Recess filler kit, cured product thereof, and recess filling method

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

[Technical Field]

[0001] This invention relates to a recess filling material kit, its cured product, and a recess filling method. Furthermore, this invention relates to a resin mortar filling method for recesses used in the construction of underground pipelines such as subway passages, sewer pipelines, and manifold pipelines for electric and gas lines, specifically for filling recesses for bolt connections opened on the periphery of segments used as materials, or for filling recesses containing worn, damaged, or broken reinforcing steel structures. This application claims priority based on Japanese Patent Application No. 2021-073532, filed in Japan on April 23, 2021, and the contents of that application are incorporated herein by reference. [Background technology]

[0002] When constructing underground pipelines such as subway passages, sewer pipelines, and manifold pipelines for power lines and gas lines, vertical shafts are excavated to a predetermined depth, and equipment for forming horizontal shafts is brought in. While operating this equipment to form the horizontal shafts, segments are sequentially connected to construct a pipeline of a predetermined diameter. These segments are made of precast concrete or steel, and are generally made from precast concrete or steel. Connecting recesses (bolt boxes, box-shaped openings) are formed on the inner periphery of these segments, and segments are arranged so that these recesses are adjacent to each other and joined with bolts and nuts or PC steel bars. The number of these recesses and bolts and nuts is enormous, proportional to the diameter and length of the pipeline.

[0003] If the pipeline is used with these recesses exposed, the bolts and nuts will corrode due to various environmental factors. Therefore, a mortar filling method has been employed to fill these recesses with cement mortar, epoxy resin mortar, polyurethane resin, etc., to prevent corrosion of the bolts and nuts and, as a result, prevent a decrease in the strength of the joint. However, the mortar filling method used during construction has deteriorated over the years, and various materials used at the time of construction are now missing or completely lost (falling off, etc.). Corrosion of the bolts and nuts inside is also becoming increasingly common.

[0004] If corroded bolts and nuts are left untreated, the connections between the pipes will weaken, leading to numerous problems such as groundwater seeping in through gaps between segments or fluids leaking out of the pipes. Furthermore, bolt boxes in mortar-filled construction that are missing or completely destroyed will increase the resistance of the fluids flowing through the pipes, so urgent countermeasures are required. Another problem, related to the repair of these depressions, is the aging deterioration of underground pipelines such as subway lines, sewer lines, power lines, and gas lines, which include reinforced concrete structures built beneath urban areas. This aging deterioration results in countless cracks and damage in these pipelines, exposing the reinforcing steel and causing various problems such as groundwater and river water seepage into the pipelines, or sewage leakage from the pipelines. Therefore, urgent countermeasures are required. However, due to issues such as adhesion to the reinforcing steel and concrete structures, and the limited time available for construction, which is a problem unique to underground structures, it was often the case that the work could not be done successfully with existing materials.

[0005] Possible applications of this mortar filling method include the rapid-setting mortar method described in Patent Document 1, which involves manually filling or spraying rapid-setting mortar containing a rapid-setting agent; the lightweight mortar method described in Patent Document 2, which involves manually filling lightweight mortar with a reduced specific gravity; and the hardened foamed urethane injection method described in Patent Document 3, which involves injecting and filling with a two-component hardening and foaming urethane composition. In addition, cases such as using epoxy resin mortar to fill holes in depressions, as described in Patent Document 4, and cases where epoxy resin is mixed with water to form an emulsion and used, as described in Patent Document 5, are also conceivable. However, no material can simultaneously solve all problems, such as adhesion to reinforcing bars, bolts, and concrete structures, as well as shrinkage due to aging. As a result, repairs are constantly plagued by problems such as re-deterioration of the repaired areas.

[0006] On the other hand, radical polymerizable resin compositions are frequently used in resin mortar filling methods. For example, when polymerization is carried out using a general liquid vinyl monomer, considerable shrinkage occurs. This shrinkage causes problems such as insufficient strength when vinyl monomer is used as a filler for recesses. Therefore, creating a resin with a low shrinkage rate during polymerization is of great industrial significance.

[0007] Radical polymerizable resin compositions, such as unsaturated polyester resins and vinyl ester resins (epoxy acrylates), also typically experience shrinkage during curing. As these often use monomers such as "styrene" and "methyl methacrylate," as shown in Table 1 of Non-Patent Document 1, unsaturated polyester resins in typical formulations experience a volume shrinkage of approximately 8-12%, while vinyl ester resins experience a shrinkage of approximately 8-10%. This figure is considerably larger than the 3-6% volume shrinkage typically seen in epoxy resins. Therefore, it has hindered the use of unsaturated polyester resins or vinyl ester resins in industrial applications, as well as their entry into other industries and applications.

[0008] As a way to solve this problem, Patent Document 6 states that by using polystyrene beads as a low-shrinkage material, the number of manufacturing steps or the manufacturing time can be reduced, and a low-shrinkage unsaturated polyester resin composition with excellent low shrinkage, dimensional stability, and surface smoothness can be produced.

[0009] Furthermore, Patent Document 7 states that by blending an AB-type block copolymer with an unsaturated polyester resin composition, a low-shrinkage unsaturated polyester resin composition can be obtained that produces molded articles with low shrinkage during curing and excellent heat resistance.

[0010] Furthermore, in Patent Document 8, by mixing an A-B type block copolymer (vinyl acetate-styrene type) composed of segments A and B and fine particle silica with an unsaturated polyester resin, it is said that a low-shrinkage unsaturated polyester resin composition having a large low-shrinkage effect during normal temperature or medium temperature molding and high water resistance can be obtained.

Prior Art Documents

Patent Documents

[0011]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Non-Patent Documents

[0012]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0013] This invention has been made in view of the above-mentioned conventional circumstances, and can provide a method for eliminating initial adhesion between cement concrete materials, polymer cement mortar materials, two-component curing / foaming urethane compositions, epoxy resin mortar materials and other materials for various mortar filling methods, as well as initial adhesion between concrete materials and steel materials used in recesses, and construction defects such as detachment due to shrinkage during the curing of resin materials. Furthermore, in conventional radical polymerizable resin compositions, to create resins with low shrinkage rates, thermoplastic resins such as polystyrene are used alone, or two or more block copolymers are utilized. These have mostly functioned as "shrinkage inhibitors." These resin compositions are based on the idea of ​​offsetting the thermal expansion of thermoplastic resins due to curing heat with the curing shrinkage of unsaturated polyester resins, and their applications have often been limited to applications where heat molding is performed at medium to high temperatures, such as sheet molding compounds (SMC) and bulk molding compounds (BMC).

[0014] This invention has been made in view of the above-mentioned conventional circumstances, and aims to provide a recess-filling material kit containing a radical polymerizable resin composition with a low shrinkage rate, a cured product thereof, and a recess-filling method using the same, by incorporating an expanding agent instead of a shrinkage-preventing agent, so that the entire resin composition expands at a constant rate during curing and then stabilizes, without being limited by the molding method, usage temperature, or application, and furthermore, by using a primer for metal bonding, adhesion to reinforcing steel structures, bolts, etc. present in the recess can also be ensured. [Means for solving the problem]

[0015] In other words, the present invention is represented by the following [1] to

[13] . [1] A recess filler kit comprising a first radical polymerizable resin composition and a second radical polymerizable resin composition, 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 recess filler kit is characterized in that 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), cement (P), an expansive agent (J), and aggregate (K). [2] The recess filler kit according to [1], wherein the first radical polymerizable compound (A-1) and the second radical polymerizable compound (A-2) each independently comprise a vinyl ester resin. [3] The recess filler kit according to [1] or [2], wherein the expansive material (J) comprises at least one selected from the group consisting of quicklime and calcium sulfoaluminate. [4] A recess filler kit according to 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. [5] The first radical polymerizable resin composition further contains a first metal-containing compound (E-1) and a first thiol compound (F-1), The recess filler kit according to any one of [1] to [4], wherein the second radical polymerizable resin composition further contains a second metal-containing compound (E-2) and a second thiol compound (F-2). [6] The amount of the expanding agent (J) is 0.3 to 30 parts by mass per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2), The cement (P) is present in an amount of 20 to 200 parts by mass relative to a total of 100 parts by mass of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). A recess filler kit according to any one of [1] to [5], wherein the aggregate (K) is in an amount of 200 to 800 parts by mass per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). [7] The amount of the first radical polymerization initiator (D-1) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1), A recess filler kit according to any one of [1] to [6], wherein the amount of the second radical polymerization initiator (D-2) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). [8] The recess filler kit according to any one of [1] to [7], wherein the acidic compound (C) is 1 to 20 parts by mass per 100 parts by mass of the first radical polymerizable resin composition, the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). [9] A recess filler kit according to any one of [1] to [8], wherein the acidic compound (C) is an unsaturated monobasic acid.

[10] A recess filler kit according to any one of [1] to [9], wherein the first radical polymerization initiator (D-1) is a photoradical polymerization initiator that is photosensitive from ultraviolet light to the visible light region.

[11] A cured product of a recess filler kit according to any one of [1] to

[10] , characterized in that a first cured product, which is a cured product of the first radical polymerizable resin composition, is formed on the surface of the recess, and a second cured product of the second radical polymerizable resin composition is formed on the first cured product. A method for filling a recess using a recess filling material kit described in any of [1] to

[10] , A base layer formation step involves applying the first radical polymerizable resin composition to the surface of the recess to form a base layer, A method for filling a recess, characterized by comprising a filling step of filling the surface of the underlayer formed on the surface of the recess with the second radical polymerizable resin composition.

[13] The recess filling method according to

[12] , wherein the recess is a bolt box. [Effects of the Invention]

[0016] According to the present invention, it is possible to protect the structure itself from initial adhesion to concrete substrates, steel jigs (bolts), and reinforcing steel structures, detachment due to shrinkage during the curing of organic resin materials, corrosion and wear caused by fluids flowing inside the box during pipeline operation, and vibrations and wind pressure from vehicles and trains, thereby enabling long-term operation of the pipeline itself. According to the present invention, the first radical polymerizable resin composition can achieve initial adhesion to concrete substrates as well as steel jigs and reinforced concrete structures by adding an acidic compound. Furthermore, according to one embodiment of the present invention, the first radical polymerizable resin composition can achieve initial adhesion to concrete substrates as well as steel jigs and reinforced concrete structures by the complex effect of a metal soap and a thiol having a specific structure, and by adding an acidic compound. As for the second radical polymerizable resin composition, by adding an appropriate amount of an expanding agent to a radical polymerizable resin composition that causes curing shrinkage due to a decrease in the free volume of the liquid component during curing, it is possible to provide a recess filler kit and a cured product thereof having a radical polymerizable resin composition with a low shrinkage rate, which expands at a constant ratio during curing and then stabilizes, without being limited by the molding method, usage temperature, or application. Furthermore, a method for filling recesses that combines these elements can be provided. [Brief explanation of the drawing]

[0017] [Figure 1] This diagram shows the method for preparing the test specimens. (a) Before concrete pouring, (b) During concrete pouring, (c) During curing. [Modes for carrying out the invention]

[0018] The present invention will be described in detail below. [Recess Filler Kit] The recess filler kit of this embodiment basically consists of a first radical polymerizable resin composition and a second radical polymerizable resin composition. However, other components, compositions, etc., may be included. 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 expansive agent (J), cement (P), and aggregate (K). In the recess to be filled, the first radical polymerizable resin composition and the second radical polymerizable resin composition are each arranged independently. The meaning of the recess filler kit of this embodiment being comprised of the first radical polymerizable resin composition and the second radical polymerizable resin composition is that both radical polymerizable compositions are independently arranged for the recess filling (repair) area. It does not mean that the two radical polymerizable compositions are mixed and used as a single recess filler mixture. Furthermore, "independently arranged" means that they are not mixed with each other before use. Examples include storing them in separate containers, or storing them in a single container with a structure that prevents mixing.

[0019] (First radical polymerizable resin composition) The first radical polymerizable resin composition of this embodiment 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 first radical polymerizable resin composition of this embodiment may optionally contain 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), etc.

[0020] <First radical polymerizable compound (A-1)> The first radical polymerizable compound (A-1) in this embodiment does not include the first radical polymerizable unsaturated monomer (B-1) and the acidic compound (C) described later, and refers to a resin or polymer compound that has one or more ethylenically unsaturated groups in its molecule and whose polymerization reaction proceeds via radicals. The first radical polymerizable compound (A-1) of this embodiment may be the radical polymerizable compound described in the second radical polymerizable compound (A-2) of this embodiment, as described later, or a preferred example thereof. It is preferable that the first radical polymerizable compound (A-1) be of the same type as the second radical polymerizable compound (A-2), and it is more preferable that the first radical polymerizable compound (A-1) be the same radical polymerizable compound as the second radical polymerizable compound (A-2). The first radical polymerizable compound (A-1) may be a different radical polymerizable compound from the second radical polymerizable compound (A-2). For example, as the first radical 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, and it is more preferable to use vinyl ester resins.

