unsaturated monomer (B-1) uses the same radically polymerizable unsaturated monomer as the second radically polymerizable unsaturated monomer (B-2).
A radically polymerizable unsaturated monomer different from the second radically polymerizable unsaturated monomer (B-2) may be used as the first radically polymerizable unsaturated monomer (B-1).
For example, as the first radically polymerizable unsaturated monomer (B-1), it is preferable to use styrene from the viewpoint of versatility. is preferred, a cyclic hydrocarbon group-containing (meth)acrylate is more preferred, dicyclopentanyl (meth)acrylate is even more preferred, and dicyclopentanyl methacrylate is even more preferred. By using the first radically polymerizable unsaturated monomer (B-1), the viscosity of the first radically polymerizable resin composition can be lowered and workability can be improved. In addition, the hardness, strength, chemical resistance, water resistance, etc. of the cured product can be improved. From such a point of view, the content of the first radically polymerizable unsaturated monomer (B-1) is 10 to 250 parts by mass with respect to 100 parts by mass of the first radically polymerizable compound (A-1). preferably 50 to 200 parts by mass, and even more preferably 80 to 150 parts by mass. When the content of the first radically polymerizable unsaturated monomer (B-1) is 10 parts by mass or more, the viscosity of the first radically polymerizable resin composition is sufficiently low, and the impregnation of the concave portion filling portion is also improve. When the content of the first radically polymerizable unsaturated monomer (B-1) is 250 parts by mass or less, sufficient coating film strength is obtained, and chemical resistance, water resistance, and the like are improved.

<Acidic compound (C)>
The acidic compound (C) used in the present embodiment is not particularly limited as long as it is a compound exhibiting acidity. As the acidic compound (C), an organic acid having a carboxy group is preferable, and a compound having an ethylenically unsaturated bond and a carboxy group is more preferable. Monobasic acids are particularly preferred. Specifically, (meth) acrylic acid, crotonic acid, cinnamic acid, unsaturated monobasic acids such as sorbic acid, acetic acid, saturated monobasic acids such as propionic acid, dicyclopentadiene and polyvalent carboxylic acid compounds (for example, succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.). From the viewpoint of curability of the first radically polymerizable resin composition, unsaturated monobasic acid is preferred, and (meth)acrylic acid is more preferred.

The amount of the acidic compound (C) used is preferably 0.00 parts per 100 parts by mass in total of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). 5 to 25 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 5 to 15 parts by mass. When the amount of the acidic compound (C) used is 0.5 parts by mass or more, sufficient adhesion to the adherend can be obtained. When the amount is 25 parts by mass or less, a sufficient effective strength is obtained and the adhesion to the adherend is not adversely affected.

<First radical polymerization initiator (D-1)>
The first radical polymerization initiator (D-1) of the present embodiment is a radical polymerization initiator described in the second radical polymerization initiator (D-2) of the present embodiment described later, or preferred examples thereof are used. be able to. The first radical polymerization initiator (D-1) is preferably the same type of radical polymerization initiator as the second radical polymerization initiator (D-2), and the first radical polymerization initiator (D-1) is , it is more preferable to use the same radical polymerization initiator as the second radical polymerization initiator (D-2).
A different radical polymerization initiator from the second radical polymerization initiator (D-2) may be used as the first radical polymerization initiator (D-1).
The content of the first radical polymerization initiator (D-1) is a total of 100 parts by mass of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). On the other hand, it is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, still more preferably 1 to 3 parts by mass. When the content of the first radical polymerization initiator (D-1) is 0.1 parts by mass or more, sufficient curability can be expected without tackiness on the surface of the cured product. When the content of the first radical polymerization initiator (D-1) is 10 parts by mass or less, the physical properties of the cured product are not adversely affected.

<First metal-containing compound (E-1)>
The first radically polymerizable resin composition of the present embodiment may contain the first metal-containing compound (E-1) as a curing accelerator, if necessary. As the first metal-containing compound (E-1), metal-containing compounds described in the second metal-containing compound (E-2) of the present embodiment described below or preferred examples thereof can be used. The first metal-containing compound (E-1) is preferably the same kind of metal-containing compound as the second metal-containing compound (E-2), and the first metal-containing compound (E-1) is the second metal It is more preferable to use the same radical polymerization initiator as the contained compound (E-2).
A metal-containing compound different from the second metal-containing compound (E-2) may be used as the first metal-containing compound (E-1).
The content of the first metal-containing compound (E-1) is based on a total of 100 parts by mass of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). , preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 3 parts by mass, still more preferably 0.005 to 1 part by mass. When the content of the first metal-containing compound (E-1) is 0.0001 parts by mass or more, curing proceeds rapidly. When the content of the first metal-containing compound (E-1) is 5 parts by mass or less, the physical properties of the cured product are not adversely affected.

<First thiol compound (F-1)>
The first radically polymerizable resin composition of the present embodiment may contain the first thiol compound (F-1) as a curing accelerator, if necessary. In addition, when used in combination with the first metal-containing compound (E-1), the first thiol compound (F-1) is coordinated in the vicinity of the metal of the first metal-containing compound (E-1). , can also be expected to prevent the deactivation of metals by water. As the first thiol compound (F-1), a thiol compound described in the second thiol compound (F-2) of the present embodiment described below or preferred examples thereof can be used. The first thiol compound (F-1) is preferably the same type of thiol compound as the second thiol compound (F-2), and the first thiol compound (F-1) is the second thiol compound (F- It is more preferable to use the same thiol compound as in 2).
A thiol compound different from the second thiol compound (F-2) may be used as the first thiol compound (F-1).
The content of the first thiol compound (F-1) is based on a total of 100 parts by mass of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). , Preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, more preferably 0.1 to 5 parts by mass The content of the first thiol compound (F-1) is 0.01 Curing advances rapidly as it is more than a part by mass. When the content of the first thiol compound (F-1) is 10 parts by mass or less, the physical properties of the cured product are not adversely affected.

<First curing accelerator (G-1)>
The first radically polymerizable resin composition of the present embodiment, for the purpose of improving the curability, the first curing accelerator other than the first metal-containing compound (E-1) and the first thiol compound (F-1) It may contain an agent (G-1). The first curing accelerator (G-1) of the present embodiment can be a curing accelerator described in the second curing accelerator (G-2) of the present embodiment described later or preferred examples thereof. . The first curing accelerator (G-1) is preferably the same type of curing accelerator as the second curing accelerator (G-2), and the first curing accelerator (G-1) is the second curing It is more preferable to use the same curing accelerator as the accelerator (G-2).
A curing accelerator different from the second curing accelerator (G-2) may be used as the first curing accelerator (G-1).
When the first radically polymerizable resin composition of the present embodiment contains the first curing accelerator (G-1), the amount thereof is the first radically polymerizable compound (A-1) and the first radically polymerizable non- With respect to a total of 100 parts by mass of the saturated monomer (B-1), preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, still more preferably 0.1 to 3 parts by mass be.

<First polymerization inhibitor (H-1)>
The first radically polymerizable resin composition of the present embodiment may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of the first radically polymerizable compound (A-1) and from the viewpoint of controlling the reaction rate. As the first polymerization inhibitor (H-1) of the present embodiment, polymerization inhibitors described in the second polymerization inhibitor (H-2) of the present embodiment described below or preferred examples thereof can be used. . The first polymerization inhibitor (H-1) is preferably the same type of polymerization inhibitor as the second polymerization inhibitor (H-2), and the first polymerization inhibitor (H-1) is the second polymerization inhibitor. It is more preferable to use the same polymerization inhibitor as the inhibitor (H-2).
A polymerization inhibitor different from the second polymerization inhibitor (H-2) may be used as the first polymerization inhibitor (H-1).
When the first radically polymerizable resin composition contains the first polymerization inhibitor (H-1), the amount thereof is the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer ( B-1) is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 3 parts by mass, still more preferably 0.01 to 1 part by mass, per 100 parts by mass of B-1).

<First curing retardant (I-1)>
The first radically polymerizable resin composition of the present embodiment may contain a curing retarder for the purpose of retarding the curing of the first radically polymerizable compound (A-1). The first curing retarder (I-1) of the present embodiment can be a curing retarder described in the second curing retarder (I-2) of the present embodiment described later or preferred examples thereof. . The first curing retarder (I-1) is preferably the same type of curing retarder as the second curing retarder (I-2), and the first curing retarder (I-1) is the second curing It is more preferable to use the same retarder as the retarder (I-2).
A different curing retarder from the second curing retarder (I-2) may be used as the first curing retarder (I-1).
When the first radically polymerizable resin composition contains the first curing retarder (I-1), the amount thereof is the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer ( B-1) is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, still more preferably 0.05 to 3 parts by mass, per 100 parts by mass of B-1).

<Other ingredients>
The first radically polymerizable resin composition of the present embodiment may contain components other than the above components as long as they do not affect the strength development and acid resistance of the cured product. Ingredients that can be contained include, for example, hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, as well as properties such as setting adjustment, curing acceleration, curing delay, thickening, water retention, defoaming, water repellency, and waterproofing. Admixtures such as fibers made of materials such as metals, polymers, and carbon, pigments, extenders, foaming materials, and clay minerals such as zeolite can be mentioned. Components that can be contained include coupling agents, plasticizers, anion-fixing components, solvents, polyisocyanato compounds, surfactants, wetting and dispersing agents, waxes, and thixotropic agents.
The other components that can be used in the first radically polymerizable resin composition of the present embodiment are those described as other components that can be used in the second radically polymerizable resin composition of the present embodiment described later. Preferred examples thereof can be used. When the same other components are used in both the first radically polymerizable resin composition and the second radically polymerizable resin composition, it is preferable to use the same type of compound, more preferably the same compound.
When the same other components are used in both the first radically polymerizable resin composition and the second radically polymerizable resin composition, different compounds may be used.
It can be used for the first radically polymerizable resin composition of the present embodiment. As the other components, in addition to the compounds exemplified in the item of the second radically polymerizable resin composition, those exemplified below can also be used. In addition, components whose purpose of addition is different from that of the second radically polymerizable resin composition will be supplemented below.

[Coupling agent]
As the coupling agent, a coupling agent that may be contained in the second radically polymerizable resin composition described later can be used. The content of the coupling agent is preferably 0.5 parts per 100 parts by mass in total of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). 1 to 20 parts by mass.

[Anion immobilization component]
As the anion-fixing component, an anion-fixing component that may be contained in the second radically polymerizable resin composition described later can be used. In particular, when a reinforcing bar or the like is exposed at the filling portion of the recess, the influence of metal corrosion, particularly metal corrosion due to salt content, can be reduced.

[First thixotropic agent]
The first radically polymerizable resin composition of the present embodiment may further contain a first thixotropic agent. As the first thixotropic agent used in this embodiment, a known one can be used. Further, the first thixotropic agent used in the present embodiment can be a second thixotropic agent that may be contained in the second radically polymerizable resin composition described later. Examples of the first thixotropic agent used in the present embodiment include inorganic silica powder (Aerosil type), mica powder, calcium carbonate powder, short fiber asbestos, and organic hydrogenated castor oil. A silica powder-based thixotropic agent is preferred. Also, a thixotropic agent or the like may be used in combination. The amount of the first thixotropic agent used in the present embodiment is 100 parts by mass in total of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). On the other hand, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass. When the amount of the first thixotropic agent used is 0.1 or more, sufficient thixotropy can be obtained, and when it is 20 parts by mass or less, sufficient curability as the first radically polymerizable resin composition can be obtained. Adhesion to the adherend is improved.

<Method for Producing First Radically Polymerizable Resin Composition>
The method for producing the first radically polymerizable resin composition of the present embodiment is not particularly limited, and methods known in the art can be used. For example, the first radically polymerizable resin composition comprises the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1), and optionally the first metal-containing compound It can be produced by mixing (E-1), mixing the acidic compound (C), and further blending and mixing the first radical polymerization initiator (D-1).
In one embodiment of the method for producing the first radically polymerizable resin composition of the present embodiment, the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1) are A step (1-S1) of obtaining a mixture (1-i) by mixing the first metal-containing compound (E-1) as necessary, and mixing the mixture (1-i) with an acidic compound (C) , a step (1-S2) of obtaining a mixture (1-ii), and a first radically polymerizable resin composition (hardening and a step (1-S3) of obtaining a primer).

In the step (1-S1) of obtaining the mixture (i) (sometimes simply referred to as “step (1-S1)”), the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated In addition to mixing the first metal-containing compound (E-1) with the monomer (B-1), if necessary, the first thiol compound (F-1) and the first polymerization inhibitor ( H-1), the first curing retarder (I-1), the first thixotropic agent, an anion fixing component, etc. may be mixed.
After the step (1-S3) of obtaining the first radically polymerizable resin composition (sometimes simply referred to as “step (1-S3)”), the resulting first radically polymerizable resin composition is optionally Fibers and the like may be further mixed in, as required.