[0021] <First radical polymerizable unsaturated monomer (B-1)> The first radical polymerizable unsaturated monomer (B-1) of this embodiment does not contain the acidic compound (C) described later and is not particularly limited as long as it is a monomer having a radical polymerizable unsaturated group. Preferably, it is a monomer having a vinyl group, an allyl group, or a (meth)acryloyl group. The first radical polymerizable unsaturated monomer (B-1) of this embodiment can be the radical polymerizable unsaturated monomer described in the second radical polymerizable unsaturated monomer (B-2) of this embodiment, described later, or a preferred example thereof. It is preferable to use the same type of radical polymerizable unsaturated monomer as the second radical polymerizable unsaturated monomer (B-2) for the first radical polymerizable unsaturated monomer (B-1), and it is more preferable to use the same radical polymerizable unsaturated monomer as the second radical polymerizable unsaturated monomer (B-2) for the first radical polymerizable unsaturated monomer (B-1). The first radical polymerizable unsaturated monomer (B-1) may be a different radical polymerizable unsaturated monomer from the second radical polymerizable unsaturated monomer (B-2). For example, as the first radical polymerizable unsaturated monomer (B-1), styrene is preferred from the viewpoint of versatility, and from the viewpoint of reducing odor and environmental burden, monomers having (meth)acryloyl groups are preferred, cyclic hydrocarbon group-containing (meth)acrylates are more preferred, dicyclopentanyl (meth)acrylates are even more preferred, and dicyclopentanyl methacrylates are even more preferred. By using the first radical polymerizable unsaturated monomer (B-1), the viscosity of the first radical polymerizable resin composition can be reduced and workability can be improved. In addition, the hardness, strength, chemical resistance, water resistance, etc. of the cured product can be improved. From such viewpoints, the content of the first radical polymerizable unsaturated monomer (B-1) is preferably 10 to 250 parts by mass, more preferably 50 to 200 parts by mass, and even more preferably 80 to 150 parts by mass, per 100 parts by mass of the first radical polymerizable compound (A-1). When the content of the first radical polymerizable unsaturated monomer (B-1) is 10 parts by mass or more, the first radical polymerizable resin composition becomes sufficiently low viscosity, and its impregnation into recessed areas is also improved. When the content of the first radical polymerizable unsaturated monomer (B-1) is 250 parts by mass or less, sufficient coating film strength is obtained, and chemical resistance and water resistance are improved.

[0022] <Acidic compound (C)> The acidic compound (C) used in this embodiment is not particularly limited as long as it is an acidic compound. Preferably, the acidic compound (C) is an organic acid having a carboxyl group, more preferably a compound having an ethylenically unsaturated bond and a carboxyl group, and particularly preferably an unsaturated monobasic acid from the viewpoint of the curability of the first radical polymerizable resin composition. Specifically, examples include unsaturated monobasic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and sorbic acid; saturated monobasic acids such as acetic acid and propionic acid; and reaction products of dicyclopentadiene with polycarboxylic acid compounds (e.g., succinic anhydride, maleic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, etc.). From the viewpoint of the curability of the first radical polymerizable resin composition, an unsaturated monobasic acid is preferred, and (meth)acrylic acid is more preferred.

[0023] The amount of acidic compound (C) used is preferably 0.5 to 25 parts by mass, more preferably 1 to 20 parts by mass, and even more preferably 5 to 15 parts by mass, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). If the amount of acidic compound (C) used is 0.5 parts by mass or more, sufficient adhesive strength to the adherend can be obtained. If it is 25 parts by mass or less, sufficient effective strength can be obtained without adversely affecting adhesion to the adherend.

[0024] <First radical polymerization initiator (D-1)> The first radical polymerization initiator (D-1) of this embodiment may be the radical polymerization initiator described in the second radical polymerization initiator (D-2) of this embodiment, described later, or a preferred example thereof. It is preferable that the first radical polymerization initiator (D-1) be of the same type as the second radical polymerization initiator (D-2), and it is more preferable that the first radical polymerization initiator (D-1) be the same radical polymerization initiator as the second radical polymerization initiator (D-2). The first radical polymerization initiator (D-1) may be a different radical polymerization initiator from the second radical polymerization initiator (D-2). The content of the first radical polymerization initiator (D-1) is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, and even more preferably 1 to 3 parts by mass, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). If the content of the first radical polymerization initiator (D-1) is 0.1 parts by mass or more, sufficient curability can be expected without tack on the surface of the cured product. If the content of the first radical polymerization initiator (D-1) is 10 parts by mass or less, it does not adversely affect the physical properties of the cured product.

[0025] <First metal-containing compound (E-1)> The first radical polymerizable resin composition of this embodiment may optionally contain a first metal-containing compound (E-1) as a curing accelerator. The first metal-containing compound (E-1) can be a metal-containing compound described in the second metal-containing compound (E-2) of this embodiment, described later, or a preferred example thereof. It is preferable that the first metal-containing compound (E-1) is of the same type as the second metal-containing compound (E-2), and it is more preferable that the first metal-containing compound (E-1) is the same radical polymerization initiator as the second metal-containing compound (E-2). The first metal-containing compound (E-1) may be a different metal-containing compound from the second metal-containing compound (E-2). The content of the first metal-containing compound (E-1) is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 3 parts by mass, and even more preferably 0.005 to 1 part by mass, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). If the content of the first metal-containing compound (E-1) is 0.0001 parts by mass or more, curing proceeds rapidly. If the content of the first metal-containing compound (E-1) is 5 parts by mass or less, it does not adversely affect the physical properties of the cured product.

[0026] <First thiol compound (F-1)> The first radical polymerizable resin composition of this embodiment may optionally contain a first thiol compound (F-1) as a curing accelerator. Furthermore, by using it in combination with the first metal-containing compound (E-1), the first thiol compound (F-1) can coordinate near the metal of the first metal-containing compound (E-1), and is expected to have the function of preventing the deactivation of the metal by water. The first thiol compound (F-1) can be the thiol compound described in the second thiol compound (F-2) of this embodiment described later, or preferred examples thereof. It is preferable to use the same type of thiol compound as the second thiol compound (F-2) for the first thiol compound (F-1), and more preferable to use the same thiol compound as the second thiol compound (F-2) for the first thiol compound (F-1). The first thiol compound (F-1) may be a different thiol compound from the second thiol compound (F-2). The content of the first thiol compound (F-1) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). When the content of the first thiol compound (F-1) is 0.01 parts by mass or more, curing proceeds rapidly. When the content of the first thiol compound (F-1) is 10 parts by mass or less, it does not adversely affect the physical properties of the cured product.

[0027] <First curing accelerator (G-1)> The first radical polymerizable resin composition of this embodiment may contain a first curing accelerator (G-1) other than the first metal-containing compound (E-1) and the first thiol compound (F-1) for the purpose of improving curability. The first curing accelerator (G-1) of this embodiment may be the curing accelerator described in the second curing accelerator (G-2) of this embodiment described later, or a preferred example thereof. It is preferable to use the same type of curing accelerator as the second curing accelerator (G-2) for the first curing accelerator (G-1), and more preferable to use the same curing accelerator as the second curing accelerator (G-2) for the first curing accelerator (G-1). The first curing accelerator (G-1) may be a different curing accelerator from the second curing accelerator (G-2). If the first radical polymerizable resin composition of this embodiment contains a first curing accelerator (G-1), the amount 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, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1).

[0028] <First polymerization inhibitor (H-1)> The first radical polymerizable resin composition of this embodiment may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of the first radical polymerizable compound (A-1) and controlling the reaction rate. The first polymerization inhibitor (H-1) of this embodiment can be the polymerization inhibitor described in the second polymerization inhibitor (H-2) of this embodiment described later, or preferred examples thereof. It is preferable to use the same type of polymerization inhibitor as the second polymerization inhibitor (H-2) for the first polymerization inhibitor (H-1), and more preferable to use the same polymerization inhibitor as the second polymerization inhibitor (H-2) for the first polymerization inhibitor (H-1). The first polymerization inhibitor (H-1) may be a different polymerization inhibitor from the second polymerization inhibitor (H-2). If the first radical polymerizable resin composition contains a first polymerization inhibitor (H-1), the amount is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 3 parts by mass each, and even more preferably 0.01 to 1 part by mass each, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1).

[0029] <First curing retarder (I-1)> The first radical polymerizable resin composition of this embodiment may contain a curing retarder for the purpose of delaying the curing of the first radical polymerizable compound (A-1). The first curing retarder (I-1) of this embodiment may be the curing retarder described in the second curing retarder (I-2) of this embodiment described later, or a preferred example thereof. It is preferable that the first curing retarder (I-1) be of the same type as the second curing retarder (I-2), and it is more preferable that the first curing retarder (I-1) be the same curing retarder as the second curing retarder (I-2). The first curing retarder (I-1) may be a different curing retarder from the second curing retarder (I-2). If the first radical polymerizable resin composition contains a first curing retarder (I-1), the amount is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass each, and even more preferably 0.05 to 3 parts by mass each, based on 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1).

[0030] <Other ingredients> The first radical polymerizable resin composition of this embodiment may contain components other than those mentioned above, as long as they do not particularly impede the strength development or acid resistance of the cured product. Examples of components that can be included include hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, as well as admixtures that can impart properties such as setting adjustment, curing acceleration, curing delay, thickening, water retention, defoaming, water repellency, and waterproofing, fibers made of materials such as metals, polymers, and carbon, pigments, fillers, foaming agents, and clay minerals such as zeolites. Other components that can be included include coupling agents, plasticizers, anion immobilization components, solvents, polyisocyanate compounds, surfactants, wetting and dispersing agents, waxes, and thixotropes. The other components that can be used in the first radical polymerizable resin composition of this embodiment may be those described later as other components that can be used in the second radical polymerizable resin composition of this embodiment, or preferred examples thereof. When the same other components are used in both the first radical polymerizable resin composition and the second radical polymerizable resin composition, it is preferable to use the same type of compound, and more preferable to use the same compound. When using the same other components in both the first radical polymerizable resin composition and the second radical polymerizable resin composition, different compounds may be used. This can be used in the first radical polymerizable resin composition of this embodiment. In addition to the compounds exemplified in the section on the second radical polymerizable resin composition, other components exemplified below can also be used. Furthermore, components whose purpose of addition differs from those in the second radical polymerizable resin composition are also explained below.

[0031] [Coupling agent] As the coupling agent, a coupling agent which may be included in the second radical polymerizable resin composition described later can be used. The content of the coupling agent is preferably 0.1 to 20 parts by mass per 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1).

[0032] [Anion-immobilizing components] As the anion immobilization component, an anion immobilization component that may be included in the second radical polymerizable resin composition described later can be used. In particular, when reinforcing bars or the like are exposed in the recessed area, the effects of metal corrosion, especially metal corrosion due to salt, can be reduced.

[0033] [First thuciform agent] The first radical polymerizable resin composition of this embodiment may further contain a first thixotrope. Known thixotropes can be used as the first thixotrope used in this embodiment. Alternatively, the first thixotrope used in this embodiment may be a second thixotrope that may be included in the second radical polymerizable resin composition described later. Examples of first thixotropes used in this embodiment include, in inorganic systems, silica powder (aerosil type), mica powder, calcium carbonate powder, short-fiber asbestos, etc., and in organic systems, hydrogenated castor oil, etc. A silica powder-based thixotrope is preferred. A thixotrope enhancer may also be used in combination. The amount of the first thixotrope used in this embodiment is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, per 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1). If the amount of the first thixotrope used is 0.1 or more, sufficient thixotropy is obtained, and if it is 20 parts by mass or less, sufficient curability is obtained as a first radical polymerizable resin composition, and the adhesion strength to the adherend is improved.

[0034] <Method for producing the first radical polymerizable resin composition> The method for producing the first radical polymerizable resin composition of this embodiment is not particularly limited, and methods known in the art can be used. For example, the first radical polymerizable resin composition can be produced by mixing a first radical polymerizable compound (A-1) and a first radical polymerizable unsaturated monomer (B-1) with a first metal-containing compound (E-1) as needed, then mixing with an acidic compound (C), and further adding a first radical polymerization initiator (D-1). One embodiment of the method for producing the first radical polymerizable resin composition of this embodiment includes the steps of: (1-S1) mixing a first radical polymerizable compound (A-1) and a first radical polymerizable unsaturated monomer (B-1) with a first metal-containing compound (E-1) as needed to obtain a mixture (1-i); (1-S2) mixing an acidic compound (C) with the mixture (1-i) to obtain a mixture (1-ii); and (1-S3) mixing a first radical polymerization initiator (D-1) with the mixture (1-ii) to obtain a first radical polymerizable resin composition (curable primer).