(Second radically polymerizable resin composition)
The second radically polymerizable resin composition of the present embodiment comprises a second radically polymerizable compound (A-2), a second radically polymerizable unsaturated monomer (B-2), and a second radical polymerization initiator. (D-2), expansive material (J), cement (P), and aggregate (K). The second radically polymerizable resin composition of the present embodiment comprises, if necessary, a second metal-containing compound (E-2), a second thiol compound (F-2), a second polymerization inhibitor (H-2), A second curing retardant (I-2), fibers (L), etc. may be contained.

<Second Radically Polymerizable Compound (A-2)>
The second radically polymerizable resin composition of the present embodiment uses the second radically polymerizable compound (A-2). In the present embodiment, the second radically polymerizable compound (A-2) does not contain a second radically polymerizable unsaturated monomer (B-2) described later, and has an ethylenically unsaturated group in the molecule. It refers to a resin or multimeric compound that has one or more and undergoes a polymerization reaction by means of radicals.
Examples of the second radically polymerizable compound (A-2) include vinyl ester resins (epoxy (meth)acrylate resins), unsaturated polyester resins, polyester (meth)acrylate resins, urethane (meth)acrylate resins, and (meth)acrylate resins. etc. Among them, one or more selected from vinyl ester resins and unsaturated polyester resins are preferable, and vinyl ester resins are more preferable. In addition, in this specification, "(meth)acrylate" means "acrylate or methacrylate."

[Vinyl ester resin]
As the vinyl ester resin, one obtained by reacting an epoxy resin with an unsaturated monobasic acid can be used.

Examples of the epoxy resins include bisphenol-type epoxy resins, biphenyl-type epoxy resins, novolak-type epoxy resins, trisphenolmethane-type epoxy resins, aralkyldiphenol-type epoxy resins, naphthalene-type epoxy resins, and aliphatic-type epoxy resins. These may be used singly or in combination. From the viewpoint of reducing the viscosity of the synthesized vinyl ester resin, it is preferable to use only an aliphatic epoxy resin or to use a combination of a bisphenol epoxy resin and an aliphatic epoxy resin.

Examples of bisphenol-type epoxy resins include those obtained by reacting bisphenols with epichlorohydrin and/or methyl epichlorohydrin, and those obtained by reacting glycidyl ether of bisphenol A with condensates of the bisphenols with epichlorohydrin and/or methyl epichlorohydrin. and the like. Bisphenols include bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A and the like.
Examples of biphenyl-type epoxy resins include those obtained by reacting biphenol with epichlorohydrin and/or methyl epichlorohydrin.

Examples of novolac-type epoxy resins include those obtained by reacting phenol novolak or cresol novolak with epichlorohydrin and/or methyl epichlorohydrin.
Examples of trisphenolmethane-type epoxy resins include those obtained by reacting trisphenolmethane, tris-cresolmethane with epichlorohydrin and/or methylepichlorohydrin.
Examples of aralkyldiphenol type epoxy resins include those obtained by reacting aralkylphenol with epichlorohydrin and/or methyl epichlorohydrin.

Examples of naphthalene-type epoxy resins include those obtained by reacting dihydroxynaphthalene with epichlorohydrin and/or methyl epichlorohydrin.

Aliphatic epoxy resins include alicyclic epoxy resins, alicyclic diol diglycidyl ether epoxy resins, aliphatic diol diglycidyl ether epoxy resins, poly(oxyalkylene) glycol diglycidyl ether epoxy resins, and the like. mentioned.

Alicyclic epoxy resins include, for example, allicyclic diepoxyacetal, allicyclic diepoxyadipate, and allicyclic diepoxycarboxylate.
Specific examples of the alicyclic diol diglycidyl ether include those having 3 carbon atoms such as cyclohexanedimethanol diglycidyl ether, dicyclopentenyldialcohol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, and dihydroxyterpene diglycidyl ether. to 20 (preferably 6 to 12 carbon atoms, more preferably 7 to 10 carbon atoms) diglycidyl ethers of alicyclic diols. Among these, "Denacol EX-216L" manufactured by Nagase ChemteX Corporation is available as a commercial product of cyclohexanedimethanol diglycidyl ether.

Specific examples of the aliphatic diol diglycidyl ether include 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, and the like. to 20 (preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, particularly preferably 4 to 6 carbon atoms), and diglycidyl ethers of aliphatic diols. Among these, commercial products of 1,6-hexanediol diglycidyl ether include "Denacol EX-212L" manufactured by Nagase ChemteX Corporation, "SR-16H" and "SR-16HL" manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., Yokkaichi Gosei Co., Ltd.'s "Epogose (registered trademark) HD" and the like. As a commercial product of 1,4-butanediol diglycidyl ether, there is "Denacol EX-214L" manufactured by Nagase ChemteX Corporation.

Specific examples of poly(oxyalkylene) glycol diglycidyl ether include diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and poly(tetramethylene) glycol diglycidyl ether. etc.

Preferred examples of aliphatic epoxy resins include 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and poly(tetramethylene) glycol diglycidyl ether. Among them, those having a number average molecular weight of 150 to 1,000 are more preferable.

The epoxy resin may be a diglycidyl ester such as diglycidyl dimer acid or diglycidyl hexahydrophthalate. Moreover, as said epoxy resin, the epoxy resin which has an oxazolidone ring obtained by reacting the said epoxy resin and diisocyanate is mentioned. Specific examples of epoxy resins having an oxazolidone ring include Araldite (registered trademark) AER4152 manufactured by Asahi Kasei Epoxy.

A known unsaturated monobasic acid can be used, and examples thereof include (meth)acrylic acid, crotonic acid, and cinnamic acid. A reaction product of a compound having one hydroxy group and one or more (meth)acryloyl groups and a polybasic acid anhydride may also be used. In the present specification, "(meth)acrylic acid" means one or both of "acrylic acid and methacrylic acid", and "(meth)acryloyl group" means "acryloyl group and methacryloyl group means one or both of
The polybasic acid is used to increase the molecular weight of the epoxy resin, and known polybasic acids can be used. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol/2 molar maleic anhydride adduct, polyethylene Glycol/2 mol maleic anhydride adduct, propylene glycol/2 mol maleic anhydride adduct, polypropylene glycol/2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16-(6 -ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyldodecane)dicarboxylic acid, carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name: Hycar CTBN), and the like.

[Unsaturated polyester resin]
As the unsaturated polyester resin, one obtained by subjecting an unsaturated dibasic acid, and optionally a dibasic acid component containing a saturated dibasic acid, to an esterification reaction with a polyhydric alcohol component can be used. .
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. These may be used alone or in combination of two or more.
Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid and isosebacic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid and terephthalic acid. , tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4 , 4′-biphenyldicarboxylic acid, aromatic dibasic acids such as dialkyl esters thereof, halogenated saturated dibasic acids, etc. These may be used alone or in combination of two or more.

The polyhydric alcohol is not particularly limited, but examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2 , 2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol , dipropylene glycol, polypropylene glycol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol , 2,6-decalin glycol, dihydric alcohols such as 2,7-decalin glycol;
Dihydric alcohols such as adducts of dihydric phenols represented by hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and alkylene oxides represented by propylene oxide or ethylene oxide ;
Examples include trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

As the unsaturated polyester, one modified with a dicyclopentadiene-based compound may be used as long as the effects of the present embodiment are not impaired. As for the modification method with a dicyclopentadiene-based compound, for example, after obtaining a dicyclopentadiene and maleic acid addition product (cidecanol monomaleate), this is used as a monobasic acid to introduce a dicyclopentadiene skeleton. and other known methods.
Oxidative polymerization (air curing) groups such as allyl groups or benzyl groups can be introduced into the vinyl ester resin or unsaturated polyester resin used in this embodiment. The introduction method is not particularly limited, but for example, addition of an oxidation polymerizable group-containing polymer, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidylphenyl allyl ether, hydroxyl group and allyl ether. A method of adding a reaction product of a compound having a group and an acid anhydride can be used.
Note that the oxidative polymerization (air curing) in the present embodiment refers to cross-linking associated with generation and decomposition of peroxide due to oxidation of the methylene bond between the ether bond and the double bond, which is found in, for example, allyl ether groups. Point.

[Polyester (meth)acrylate resin, urethane (meth)acrylate resin, and (meth)acrylate resin]
As the polyester (meth)acrylate resin in the present embodiment, for example, a polyester obtained by reacting a polyhydric carboxylic acid and a polyhydric alcohol, specifically, for hydroxyl groups at both terminals such as polyethylene terephthalate, ( A resin obtained by reacting meth)acrylic acid can be used.
As the urethane (meth)acrylate resin, for example, a polyurethane obtained by reacting an isocyanate and a polyhydric alcohol is obtained by reacting hydroxyl groups or isocyanato groups at both ends of the polyurethane with (meth)acrylic acid. Resin can be used.
Examples of (meth)acrylate resins include, for example, poly(meth)acrylic resins having one or more substituents selected from hydroxyl groups, isocyanato groups, carboxyl groups and epoxy groups, and monomers having the substituents and (meth ) A resin obtained by reacting a (meth)acrylic acid ester having a hydroxyl group with a substituent of a polymer with an acrylate can be used.

The second radically polymerizable compound (A-2) may contain residual catalysts or polymerization inhibitors used in synthesizing the resin or the like. Examples of the catalyst include compounds containing tertiary nitrogen such as triethylamine, pyridine derivatives and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; phosphorus compounds such as trimethylphosphine and triphenylphosphine.
Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, and phenothiazine.
When the catalyst or polymerization inhibitor remains in the second radically polymerizable compound (A-2), the amount thereof is preferably 0.001 to 2% by mass.

[Second Radically Polymerizable Unsaturated Monomer (B-2)]
The second radically polymerizable unsaturated monomer (B-2) is not particularly limited as long as it is a monomer having a radically polymerizable unsaturated group, but a vinyl group, an allyl group or a (meth)acryloyl group is preferred. Also, it may be an unsaturated monobasic acid.
Specific examples of vinyl group-containing monomers include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyl acetate, diallyl phthalate, and triallyl isocyanurate. etc.

Specific examples of monomers having a (meth)acryloyl group include (meth)acrylic acid esters. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, (meth) acrylic 2-ethylhexyl acid, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylates, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono-2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, Diethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monohexyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, neopentyl glycol di(meth)acrylate, PTMG dimethacrylate, 1,3-butylene glycol di (meth) acrylate, 1,6-hexanediol di(meth) acrylate, neopentyl glycol di(meth) acrylate, 2-hydroxy-1,3-dimethacryloxypropane, 2,2-bis[4-(methacryloylethoxy ) phenyl]propane, 2,2-bis[4-(methacryloxy-diethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy-polyethoxy)phenyl]propane, tetraethylene glycol di(meth)acrylate, bisphenol AEO Modified (n=2) di(meth)acrylate, isocyanuric acid EO modified (n=3) di(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxy Ethyl (meth)acrylate, trisic Rhodecanyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate (meth)acrylate and the like can be mentioned.

Furthermore, polyfunctional (meth)acrylic acid esters include, for example, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1, alkanediol di(meth)acrylates such as 4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol Polyoxyalkylene glycol di(meth)acrylates such as di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (meth)acrylate; trimethylolpropane di(meth)acrylate, Glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate and the like.

Furthermore, the following compounds can also be used as the second radically polymerizable unsaturated monomer (B-2). Specifically, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl fumarate, allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl Ether, Vinylbenzyl(2-ethylhexyl)ether, Vinylbenzyl(β-methoxymethyl)ether, Vinylbenzyl(n-butoxypropyl)ether, Vinylbenzylcyclohexyl ether, Vinylbenzyl(β-phenoxyethyl)ether, Vinylbenzyldicyclo Mention may be made of pentenyl ether, vinylbenzyldicyclopentenyloxyethyl ether, vinylbenzyldicyclopentenylmethyl ether, divinylbenzyl ether, (meth)acrylic acid.
These may be used alone or in combination of two or more.
Among them, it is preferable to use styrene from the viewpoint of versatility, and from the viewpoint of reducing odor and reducing the burden on the environment, a (meth) acryloyl group-containing monomer is preferable, and a cyclic hydrocarbon group-containing (meth) acrylate is more preferred, and dicyclopentanyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate are even more preferred.