[0035] In the step (1-S1) (sometimes simply referred to as "step (1-S1)") for obtaining the mixture (i), in addition to mixing the first metal-containing compound (E-1) with the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1), a first thiol compound (F-1), a first polymerization inhibitor (H-1), a first curing retarder (I-1), a first thixotrope, an anion immobilizing component, etc., may be further mixed as needed. After the step of obtaining the first radical polymerizable resin composition (1-S3) (sometimes simply referred to as "step (1-S3)"), fibers or the like may be further mixed into the obtained first radical polymerizable resin composition as needed.

[0036] (Second radical polymerizable resin composition) The second radical polymerizable resin composition of this embodiment contains a second radical polymerizable compound (A-2), a second radical polymerizable unsaturated monomer (B-2), a second radical polymerization initiator (D-2), an expanding agent (J), cement (P), and aggregate (K). The second radical polymerizable resin composition of this embodiment may optionally contain a second metal-containing compound (E-2), a second thiol compound (F-2), a second polymerization inhibitor (H-2), a second curing retarder (I-2), fibers (L), etc.

[0037] <Second radical polymerizable compound (A-2)> The second radical polymerizable resin composition of this embodiment uses a second radical polymerizable compound (A-2). In this embodiment, the second radical polymerizable compound (A-2) does not contain the second radical polymerizable unsaturated monomer (B-2) described later, and refers to a resin or polymer compound that has one or more ethylenically unsaturated groups in its molecule and whose polymerization reaction proceeds by radicals. Examples of the second radical 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. Among these, one or more selected from vinyl ester resins and unsaturated polyester resins are preferred, with vinyl ester resins being more preferred. In this specification, "(meth)acrylate" means "acrylate or methacrylate."

[0038] [Vinyl ester resin] As the vinyl ester resin, one obtained by reacting an epoxy resin with an unsaturated monobasic acid can be used.

[0039] Examples of the epoxy resins mentioned above include bisphenol-type epoxy resins, biphenyl-type epoxy resins, novolac-type epoxy resins, trisphenolmethane-type epoxy resins, aralkyldiphenol-type epoxy resins, naphthalene-type epoxy resins, and aliphatic-type epoxy resins. These may be used individually or in combination. From the viewpoint of reducing the viscosity of the vinyl ester resin after synthesis, it is preferable to use only aliphatic-type epoxy resins or to use a combination of bisphenol-type epoxy resins and aliphatic-type epoxy resins.

[0040] Examples of bisphenol-type epoxy resins include those obtained by reacting bisphenols with epichlorohydrin and / or methylepichlorohydrin, and those obtained by reacting a glycidyl ether of bisphenol A with a condensate of the aforementioned bisphenols with epichlorohydrin and / or methylepichlorohydrin. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A. Examples of biphenyl-type epoxy resins include those obtained by reacting biphenol with epichlorohydrin and / or methylepichlorohydrin.

[0041] Examples of novolac-type epoxy resins include those obtained by reacting phenol novolac or cresol novolac with epichlorohydrin and / or methyl epichlorohydrin. Examples of trisphenolmethane-type epoxy resins include those obtained by reacting trisphenolmethane, triscresolmethane with epichlorohydrin and / or methylepichlorohydrin. Examples of aralkyldiphenol-type epoxy resins include those obtained by reacting aralkylphenol with epichlorohydrin and / or methylepichlorohydrin.

[0042] Examples of naphthalene-type epoxy resins include those obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methylepichlorohydrin.

[0043] Examples of aliphatic epoxy resins include alicyclic epoxy resins, alicyclic diol diglycidyl ether type epoxy resins, aliphatic diol diglycidyl ether type epoxy resins, and poly(oxyalkylene) glycol diglycidyl ether type epoxy resins.

[0044] Examples of alicyclic epoxy resins include alicyclic diepoxy acetal, alicyclic diepoxy adipate, and alicyclic diepoxy carboxylate. Specific examples of alicyclic diol diglycidyl ethers include, for example, cyclohexanedimethanol diglycidyl ether, dicyclopentenyl dialcohol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, and dihydroxyterpene diglycidyl ether, which are diglycidyl ethers of alicyclic diols having 3 to 20 carbon atoms (preferably 6 to 12 carbon atoms, more preferably 7 to 10 carbon atoms). Among these, a commercially available cyclohexanedimethanol diglycidyl ether is "Denacol EX-216L" from Nagase ChemteX Corporation.

[0045] Specific examples of aliphatic diol diglycidyl ethers include, for example, diglycidyl ethers of aliphatic diols having 2 to 20 carbon atoms (preferably 4 to 12 carbon atoms, more preferably 4 to 8 carbon atoms, and particularly preferably 4 to 6 carbon atoms), such as 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. Among these, commercially available products of 1,6-hexanediol diglycidyl ether include "Denacol EX-212L" from Nagase ChemteX Corporation, "SR-16H" and "SR-16HL" from Sakamoto Pharmaceutical Co., Ltd., and "Epogosei (registered trademark) HD" from Yokkaichi Synthetic Co., Ltd. A commercially available product of 1,4-butanediol diglycidyl ether is "Denacol EX-214L" from Nagase ChemteX Corporation.

[0046] Specific examples of poly(oxyalkylene) glycol diglycidyl ethers include, for example, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and poly(tetramethylene) glycol diglycidyl ether.

[0047] Preferred examples of aliphatic epoxy resins include 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, and poly(tetramethylene) glycol diglycidyl ether. Among these, those with a number average molecular weight of 150 to 1000 are more preferred.

[0048] The epoxy resin may be a diglycidyl ester such as diglycidyl dimer acid ester or diglycidyl hexahydrophthalate ester. The epoxy resin may also be an epoxy resin having an oxazolidone ring obtained by reacting the epoxy resin with a diisocyanate. Specific examples of epoxy resins having an oxazolidone ring include Asahi Kasei Epoxy's Araldite® AER4152.

[0049] The aforementioned unsaturated monobasic acid can be any known one, such as (meth)acrylic acid, crotonic acid, or cinnamic acid. Alternatively, a reaction product of a compound having one hydroxyl group and one or more (meth)acryloyl groups with a polybasic acid anhydride may be used. In this specification, "(meth)acrylic acid" means either or both of "acrylic acid and methacrylic acid," and "(meth)acryloyl group" means either or both of "acryloyl group and methacryloyl group." The polybasic acid mentioned above is used to increase the molecular weight of the epoxy resin, and known polybasic acids can be used. Examples include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol 2mol maleic anhydride adduct, polyethylene glycol 2mol maleic anhydride adduct, propylene glycol 2mol maleic anhydride adduct, polypropylene glycol 2mol maleic anhydride adduct, dodecanediic acid, tridecanediic acid, octadecanediic acid, 1,16-(6-ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyldodecane)dicarboxylic acid, carboxyl-terminated butadiene / acrylonitrile copolymer (trade name Hycar CTBN), etc.

[0050] [Unsaturated polyester resin] As the unsaturated polyester resin, one can be obtained by esterifying a dibasic acid component containing an unsaturated dibasic acid, and optionally a saturated dibasic acid, with a polyhydric alcohol component. Examples of the aforementioned unsaturated dibasic acids include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride, which may be used individually or in combination of two or more. Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suveric acid, azelaic acid, sebacic acid, and isosebacic acid; aromatic dibasic acids such as phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid, and their dialkyl esters; halogenated saturated dibasic acids; and these may be used individually or in combination of two or more.

[0051] There are no particular restrictions on the polyhydric alcohols mentioned above, but for example, 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- Dihydric alcohols such as 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, and 2,7-decalin glycol; Dihydric alcohols such as dihydric phenols represented by hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc., and adducts of alkylene oxides represented by propylene oxide or ethylene oxide; Examples include trivalent or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

[0052] The unsaturated polyester may be one modified with a dicyclopentadiene compound, to the extent that it does not impair the effects of this embodiment. Examples of known methods for modification with dicyclopentadiene compounds include obtaining a dicyclopentadiene-maleic acid addition product (sidecanol monomalate) and then using this as a monobasic acid to introduce the dicyclopentadiene skeleton. The vinyl ester resin or unsaturated polyester resin used in this embodiment may be given oxidative polymerization (air curing) groups such as allyl groups or benzyl groups. There are no particular restrictions on the method of introduction, but examples include adding a polymer containing oxidative polymerization groups, condensation of a compound having a hydroxyl group and an allyl ether group, and adding a reaction product of a compound having a hydroxyl group and an allyl ether group and an acid anhydride to allyl glycidyl ether or 2,6-diglycidylphenylallyl ether. In this embodiment, oxidative polymerization (air curing) refers to crosslinking resulting from the formation and decomposition of peroxides by oxidation of the methylene bond between the ether bond and the double bond, as seen in allyl ether groups, for example.

[0053] [Polyester (meth)acrylate resin, urethane (meth)acrylate resin, and (meth)acrylate resin] In this embodiment, the polyester (meth)acrylate resin can be, for example, a polyester obtained by reacting a polycarboxylic acid with a polyhydric alcohol, specifically a resin obtained by reacting (meth)acrylic acid with the hydroxyl groups at both ends of polyethylene terephthalate or the like. Furthermore, as the urethane (meth)acrylate resin, for example, a resin obtained by reacting (meth)acrylic acid with the hydroxyl groups or isocyanate groups at both ends of a polyurethane obtained by reacting an isocyanate with a polyhydric alcohol can be used. As the (meth)acrylate resin, for example, a poly(meth)acrylic resin having one or more substituents selected from hydroxyl groups, isocyanate groups, carboxyl groups, and epoxy groups, or a resin obtained by reacting a substituent of a polymer of the monomer having the substituent with a (meth)acrylate with a (meth)acrylic acid ester having a hydroxyl group can be used.

[0054] The second radical polymerizable compound (A-2) may contain residual catalysts or polymerization inhibitors used when synthesizing resins, etc. Examples of catalysts include compounds containing tertiary nitrogen such as triethylamine, pyridine derivatives, and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; and phosphorus compounds such as trimethylphosphine and triphenylphosphine. Examples of polymerization inhibitors include hydroquinone, methylhydroquinone, and phenothiazine. If a catalyst or polymerization inhibitor remains in the second radical polymerizable compound (A-2), the amount is preferably 0.001 to 2% by mass, respectively.

[0055] [Second radical polymerizable unsaturated monomer (B-2)] The second radical polymerizable unsaturated monomer (B-2) is not particularly limited as long as it is a monomer having a radical polymerizable unsaturated group, but it is preferable that it has a vinyl group, an allyl group, or a (meth)acryloyl group. It may also be an unsaturated monobasic acid. Specific examples of monomers having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyl acetate, diallyl phthalate, and triallyl isocyanurate.

[0056] Specific examples of monomers having a (meth)acryloyl group include (meth)acrylic acid esters. Specifically, these include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 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)acrylate, ethylene glycol monobutyl ether (meth)acrylate, and ethylene glycol monohexyl ether (meth)acrylate. )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,Examples include 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, dicyclopentenyloxyethyl(meth)acrylate, tricyclodecanyl(meth)acrylate, tris(2-hydroxyethyl)isocyanur(meth)acrylate, etc.

[0057] Furthermore, polyfunctional (meth)acrylic acid esters include, for example, alkane diol di(meth)acrylates such as ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, and triethylene glycol (meth)acrylate. Examples include polyoxyalkylene glycol di(meth)acrylates such as tetraethylene glycol di(meth)acrylate and 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, and dipentaerythritol hexa(meth)acrylate.

[0058] Furthermore, the following compounds can also be used as the second radical polymerizable unsaturated monomer (B-2). Specifically, these include 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, vinyl benzyl (2-ethylhexyl) ether, vinyl benzyl (β-methoxymethyl) ether, vinyl benzyl (n-butoxypropyl) ether, vinyl benzyl cyclohexyl ether, vinyl benzyl (β-phenoxyethyl) ether, vinyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxyethyl ether, vinyl benzyl dicyclopentenyl methyl ether, divinyl benzyl ether, and (meth)acrylic acid. These can be used individually or in combination of two or more types. In particular, styrene is preferred from the viewpoint of versatility, and monomers having a (meth)acryloyl group are preferred from the viewpoint of odor reduction and reduction of environmental burden, cyclic hydrocarbon group-containing (meth)acrylates are more preferred, and dicyclopentanyl (meth)acrylate and dicyclopentenyloxyethyl (meth)acrylate are even more preferred.