The second radically polymerizable unsaturated monomer (B-2) lowers the viscosity of the second radically polymerizable resin composition of the present embodiment, and improves hardness, strength, chemical resistance, water resistance, etc. can be used for From the viewpoint of preventing deterioration of the cured product and environmental pollution, the content of the second radically polymerizable unsaturated monomer (B-2) is It is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total amount of the unsaturated monomer (B-2).

The total content of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) in the second radically polymerizable resin composition of the present embodiment is preferably 5 to 99.9% by mass, more preferably 10 to 80% by mass, still more preferably 15 to 60% by mass, and even more preferably 18 to 40% by mass. When the total content of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) in the second radically polymerizable resin composition is within the above range, The hardness of the cured product is further improved.

<Second radical polymerization initiator (D-2)>
The second radically polymerizable resin composition of the present embodiment contains a second radical polymerization initiator (D-2) as a curing agent. The second radical polymerization initiator (D-2) includes a thermal radical polymerization initiator (D-21) and a photoradical polymerization initiator (D-22). Among them, the thermal radical polymerization initiator (D-21) is preferred.
Examples of the thermal radical polymerization initiator (D-21) include diacyl peroxides such as benzoyl peroxide, peroxyesters such as tert-butyl peroxybenzoate, cumene hydroperoxide (CHP), and diisopropylbenzene. Hydroperoxide, tert-butyl hydroperoxide, hydroperoxide such as paramenthane hydroperoxide (RCOOH, Hydroperoxide), dialkyl peroxide such as dicumyl peroxide, ketone peroxide such as methyl ethyl ketone peroxide, acetylacetone peroxide, peroxy Organic peroxides such as ketal, alkyl perester, and carbonate may be mentioned. Among them, hydroperoxide-based radical polymerization initiators (RCOOH) (also simply referred to as hydroperoxides) are preferred, and cumene hydroperoxides (CHP) such as Parkmil (registered trademark) H-80 manufactured by NOF Corporation, manufactured by NOF Corporation Diisopropylbenzene hydroperoxides such as Percumyl® P are more preferred.

Examples of photoradical polymerization initiators (D-22) include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl, and methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy -Acetophenones such as 2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. A thioxanthone type etc. are mentioned.

The photoradical polymerization initiator (D-22) having photosensitivity from ultraviolet light to the visible light region includes known initiators such as acetophenone-based, benzyl ketal-based, and (bis)acylphosphine oxide-based initiators. Specifically, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis(2,6-dimethoxybenzoyl)-2,4 , 4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) at a ratio of 75%/25%, trade name Irgacure-1700 (manufactured by Ciba Specialty Chemicals Co., Ltd.); 1-hydroxycyclohexyl phenyl Ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) Irgacure 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.) mixed at a ratio of 75%/25%; )); bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.); 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucirin TPO, manufactured by BASF Corporation); 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyl There is Darocur 4265 (trade name) in which diphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF Corporation) is mixed at a ratio of 50%/50%.

Photoradical polymerization initiators (D-22) having photosensitivity in the visible light region include camphorquinone, benzyltrimethylbenzoyldiphenylphosphinoxide, methylthioxanthone, dicyclopentadiethyltitanium-di(pentafluorophenyl), and the like. mentioned.
These second radical polymerization initiators (D-2) may be used alone or in combination of two or more. The other reaction may be incorporated for the purpose of assisting the main reaction of heat curing and photocuring, and a thermal radical polymerization initiator (D-21) and a photoradical polymerization initiator (D-22) are used. You may use together as needed.

In addition, depending on the molding conditions, organic peroxide/dye, diphenyliodine salt/dye, imidazole/keto compound, hexaallylbiimidazole compound/hydrogen donating compound, mercaptobenzothiazole/thiopyrylium salt, metal arene/cyanine It can also be used in a composite form such as a dye, hexaallylbiimidazole/radical generator and the like.

When the second radically polymerizable resin composition of the present embodiment contains the second radical polymerization initiator (D-2), the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable Preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, still more preferably 0.3 to 6 parts by mass with respect to a total of 100 parts by mass of the unsaturated monomer (B-2) and most preferably 0.5 to 5 parts by mass.

<Second metal-containing compound (E-2)>
The second radically polymerizable resin composition of the present embodiment contains one or more second metals selected from metal soaps (E-21) and metal complexes having a β-diketone skeleton (E-22) as curing accelerators. Compound (E-2) can be used. The metal soap (E-21) in the present embodiment refers to a salt of a long-chain fatty acid or an organic acid other than a long-chain fatty acid and a metal element other than potassium and sodium. Further, the metal complex (E-22) having a β-diketone skeleton in the present embodiment refers to a complex in which a compound having a structure in which one carbon atom is present between two carbonyl groups is coordinated to a metal element. .

The content of the second metal-containing compound (E-2) in the second radically polymerizable resin composition in terms of the metal component is the above-described second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated It is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 4 parts by mass, and still more preferably 0.005 to 3 parts by mass with respect to the total 100 parts by mass of the monomer (B-2). is. When the content of the second metal-containing compound (E-2) in terms of metal component is within the above range, curing proceeds rapidly.

[Metallic soap (E-21)]
The long-chain fatty acid in the metal soap (E-21) is not particularly limited, but fatty acids having 6 to 30 carbon atoms are preferred. Specifically, heptanoic acid, octanoic acid such as 2-ethylhexanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoic acid, eicosanoic acid, docosanoic acid, tetracosanoic acid Chain or cyclic saturated fatty acids such as hexacosanoic acid, octacosanoic acid, triacontanoic acid and naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid are preferred.
In addition, rosin acid, linseed oil fatty acid, soybean oil fatty acid, tall oil acid and the like can also be used.

In addition, the organic acid other than the long-chain fatty acid in the metal soap (E-21) is not particularly limited, but weakly acidic compounds having a carboxy group, a hydroxy group and an enol group and soluble in organic solvents are preferred.
Examples of compounds having a carboxy group include carboxylic acids such as formic acid, acetic acid, and oxalic acid; hydroxy acids such as citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, and folic acid; alanine, Amino acids such as arginine; aromatic acids such as benzoic acid and phthalic acid;
Examples of compounds having a hydroxy group and an enol group include ascorbic acid, α acid, imidic acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, phosphonic acid and the like.
Among these, long-chain fatty acids are preferred, chain or cyclic saturated fatty acids having 6 to 16 carbon atoms, or unsaturated fatty acids having 6 to 16 carbon atoms are more preferred, octanoic acid, 2-ethylhexanoic acid, and Naphthenic acid is more preferred, and 2-ethylhexanoic acid and naphthenic acid are even more preferred.

Metal elements constituting the metal soap (E-21) include group 1-2 metal elements such as lithium, magnesium, calcium, and barium (excluding potassium and sodium), titanium, zirconium, vanadium, and manganese. , iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, zinc and other group 3-12 metal elements, aluminum, indium, tin, lead and other group 13-14 metal elements , rare earth metal elements such as neodymium and cerium, and bismuth.
In the present embodiment, metal elements of Groups 2 to 12 are preferred, and zirconium, barium, vanadium, manganese, iron, cobalt, copper, titanium, bismuth, calcium, lead, tin and zinc are more preferred, and zirconium, manganese, More preferred are iron, cobalt, copper, titanium, bismuth, calcium, lead, tin and zinc, and even more preferred are zirconium, manganese, cobalt, bismuth and calcium.

Specific metal soaps (E-21) include zirconium octylate, manganese octylate, cobalt octylate, bismuth octylate, calcium octylate, zinc octylate, vanadium octylate, lead octylate, tin octylate, and naphthene. Cobalt acid, copper naphthenate, barium naphthenate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate are preferred, among which zirconium octylate, manganese octylate, cobalt octylate, bismuth octylate, and calcium octylate. , lead octoate, tin octoate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate are more preferred. Among these, manganese octylate and cobalt octylate are particularly preferred. A specific example of cobalt octylate is hexoate cobalt manufactured by Toei Kako Co., Ltd. (content of cobalt in the total amount of product: 8% by mass, molecular weight: 345.34). Moreover, as a specific example of manganese octylate, Toei Kako Co., Ltd. make hexoate manganese (8 mass % of manganese content in product whole quantity, molecular weight 341.35) is mentioned.

[Metal complex having a β-diketone skeleton (E-22)]
Metal complex (E-22) having a β-diketone skeleton (hereinafter also referred to as “metal complex (E-22)”. Examples of metal complex (E-22) include acetylacetone, ethyl acetoacetate, benzoylacetone, and the like. Metal complexes (E-22) also exhibit the same function as the metal soap (E-21).
Examples of the metal element constituting the metal complex (E-22) include the same metal elements as those of the metal soap (E-21).

Specific metal complexes (E-22) include zirconium acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis(acetylacetonate), iron acetylacetonate, and acetoacetonate. Ethyl ester cobalt acetate is preferred, and zirconium acetylacetonate, titanium acetylacetonate, and titanium dibutoxybis(acetylacetonate) are more preferred.

<Second thiol compound (F-2)>
The second radically polymerizable resin composition of the present embodiment contains at least one second thiol compound (F-2) selected from secondary thiol compounds (F-21) and tertiary thiol compounds (F-22). may contain. In the present embodiment, the second thiol compound (F-2) functions as a curing accelerator and is coordinated in the vicinity of the metal of the second metal-containing compound (E-2) to deactivate the metal with water. It is presumed that it also has a function to prevent
The second thiol compound (F-2) used in the present embodiment has a mercapto group that binds to a secondary or tertiary carbon atom in the molecule (hereinafter referred to as "secondary mercapto group" and "tertiary mercapto group", respectively). There is no particular limitation as long as it is a compound having one or more of (sometimes referred to as " Difunctional thiols, which are compounds having two primary or tertiary mercapto groups, are preferred. Also, the secondary thiol compound (F-21) is more preferable than the tertiary thiol compound (F-22).
The term "polyfunctional thiol" as used herein means a thiol compound having two or more mercapto groups as functional groups, and the term "bifunctional thiol" refers to two mercapto groups as functional groups. is a thiol compound.

The compound having two or more secondary or tertiary mercapto groups in the molecule is not particularly limited. For example, it has at least one structure represented by the following formula (Q), and Compounds having two or more secondary or tertiary mercapto groups in the molecule are preferred, including the mercapto groups in the structure.

(In formula (Q), R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and R ² is an alkyl group having 1 to 10 carbon atoms or a carbon It is an aromatic group of numbers 6 to 18, * indicates that it is connected to an arbitrary organic group, and a is an integer of 0 to 2.)

[Secondary thiol compound (F-21)]
When the second thiol compound (F-2) having the structure represented by the formula (Q) is a secondary thiol compound (F-21), specific examples thereof include 3-mercaptobutyric acid, 3-mercapto Di(1-mercaptoethyl) phthalate, di(2-mercaptopropyl) phthalate, di(3-mercaptobutyl) phthalate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate) ), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2- mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate) pionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol bis (4-mercapto valerate), diethylene glycol bis (4-mercapto valerate) , butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane tris(4-mercaptovalerate), pentaerythritol tetrakis(4-mercaptovalerate), dipentaerythritol hexa kiss (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate) ), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3-mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipe ntaerythritol hexakis(3-mercaptovalerate), hydrogenated bisphenol A bis(3-mercaptobutyrate), bisphenol A dihydroxyethyl ether-3-mercaptobutyrate, 4,4'-(9-fluorenylidene) bis(2) -phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate), diethylene glycol bis (3-mercapto-3) -phenylpropionate), butanediol bis(3-mercapto-3-phenylpropionate), octanediol bis(3-mercapto-3-phenylpropionate), trimethylolpropane tris(3-mercapto-3-phenylpropionate) ), tris-2-(3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate), dipentaerythritol hexakis (3-mercapto-3-phenylpropionate nate) and the like.

Among the secondary thiol compounds (F-21), commercially available compounds having two or more secondary mercapto groups in the molecule include 1,4-bis(3-mercaptobutyryloxy)butane (Showa Denko K.K. manufactured by Karenz MT (registered trademark) BD1), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko K.K., Karenz MT (registered trademark) PE1), 1,3,5-tris[2-(3- mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko K.K., Karenz MT (registered trademark) NR1), trimethylolethane tris (3-mercaptobutyrate) (manufactured by Showa Denko KK, TEMB), trimethylolpropane tris (3-mercaptobutyrate) (manufactured by Showa Denko KK, TPMB), etc., and one or more of these may be used. is preferred. Among them, 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Showa Denko KK, Karenz MT (registered trademark) BD1) is preferable.