[0059] The second radical polymerizable unsaturated monomer (B-2) can be used to reduce the viscosity of the second radical polymerizable resin composition of this embodiment and to improve its hardness, strength, chemical resistance, and water resistance. From the viewpoint of preventing deterioration of the cured product and environmental pollution, the content of the second radical polymerizable unsaturated monomer (B-2) is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, based on the total amount of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0060] The total content of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2) in the second radical polymerizable resin composition of this embodiment is preferably 5 to 99.9% by mass, more preferably 10 to 80% by mass, even more preferably 15 to 60% by mass, and even more preferably 18 to 40% by mass. When the total content of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2) in the second radical polymerizable resin composition is within the above range, the hardness of the cured product is further improved.

[0061] <Second radical polymerization initiator (D-2)> The second radical polymerizable resin composition of this embodiment contains a second radical polymerization initiator (D-2) as a curing agent. Examples of the second radical polymerization initiator (D-2) include a thermal radical polymerization initiator (D-21) and a photoradical polymerization initiator (D-22). Among these, the thermal radical polymerization initiator (D-21) is preferred. Examples of thermal radical polymerization initiators (D-21) include diacyl peroxides such as benzoyl peroxide, peroxyesters such as tert-butyl peroxybenzoate, hydroperoxides such as cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, paramentane hydroperoxide (RCOOH, Hydroperoxide), dialkyl peroxides such as dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxyketals, alkyl peresters, and parkerbonates. Among these, hydroperoxide-based radical polymerization initiators (RCOOH) (also simply called hydroperoxides) are preferred, and cumene hydroperoxide (CHP) such as Permil® H-80 manufactured by NOF Corporation, and diisopropylbenzene hydroperoxide such as Permil® P manufactured by NOF Corporation are more preferred.

[0062] Examples of photoradical polymerization initiators (D-22) include benzoin ethers such as benzoin alkyl ethers, benzophenones such as benzophenone, benzyl, and methyl orthobenzoyl benzoate, acetophenones such as benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 1,1-dichloroacetophenone, and thioxanthones such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.

[0063] Examples of photoradical polymerization initiators (D-22) that are photosensitive from ultraviolet light to the visible light region include known initiators such as acetophenone-based, benzyl ketal-based, and (bis)acylphosphine oxide-based initiators. Specifically, examples include 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.) mixed in a ratio of 75% / 25%, known as trade name Irgacure-1700 (manufactured by Ciba Specialty Chemicals Co., Ltd.); and 1-hydroxycyclohexylphenyl Product names include: Irgacure 1800 (manufactured by Ciba Specialty Chemicals Co., Ltd.), a mixture of ketone (product 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.) in a 75% / 25% ratio; Irgacure 1850 (manufactured by Ciba Specialty Chemicals Co., Ltd.), a mixture in a 50% / 50% ratio; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (product name: Irgacure 819, manufactured by Ciba Specialty Chemicals Co., Ltd.); and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (product name: Lucirin). Examples include TPO (manufactured by BASF Corporation), and Darocur 4265, which is a mixture of 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF Corporation) in a 50 / 50 ratio.

[0064] Examples of photoradical polymerization initiators (D-22) that are photosensitive in the visible light region include camphorquinone, benzyltrimethylbenzoyldiphenylphosphinoxide, methylthioxanthone, and dicyclopentadiethyltitanium-di(pentafluorophenyl). These second radical polymerization initiators (D-2) may be used individually or in mixtures of two or more. The other reaction may be incorporated to assist the primary reaction of either thermal curing or photocuring, and thermal radical polymerization initiators (D-21) and photoradical polymerization initiators (D-22) may be used in combination as needed.

[0065] Furthermore, depending on the molding conditions, it can also be used in complex forms such as organic peroxide / dye systems, diphenyliodine salt / dye systems, imidazole / keto compounds, hexaaryl biimidazole compounds / hydrogen-donating compounds, mercaptobenzothiazole / thiopyrillium salts, metal arenes / cyanine dyes, and hexaaryl biimidazole / radical generators.

[0066] When the second radical polymerizable resin composition of this embodiment contains a second radical polymerization initiator (D-2), the amount is preferably 0.1 to 10 parts by mass, more preferably 0.2 to 8 parts by mass, even more preferably 0.3 to 6 parts by mass, and most preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0067] <Second metal-containing compound (E-2)> The second radical polymerizable resin composition of this embodiment can use one or more second metal-containing compounds (E-2) selected from metal soaps (E-21) and metal complexes having a β-diketone skeleton (E-22) as a curing accelerator. In this embodiment, metal soap (E-21) refers to a salt of a long-chain fatty acid or an organic acid other than a long-chain fatty acid with a metal element other than potassium and sodium. In this embodiment, metal complexes having a β-diketone skeleton (E-22) refer to a complex in which a compound having a structure with one carbon atom between two carbonyl groups is coordinated to a metal element.

[0068] The content of the second metal-containing compound (E-2) in the second radical polymerizable resin composition, in terms of metal component, is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 4 parts by mass, and even more preferably 0.005 to 3 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2) described above. When the content of the second metal-containing compound (E-2), in terms of metal component, is within the above range, curing proceeds rapidly.

[0069] [Metallic soap (E-21)] There are no particular restrictions on the long-chain fatty acids in metal soap (E-21), but fatty acids with 6 to 30 carbon atoms are preferred, for example. Specifically, chain-like or cyclic saturated fatty acids such as 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, hexacosanoic acid, octacosanoic acid, triacontanoic acid, naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid are preferred. Other examples include rosin acid, flaxseed oil fatty acids, soybean oil fatty acids, and tall oil fatty acids.

[0070] Furthermore, there are no particular restrictions on organic acids other than long-chain fatty acids in the metal soap (E-21), but compounds of weak acids having a carboxyl group, a hydroxyl group, and an enol group that are soluble in organic solvents are preferred. Examples of compounds containing a carboxyl 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; amino acids such as alanine and arginine; and aromatic acids such as benzoic acid and phthalic acid. Examples of compounds having hydroxyl groups and enol groups include ascorbic acid, alpha acids, imido acids, erythorbic acid, croconic acid, kojic acid, squalane acid, sulfinic acid, taichoic acid, dehydroacetic acid, delta acids, uric acid, hydroxamic acid, humic acid, fulvic acid, and phosphonic acid. Among these, long-chain fatty acids are preferred, chain-like or cyclic saturated fatty acids having 6 to 16 carbon atoms are more preferred, octanoic acid, 2-ethylhexanoic acid, and naphthenic acid are even more preferred, and 2-ethylhexanoic acid and naphthenic acid are even more preferred.

[0071] Examples of metal elements that make up metal soap (E-21) include group 1-2 metal elements such as lithium, magnesium, calcium, and barium (excluding potassium and sodium), group 3-12 metal elements such as titanium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, and zinc, group 13-14 metal elements such as aluminum, indium, tin, and lead, rare earth metal elements such as neodymium and cerium, and bismuth. In this embodiment, metal elements from groups 2 to 12 are preferred, zirconium, barium, vanadium, manganese, iron, cobalt, copper, titanium, bismuth, calcium, lead, tin, and zinc are more preferred, zirconium, manganese, iron, cobalt, copper, titanium, bismuth, calcium, lead, tin, and zinc are even more preferred, and zirconium, manganese, cobalt, bismuth, and calcium are even more preferred.

[0072] Specific metal soaps (E-21) that are preferred include zirconium octate, manganese octate, cobalt octate, bismuth octate, calcium octate, zinc octate, vanadium octate, lead octate, tin octate, cobalt naphthenate, copper naphthenate, barium naphthenate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate, with zirconium octate, manganese octate, cobalt octate, bismuth octate, calcium octate, lead octate, tin octate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate being more preferred. Among these, manganese octate and cobalt octate are particularly preferred. A specific example of cobalt octoate is hexoate cobalt manufactured by Toei Chemical Co., Ltd. (cobalt content of 8% by mass in the total product, molecular weight 345.34). Similarly, a specific example of manganese octoate is hexoate manganese manufactured by Toei Chemical Co., Ltd. (manganese content of 8% by mass in the total product, molecular weight 341.35).

[0073] [Metal complex with a β-diketone skeleton (E-22)] Metal complexes (E-22) having a β-diketone skeleton (hereinafter also referred to as "metal complex (E-22)"). Examples of metal complexes (E-22) include those formed by the complex formation of acetylacetone, ethyl acetoethyl, benzoylacetone, etc., with a metal, and these metal complexes (E-22) also exhibit the same functions as the metal soap (E-21) mentioned above. Examples of metal elements constituting the metal complex (E-22) include the same metal elements as those in the metal soap (E-21).

[0074] Specific metal complexes (E-22) that are preferred include zirconium acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis(acetylacetonate), iron acetylacetonate, and acetate ethyl cobalt, with zirconium acetylacetonate, titanium acetylacetonate, and titanium dibutoxybis(acetylacetonate) being more preferred.

[0075] <Second thiol compound (F-2)> The second radical polymerizable resin composition of this embodiment may contain one or more second thiol compounds (F-2) selected from secondary thiol compounds (F-21) and tertiary thiol compounds (F-22). In this embodiment, the second thiol compound (F-2) is presumed to have the function of acting as a curing accelerator, as well as coordinating near the metal of the second metal-containing compound (E-2) and preventing the deactivation of the metal by water. The second thiol compound (F-2) used in this embodiment is not particularly limited as long as it is a compound having one or more mercapto groups (hereinafter sometimes referred to as "secondary mercapto group" and "tertiary mercapto group," respectively) bonded to a secondary or tertiary carbon atom in its molecule. However, polyfunctional thiols having two or more secondary or tertiary mercapto groups in their molecule are preferred, and among these, difunctional thiols having two secondary or tertiary mercapto groups in their molecule are preferred. Furthermore, the secondary thiol compound (F-21) is preferred over the tertiary thiol compound (F-22). In this context, "polyfunctional thiol" refers to a thiol compound having two or more mercapto groups as functional groups, while "difunctional thiol" refers to a thiol compound having two mercapto groups as functional groups.

[0076] There are no particular restrictions on compounds having two or more secondary or tertiary mercapto groups in the molecule, but for example, compounds having at least one structure represented by the following formula (Q), and including the mercapto group in the structure represented by the following formula (Q), having two or more secondary or tertiary mercapto groups in the molecule are preferred.

[0077] [ka]

[0078] (In formula (Q), R 1 R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. 2 is an alkyl group with 1 to 10 carbon atoms or an aromatic group with 6 to 18 carbon atoms, and * indicates that it is linked to any organic group. a is an integer from 0 to 2.

[0079] [Secondary thiol compound (F-21)] When the secondary thiol compound (F-2) having the structure represented by formula (Q) is a secondary thiol compound (F-21), specific examples include 3-mercaptobutyric acid, 3-mercaptophthalate di(1-mercaptoethyl), phthalate di(2-mercaptopropyl), phthalate di(3-mercaptobutyl), ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), and octanediol bi S(3-mercaptobutyrate), trimethylolethanetris(3-mercaptobutyrate), trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), dipentaerythritolhexakis(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octane Diolbis(2-mercaptopropionate), Trimethylolpropanetris(2-mercaptopropionate), Pentaerythritoltetrakis(2-mercaptopropionate), Dipentaerythritolhexakis(2-mercaptopropionate), Ethylene glycol bis(4-mercaptovalerate), Diethylene glycol bis(4-mercaptovalerate), Butanediol bis(4-mercaptovalerate), Octanediol bis(4-mercaptovalerate), Trimethylolpropanetris(4-mercaptovalerate) Pentaerythritol tetrakis(4-mercaptovalerate), dipentaerythritol hexakis(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),Dipentaerythritol 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) Examples include tris-2-(3-mercapto-3-phenylpropionate), tris-2-(3-mercapto-3-phenylpropionate)ethyl isocyanurate, pentaerythritol tetrakis(3-mercapto-3-phenylpropionate), and dipentaerythritol hexakis(3-mercapto-3-phenylpropionate).

[0080] Among secondary thiol compounds (F-21), commercially available compounds having two or more secondary mercapto groups in their molecule include 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Showa Denko K.K., Karenz MT® BD1), pentaerythritol tetrakis(3-mercaptobutyrate) (manufactured by Showa Denko K.K., Karenz MT® 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® NR1), trimethylolethanetris(3-mercaptobutyrate) (manufactured by Showa Denko K.K., TEMB), trimethylolpropanetris(3-mercaptobutyrate) (manufactured by Showa Denko K.K., TPMB), and it is preferable to use one or more of these. Among these, 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Showa Denko K.K., Karens MT® BD1) is preferred.