[Tertiary thiol compound (F-22)]
When the second thiol compound (F-2) having the structure represented by the formula (Q) is a tertiary thiol compound (F-22), specific examples include di(2-mercaptoisobutyl phthalate) ), ethylene glycol bis(2-mercaptoisobutyrate), propylene glycol bis(2-mercaptoisobutyrate), diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis(2-mercaptoisobutyrate), octane Diol bis (2-mercaptoisobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), di Pentaerythritol hexakis(2-mercaptoisobutyrate), di(3-mercapto-3-methylbutyl) phthalate, ethylene glycol bis(3-mercapto-3-methylbutyrate), propylene glycol bis(3-mercapto-3 -methyl butyrate), diethylene glycol bis(3-mercapto-3-methylbutyrate), butanediol bis(3-mercapto-3-methylbutyrate), octanediol bis(3-mercapto-3-methylbutyrate), Trimethylolethane tris (3-mercapto-3-methylbutyrate), trimethylolpropane tris (3-mercapto-3-methylbutyrate), pentaerythritol tetrakis (3-mercapto-3-methylbutyrate), dipentaerythritol hexakis(3-mercapto-3-methylbutyrate) and the like.

The total amount of the second thiol compound (F-2) in the second radically polymerizable resin composition of the present embodiment is the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer. Preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, even more preferably 0.1 to 5 parts by mass, and still more It is preferably 0.2 to 4 parts by mass. When the amount of the second thiol compound (F-2) is 0.01 parts by mass or more, a sufficient curing function can be obtained, and when it is 10 parts by mass or less, curing progresses rapidly.

Further, the total molar ratio [(F-2)/(E-2)] of the second thiol compound (F-2) to the metal component of the second metal-containing compound (E-2) is 0.1 to 15. It is preferably 0.5 to 15, more preferably 1 to 12, even more preferably 1.5 to 10, and even more preferably 3 to 9. When the molar ratio [(F-2)/(E-2)] is 0.1 or more, the second thiol compound (F-2) is sufficiently close to the metal of the second metal-containing compound (E-2). can be coordinated, and by setting the molar ratio to 15 or less, the balance between the production cost and the effect is improved.

The second thiol compound (F-2) may be used alone or in combination of two or more. When the secondary thiol compound (F-21) and the tertiary thiol compound (F-22) are used in combination, the molar ratio of the two [(F-21)/(F-22)] is 0.001 to 1000. is preferred, and 1 to 10 are more preferred. When the molar ratio [(F-21)/(F-22)] is within the above range, the second metal-containing compound (E-2) and the second thiol compound ( F-2) is stable, and no disulfide compound is generated as a by-product due to bonding between the second thiol compounds (F-2). From the viewpoint of preserving the second radically polymerizable resin composition while the second metal-containing compound (E-2) and the second thiol compound (F-2) are in a stable state, the secondary thiol compound (F- 21) or the tertiary thiol compound (F-22) is preferably used alone.

<Second curing accelerator (G-2)>
For the purpose of improving curability, the second radically polymerizable resin composition of the present embodiment has a second curing accelerator other than the second metal-containing compound (E-2) and the second thiol compound (F-2). It may contain an agent (G-2).
Examples of the second curing accelerator (G-2) other than the second metal-containing compound (E-2) and the second thiol compound (F-2) include amines, specifically aniline, N, N-dimethylaniline, N,N-diethylaniline, p-toluidine, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N,N-dimethyl amino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethylamino)benzaldehyde, N,N-bis(2-hydroxypropyl)-p - N,N-substituted anilines such as toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N-bis(hydroxyethyl)aniline, diethanolaniline, etc. , N,N-substituted-p-toluidine and 4-(N,N-substituted amino)benzaldehyde.
When the second radically polymerizable resin composition of the present embodiment contains the second curing accelerator (G-2), the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and even more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the saturated monomer (B-2) in total.

<Second polymerization inhibitor (H-2)>
The second radically polymerizable resin composition of the present embodiment contains a second polymerization inhibitor (H-2) from the viewpoint of suppressing excessive polymerization of the second radically polymerizable compound (A-2) and controlling the reaction rate ) may be included.
Examples of the second polymerization inhibitor (H-2) include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-tert-butylcatechol.
When the second radically polymerizable resin composition contains the second polymerization inhibitor (H-2), the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer ( B-2) is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 3 parts by mass, still more preferably 0.01 to 1 part by mass, relative to the total 100 parts by mass of B-2) be.

<Second curing retarder (I-2)>
The second radically polymerizable resin composition of the present embodiment may contain a second curing retarder (I-2) for the purpose of delaying the curing of the second radically polymerizable compound (A-2). The second curing retarder (I-2) includes free radical curing retarders such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2 , 2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4-Oxo-TEMPO), etc. TEMPO derivatives are mentioned. Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (4H-TEMPO) is preferred from the viewpoint of cost and ease of handling.
When the second radically polymerizable resin composition contains the second curing retarder (I-2), the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer ( B-2) with respect to 100 parts by mass in total, preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, still more preferably 0.05 to 3 parts by mass be.

<Expansion material (J)>
The expansive material (J) used in the present embodiment is any expansive material that satisfies the standard of Japanese Industrial Standards JIS A 6202 "expansive material for concrete" generally used as an expansive material for concrete. may be used. Specifically, any substance may be used as long as it produces calcium hydroxide or ettringite by a hydration reaction. For example, an expansive material (J) containing at least one selected from the group consisting of quicklime and calcium sulfoaluminate is preferred. More preferable expanding materials include (1) expanding material containing quicklime as an active ingredient (quicklime-based expanding material), (2) expanding material containing calcium sulfoaluminate as an active ingredient (ettringite-based expanding material), and (3) A quicklime-ettringite composite expansion material and the like are included.

Specific examples of quicklime-based expansive materials include Taiheiyo Hyper Expan-K, Taiheiyo Hyper Expan-M, Taiheiyo Expan-K, Taiheiyo Expan-M, and N-EX manufactured by Taiheiyo Materials Co., Ltd.
Specific examples of the ettringite expansion material include Denka CSA #10 and Denka CSA #20 manufactured by Denka.
Specific examples of the quicklime-ettringite composite expansive material include Denka Power CSA Type S, Denka Power CSA Type R, Denka Power CSA Type T manufactured by Denka.

The content of the expanding material (J) in the present embodiment is It is preferably 0.3 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, still more preferably 1 to 20 parts by mass, and most preferably 3 to 16 parts by mass. If the content of the expanding agent (J) is 30 parts by mass or less, the expansion rate will not exceed the elongation of the resin when the second radically polymerizable resin composition is cured. Conversely, if it is 0.3 parts by mass or more, the expansion performance for the second radically polymerizable compound (A-2) is not exhibited. Moreover, these expansive materials (J) may be used alone, or two or more of them may be mixed and used.

<Cement (P)>
The second radically polymerizable resin composition of the present embodiment contains cement (P).

As cement (P), Portland cement, other mixed cements, ultra-rapid hardening cements, and the like can be used without particular limitation. Examples of Portland cement include various Portland cements such as low heat, moderate heat, normal, high early strength, ultra early strength, and sulfate resistant. Mixed cement includes blast furnace cement, fly ash cement, silica cement, and the like. Among these, inexpensive Portland cement is preferred, and early-strength and ultra-early-strength Portland cements are more preferred. As these cements, the cements exemplified above can be used singly or in any combination at any mixing ratio.
The content of cement (P) is 20 to 200 parts by mass with respect to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). parts, more preferably 30 to 180 parts by mass, and even more preferably 40 to 150 parts by mass.
The content of the cement (P) is not particularly limited, but is preferably 1 part by mass to 80 parts by mass, more preferably 5 parts by mass to 50 parts by mass, relative to 100 parts by mass of the aggregate (K). , and more preferably 10 to 30 parts by mass. In particular, if the content of cement is 1 part by mass or more, the particle size distribution of the aggregate can be optimized and practical fluidity can be ensured. Moreover, when the content of cement is 80 parts by mass or less, stickiness due to poor fluidity can be prevented.

<Aggregate (K)>
The second radical polymerizable resin composition of the present embodiment contains an aggregate (K). The aggregate (K) is not particularly limited, and those used in mortar and concrete can be used. Aggregates include, for example, calcium carbonate, crushed stone, sandstone, Kansuiseki, marble, quartz, limestone, silica sand, silica stone, and river sand. Moreover, from the viewpoint of weight reduction, lightweight aggregates such as sintered shale, silicic acid-based balloon, and non-silicic acid-based balloon perlite can also be used. Among these, silica sand is preferred, and No. 7 silica sand and No. 8 silica sand are more preferred.
Calcium carbonate functions as an extender pigment that is transparent in the coating film and does not hide the surface to be coated (substrate surface), and has functions such as filling of recesses and reduction of coating cost. TM-2 (manufactured by Yuko Mining Co., Ltd.), for example, is commercially available as this calcium carbonate.
Calcium carbonate has a specific particle size distribution, is excellent in dispersibility, and is porous, so that the specific gravity of the aggregate itself can be reduced to make it difficult to sag and improve film formability.

Silicic acid balloons include shirasu balloons, perlite, glass (silica) pearls, fly ash balloons, and the like. Examples of non-silicic acid balloons include alumina balloons, zirconia balloons, and carbon balloons. Specific examples of perlite include Perlite FL-0 (trade name, manufactured by Fuyo Perlite Co., Ltd.), and Hard Light B-03, Hard Light B-04, and Hard Light B-05 (these are the products (manufactured by Showa Chemical Industry Co., Ltd.) and the like.

The content of the aggregate (K) in the composition of the present embodiment is not particularly limited, but the content of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) It is preferably 200 parts by mass to 800 parts by mass, more preferably 250 parts by mass to 700 parts by mass, and still more preferably 300 parts by mass to 500 parts by mass, relative to the total of 100 parts by mass. In particular, when the aggregate content is 200 parts by mass or more, practical fluidity can be ensured. In addition, if the content of the aggregate is 800 parts by mass or less, the amount of iron adhered is reduced, and deterioration of workability can be prevented.

<Fiber (L)>
The radically polymerizable composition of the present embodiment may contain fibers, if necessary. Specific examples of fibers that can be used in the present embodiment include glass fibers, carbon fibers, vinylon fibers, nylon fibers, aramid fibers, polyolefin fibers, acrylic fibers, polyester fibers such as polyethylene terephthalate fibers, cellulose fibers, metal fibers such as steel fibers, and the like. fibers, ceramic fibers such as alumina fibers, and the like. Among them, for example, polyolefin fibers can be used as thixotropic agents. A thixotropic agent (thixotropy-imparting agent) is added for the purpose of imparting thixotropy.

Currently commercially available polyolefin fibers include polyethylene-based Chembest (registered trademark) FDSS-2 (average fiber length 0.6 mm), Chembest (registered trademark) FDSS-5 (average fiber length 0.1 mm), Chembest (registered trademark) FDSS-25 (average fiber length 0.6 mm, hydrophilic product), Chembest (registered trademark) FDSS-50 (average fiber length 0.1 mm, hydrophilic product), etc. (manufactured by Mitsui Petrochemical Industries, Ltd.).

The carbon fiber is not particularly limited, and any known carbon fiber can be used. Examples thereof include polyacrylonitrile-based (PAN-based) carbon fiber, rayon-based carbon fiber, and pitch-based carbon fiber. Carbon fibers may be used alone or in combination of two or more. From the viewpoint of low cost and good mechanical properties, it is preferable to use PAN-based carbon fiber. Such carbon fibers are commercially available. Carbon fiber reinforced plastic (CFRP) may be used as the carbon fiber.

The diameter of the carbon fiber is preferably 3-15 μm, more preferably 5-10 μm. The carbon fiber length is usually 5-100 mm. In this embodiment, the carbon fiber may be cut to 10.0 mm to 100.0 mm, further 12.5 mm to 50.0 mm and used.

These fibers are used in the form of fiber structures, biaxial meshes, triaxial meshes selected from, for example, plain weaves, satin weaves, nonwoven fabrics, mats, rovings, chops, knits, braids, and composite structures thereof. preferably. For example, the fiber structure may be impregnated with a radically polymerizable composition, optionally prepolymerized, and used as a prepreg.
As the mesh, for example, a biaxial mesh and a triaxial mesh are used. The length (mesh) of one side of the square of the biaxial mesh and the length (mesh) of one side of the equilateral triangle of the triaxial mesh are each preferably 5 mm or more, more preferably 10 to 20 mm. By using a biaxial mesh or a triaxial mesh, it is possible to obtain a curable material for preventing spalling of concrete which is lightweight, excellent in economy, workability and durability.
These fibers are preferably used to reinforce coating film properties such as concrete spalling resistance and FRP waterproofness, and to manufacture FRP molded articles.
In applications such as prevention of spalling of concrete, among fibers, glass fiber, cellulose fiber, and the like, which are excellent in transparency, are preferable from the viewpoint that deterioration of the substrate can be visually inspected from the outside.