[0081] [Tertiary thiol compound (F-22)] When the secondary thiol compound (F-2) having the structure represented by 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), octanediol bis(2-mercaptoisobutyrate), trimethylolethanetris(2-mercaptoisobutyrate), trimethylolpropanetris(2-mercaptoisobutyrate), pentaerythritol tetrakis(2-mercaptoisobutyrate), and dipentaerythritol hexakis(2-mercapto Examples include isobutyrate, di(3-mercapto-3-methylbutyl) phthalate, ethylene glycol bis(3-mercapto-3-methylbutyrate), propylene glycol bis(3-mercapto-3-methylbutyrate), diethylene glycol bis(3-mercapto-3-methylbutyrate), butanediol bis(3-mercapto-3-methylbutyrate), octanediol bis(3-mercapto-3-methylbutyrate), trimethylolethanetris(3-mercapto-3-methylbutyrate), trimethylolpropanetris(3-mercapto-3-methylbutyrate), pentaerythritol tetrakis(3-mercapto-3-methylbutyrate), and dipentaerythritol hexakis(3-mercapto-3-methylbutyrate).

[0082] The total amount of the second thiol compound (F-2) in the second radical polymerizable resin composition of this embodiment is 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 even more preferably 0.2 to 4 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2) described above. If the amount of the second thiol compound (F-2) is 0.01 parts by mass or more, sufficient curing function can be obtained, and if it is 10 parts by mass or less, curing proceeds rapidly.

[0083] Furthermore, 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 preferably 0.1 to 15, more preferably 0.5 to 15, even 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 higher, the second thiol compound (F-2) can be sufficiently coordinated near the metal of the second metal-containing compound (E-2), and when the molar ratio is 15 or lower, the balance between manufacturing cost and effectiveness is improved.

[0084] The secondary thiol compound (F-2) may be used alone or in combination of two or more. When a secondary thiol compound (F-21) and a tertiary thiol compound (F-22) are used in combination, the molar ratio of the two [(F-21) / (F-22)] is preferably 0.001 to 1000, and more preferably 1 to 10. When the molar ratio [(F-21) / (F-22)] is within the above range, the secondary metal-containing compound (E-2) and the secondary thiol compound (F-2) are stable in the secondary radical polymerizable resin composition, and no disulfide compounds are generated as by-products due to the bonding of secondary thiol compounds (F-2) together. From the viewpoint of preserving the secondary radical polymerizable resin composition in a stable state of the secondary metal-containing compound (E-2) and the secondary thiol compound (F-2), it is preferable to use the secondary thiol compound (F-21) or the tertiary thiol compound (F-22) alone.

[0085] <Second curing accelerator (G-2)> The second radical polymerizable resin composition of this embodiment may also contain a second curing accelerator (G-2) other than the second metal-containing compound (E-2) and the second thiol compound (F-2) for the purpose of improving curability. Examples of secondary hardening accelerators (G-2) other than the secondary metal-containing compounds (E-2) and secondary thiol compounds (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-dimethylamino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-dimethylamino)benzaldehyde N,N-substituted anilines such as 4-(N,N-substituted amino)benzaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylimorpholine, piperidine, N,N-bis(hydroxyethyl)aniline, and diethanolaniline, as well as N,N-substituted-p-toluidines and amines such as 4-(N,N-substituted amino)benzaldehyde, can be used. When the second radical polymerizable resin composition of this embodiment contains a second curing accelerator (G-2), the amount 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, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0086] <Second polymerization inhibitor (H-2)> The second radical polymerizable resin composition of this embodiment may also contain a second polymerization inhibitor (H-2) from the viewpoint of suppressing excessive polymerization of the second radical polymerizable compound (A-2) and controlling the reaction rate. Examples of known secondary polymerization inhibitors (H-2) include hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-tert-butylcatechol. If the second radical polymerizable resin composition contains a second polymerization inhibitor (H-2), the amount is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 3 parts by mass, and even more preferably 0.01 to 1 part by mass, per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0087] <Second curing retarder (I-2)> The second radical polymerizable resin composition of this embodiment may contain a second curing retarder (I-2) for the purpose of delaying the curing of the second radical polymerizable compound (A-2). Examples of the second curing retarder (I-2) include free radical-based curing retarders, such as TEMPO derivatives including 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), and 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4-Oxo-TEMPO). Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO) is preferred in terms of cost and ease of handling. When the second radical polymerizable resin composition contains a second curing retarder (I-2), the amount is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 5 parts by mass, and even more preferably 0.05 to 3 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0088] <Expansion material (J)> The expansive material (J) used in this embodiment may be any expansive material that satisfies the standards of the Japanese Industrial Standard JIS A 6202 "Expansive Material for Concrete," which is commonly used as an expansive material for concrete. Specifically, any expansive material that produces calcium hydroxide or ettringite through a hydration reaction is acceptable. For example, an expansive material (J) containing at least one selected from the group consisting of quicklime and calcium sulfoaluminate is preferred. More preferred expansive materials include (1) an expansive material with quicklime as an active ingredient (quicklime-based expansive material), (2) an expansive material with calcium sulfoaluminate as an active ingredient (ettringite-based expansive material), and (3) a quicklime-ettringite composite expansive material.

[0089] Specific examples of quicklime-based expansive materials include, for example, Taiheiyo HyperExpan-K, Taiheiyo HyperExpan-M, Taiheiyo Expand-K, Taiheiyo Expand-M, and N-EX, all manufactured by Taiheiyo Material. Specific examples of ettringite-based expansive materials include Denka CSA #10 and Denka CSA #20 manufactured by Denka. Specific examples of quicklime-ettringite composite expansion agents include Denka Power CSA Type S, Denka Power CSA Type R, and Denka Power CSA Type T, all manufactured by Denka.

[0090] The content of the expanding agent (J) in this embodiment is preferably 0.3 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 1 to 20 parts by mass, and most preferably 3 to 16 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). 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 radical polymerizable resin composition is cured. Conversely, if it is 0.3 parts by mass or more, the expansion performance for the second radical polymerizable compound (A-2) will not be absent. Furthermore, these expanding agents (J) may be used individually or as a mixture of two or more.

[0091] <Cement (P)> The second radical polymerizable resin composition of this embodiment contains cement (P).

[0092] As cement (P), Portland cement, other blended cements, ultrafast-setting cements, etc., can be used without particular restriction. Examples of Portland cement include low-heat, moderate-heat, ordinary, rapid-hardening, ultra-rapid-hardening, and sulfate-resistant types of Portland cement. Examples of blended cements include blast furnace cement, fly ash cement, and silica cement. Among these, inexpensive Portland cement is preferred, and rapid-hardening and ultra-rapid-hardening Portland cement are even more preferred. These cements can be used individually or as a mixture of any combination and in any mixing ratio as exemplified above. The cement (P) content is preferably 20 to 200 parts by mass, more preferably 30 to 180 parts by mass, and even more preferably 40 to 150 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). Furthermore, the cement (P) content is not particularly limited, but is preferably 1 to 80 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 10 to 30 parts by mass, per 100 parts by mass of aggregate (K). In particular, if the cement content is 1 part by mass or more, the particle size distribution of the aggregate can be optimized and practical fluidity can be ensured. Also, if the cement content is 80 parts by mass or less, stickiness due to deterioration of fluidity can be prevented.

[0093] <Aggregate (K)> The second radical polymerizable resin composition of this embodiment contains aggregate (K). Aggregate (K) is not particularly limited, and any aggregate used in mortar and concrete can be used. Examples of aggregates include calcium carbonate, crushed stone, sandstone, crescent stone, marble, quartz, limestone, silica sand, silica stone, and river sand. From the viewpoint of weight reduction, lightweight aggregates such as sintered shale, silica-based balloons, and non-silica-based balloon perlite can also be used. Among these, silica sand is preferred, and silica sand No. 7 and silica sand No. 8 are more preferred. Calcium carbonate functions as a transparent extender pigment in the coating film that does not obscure the coated surface (substrate surface), and has functions such as filling depressions and reducing paint costs. An example of commercially available calcium carbonate is TM-2 (manufactured by Yukou Mining Co., Ltd.). Calcium carbonate has a specific particle size distribution, excellent dispersibility, and is porous, which can reduce the specific gravity of the aggregate itself, making it less prone to sagging, and improve film-forming properties.

[0094] Examples of silica-based balloons include shirasu balloons, perlite, glass (silica) balloons, and fly ash balloons. Examples of non-silicic acid-based balloons include alumina balloons, zirconia balloons, and carbon balloons. Specific examples of perlite include Perlite FL-0 (product name, manufactured by Fuyo Perlite Co., Ltd.), as well as Hardlite B-03, Hardlite B-04, and Hardlite B-05 (all product names, manufactured by Showa Chemical Industry Co., Ltd.).

[0095] The aggregate (K) content in the composition of this embodiment is not particularly limited, but is preferably 200 to 800 parts by mass, more preferably 250 to 700 parts by mass, and even more preferably 300 to 500 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). In particular, if the aggregate content is 200 parts by mass or more, practical fluidity can be ensured. Furthermore, if the aggregate content is 800 parts by mass or less, the amount of material adhering to the trowel will be reduced, preventing a decrease in workability.

[0096] <Fiber (L)> The radical polymerizable composition of this embodiment may contain fibers as needed. Specific examples of fibers that can be used in this embodiment include glass fibers, carbon fibers, vinylon fibers, nylon fibers, aramid fibers, polyolefin fibers, polyester fibers such as acrylic fibers and polyethylene terephthalate fibers, metal fibers such as cellulose fibers and steel fibers, and ceramic fibers such as alumina fibers. Among these, polyolefin fibers can be used as a thixotropic agent, for example. A thixotropic agent is a compound added for the purpose of imparting thixotropy.

[0097] Currently available polyolefin fibers include polyethylene-based products such as Chemivest® FDSS-2 (average fiber length 0.6 mm), Chemivest® FDSS-5 (average fiber length 0.1 mm), Chemivest® FDSS-25 (average fiber length 0.6 mm, hydrophilic product), and Chemivest® FDSS-50 (average fiber length 0.1 mm, hydrophilic product) (all manufactured by Mitsui Petrochemical Industries, Ltd.).

[0098] The carbon fiber is not particularly limited, and any known carbon fiber can be used. Examples include polyacrylonitrile (PAN) carbon fiber, rayon carbon fiber, pitch carbon fiber, etc. The carbon fibers may be used individually or in mixtures of two or more types. From the viewpoint of low cost and good mechanical properties, it is preferable to use PAN carbon fiber. Such carbon fibers are available commercially. Carbon fiber reinforced plastic (CFRP) may also be used as the carbon fiber.

[0099] The diameter of the carbon fiber is preferably 3 to 15 μm, more preferably 5 to 10 μm. The length of the carbon fiber is usually 5 to 100 mm. In this embodiment, the carbon fiber may be cut to lengths of 10.0 mm to 100.0 mm, or even 12.5 mm to 50.0 mm.

[0100] These fibers are preferably used in the form of fiber structures, biaxial meshes, or triaxial meshes selected from, for example, plain weave, satin weave, nonwoven fabric, mat, roving, chop, knit, braid, and composite structures thereof. For example, the fiber structure can be impregnated with a radical polymerizable composition and, in some cases, prepolymerized to form a prepreg for use. For example, biaxial mesh and triaxial mesh can be used. The side length (mesh size) of the squares in biaxial mesh and the side length (mesh size) of the equilateral triangles in triaxial mesh are preferably 5 mm or more, and more preferably 10 to 20 mm. By using biaxial or triaxial mesh, a lightweight, economical, workable, and durable hardening material for preventing concrete spalling can be obtained. These fibers are preferably used to reinforce coating properties such as concrete spalling prevention and FRP waterproofing, or in the manufacture of FRP molded products. For applications such as preventing concrete spalling, glass fibers and cellulose fibers, which have excellent transparency, are preferred because they allow for visual inspection of the substrate's deterioration from the outside.

[0101] The content of such fibers is preferably 0.3 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and even more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0102] <Water-reducing agent (M)> The second radical polymerizable resin composition of this embodiment may optionally contain a usable water-reducing agent (M) that can impart a water-reducing property. The water-reducing agent can be any known water-reducing agent used in concrete, such as a liquid or powder water-reducing agent, an AE water-reducing agent, a high-performance water-reducing agent, or a high-performance AE water-reducing agent, without limitation. Polycarboxylic acid-based water-reducing agents can suppress the decrease in concrete fluidity that occurs when aluminosilicate, which has the aforementioned swelling properties, is added, and are therefore preferable from the viewpoint of maintaining good fluidity and improving workability. Naphthalene sulfonic acid-based water-reducing agents are preferred from the viewpoint of improving workability because they have high dispersibility and high water-reducing effect.

[0103] The water-reducing agent is preferably present in the second radical polymerizable resin composition in an amount of 0.1 to 3.0% by mass.

[0104] <Other ingredients> The second radical polymerizable resin composition of this embodiment may contain components other than those mentioned above, as long as they do not particularly impede the strength development or acid resistance of the cured product. Examples of components that can be included include hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, as well as admixtures usable in mortar or concrete that can impart properties such as setting adjustment, curing acceleration, curing delay, thickening, water retention, defoaming, water repellency, and waterproofing, and admixtures usable in mortar or concrete such as fibers made of metal, polymers, or carbon, pigments, fillers, foaming agents, and clay minerals such as zeolites. Other components that can be included include coupling agents, plasticizers, anion immobilization components, solvents, polyisocyanate compounds, surfactants, wetting and dispersing agents, waxes, and thixotropes.

[0105] [Coupling agent] The second radical polymerizable resin composition of this embodiment may use a coupling agent for the purpose of improving processability and adhesion to the substrate. Examples of coupling agents include known silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like. Examples of such coupling agents include R 3 -Si(OR 4 A second silane coupling agent represented by )3 can be given. 3Examples include aminopropyl group, glycidyloxy group, methacrylateoxy group, N-phenylaminopropyl group, mercapto group, vinyl group, etc. 4 Examples include methyl groups and ethyl groups. If the second radical polymerizable resin composition contains a coupling agent, the amount is preferably 0.001 to 10 parts by mass per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0106] [Plasticizer] The second radical polymerizable resin composition of this embodiment may contain a plasticizer as needed. The plasticizer is not particularly limited, but may be used for purposes such as adjusting physical properties or characteristics. Examples include: phthalate esters such as dibutyl phthalate, diheptyl phthalate, di(2-ethylhexyl) phthalate, and butyl benzyl phthalate; non-aromatic dibasic acid esters such as dioctyl adipate, dioctyl sebacate, dibutyl sebacate, and isodecyl succinate; aliphatic esters such as butyl oleate and methyl acetylricylinoleate; esters of polyalkylene glycols such as diethylene glycol dibenzoate, triethylene glycol dibenzoate, and pentaerythritol ester; phosphate esters such as tricresyl phosphate and tributyl phosphate; trimellitic acid esters; polystyrenes such as polystyrene and poly-α-methylstyrene; and polybutadiene, polybutene, polyisobutylene, and butadiene. Examples include n-acrylonitrile, polychloroprene; chlorinated paraffins; hydrocarbon oils such as alkyldiphenyl and partially hydrogenated terphenyl; process oils; polyether polyols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol, and polyethers such as derivatives obtained by converting the hydroxyl groups of these polyether polyols to ester groups, ether groups, etc.; epoxy plasticizers such as epoxidized soybean oil and epoxy benzyl stearate; polyester plasticizers obtained from dibasic acids such as sebaciic acid, adipic acid, azelaic acid, and phthalic acid, and dihydric alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, and dipropylene glycol; and vinyl polymers obtained by polymerizing vinyl monomers, including acrylic plasticizers, by various methods. Among them, since the viscosity of the radical polymerizable composition and the mechanical properties such as the tensile strength and elongation of the cured product obtained by curing the composition can be adjusted, it is preferable to add a polymer plasticizer which is a polymer having a number average molecular weight of 500 to 15,000. Further, the polymer plasticizer is suitable because it can maintain the initial physical properties over a long period as compared with the case where a low molecular weight plasticizer which does not contain a polymer component in the molecule is used. Incidentally, although not limited, this polymer plasticizer may have a functional group or may not have a functional group. The number average molecular weight of the above polymer plasticizer is more preferably 800 to 10,000, and still more preferably 1,000 to 8,000. When the number average molecular weight is 500 or more, the elution of the plasticizer over time due to the influence of heat, rainfall and water can be suppressed, and the initial physical properties can be maintained over a long period. Further, when the number average molecular weight is 15,000 or less, an increase in viscosity can be suppressed and sufficient workability can be ensured.

[0107] 〔Anionic immobilization component〕 In addition, 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 or the presence or absence of crystal water. For example, the following general formula (R)

[0108] M x ·Mg y ·Al Z CO3(OH) xr+2y+3z-2 ·mH2O (R)

[0109] (In the formula, 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, and m is the number of crystal waters from 0 to 100) The basic carbonate represented by can be mentioned. In addition, hydrocalumites may be natural products or synthetic products, and can be used regardless of the presence or absence of surface treatment or the presence or absence of crystal water. For example, the following general formulas (S) and (T)

[0110] 3CaO·Al2O3·CaX2·kH2O (S)

[0111] (X is a monovalent anion, k ≤ 20)

[0112] 3CaO·Al2O3·CaY·kH2O (T)

[0113] (Y is a divalent anion, k ≤ 20) We can list things that can be represented by this.

[0114] Furthermore, these calmites contain nitrite ions (NO2), which are believed to have an effect of inhibiting the corrosion of reinforcing steel during the manufacturing process. - ) is supported, but an example of anion that can be supported is the nitrate ion (NO3 - ), hydroxide ion (OH - ), oxalate ion (CH3COO - ), carbonate ions (CO3 - ), sulfate ions (SO4 2- ) are some examples.

[0115] These hydrotalcite or hydrocalmite compounds can be used on their own, but they can also be used by mixing them into cement paste. When mixed with cement paste, the hydroxide ions (OH) that coexist during the hydration reaction - ) or sulfate ions (SO4) contained in cement 2- It is anticipated that this will have various effects on the anion exchange reaction, which is a characteristic of calmite. From the perspective of maintaining the desired exchange reaction with chloride ions, hydrocalmites supported with nitrite ions are preferable.

[0116] 〔solvent〕 The second radical polymerizable resin composition of this embodiment may contain solvents as needed. Examples of solvents that can be added include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate; and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. These solvents may also be used during the production of the polymer.

[0117] [Polyisocyanato compounds] The second radical polymerizable resin composition of this embodiment may also contain a polyisocyanato compound. The polyisocyanato compound reacts with the hydroxyl group of the second radical polymerizable compound (A-2) to form a cured coating film. The polyisocyanato compound contains two or more isocyanate groups in its molecule, and these isocyanate groups may be blocked by a blocking agent or the like. Examples of polyisocyanato compounds that have not been blocked by a blocking agent include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), and 1,3-(isocyanatomethyl)cyclohexane; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; 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, as well as cyclized polymers of the above-mentioned diisocyanates (e.g., isocyanurates) and biuret-type adducts. Among these, isocyanurate of hexamethylene diisocyanate is preferred. These polyisocyanate compounds may be used individually or in combination of two or more.

[0118] If the second radical polymerizable resin composition contains a polyisocyanato compound, the amount is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 2 to 20 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0119] Blocked polyisocyanato compounds are obtained by blocking the isocyanate groups of the above-mentioned polyisocyanato compounds with a blocking agent. Examples of blocking agents include phenolic agents such as phenol, cresol, and xylenol; lactam agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcoholic agents such as 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, and benzyl alcohol; oxime agents such as formamidexime, acetaldehydexime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, and cyclohexane oxime; and active methylene agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone. The isocyanate group of the polyisocyanate can be easily blocked by mixing the polyisocyanate with the blocking agent.

[0120] If the polyisocyanato compound is an unblocked polyisocyanato compound, a reaction will occur between the second radical polymerizable compound (A-2) and the polyisocyanato compound when they are mixed in the second radical polymerizable resin composition of this embodiment. Therefore, it is preferable to keep the second radical polymerizable compound (A-2) and the polyisocyanato compound separate until just before use, and then mix them at the time of use. Furthermore, a curing catalyst can be used to react the second radical polymerizable compound (A-2) with the polyisocyanate compound. Suitable curing catalysts include, for example, organometallic catalysts such as tin octoate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, and lead 2-ethylhexanoate. When the second radical polymerizable resin composition contains the curing catalyst, the amount is preferably 0.01 to 5 parts by mass, more preferably 0.05 to 4 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0121] [Surfactants] The second radical polymerizable resin composition of this embodiment may contain a surfactant. Examples of surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used individually or in combination of two or more types. Among these surfactants, one or more selected from anionic surfactants and nonionic surfactants are preferred.

[0122] Examples of anionic surfactants include alkyl sulfate esters such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene alkyl ether sulfate esters such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; sulfonates such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate; fatty acid salts such as sodium stearate soap, potassium oleate soap, and potassium castor oil soap; naphthalenesulfonic acid formalin condensate, and special polymer systems.

[0123] Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene derivatives such as polyoxyethylene distylentaneated phenyl ether, polyoxyethylene tripenzyl phenyl ether, and polyoxyethylene polyoxypropylene glycol; sorbitan fatty acid esters such as polyoxyalkylene alkyl ether, sorbitan monolaurate, sorbitan monopalmitate, and sorbitan monostearate; polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbitan tetraoleate; and glycerin fatty acid esters such as glycerin monostearate and glycerin monooleate. Among these, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene alkyl ether are preferred. Furthermore, the HLB (Hydrophile-Lipophil Balance) of the nonionic surfactant is preferably 5 to 15, and more preferably 6 to 12.

[0124] If the second radical polymerizable resin composition contains a surfactant, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and even more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0125] [Wetting and dispersing agent] The second radical polymerizable resin composition of this embodiment may, for example, contain a wetting and dispersing agent to improve penetration into wet or submerged repair sites. Examples of wetting and dispersing agents include fluorine-based wetting and dispersing agents and silicone-based wetting and dispersing agents, which may be used individually or in combination of two or more types. Commercially available fluorine-based wetting and dispersing agents include Megafac® F176, Megafac® R08 (manufactured by Dainippon Ink and Chemicals, Inc.), PF656, PF6320 (manufactured by OMNOVA Corporation), Troisol S-366 (manufactured by Troy Chemical Co., Ltd.), Florard FC430 (manufactured by 3M Japan Limited), and Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.). 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, BYK(registered trademark)-302, BYK(registered trademark)-UV3500, BYK-306 (manufactured by BIC Chemie Japan Co., Ltd.), and polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0126] Furthermore, the silicone-based wetting and dispersing agent preferably contains a compound represented by the following formula (U).

[0127] [ka]

[0128] (In the formula, R 5 and R 6 Each of these independently may contain a hydrocarbon group having 1 to 12 carbon atoms in an aromatic ring, or -(CH2)3O(C2H4O) p (CH2CH(CH3)O) q R' represents an alkyl group with 1 to 12 carbon atoms, where n is an integer between 1 and 200, p and q are integers, and q / p = between 0 and 10. Commercially available silicone-based wetting and dispersing agents containing the compound represented by formula (U) include BYK(registered trademark)-302 and BYK(registered trademark)-322 (manufactured by BYK Chemie Japan Co., Ltd.). If the second radical polymerizable resin composition of this embodiment contains a wetting dispersant, the amount 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 the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0129] 〔wax〕 The second radical polymerizable resin composition of this embodiment may contain wax. Examples of waxes include paraffin waxes and polar waxes, which may be used individually or in combination of two or more types. As paraffin waxes, known types with various melting points can be used. As polar waxes, those having both polar and nonpolar groups in their structure can be used, specifically including NPS(registered trademark)-8070, NPS(registered trademark)-9125 (manufactured by Nippon Seiro Co., Ltd.), Emanone(registered trademark) 3199, and Emanone(registered trademark) 3299 (manufactured by Kao Corporation). If the second radical polymerizable resin composition of this embodiment contains wax, the amount is preferably 0.05 to 4 parts by mass, more preferably 0.1 to 2.0 parts by mass, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0130] [Second thujamatic modifier] The second radical polymerizable resin composition of this embodiment may also use a second thixotrope for purposes such as viscosity adjustment to ensure workability on vertical or ceiling surfaces. Examples of the second oscillating agent include inorganic and organic oscillating agents. Examples of organic oscillating agents include hydrogenated castor oil-based, amide-based, oxidized polyethylene-based, polymerized vegetable oil-based, surfactant-based, and composite systems using these in combination. Specifically, examples include DISPARLON® 6900-20X (Kusumoto Chemical Co., Ltd.). Furthermore, examples of inorganic thixotropes include silica and bentonite-based materials. Hydrophobic examples include Rheorosil® PM-20L (vapor-phase silica manufactured by Tokuyama Corporation) and Aerosil® R-106 (Aerosil Japan Co., Ltd.), while hydrophilic examples include Aerosil® AEROSIL-200 (Aerosil Japan Co., Ltd.). From the viewpoint of further improving thixotropy, hydrophilic calcined silica to which thixotropy modifiers such as BYK®-R605 and BYK®-R606 (manufactured by Bic Chemie Japan Co., Ltd.) have been added can also be suitably used. When the second radical polymerizable resin composition of this embodiment contains a second thixotrope, the amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0131] <Water> The second radical polymerizable resin composition of this embodiment is substantially water-free from the viewpoint of obtaining practical strength. That is, water is not added as a component of the composition when preparing the second radical polymerizable resin composition. For example, the water content of the second radical polymerizable resin composition is 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, and most preferably 0.10 parts by mass or less, based on 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

[0132] <Method for producing a second radical polymerizable resin composition> The method for producing the second radical polymerizable resin composition of this embodiment is not particularly limited, and methods known in the art can be used. For example, the second radical polymerizable resin composition can be produced by mixing a second radical polymerizable compound (A-2) and a second radical polymerizable unsaturated monomer (B-2) with a second metal-containing compound (E-2) as needed, and further blending and mixing a second radical polymerization initiator (D-2), cement (P), aggregate (K), and expansive agent (J). One embodiment of the method for producing the second radical polymerizable resin composition of this embodiment includes the steps of: (2-S1) mixing a second radical polymerizable compound (A-2) and a second radical polymerizable unsaturated monomer (B-2) with a second metal-containing compound (E-2) as needed to obtain a mixture (2-i); (2-S2) mixing a second radical polymerization initiator (D-2) with the obtained mixture (2-i) to obtain a mixture (2-ii); and (2-S3) mixing cement (P), aggregate (K), and expansive agent (J) with the obtained mixture (2-ii) to obtain a second radical polymerizable resin composition.