The content of such fibers is 0.3 to 200 parts per 100 parts by mass in total of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). It is preferably 0.5 to 100 parts by mass, even more preferably 1.0 to 50 parts by mass.

<Water reducing agent (M)>
The second radically polymerizable resin composition of the present embodiment may optionally contain a usable water reducing agent (M) capable of imparting water reducing properties. As the water reducing agent, known water reducing agents used for concrete, such as liquid or powder water reducing agents, AE water reducing agents, high performance water reducing agents, and high performance AE water reducing agents, can be applied without limitation.
The polycarboxylic acid-based water reducing agent can suppress the decrease in the fluidity of concrete due to the addition of the above-mentioned swelling aluminosilicate, and from the viewpoint of maintaining good fluidity and improving workability. preferred.
A naphthalenesulfonic acid-based water reducing agent has a high dispersibility and a high water reducing effect, and is therefore suitable from the viewpoint of improving workability.

The water reducing agent is preferably contained in an amount of 0.1 to 3.0% by mass in the second radically polymerizable resin composition.

<Other ingredients>
The second radically polymerizable resin composition of the present embodiment may contain components other than the above components as long as they do not particularly affect the strength development and acid resistance of the cured product. Ingredients that can be contained include, for example, hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, as well as properties such as setting adjustment, curing acceleration, curing delay, thickening, water retention, defoaming, water repellency, and waterproofing. admixtures that can be used for mortar or concrete, admixtures that can be used for mortar or concrete, such as fibers made of materials such as metals, polymers, and carbon, pigments, extenders, foaming materials, and clay minerals such as zeolite. be able to. Components that can be contained include coupling agents, plasticizers, anion-fixing components, solvents, polyisocyanato compounds, surfactants, wetting and dispersing agents, waxes, and thixotropic agents.

[Coupling agent]
A coupling agent may be used in the second radically polymerizable resin composition of the present embodiment for the purpose of improving workability, and for the purpose of improving adhesion to a substrate. Coupling agents include known silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like.
Examples of such a coupling agent include a second silane coupling agent represented by R ³ —Si(OR ⁴ ) ₃ . Examples of R ³ include aminopropyl group, glycidyloxy group, methacryloxy group, N-phenylaminopropyl group, mercapto group, and vinyl group. Examples of R ⁴ include methyl group and ethyl group. etc.
When the second radically polymerizable resin composition contains a coupling agent, the amount thereof is the sum of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). It is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass.

[Plasticizer]
The second radically polymerizable resin composition of the present embodiment may contain a plasticizer, if necessary. Although the plasticizer is not particularly limited, for the purpose of adjusting physical properties and properties, for example, phthalates such as dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, butylbenzyl phthalate; dioctyl adipate , dioctyl sebacate, dibutyl sebacate, isodecyl succinate and other non-aromatic dibasic acid esters; butyl oleate, methyl acetylricinoleate and other aliphatic esters; diethylene glycol dibenzoate, triethylene glycol dibenzoate, penta Polyalkylene glycol esters such as erythritol esters; Phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; Polystyrenes such as polystyrene and poly-α-methylstyrene; , butadiene-acrylonitrile, polychloroprene; chlorinated paraffins; alkyldiphenyl, partially hydrogenated terphenyl and other hydrocarbon oils; process oils; polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other polyether polyols and these poly Polyethers such as derivatives in which hydroxyl groups of ether polyols are converted to ester groups, ether groups, etc.; epoxy plasticizers such as epoxidized soybean oil and benzyl epoxy stearate; sebacic acid, adipic acid, azelaic acid, phthalic acid, etc. Dibasic acids and polyester plasticizers obtained from dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and dipropylene glycol; acrylic plasticizers and other vinyl monomers by various methods. Examples thereof include vinyl-based polymers obtained by polymerization.
Among them, the viscosity of the radical polymerizable composition and the mechanical properties such as tensile strength and elongation of the cured product obtained by curing the composition can be adjusted. It is preferred to add an agent. In addition, the polymer plasticizer is preferable because it can maintain the initial physical properties for a long period of time as compared with the case of using a low-molecular-weight plasticizer, which is a plasticizer that does not contain a polymer component in the molecule. Although not limited, this polymeric plasticizer may or may not have a functional group.
The number average molecular weight of the polymer plasticizer is more preferably 800-10,000, more preferably 1,000-8,000. When the number average molecular weight is 500 or more, the plasticizer is prevented from flowing out over time under the influence of heat, rainfall, and water, and the initial physical properties can be maintained for a long period of time. Moreover, if the number average molecular weight is 15,000 or less, it is possible to suppress the increase in viscosity and ensure sufficient workability.

[Anion immobilization component]
Hydrotalcites or hydrocalumites can also be used to immobilize anions such as chloride ions.
These hydrotalcites may be natural products or synthetic products, and can be used regardless of the presence or absence of surface treatment and the presence or absence of water of crystallization. For example, the following general formula (R)

_{Mx.Mgy.AlZCO3} ₍ OH) _xr+2y+3z- _2.mH2O ₍ _R )

(Wherein, M is an alkali metal or zinc, x is a number from 0 to 6, y is a number from 0 to 6, z is a number from 0.1 to 4, r is the valence of M, m is (the number of water of crystallization from 0 to 100).
The hydrocalumites may be natural products or synthetic products, and can be used regardless of the presence or absence of surface treatment and the presence or absence of water of crystallization. For example, the following general formulas (S), (T)

_{3CaO.Al2O3.CaX2.kH2O} ₍ _S ₎

(X is a monovalent anion, k ≤ 20)

_{3CaO.Al2O3.CaY.kH2O} ₍ _T )

(Y is a divalent anion, k ≤ 20)
can be mentioned.

In addition, the _calumites carry nitrite ions (NO ₂ ⁻ ), which are said to have the effect of suppressing the corrosion of reinforcing bars in the manufacturing stage. ⁻ ), hydroxide ion (OH ⁻ ), oxalate ion (CH ₃ COO ⁻ ), carbonate ion (CO ₃ ⁻ ), sulfate ion (SO ₄ ²⁻ ), and the like.

These hydrotalcites or hydrocalumites may be used alone, but can be used by being mixed in the cement paste.
When mixed with cement paste, hydroxide ions (OH ^- ) that coexist during the hydration reaction or sulfate ions (SO ₄ ^2- ) contained in cement have various effects on the anion exchange reaction that is characteristic of Calmite. is assumed to give From the viewpoint of maintaining the desired exchange reaction with chloride ions, hydrocalumites supporting nitrite ions are preferred.

〔solvent〕
A solvent can be blended into the second radically polymerizable resin composition of the present embodiment, if necessary. Examples of solvents that can be blended include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate and cellosolve acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and diisobutyl ketone. are mentioned. These solvents may be used during polymer production.

[Polyisocyanato compound]
The second radical polymerizable resin composition of the present embodiment may contain a polyisocyanato compound. The polyisocyanato compound reacts with the hydroxyl groups of the second radically polymerizable compound (A-2) to form a cured coating film.
The polyisocyanato compound contains two or more isocyanato groups in the molecule, and the isocyanato groups may be blocked with a blocking agent or the like.
Examples of polyisocyanate compounds that are not blocked with a blocking agent include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 ( or cyclic aliphatic diisocyanates such as 2,6)-diisocyanate, 4,4′-methylenebis(cyclohexylisocyanate), 1,3-(isocyanatomethyl)cyclohexane; aromatics such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate Group diisocyanates; polyisocyanates such as trivalent or higher polyisocyanates such as lysine triisocyanate, and adducts of these polyisocyanates with polyhydric alcohols, low-molecular-weight polyester resins or water, etc., cyclization of the above diisocyanates Polymers (eg, isocyanurate), biuret-type adducts, and the like are included. Among them, the isocyanurate of hexamethylene diisocyanate is preferred.
These polyisocyanato compounds may be used alone or in combination of two or more.

When the second radically polymerizable resin composition contains a polyisocyanato compound, the amount of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) It is preferably from 0.1 to 50 parts by mass, more preferably from 1 to 30 parts by mass, and even more preferably from 2 to 20 parts by mass, based on a total of 100 parts by mass.

The blocked polyisocyanate compound is obtained by blocking the isocyanate groups of the above polyisocyanate compound with a blocking agent.
Examples of blocking agents include phenols such as phenol, cresol and xylenol; ε-caprolactam; lactams such as δ-valerolactam, γ-butyrolactam and β-propiolactam; methanol, ethanol, n- or iso-propyl alcohol. , n-, iso- or tert-butyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, alcohols such as benzyl alcohol; formamide Blocking of oximes such as xime, acetaldoxime, acetoxime, methylethylketoxime, diacetylmonoxime, benzophenone oxime, cyclohexane oxime; active methylenes such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone agents. By mixing the polyisocyanate and the blocking agent, the isocyanate groups of the polyisocyanate can be easily blocked.

When the polyisocyanato compound is an unblocked polyisocyanato compound, the second radically polymerizable compound (A-2) in the second radically polymerizable resin composition of the present embodiment and the polyisocyanate compound are Since the reaction between the two occurs when they are mixed, it is preferable to separate the second radically polymerizable compound (A-2) and the polyisocyanato compound before use, and then mix the two at the time of use.
A curing catalyst can be used to react the second radically polymerizable compound (A-2) with the polyisocyanato compound. Suitable curing catalysts include, for example, tin octoate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyl Examples include organometallic catalysts such as tin oxide and lead 2-ethylhexanoate.
When the second radically polymerizable resin composition contains the curing catalyst amount, the amount of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) It is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, based on a total of 100 parts by mass.

[Surfactant]
The second radically polymerizable resin composition of this embodiment may contain a surfactant.
Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.
Among these surfactants, one or more selected from anionic surfactants and nonionic surfactants are preferred.

Examples of anionic surfactants include alkyl sulfate ester salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene alkyl salts such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; Ether sulfate ester salts; sulfonates such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate; fatty acid salts such as sodium stearate soap, potassium oleate soap, and castor oil potassium soap ; naphthalenesulfonic acid formalin condensates, special polymer systems, and the like.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene distyrenated phenyl ether, poly Polyoxyethylene derivatives such as oxyethylene tribenzylphenyl ether and polyoxyethylene polyoxypropylene glycol; Sorbitan fatty acid esters such as polyoxyalkylene alkyl ether, sorbitan monolaurylate, sorbitan monopalmitate and sorbitan monostearate; polyoxyethylene polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbit tetraoleate; glycerin monostearate; Glycerin fatty acid esters such as glycerin monooleate can be mentioned.
Among these, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene alkyl ether are preferred. The HLB (Hydrophile-Lipophil Balance) of the nonionic surfactant is preferably 5-15, more preferably 6-12.

When the second radically polymerizable resin composition contains a surfactant, the amount thereof is the sum of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). It is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and still more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass.

[Wetting and dispersing agent]
The second radically polymerizable resin composition of the present embodiment may contain, for example, a wetting and dispersing agent in order to improve permeability to a wet or submerged site to be repaired.
Examples of wetting and dispersing agents include fluorine-based wetting and dispersing agents and silicone-based wetting and dispersing agents, and these may be used alone or in combination of two or more.
Commercially available fluorine-based wetting and dispersing agents include Megafac (registered trademark) F176, Megafac (registered trademark) R08 (manufactured by Dainippon Ink and Chemicals), PF656, PF6320 (manufactured by OMNOVA), Troisol S- 366 (manufactured by Troy Chemical Co., Ltd.), Florard FC430 (manufactured by 3M Japan Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Commercially available silicone-based wetting and dispersing agents include BYK (registered trademark)-322, BYK (registered trademark)-377, BYK (registered trademark)-UV3570, BYK (registered trademark)-330, and BYK (registered trademark)-302. , BYK (registered trademark)-UV3500, BYK-306 (manufactured by BYK-Chemie Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.

In addition, the silicone-based wetting and dispersing agent preferably contains a compound represented by the following formula (U).

(wherein R ⁵ and R ⁶ are each independently a hydrocarbon group optionally containing an aromatic ring having 1 to 12 carbon atoms, or —(CH ₂ ) ₃ O(C ₂ H ₄ O) _p ( CH ₂ CH(CH ₃ )O) _q R′, n is an integer of 1 to 200, R′ is an alkyl group having 1 to 12 carbon atoms, p and q are each an integer, and satisfies q/p = 0 to 10.)
Examples of commercially available silicone-based wetting and dispersing agents containing the compound represented by the formula (U) include BYK (registered trademark)-302 and BYK (registered trademark)-322 (manufactured by BYK-Chemie Japan Co., Ltd.). be done.
When the second radically polymerizable resin composition of the present embodiment contains a wetting and dispersing agent, the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B- It is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 2 parts by mass, based on 100 parts by mass of 2).