[0133] In the step (2-S1) (sometimes simply referred to as "step (2-S1)") for obtaining the mixture (i), in addition to mixing the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2) with the second metal-containing compound (E-2), a second polymerization inhibitor (H-2), a second curing retarder (I-2), a second thiol compound (F-2), etc., may be further mixed as needed. In the step of obtaining the second radical polymerizable resin composition (2-S3) (sometimes simply referred to as "step (2-S3)"), in addition to mixing the mixture (2-ii) obtained in the step of obtaining the mixture (2-ii) (2-S2) (sometimes simply referred to as "step (2-S2)") with an expansive agent (J), cement (P), and aggregate (K), fibers (L), water-reducing agents (M), etc., may be further mixed as needed. Specific examples of aggregate (K) include, for example, rapid-hardening Portland cement, calcium carbonate TM-2, perlite FL-0, hardlite B-04, Enshu 5.5 silica sand, N50 silica sand, N40 silica sand, N90 silica sand, etc.

[0134] The second radical polymerizable resin composition produced in this manner can be cured at room temperature and exhibits excellent workability, early strength development, and curability. Because it contains an expansive agent (J), the shrinkage rate during curing is small, and under certain conditions, the expansion rate of the cured product can be greater than 0.

[0135] [Cured product from the recess filler kit] The cured product of the recess filler kit of this embodiment comprises a first cured product which is the cured product of the first radical polymerizable resin composition and a second cured product which is the cured product of the second radical polymerizable resin composition. The cured product of the recess filler kit is formed in the recess such that the first cured product is formed on the surface of the recess and the second cured product is formed on the surface of the first cured product.

[0136] <Cured product of the first radical polymerizable resin composition> The cured product of the first radical polymerizable resin composition of this embodiment is obtained by curing the above-described first radical polymerizable resin composition.

[0137] "Method for curing a first radical polymerizable resin composition" For example, if the first radical polymerizable resin composition contains a thermal radical polymerization initiator, the same curing method as the second radical polymerizable resin composition described later can also be used.

[0138] <Cured product of a second radical polymerizable resin composition> The cured product of the second radical polymerizable resin composition of this embodiment is obtained by curing the above-mentioned second radical polymerizable resin composition.

[0139] "Method for curing a second radical polymerizable resin composition" When the second radical polymerizable resin composition of this embodiment contains a thermal radical polymerization initiator (D-21), one example of a curing method for the second radical polymerizable resin composition of this embodiment is to apply the second radical polymerizable resin composition of this embodiment to the surface of a substrate and cure it at room temperature. For example, the second radical polymerizable resin composition of this embodiment is used as a filler for recesses in an inorganic structure. Because the second radical polymerizable resin composition of this embodiment contains an expansive agent (J), the resulting cured product does not shrink significantly even after a certain period of time has elapsed, unlike conventional products. Examples of base material include concrete, asphalt concrete, mortar, brick, wood, and metal, as well as thermosetting resins such as phenolic resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, vinyl ester resin, alkyd resin, polyurethane, and polyimide; and thermoplastic resins such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, Teflon (registered trademark), ABS resin, AS resin, and acrylic resin.

[0140] When the second radical polymerizable resin composition of this embodiment contains a photoradical polymerization initiator (D-22), the timing of photocuring can be such as applying the second radical polymerizable resin composition to a substrate and then photocuring it, or preparing a sheet by pre-polymerizing (also called B-stage or prepreg formation) the second radical polymerizable resin composition in advance, attaching the sheet to a substrate, and then photocuring it.

[0141] Any light source with a spectral distribution in the photosensitive wavelength range of the photoradical polymerization initiator (D-22) is acceptable. For example, sunlight, ultraviolet lamps, near-infrared lamps, sodium lamps, halogen lamps, fluorescent lamps, metal halide lamps, and LEDs can be used. Furthermore, by using two or more types of photoradical polymerization initiators (D-22) in combination, and by using wavelength cut filters on the light source or specific wavelengths of LEDs, the wavelengths required for prepolymerization and main polymerization can be differentiated. For prepolymerization, long wavelengths with low energy levels are preferable, and near-infrared light is particularly useful for controlling the degree of polymerization. In this embodiment, ultraviolet light refers to light rays in the wavelength range of 280-380 nm, visible light refers to light rays in the wavelength range of 380-780 nm, and near-infrared light refers to light rays in the wavelength range of 780-1200 nm. The irradiation time of the lamp required for prepolymerization cannot be specified definitively because it is affected by the effective wavelength range of the light source, output, irradiation distance, and thickness of the composition, but for example, irradiation for 0.01 hours or more, preferably 0.05 hours or more, is sufficient.

[0142] [Recess Filling Method (Mortar Filling Method for Recesses)] The recess filling method, or mortar filling method for recesses, of this embodiment can be widely used in civil engineering and construction work where filling is required. Furthermore, the material constituting the recess can be any structure that includes one or more of the following: concrete members, metal members, or resin members. Also, the recess is shown as an example because a 10cm cube is the most suitable when considering material shrinkage, but its shape can be a cube, a rectangular prism, a sphere, or a cone.

[0143] Structures in which recesses occur according to this embodiment include, regardless of material, tunnels, manholes, waterways, pipelines, guardrails, signs, anchor bolts, rock bolts, and reinforced concrete structures. Alternatively, they may occur in areas that have been previously repaired and are undergoing further repair, such as areas repaired with cement concrete, polymer cement mortar, epoxy resin mortar, urethane resin, or steel plate reinforcement sections.

[0144] Another embodiment of the recess filling method of this embodiment, or the mortar filling method for recesses, comprises a base layer formation step of applying a first radical polymerizable resin composition to the surface of the recess to form a base layer, and a filling step of filling the surface of the base layer formed on the surface of the recess with a second radical polymerizable resin composition.

[0145] Another embodiment of the recess filling method of this embodiment, or the mortar filling method for recesses, comprises the steps of applying a first radical polymerizable resin composition to part or all of the surface of the recess, filling it with a second radical polymerizable resin composition, and curing the first radical polymerizable resin composition and the second radical polymerizable resin composition.

[0146] One embodiment of the recess filling method or mortar filling method for recesses according to this embodiment may include the steps of: applying a first radical polymerizable resin composition to part or all of the surface of the recess; curing the first radical polymerizable resin composition to form a cured layer of the first radical polymerizable resin composition on the surface of the recess; filling the recess having the cured layer of the first radical polymerizable resin composition with a second radical polymerizable resin composition; and curing the second radical polymerizable resin composition.

[0147] Furthermore, another embodiment of the recess filling method or mortar filling method for recesses according to this embodiment may include the steps of: applying a first radical polymerizable resin composition to part or all of the surface of the recess; drying or semi-curing the first radical polymerizable resin composition to form a first radical polymerizable resin composition layer or semi-cured layer on the surface of the recess; filling the recess having the first radical polymerizable resin composition layer or semi-cured layer with a second radical polymerizable resin composition; and curing the first radical polymerizable resin composition and the second radical polymerizable resin composition.

[0148] Furthermore, another embodiment of the recess filling method of this embodiment, or the mortar filling method for recesses, may include the steps of applying a first radical polymerizable resin composition to part or all of the surface of the recess, filling it with a second radical polymerizable resin composition, and curing the first radical polymerizable resin composition and the second radical polymerizable resin composition.

[0149] If the recess is, for example, a bolt box, the bolt box can be filled using the recess filling method described above. For example, the bolt box filling method may include a base layer formation step of applying the first radical polymerizable resin composition to the surface of the bolt box to form a base layer, and a filling step of filling the surface of the base layer formed on the surface of the bolt box with the second radical polymerizable resin composition. [Examples]

[0150] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0151] The raw materials used in the production of the first radical polymerizable resin composition and the second radical polymerizable resin composition in the examples and comparative examples are as follows.

[0152] <First radical polymerizable compound (A-1) and first radical polymerizable unsaturated monomer (B-1)> (Synthesis Example 1) [Synthesis of radical polymerizable compound (Ai) and mixing with first radical polymerizable unsaturated monomer (B-1)] In a 1 L four-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 386.3 g of SR-16H (1,6-hexanediol diglycidyl ether; epoxy equivalent 157, manufactured by Sakamoto Pharmaceutical Co., Ltd.), 0.30 g of methyl hydroquinone, and 1.80 g of 2,4,6-tris(dimethylaminomethyl)phenol ("Seikol TDMP," manufactured by Seiko Chemical Co., Ltd.) were added and the mixture was heated to 110°C. 211.6 g of methacrylic acid was added dropwise over approximately 30 minutes, and the mixture was then heated to 130°C and reacted for approximately 4 hours until the acid value reached 20 mg / KOHg to synthesize a vinyl ester resin, which is a radical polymerizable compound (Ai). Next, 400.0 g of dicyclopentenyloxyethyl methacrylate ("FA-512MT", manufactured by Hitachi Chemical Co., Ltd.) was added as the first radical polymerizable unsaturated monomer (B-1) to obtain 1000.0 g of a non-styrene type mixture with a viscosity of 250 mPa·s at 25°C and a radical polymerizable compound (Ai) component ratio of 60% by mass.

[0153] [Radical polymerizable compounds (A-ii)] As the vinyl ester resin, Lipoxy® R-806 (manufactured by Showa Denko K.K., with a styrene content of 45% by mass as the first radical polymerizable unsaturated monomer (B-1)) was used.

[0154] <First radical polymerization initiator (D-1)> Perkmyl® H-80 (cumene hydroperoxide (CHP), manufactured by NOF Corporation) was used as the thermal radical polymerization initiator (Di). As the thermal radical polymerization initiator (D-ii), Permec® N (methyl ethyl ketone peroxide, manufactured by NOF Corporation) was used. Perkmyl® P (diisopropylbenzene hydroperoxide, manufactured by NOF Corporation) was used as the thermal radical polymerization initiator (D-iii).

[0155] <First metal-containing compound (E-1)> Manganese octoate (manufactured by Toei Chemical Co., Ltd., hexoate manganese, manganese content of 6% by mass in the total product, molecular weight 341.35) was used as the metal soap (Ei). Cobalt octylate (manufactured by Toei Chemical Co., Ltd., hexoate cobalt, cobalt content of 8% by mass in the total product, molecular weight 345.34) was used as the metal soap (E-ii).

[0156] <First thiol compound (F-1)> As the secondary thiol compound (Fi), we used Karenz MT® BD1 (1,4-bis(3-mercaptobutyryloxy)butane, molecular weight 299.43), a bifunctional secondary thiol manufactured by Showa Denko K.K.

[0157] <First polymerization inhibitor H-1> Tertiary butylcatechol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the polymerization inhibitor (Hi).

[0158] <First curing retarder (I-1)> As the first curing retarder (Ii), 4-H-TEMPO (Hakuto Co., Ltd., Polystop 7300P, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical) was used.