〔wax〕
The second radically polymerizable resin composition of the present embodiment may contain wax.
Waxes include paraffin waxes and polar waxes, and these may be used alone or in combination of two or more.
As paraffin waxes, known waxes having various melting points can be used. Moreover, as the polar waxes, those having both a polar group and a non-polar group in the structure can be used. Rou Co., Ltd.), Emanone (registered trademark) 3199, Emanone (registered trademark) 3299 (manufactured by Kao Corporation), and the like.
When the second radically polymerizable resin composition of the present embodiment contains wax, the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). It is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 2.0 parts by mass, based on a total of 100 parts by mass.

[Secondary thixotropic agent]
The second radically polymerizable resin composition of the present embodiment may contain a second thixotropic agent for the purpose of viscosity adjustment and the like for securing workability on vertical surfaces and ceiling surfaces.
Examples of the second thixotropic agent include inorganic thixotropic agents and organic thixotropic agents. Organic thixotropic agents include hydrogenated castor oil, amide, polyethylene oxide, polymerized vegetable oil, Examples thereof include surfactant systems and composite systems using these in combination, and specific examples include DISPARLON (registered trademark) 6900-20X (Kusumoto Kasei Co., Ltd.).
Examples of inorganic thixotropic agents include silica and bentonite. Hydrophobic ones include Rheolosil (registered trademark) PM-20L (vapor-phase silica manufactured by Tokuyama Corporation) and Aerosil (registered trademark) AEROSIL. R-106 (Nippon Aerosil Co., Ltd.) and the like, and hydrophilic ones include Aerosil (registered trademark) AEROSIL-200 (Nippon Aerosil Co., Ltd.) and the like. From the viewpoint of further improving thixotropy, thixotropic modifier BYK (registered trademark)-R605 or BYK (registered trademark)-R606 (manufactured by BYK-Chemie Japan Co., Ltd.) is added to hydrophilic pyrogenic silica. can also be preferably used. When the second radically polymerizable resin composition of the present embodiment contains the second thixotropic agent, the amount thereof is the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of (B-2) in total.

<Water>
The second radically polymerizable resin composition of the present embodiment does not substantially contain water from the viewpoint of obtaining strength at a practical level. That is, when preparing the second radically polymerizable resin composition, water is not added as a constituent of the composition. For example, the water content of the second radically polymerizable resin composition is based on a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). , preferably less than 0.25 parts by mass, more preferably 0.20 parts by mass or less, even more preferably 0.15 parts by mass or less, most preferably 0.10 parts by mass or less preferable.

<Method for Producing Second Radically Polymerizable Resin Composition>
The method for producing the second radically polymerizable resin composition of the present embodiment is not particularly limited, and methods known in the art can be used. For example, the second radically polymerizable resin composition comprises a second radically polymerizable compound (A-2) and a second radically polymerizable unsaturated monomer (B-2), and optionally a second metal-containing compound (E-2) is mixed, and the second radical polymerization initiator (D-2), cement (P), aggregate (K), and expansive agent (J) are blended and mixed. can be done.
In one embodiment of the method for producing the second radically polymerizable resin composition of the present embodiment, the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) are A step (2-S1) of obtaining a mixture (2-i) by mixing a second metal-containing compound (E-2) as necessary, and adding a second radical polymerization initiator to the obtained mixture (2-i) (D-2) is mixed to obtain a mixture (2-ii) (2-S2), and cement (P), aggregate (K) and expansive material (J) are added to the resulting mixture (2-ii). ) to obtain a second radically polymerizable resin composition (2-S3).

In the step (2-S1) of obtaining the mixture (i) (sometimes simply referred to as “step (2-S1)”), the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated In addition to mixing the second metal-containing compound (E-2) with the monomer (B-2), if necessary, a second polymerization inhibitor (H-2) or a second curing retarder (I-2), the second thiol compound (F-2), etc. may be mixed.
In the step (2-S3) of obtaining the second radical polymerizable resin composition (sometimes simply referred to as “step (2-S3)”), the step of obtaining the mixture (2-ii) (2-S2) (simply In addition to mixing the mixture (2-ii) obtained in "step (2-S2)") with the expansive agent (J), cement (P) and aggregate (K), if necessary Fibers (L), water reducing agents (M), etc. may be further mixed according to need. Specific examples of the aggregate (K) include, for example, early-strength Portland cement, calcium carbonate TM-2, Perlite FL-0, Hardlite B-04, Enshu No. 5.5 silica sand, N50 silica sand, N40 silica sand, N90 Silica sand, etc. can be used.

The second radically polymerizable resin composition produced in this way can be cured at room temperature and is excellent in workability, early strength development and curability. Since the expansion material (J) is included, the shrinkage rate during curing is small, and the expansion rate of the cured product can be made greater than 0 depending on the conditions.

[Hardened product of recess filling material kit]
The cured product of the recess filling material kit of the present embodiment includes a first cured product that is a cured product of the first radically polymerizable resin composition and a second cured product that is a cured product of the second radically polymerizable resin composition. and A hardened product of the recess filling material kit is formed in the recess such that the first hardened product is formed on the surface of the recess and the second hardened product is formed on the surface of the first hardened product.

<Cured Product of First Radically Polymerizable Resin Composition>
A cured product of the first radically polymerizable resin composition of the present embodiment is obtained by curing the first radically polymerizable resin composition.

"Method for Curing First Radically Polymerizable Resin Composition"
For example, when the first radically polymerizable resin composition contains a thermal radical polymerization initiator, the same method as the curing method for the second radically polymerizable resin composition, which will be described later, can also be used.

<Cured Product of Second Radically Polymerizable Resin Composition>
A cured product of the second radically polymerizable resin composition of the present embodiment is obtained by curing the second radically polymerizable resin composition.

"Method for Curing Second Radically Polymerizable Resin Composition"
When the second radically polymerizable resin composition of the present embodiment contains a thermal radical polymerization initiator (D-21), as an example of a method of curing the second radically polymerizable resin composition of the present embodiment, A curing method in which the second radically polymerizable resin composition of the present embodiment is applied to the surface of a substrate and cured at room temperature can be mentioned. For example, the second radically polymerizable resin composition of the present embodiment is used as a recess filling material for inorganic structures. Since the second radically polymerizable resin composition of the present embodiment contains the expansive agent (J), the obtained cured product does not shrink significantly even after a certain period of time has passed, unlike conventional cases.
Base materials include concrete, asphalt concrete, mortar, brick, wood, metal, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, vinyl ester resin, alkyd resin, polyurethane, polyimide, etc. thermosetting resin; thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, Teflon (registered trademark), ABS resin, AS resin, and acrylic resin.

When the second radically polymerizable resin composition of the present embodiment contains a radical photopolymerization initiator (D-22), the timing of photocuring is to apply the second radically polymerizable resin composition to the substrate. A method of photocuring after curing, a method of preparing a sheet in which the second radically polymerizable resin composition is prepolymerized (also referred to as B-stage or prepreg), attaching the sheet to a base material, and then photocuring. There is

The light source may be a light source having a spectral distribution in the photosensitive wavelength range of the radical photopolymerization initiator (D-22), such as sunlight, an ultraviolet lamp, a near-infrared lamp, a sodium lamp, a halogen lamp, and a fluorescent lamp. , metal halide lamps, LEDs, etc. can be used. In addition, by using two or more photoradical polymerization initiators (D-22) in combination, using a wavelength cut filter for the light source, or using a specific wavelength of the LED, the wavelength necessary for prepolymerization and main polymerization can also be used separately. The wavelength used for prepolymerization is desirably a long wavelength with a low energy level, and the use of near-infrared light makes it easy to control the degree of polymerization. In the present embodiment, ultraviolet light (ultraviolet rays) refers to light in the wavelength range of 280 to 380 nm, visible light (visible rays) in the range of 380 to 780 nm, and near-infrared light (near infrared rays) in the wavelength range of 780 to 1200 nm. The irradiation time of the lamp necessary for prepolymerization cannot be generally specified because it is affected by the effective wavelength range of the light source, output, irradiation distance, thickness of the composition, etc., but for example, 0.01 hours or more, preferably 0.05 hours. Irradiate for more than an hour.

[Recess filling method (mortar filling method for recesses)]
The method of filling recesses or the method of filling recesses with mortar according to the present embodiment can be widely used in civil engineering work and construction work that require filling. Moreover, the material for forming the recess may be a structure containing at least one of a concrete member, a metal member, and a resin member. In addition, considering the shrinkage of the material, the concave portion is only an example because a 10 cm square cube is most suitable, and the shape may be a cube, a rectangular parallelepiped, or a spherical shape. It may be a conical body.

Structures in which concave portions according to this embodiment are generated include, for example, tunnels, manholes, waterways, conduits, guardrails, signs, anchor bolts, rock bolts, and reinforced structures, regardless of the material. Alternatively, a re-repaired portion of a previously repaired portion includes a portion repaired with cement concrete, a portion repaired with polymer cement mortar, a portion repaired with epoxy resin mortar or urethane resin, a steel plate reinforcement portion, and the like.

Another embodiment of the recess filling method of the present embodiment or the method of filling recesses with mortar includes a base layer forming step of applying a first radically polymerizable resin composition to the surface of the recess to form a base layer; and a filling step of filling the surface of the underlayer formed on the surface of the recess with a second radically polymerizable resin composition.

Another embodiment of the recess filling method of the present embodiment or the method of filling recesses with mortar includes a step of applying a first radically polymerizable resin composition to a part or all of the surface of a recess, and a second radical polymerization. and curing the first radically polymerizable resin composition and the second radically polymerizable resin composition.

One embodiment of the recess filling method or the recess mortar filling method of the present embodiment includes the steps of applying the first radically polymerizable resin composition to a part or all of the surface of the recess; a step of curing the composition to form a cured product layer of the first radically polymerizable resin composition on the surface of the recess; You may have the process of filling a resin composition, and the process of hardening a 2nd radically polymerizable resin composition.

Further, another embodiment of the recess filling method of the present embodiment or the method of filling recesses with mortar includes a step of applying the first radically polymerizable resin composition to a part or all of the surface of the recess; a step of drying or semi-curing the radically polymerizable resin composition to form a first radically polymerizable resin composition layer or semi-cured layer on the surface of the recess; A step of filling the concave portion with the second radically polymerizable resin composition and a step of curing the first radically polymerizable resin composition and the second radically polymerizable resin composition may be provided.

Further, another embodiment of the recess filling method of the present embodiment or the method of filling recesses with mortar includes the step of applying the first radically polymerizable resin composition to a part or all of the surface of the recess; You may have the process of filling a radically polymerizable resin composition, and the process of hardening a 1st radically polymerizable resin composition and a 2nd radically polymerizable resin composition.

When the recess is, for example, a bolt box, the bolt box can be filled by the recess filling method described above.
For example, the bolt box filling method includes a base layer forming step of applying the first radically polymerizable resin composition to the surface of the bolt box to form a base layer, and removing the base layer formed on the surface of the bolt box. and a filling step of filling the surface with the second radically polymerizable resin composition.

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

The raw materials used in the production of each of the first radically polymerizable resin composition and the second radically polymerizable resin composition in Examples and Comparative Examples are as follows.

<First Radically Polymerizable Compound (A-1) and First Radically Polymerizable Unsaturated Monomer (B-1)>
(Synthesis example 1)
[Synthesis of Radically Polymerizable Compound (Ai) and Mixing with First Radically Polymerizable Unsaturated Monomer (B-1)]
SR-16H (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd., 1,6-hexanediol diglycidyl ether; epoxy equivalent: 157) was added to a 1 L four-necked separable flask equipped with a stirrer, reflux condenser, gas inlet tube and thermometer. 386.3 g of methylhydroquinone, 0.30 g of methylhydroquinone, and 1.80 g of 2,4,6-tris(dimethylaminomethyl)phenol (“Seikuol TDMP” manufactured by Seiko Kagaku Co., Ltd.) were added, and the temperature was raised to 110.degree. After 211.6 g of methacrylic acid was added dropwise over about 30 minutes, the temperature was raised to 130° C. and the reaction was allowed to proceed for about 4 hours until the acid value reached 20 mg/KOHg to form the radically polymerizable compound (Ai). A vinyl ester resin was synthesized.
Next, by adding 400.0 g of dicyclopentenyloxyethyl methacrylate (“FA-512MT”, manufactured by Hitachi Chemical Co., Ltd.) as the first radically polymerizable unsaturated monomer (B-1), the viscosity at 25° C. was 250 mPa·s, and 1000.0 g of a non-styrene type mixture having a radically polymerizable compound (Ai) component ratio of 60% by mass was obtained.

[Radical polymerizable compound (A-ii)]
As the vinyl ester resin, Lipoxy (registered trademark) R-806 (manufactured by Showa Denko KK, 45% by mass of styrene as the first radically polymerizable unsaturated monomer (B-1)) was used.

<First radical polymerization initiator (D-1)>
As the thermal radical polymerization initiator (Di), Percumyl (registered trademark) H-80 (cumene hydroperoxide (CHP), manufactured by NOF Corporation) was used.
Permec (registered trademark) N (methyl ethyl ketone peroxide, manufactured by NOF Corporation) was used as the thermal radical polymerization initiator (D-ii).
As the thermal radical polymerization initiator (D-iii), Permir (registered trademark) P (diisopropylbenzene hydroperoxide, manufactured by NOF Corporation) was used.

<First metal-containing compound (E-1)>
Manganese octylate (manganese hexoate, manufactured by Toei Kako Co., Ltd., manganese content of 6% by mass in the total product, molecular weight 341.35) was used as the metallic soap (Ei).
As the metal soap (E-ii), cobalt octylate (hexoate cobalt, manufactured by Toei Kako Co., Ltd., cobalt content in the total product amount: 8% by mass, molecular weight: 345.34) was used.

<First thiol compound (F-1)>
The secondary thiol compound (Fi), which is a bifunctional secondary thiol, manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) BD1 (1,4-bis (3-mercaptobutyryloxy) butane, molecular weight 299 .43) was used.

<First polymerization inhibitor H-1>
Tertiary butyl catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the polymerization inhibitor (Hi).

<First curing retardant (I-1)>
As the first curing retarder (Ii), 4-H-TEMPO (manufactured by Hakuto Co., Ltd., Polystop 7300P, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical) Using.

<Second radically polymerizable compound (A-2) and second radically polymerizable unsaturated monomer (B-2)>
(Synthesis Example 2)
[Synthesis of Radically Polymerizable Compound (A-iii) and Mixing with Second Radically Polymerizable Unsaturated Monomer (B-2)]
A bisphenol A type epoxy resin (“Epomic (registered trademark) R140P” manufactured by Mitsui Chemicals, Inc.; epoxy equivalent 188) 179.0 g, Denacol EX-212 (1,6-hexanediol diglycidyl ether manufactured by Nagase ChemteX Corporation; epoxy equivalent 150) 214.2 g, methylhydroquinone 0.30 g, DMP-30 (Tokyo Chemical Industry Co., Ltd. Product: 2,4,6-tris(dimethylaminomethyl)phenol) (1.80 g) was added, and the temperature was raised to 110°C. After raising the temperature to 110°C, 204.7 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) was added dropwise over about 30 minutes, then the temperature was raised to 130°C and the reaction was continued for about 4 hours until the acid value reached 14 mg/KOHg. Thus, a vinyl ester resin, which is a radically polymerizable compound (A-iii), was synthesized.
Then, as the second radically polymerizable unsaturated monomer (B-2), 300.0 g of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512MT), dicyclopentanyl methacrylate ( By adding 100.0 g of FA-513M manufactured by Hitachi Chemical Co., Ltd., a non-styrene type mixture 1000 having a viscosity at 25 ° C. of 280 mPa s and a radically polymerizable compound (A-iii) component ratio of 60% by mass. .0 g was obtained.

[Radical polymerizable compound (A-iv)]
As the unsaturated polyester resin, Rigorac (registered trademark) SR-110N (Showa Denko KK, 40% by mass of styrene as the second radically polymerizable unsaturated monomer (B-2)) was used.

(Synthesis Example 3)
[Synthesis of Radically Polymerizable Compound (Av) and Mixing with Second Radically Polymerizable Unsaturated Monomer (B-2)]
170.44 g of diphenylmethane diisocyanate (Millionate MT manufactured by Tosoh Corporation), Adeka Polyether P-400 (polyether Diol (manufactured by ADEKA Co., Ltd.) 136.35 g, dibutyl hydroxytoluene (BHT manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor: 0.11 g, dibutyltin dilaurate (manufactured by Kyodo Chemical Co., Ltd. KS-1260): 0.02 g. , and 60° C. for 3 hours. Next, 93.08 g of 2-hydroxyethyl methacrylate (manufactured by 2-HEMA Nippon Shokubai Co., Ltd.) was added dropwise to the reactant while stirring over 30 minutes, and the reaction was allowed to proceed for about 3 hours after completion of the dropwise addition to obtain a radically polymerizable compound ( Av) urethane methacrylate resins were synthesized.
Then, dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512MT): 600.0 g was added as the second radically polymerizable unsaturated monomer (B-2), and the temperature was adjusted to 25°C. Thus, 1000.0 g of a non-styrene type mixture having a viscosity of 420 mPa·s at 40% by mass and a radically polymerizable compound (A−v) component ratio was obtained.

(Synthesis Example 4)
[Synthesis of Radically Polymerizable Compound (A-vi) and Mixing with Second Radically Polymerizable Unsaturated Monomer (B-2)]
140.95 g of diphenylmethane diisocyanate (Millionate MT manufactured by Tosoh Corporation), Actcol D-1000 (polypropylene glycol, Mitsui Chemical Co., Ltd.) 281.91 g, dibutyl hydroxytoluene (BHT manufactured by Tokyo Chemical Industry Co., Ltd.) as a polymerization inhibitor: 0.15 g, dioctyltin dilaurate (Nitto Kasei Co., Ltd. Neostan U-810): 0.03 g. , and 70° C. for 2 hours. Next, 76.96 g of 2-hydroxyethyl methacrylate (manufactured by 2-HEMA Nippon Shokubai Co., Ltd.) was added dropwise to the reactant while stirring over 30 minutes, and the reaction was allowed to proceed for about 3 hours after completion of the dropwise addition to obtain a radically polymerizable compound ( A-vi) urethane methacrylate resin was synthesized.
Then, as the second radically polymerizable unsaturated monomer (B-2), phenoxyethyl methacrylate (light ester PO manufactured by Kyoeisha Chemical Co., Ltd.): 150.0 g, dicyclopentenyloxyethyl methacrylate (FA-512MT) , manufactured by Hitachi Chemical Co., Ltd.): 1000.0 g of a non-styrene type mixture having a viscosity of 570 mPa s at 25 ° C. and a radically polymerizable compound (A-vi) component ratio of 50% by mass. got

(Synthesis Example 5)
[Mixing with Radically Polymerizable Compound (A-vii) and Second Radically Polymerizable Unsaturated Monomer (B-2)]
135.72 g of diphenylmethane diisocyanate (Millionate MT manufactured by Tosoh Corporation), Adeka Polyether P-400 (polyether Diol manufactured by ADEKA Co., Ltd.) 54.28 g, Actcol D-1000 (polypropylene glycol manufactured by Mitsui Chemicals, Inc.) 135.72 g, dibutyl hydroxytoluene as a polymerization inhibitor (BHT manufactured by Tokyo Chemical Industry Co., Ltd.): 0.15 g, dioctyl Tin dilaurate (Neostan U-810 manufactured by Nitto Kasei Co., Ltd.): 0.03 g was added and reacted at 70°C for 2 hours. Next, 74.10 g of 2-hydroxyethyl methacrylate (manufactured by 2-HEMA Nippon Shokubai Co., Ltd.) was added dropwise to the reactant while stirring over 30 minutes, and the reaction was allowed to proceed for about 3 hours after completion of the dropwise addition to obtain a radically polymerizable compound ( A-vii) urethane methacrylate resin was synthesized.
Then, as the second radically polymerizable unsaturated monomer (B-2), lauryl methacrylate (Light Ester L, manufactured by Kyoeisha Chemical Co., Ltd.): 150.0 g, dicyclopentenyloxyethyl methacrylate (FA-512MT, Hitachi Chemical Co., Ltd.): By adding 450.0 g, 1000.0 g of a non-styrene type mixture having a viscosity of 320 mPa s at 25 ° C. and a radical polymerizable compound (A-vii) component ratio of 40% by mass Obtained.

<Second radical polymerization initiator (D-2)>
As the thermal radical polymerization initiator (Di), Percumyl (registered trademark) H-80 (cumene hydroperoxide (CHP), manufactured by NOF Corporation) was used.
Permec (registered trademark) N (methyl ethyl ketone peroxide, manufactured by NOF Corporation) was used as the thermal radical polymerization initiator (D-ii).
As the thermal radical polymerization initiator (D-iii), Permir (registered trademark) P (diisopropylbenzene hydroperoxide, manufactured by NOF Corporation) was used.

<Second metal-containing compound (E-2)>
Manganese octylate (manganese hexoate, manufactured by Toei Kako Co., Ltd., manganese content of 6% by mass in the total product, molecular weight 341.35) was used as the metallic soap (Ei).
As the metal soap (E-ii), cobalt octylate (hexoate cobalt, manufactured by Toei Kako Co., Ltd., cobalt content in the total product amount: 8% by mass, molecular weight: 345.34) was used.

<Second thiol compound (F-2)>
The secondary thiol compound (Fi), which is a bifunctional secondary thiol, manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) BD1 (1,4-bis (3-mercaptobutyryloxy) butane, molecular weight 299 .43) was used.

<Second polymerization inhibitor (H-2)>
Tertiary butyl catechol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the polymerization inhibitor (Hi).
As the polymerization inhibitor (H-ii), 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used.

<Second curing retarder (I-2)>
As the second curing retarder (Ii), 4-H-TEMPO (manufactured by Hakuto Co., Ltd., Polystop 7300P, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical) Using.

<Expanding material (J)>
As the expansive material (Ji), Denka Power CSA Type S (quicklime-ettringite composite expansive material, manufactured by Denka) was used.
As the expansive material (J-ii), N-EX (quicklime-based expansive material, manufactured by Taiheiyo Materials Co., Ltd.) was used.

<Cement (P)>
Early Strength Portland Cement

<Aggregate (K)>
Calcium carbonate TM-2
Perlite FL-0 Hard Light B-04
Enshu No. 5.5 silica sand N50 silica sand N40 silica sand

<Fiber (L)>
Chembest (registered trademark) FDSS-5 (manufactured by Mitsui Chemicals Fine Co., Ltd., polyolefin hyperbranched fiber)

(Examples 1-6, Comparative Examples 1-2)
"Adjustment of first radically polymerizable resin composition"
(1) Resin adjustment step (1-S1):
A mixture of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1), in the amount shown in Table 1, the first metal-containing compound (E-1) , the first thiol compound (F-1), the first polymerization inhibitor (H-1), and the first curing retarder (I-1) were mixed well to prepare a mixture (1-i).
(2) Acidic compound mixing step (1-S2):
The mixture (1-i) obtained in step (1-S1) was mixed with the acidic compound (C) in the amount shown in Table 1 to prepare the mixture (1-ii). .
(3) Curing agent mixing step (1-S3):
The mixture (1-ii) obtained in the step (1-S2) is mixed with the first radical polymerization initiator (D-1) in the amount shown in Table 1 to obtain the first radically polymerizable resin composition. (curable primer) was prepared.

The first radically polymerizable resin compositions PC-1 to PC-6 and cPC-1 to cPC obtained by the above method with the blending amounts of the raw materials of Examples 1 to 6 and Comparative Examples 1 and 2 shown in Table 1 In -2, various evaluations were made according to the following methods. Table 1 shows the results.

"Adjustment of second radically polymerizable resin composition"
(1) Resin adjustment step (2-S1):
To the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2), the second metal-containing compound (E-2), the second The 2-thiol compound (F-2), the second polymerization inhibitor (H-2), and the second curing retarder (I-2) were thoroughly mixed to prepare a mixture (2-i).
(2) Curing agent mixing step (2-S2):
The mixture (2-i) obtained in step (2-S1) was mixed with the second radical polymerization initiator (D-2) in the amount shown in Table 1 to prepare the mixture (2-ii). did.
(3) Aggregate mixing step (2-S3):
The mixture (2-ii) obtained in the step (2-S2) was mixed well with the expansive agent (J), the aggregate (K), and the fiber (L) in the respective components and blending amounts shown in Table 1. , to obtain the second radically polymerizable resin composition of this example.

The mixing conditions in each step are as follows.
Stirrer: HOMOGENIZING DISPER Model 2.5 (manufactured by Primix)
Stirring rotation speed: 1000-5000rpm
Temperature: 25°C

Second radically polymerizable resin compositions RC-1 to RC-10 and cRC-1 to cRC obtained by the above-described method at the blending amounts of the raw materials of Examples 7 to 16 and Comparative Examples 3 to 4 shown in Table 2. In -2, various evaluations were made according to the following methods. Table 2 shows the results.　

<Curability test (measurement of gelling time, curing time, and curing temperature)>
The first radically polymerizable resin compositions PC-1 to PC-6 and cPC-1 to cPC-2 of Examples 1 to 6 and Comparative Examples 1 and 2 shown in Table 1 were tested at 25°C. A tube (outer diameter 18 mm, length 165 mm) was inserted 100 mm from the bottom and the temperature was measured using a thermocouple.
The time required for the temperature of the radically polymerizable resin composition to rise from 25°C to 30°C was defined as the gelling time. The time from 25° C. to the maximum exothermic temperature of the radically polymerizable resin composition was defined as curing time, and the maximum exothermic temperature was defined as curing temperature, and measured according to JIS K 6901:2008.
In addition, the radically polymerizable resin composition is adjusted to 25° C. in advance before the measurement. Table 1 shows the results.

<Adhesion strength test>
On the upper surface of a stainless steel plate (SUS304) of 300 mm × 300 mm × 5 mm, 150 g / m ² of the first radically polymerizable resin composition (curable primer) obtained in Examples 1 to 6 and Comparative Examples 1 to 2 was applied with a brush. It was applied and cured for 1 day at a temperature of 25° C. and a humidity of 50%, and then an adhesion strength test was conducted. In the adhesion strength test, each specimen was tested for adhesion strength using a 106 pull-off type adhesion tester manufactured by Elcometer, and the average value of three specimens was shown as a result. In the adhesion strength test, the adhesion strength of 1.0 N/mm ² or more was evaluated as "◯", and the adhesion strength of less than 1.0 N/mm ² was evaluated as "x" from the viewpoint of adhesion to the building body. Table 1 shows the results.

<Viscosity measurement>
Resin viscosity was measured at 25° C. and 50 rpm using an E-type viscometer RE85U (manufactured by Toki Sangyo Co., Ltd.) and cone plate 1°34′×R24 (standard). Table 1 shows the results.

<Compressive strength test>
Regarding each of the second radically polymerizable resin compositions (resin mortar compositions) RC-1 to RC-10 and cRC-1 to cRC-2 of Examples 7 to 16 and Comparative Examples 3 to 4 shown in Table 2 , the compressive strength value was evaluated according to the following method. Table 2 shows the results.
A specimen for compressive strength test was produced in accordance with JIS A 1132:2020. The specimen had a diameter of 50 mm and a height of 100 mm, and a mold made of steel was used for producing the specimen. Using a Shimadzu concrete compressive strength tester "CCM-1000kNI" (manufactured by Shimadzu Corporation) for the test, each specimen was prepared and then cured for 6 hours, 1 day, 3 days, and 7 days. .

<Method for measuring curing shrinkage>
For the cured product of the second radically polymerizable resin composition of the present embodiment, the shrinkage/expansion rate after curing (change rate: negative number is shrinkage rate, positive number is expansion rate) was measured according to Japanese standard JIS A 1129. -3 (dial gauge method). For the method for producing the molded body (cured product), molding was performed with reference to Appendix A of Japanese Standard JIS A 1129. A mold for a specimen of 40×40×160 mm defined in Japanese standard JIS R 5201 was used as the mold. The specimen of the cured product is molded according to the method of making the specimen for strength test specified in JIS R 5201 10, and after molding, it is left in the formwork and left in a room at a temperature of 23 ° C ± 2 ° C and a humidity of 50%. It was placed (cured) and removed from the mold about 24 hours after molding. Then, using the instrument specified in JIS A 1129-3-3, measurement was started under the conditions specified in 4.3 of JIS A 1129-3 (time 0).

　Amount of change (negative number: amount of contraction, positive number: amount of expansion) = long side length at the time of passage - long side length at start (0 o'clock) (160 mm) (1)

Rate of change (negative number: contraction rate, positive number: expansion rate) = change amount / long side length at start (0 o'clock) (160 mm) (2)

The results are shown in Table 2.

<Combination of First Radically Polymerizable Compound and Second Radically Polymerizable Composition>
Test methods and results for combinations of the first radically polymerizable compound and the second radically polymerizable composition are described below.

(Examples 17-23, Comparative Examples 5-6)
<Regarding the 5-face restraint test>
The concrete mold used for the five-face restraint test was Zero Cube L (10 cm x 10 cm x height 9 cm) manufactured by Ohmi Kagaku Shoji Co., Ltd. (Rde). In addition, since it is a pot used for gardening flower pots, there is a hole with a diameter of about 2 cm on the bottom.
When performing the simple five-sided restraint test shown below, use a suitable concrete plate to cover the bottom hole before use.

The obtained first radically polymerizable resin compositions (primer compositions) PC-1, PC-2, PC-4, PC-6, and cPC-1, and the second radically polymerizable resin composition (resin mortar composition ) RC-1, RC-2, RC-7, RC-8, RC-9, RC-10 and cRC-1 were used. First, the first radically polymerizable resin composition was applied to the inner wall of the concrete wall at a coating amount of 0.3 kg/m ² . Next, the second radically polymerizable resin composition was tightly packed and cured at 25° C. for 24 hours to prepare a specimen. The specimens were evaluated according to the following evaluation criteria. Next, as a dry-wet repeated test, dry conditions (temperature 15 ° C., humidity 60% for 4 days) and wet conditions (temperature 60 ° C., humidity 90% for 3 days) are repeated for 30 cycles. was evaluated according to the following evaluation criteria. Similarly, as a repeated heating and cooling test, submersion conditions (temperature 25 ° C., underwater curing for 18 hours), cooling conditions (temperature -20 ° C. for 3 hours) and heating conditions (temperature 50 ° C. for 3 hours) are set as one cycle. , and the test body after repeating 30 cycles was evaluated according to the following evaluation criteria.
The combinations of Examples 17 to 23 and Comparative Examples 5 to 6 shown in Table 3 were evaluated in the 5-face restraint test according to the method described above. Evaluation criteria are shown below.
Cracks and peeling are visually checked, and floats are checked by hammering sound and judged by the pitch of the sound. (If it floats, it will sound high-pitched when struck.)

◯: The resin mortar remained adhered to the 5 surfaces to which it adhered, and there were no cracks or floats on the side of the concrete structure. In addition, no peeling was observed on the resin mortar and primer sides. △: The resin mortar continued to adhere to the five surfaces to which it adhered, but cracks and floats were observed on the concrete structure side. x: Cracks and floats are observed on two or more of the five-face restraints (adhesion). In addition, peeling can be seen on one or more surfaces

The results are shown in Table 3.

(Rebar pull-out test)
"Method for preparing specimen"
As shown in FIG. 1, a formwork (2) having a side of 10 cm was prepared according to JSTM C 2101T (testing method for bond strength between reinforcing bars and concrete by pull-out test). A deformed reinforcing bar (1) D16 coated with the first radically polymerizable composition (curable primer) (3a) was placed in a mold (2). In this state, the second radically polymerizable composition (4a) was tightly packed in the mold (2).
After 24 hours of curing, the mold (2) was removed to obtain a specimen. A reinforcing bar pull-out test was performed on the obtained specimen according to the following evaluation method and evaluation criteria. Similarly, as a dry-wet repeated test, dry conditions (temperature 15 ° C., humidity 60% for 4 days) and wet conditions (temperature 60 ° C., humidity 90% for 3 days) are repeated for 30 cycles. The sample was also subjected to a rebar pull-out test. In addition, as a repeated heating and cooling test, the submersion condition (temperature of 25 ° C., 18 hours of underwater curing), cooling condition (temperature of -20 ° C. for 3 hours) and heating condition (temperature of 50 ° C. for 3 hours) were used as one cycle, and 30 Rebar pull-out tests were also conducted on the specimens after repeated cycles.

"test equipment"
Measurement was performed using an Amsler universal testing machine (MR type) manufactured by Mayekawa Test Instruments Co., Ltd.

"Test method"
The tensile load was measured according to JSTM C 2101T, and the degree of adhesion stress was calculated by the following formula (3). As the tensile load used for calculating the degree of bond stress, the value measured when the amount of slippage at the free end was 0.002D (D is the diameter of the reinforcing bar) was adopted.

γ=P/(4πD ² )×α (3)

γ: Adhesion stress (N/mm ² )
P: Tensile load (N)
D: Diameter of reinforcing bar (nominal diameter; 16 mm for D16)
α: Correction factor for concrete compressive strength (30/σc)
σc: Compressive strength (N/mm ² ) of the cylindrical specimen prepared at the same time

"Evaluation method of test results"
A bond stress of 2.0 N/mm ² or more at a rebar slip of 0.002 D (=0.032 mm), which is regarded as an acceptable value of JSTM C 2101T, was evaluated as ◯. Less than 2.0 N/mm ² was marked as x. Moreover, the maximum adhesive stress degree was shown numerically. Table 3 shows the results.

In addition, in the above hole-filling method, it is described as a hole-filling material for bolt boxes, but as an application, it can also be applied to a method for repairing defective parts of concrete structures such as box culverts and waterways.

REFERENCE SIGNS LIST 1 Reinforcing bar 2 Formwork 3a First radically polymerizable composition 3b Cured product of first radically polymerizable composition 4a Second radically polymerizable composition 4b Cured product of second radically polymerizable composition 5 …container

Claims

A recess filling material kit comprising a first radically polymerizable resin composition and a second radically polymerizable resin composition,
The first radically polymerizable resin composition comprises a first radically polymerizable compound (A-1), a first radically polymerizable unsaturated monomer (B-1), an acidic compound (C), and a first containing a radical polymerization initiator (D-1),
The second radically polymerizable resin composition comprises a second radically polymerizable compound (A-2), a second radically polymerizable unsaturated monomer (B-2), and a second radical polymerization initiator (D- 2), an expanding material (J), cement (P), and an aggregate (K).
The recess filling material kit according to claim 1, wherein the first radically polymerizable compound (A-1) and the second radically polymerizable compound (A-2) each independently contain a vinyl ester resin.
The recess filling material kit according to claim 1 or 2, wherein the expanding material (J) contains at least one selected from the group consisting of quicklime and calcium sulfoaluminate.
The recess according to any one of claims 1 to 3, wherein the first radical polymerization initiator (D-1) and the second radical polymerization initiator (D-2) are each independently hydroperoxides. filler kit.
The first radically polymerizable resin composition further contains a first metal-containing compound (E-1) and a first thiol compound (F-1),
The recess according to any one of claims 1 to 4, wherein the second radically polymerizable resin composition further contains a second metal-containing compound (E-2) and a second thiol compound (F-2). filler kit.
From 0.3 parts by mass of the expanding material (J) to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) 30 parts by mass,
20 parts by mass to 200 parts by mass of the cement (P) with respect to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) and
200 parts by mass to 800 parts by mass of the aggregate (K) with respect to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2) The recess filling material kit according to any one of claims 1 to 5, which is a part.
The first radical polymerization initiator (D-1) is added to a total of 100 parts by mass of the first radically polymerizable compound (A-1) and the first radically polymerizable unsaturated monomer (B-1). 0.1 parts by mass to 10 parts by mass,
The second radical polymerization initiator (D-2) is added to a total of 100 parts by mass of the second radically polymerizable compound (A-2) and the second radically polymerizable unsaturated monomer (B-2). The recess filling material kit according to any one of claims 1 to 6, which is 0.1 to 10 parts by mass.
In the first radical polymerizable resin composition, the acidic compound is added to a total of 100 parts by mass of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). The recess filling material kit according to any one of claims 1 to 7, wherein (C) is 1 to 20 parts by mass.
The recess filling material kit according to any one of claims 1 to 8, wherein the acidic compound (C) is an unsaturated monobasic acid.
The recess filling material kit according to any one of claims 1 to 9, wherein the first radical polymerization initiator (D-1) is a photoradical polymerization initiator having photosensitivity from ultraviolet light to visible light.
A cured product of the recess filling material kit according to any one of claims 1 to 10,
A first cured product, which is a cured product of the first radically polymerizable resin composition, is formed on the surface of the recess, and a second cured product of the second radically polymerizable resin composition is formed on the surface of the first cured product. A hardened product of a recess filling material kit, characterized by being formed.
A recess filling method for filling recesses using the recess filling material kit according to any one of claims 1 to 10,
a base layer forming step of applying the first radically polymerizable resin composition to the surface of the recess to form a base layer;
and a filling step of filling the surface of the underlayer formed on the surface of the recess with the second radically polymerizable resin composition.
The recess filling method according to claim 12, wherein the recess is a bolt box.