[0159] <Second radical polymerizable compound (A-2) and second radical polymerizable unsaturated monomer (B-2)> (Synthesis Example 2) [Synthesis of radical polymerizable compounds (A-iii) and mixing with second radical polymerizable unsaturated monomer (B-2)] In a 1L four-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 179.0g of bisphenol A type epoxy resin ("Epomic® R140P", manufactured by Mitsui Chemicals, Inc.; epoxy equivalent 188), 214.2g of Denacol EX-212 (manufactured by Nagase ChemteX Corporation; 1,6-hexanediol diglycidyl ether; epoxy equivalent 150), 0.30g of methyl hydroquinone, and 1.80g of DMP-30 (manufactured by Tokyo Chemical Industry Co., Ltd.; 2,4,6-tris(dimethylaminomethyl)phenol) were added, and the mixture was heated to 110°C. After raising the temperature to 110°C, 204.7g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) was added dropwise over approximately 30 minutes. The temperature was then raised to 130°C, and the mixture was reacted for approximately 4 hours until the acid value reached 14mg / KOHg, thereby synthesizing a vinyl ester resin, which is a radical polymerizable compound (A-iii). Next, 300.0 g of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512MT) and 100.0 g of dicyclopentanyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513M) were added as the second radical polymerizable unsaturated monomer (B-2) to obtain 1000.0 g of a non-styrene type mixture with a viscosity of 280 mPa·s at 25°C and a radical polymerizable compound (A-iii) component ratio of 60% by mass.

[0160] [Radical polymerizable compounds (A-iv)] As the unsaturated polyester resin, Rigolac® SR-110N (Showa Denko Corporation, styrene content 40% by mass as a second radical polymerizable unsaturated monomer (B-2)) was used.

[0161] (Synthesis Example 3) [Synthesis of radical polymerizable compound (Av) and mixing with second radical polymerizable unsaturated monomer (B-2)] In a 1L four-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 170.44g of diphenylmethane diisocyanate (Millionate MT, manufactured by Tosoh Corporation), 136.35g of ADEKA polyether P-400 (polyetherdiol, manufactured by ADEKA Corporation), and 0.11g of dibutylhydroxytoluene (BHT, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.02g of dibutyltin dilaurate (KS-1260, manufactured by Kyodo Pharmaceutical Co., Ltd.) were added as polymerization inhibitors, and the mixture was reacted at 60°C for 3 hours. Next, 93.08g of 2-hydroxyethyl methacrylate (2-HEMA, manufactured by Nippon Shokubai Co., Ltd.) was added dropwise to the reaction product over 30 minutes while stirring, and the mixture was reacted for approximately 3 hours after the completion of the dropwise addition to synthesize a urethane methacrylate resin, which is a radical polymerizable compound (Av). Next, 600.0 g of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512MT) was added as the second radical polymerizable unsaturated monomer (B-2) to obtain 1000.0 g of a non-styrene type mixture with a viscosity of 420 mPa·s at 25°C and a radical polymerizable compound (Av) component ratio of 40% by mass.

[0162] (Synthesis Example 4) [Synthesis of radical polymerizable compounds (A-vi) and mixing with second radical polymerizable unsaturated monomer (B-2)] In a 1L four-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 140.95g of diphenylmethane diisocyanate (Millionate MT, manufactured by Tosoh Corporation), 281.91g of Actcol D-1000 (polypropylene glycol, manufactured by Mitsui Chemicals, Inc.), 0.15g of dibutylhydroxytoluene (BHT, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.03g of dioctyl tin dilaurate (Neostan U-810, manufactured by Nitto Chemical Co., Ltd.) were added as polymerization inhibitors, and the mixture was reacted at 70°C for 2 hours. Next, 76.96g of 2-hydroxyethyl methacrylate (2-HEMA, manufactured by Nippon Shokubai Co., Ltd.) was added dropwise to the reaction product over 30 minutes while stirring, and the mixture was reacted for approximately 3 hours after the completion of the dropwise addition to synthesize a urethane methacrylate resin, which is a radical polymerizable compound (A-vi). Next, 150.0 g of phenoxyethyl methacrylate (light ester PO, manufactured by Kyoeisha Chemical Co., Ltd.) and 350.0 g of dicyclopentenyloxyethyl methacrylate (FA-512MT, manufactured by Hitachi Chemical Co., Ltd.) were added as the second radical polymerizable unsaturated monomer (B-2) to obtain 1000.0 g of a non-styrene type mixture with a viscosity of 570 mPa·s at 25°C and a radical polymerizable compound (A-vi) component ratio of 50% by mass.

[0163] (Synthesis Example 5) [Mixing of radical polymerizable compounds (A-vii) and second radical polymerizable unsaturated monomer (B-2)] In a 1L four-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 135.72g of diphenylmethane diisocyanate (Millionate MT, manufactured by Tosoh Corporation), 54.28g of Adeka polyether P-400 (polyetherdiol, manufactured by ADEKA Corporation), 135.72g of Actcol D-1000 (polypropylene glycol, manufactured by Mitsui Chemicals, Inc.), and 0.15g of dibutylhydroxytoluene (BHT, manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.03g of dioctyl tin dilaurate (Neostan U-810, manufactured by Nitto Chemical Co., Ltd.) were added as polymerization inhibitors, and the mixture was reacted at 70°C for 2 hours. Next, 74.10g of 2-hydroxyethyl methacrylate (2-HEMA, manufactured by Nippon Shokubai Co., Ltd.) was added dropwise to the reaction product over 30 minutes while stirring, and the mixture was reacted for approximately 3 hours after the completion of the dropwise addition to synthesize a urethane methacrylate resin, which is a radical polymerizable compound (A-vii). Next, 150.0 g of lauryl methacrylate (light ester L, manufactured by Kyoeisha Chemical Co., Ltd.) and 450.0 g of dicyclopentenyloxyethyl methacrylate (FA-512MT, manufactured by Hitachi Chemical Co., Ltd.) were added as the second radical polymerizable unsaturated monomer (B-2) to obtain 1000.0 g of a non-styrene type mixture with a viscosity of 320 mPa·s at 25°C and a radical polymerizable compound (A-vii) component ratio of 40% by mass.

[0164] <Second radical polymerization initiator (D-2)> Perkmyl® H-80 (cumene hydroperoxide (CHP), manufactured by NOF Corporation) was used as the thermal radical polymerization initiator (Di). As the thermal radical polymerization initiator (D-ii), Permec® N (methyl ethyl ketone peroxide, manufactured by NOF Corporation) was used. Perkmyl® P (diisopropylbenzene hydroperoxide, manufactured by NOF Corporation) was used as the thermal radical polymerization initiator (D-iii).

[0165] <Second metal-containing compound (E-2)> Manganese octoate (manufactured by Toei Chemical Co., Ltd., hexoate manganese, manganese content of 6% by mass in the total product, molecular weight 341.35) was used as the metal soap (Ei). Cobalt octylate (manufactured by Toei Chemical Co., Ltd., hexoate cobalt, cobalt content of 8% by mass in the total product, molecular weight 345.34) was used as the metal soap (E-ii).

[0166] <Second thiol compound (F-2)> As the secondary thiol compound (Fi), we used Karenz MT® BD1 (1,4-bis(3-mercaptobutyryloxy)butane, molecular weight 299.43), a bifunctional secondary thiol manufactured by Showa Denko K.K.

[0167] <Second polymerization inhibitor (H-2)> Tertiary butylcatechol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the polymerization inhibitor (Hi). 2,6-di-tert-butyl-4-methylphenol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used as the polymerization inhibitor (H-ii).

[0168] <Second curing retarder (I-2)> As the second curing retarder (Ii), 4-H-TEMPO (Hakuto Co., Ltd., Polystop 7300P, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical) was used.

[0169] <Expansion 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 Material Co., Ltd.) was used.

[0170] <Cement (P)> High-early-strength Portland cement

[0171] <Aggregate (K)> Calcium carbonate TM-2 Perlite FL-0 Hardlight B-04 Enshu No. 5.5 silica sand N50 silica sand N40 silica sand

[0172] <Fiber (L)> Chemivest® FDSS-5 (manufactured by Mitsui Chemicals Fine, Inc., a polyolefin-based multi-branched fiber)

[0173] (Examples 1-6, Comparative Examples 1-2) "Preparation of a first radical polymerizable resin composition" (1) Resin adjustment process (1-S1): A mixture of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1) was thoroughly mixed with 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) in the amounts shown in Table 1 to prepare 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 proportions shown in Table 1 to prepare mixture (1-ii). (3) Hardening agent mixing step (1-S3): The mixture (1-ii) obtained in step (1-S2) was mixed with the first radical polymerization initiator (D-1) in the amounts shown in Table 1 to prepare a first radical polymerizable resin composition (curable primer).

[0174] The first radical polymerizable resin compositions PC-1 to PC-6 and cPC-1 to cPC-2 obtained by the above method, using the respective raw material blending amounts shown in Table 1 for Examples 1 to 6 and Comparative Examples 1 to 2, were evaluated according to the following methods. The results are shown in Table 1.

[0175] [Table 1]

[0176] "Preparation of a second radical polymerizable resin composition" (1) Resin adjustment process (2-S1): A mixture (2-i) was prepared by thoroughly mixing a second radical polymerizable compound (A-2) and a second radical polymerizable unsaturated monomer (B-2) with a second metal-containing compound (E-2), a second thiol compound (F-2), a second polymerization inhibitor (H-2), and a second curing retarder (I-2) in the amounts shown in Table 1. (2) Hardening agent mixing process (2-S2): The mixture (2-i) obtained in step (2-S1) was mixed with the second radical polymerization initiator (D-2) in the proportions shown in Table 1 to prepare mixture (2-ii). (3) Aggregate mixing process (2-S3): The mixture (2-ii) obtained in step (2-S2) was thoroughly mixed with the leavening agent (J), aggregate (K), and fiber (L) in the amounts and components shown in Table 1 to obtain the second radical polymerizable resin composition of this example.

[0177] The mixing conditions for each step are as follows: Mixer: Homogenezing Disper Model 2.5 (manufactured by Primix) Stirring rotation speed: 1000~5000 rpm Temperature: 25℃

[0178] The second radical polymerizable resin compositions RC-1 to RC-10 and cRC-1 to cRC-2 obtained by the above method, using the respective raw material blending amounts shown in Table 2 for Examples 7 to 16 and Comparative Examples 3 to 4, were evaluated according to the following methods. The results are shown in Table 2.

[0179] [Table 2]

[0180] <Curing Test (Measurement of gelation time, curing time, and curing temperature)> The first radical polymerizable resin compositions PC-1 to PC-6 and cPC-1 to cPC-2 of Examples 1 to 6 and Comparative Examples 1 to 2, as described in Table 1, were placed in test tubes (outer diameter 18 mm, length 165 mm) to a depth of 100 mm from the bottom, and the temperature was measured using a thermocouple under conditions of 25°C. The time it took for the temperature of the radical polymerizable resin composition to rise from 25°C to 30°C was defined as the gelation time. The time it took for the radical polymerizable resin composition to reach its maximum exothermic temperature from 25°C was defined as the curing time, and the maximum exothermic temperature was defined as the curing temperature. These measurements were taken in accordance with JIS K 6901:2008. The radical polymerizable resin composition was pre-adjusted to 25°C before measurement. The results are shown in Table 1.

[0181] <Adhesion Strength Test> On the top surface of a 300mm x 300mm x 5mm stainless steel plate (SUS304), apply 150g / m² of the first radical polymerizable resin composition (curable primer) obtained in Examples 1-6 and Comparative Examples 1-2 using a brush. 2 The coating was applied and cured for one day at 25°C and 50% humidity, after which an adhesion strength test was performed. The adhesion strength test was conducted using an Elcometer 106 pull-off adhesion tester, and the average value of the three test specimens is shown as the result. The adhesion strength test was performed with an adhesion strength of 1.0 N / mm² from the perspective of adhesion to the building structure. 2 The above is marked with "〇", and the adhesion strength is 1.0 N / mm. 2 Values ​​less than a certain value were marked with "×". The results are shown in Table 1.

[0182] <Viscosity measurement> The resin viscosity was measured at 25 °C and 50 rpm using an E-type viscometer RE85U (manufactured by Toki Sangyo Co., Ltd.) and a cone plate of 1°34’×R24 (standard). The results are shown in Table 1.

[0183] <Compressive strength test> For 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 described in Table 2, the compressive strength values were evaluated according to the following method. The results are shown in Table 2. The specimens for the compressive strength test were prepared in accordance with JIS A 1132:2020. The dimensions of the specimens were 50 mm in diameter and 100 mm in height, and the mold used for specimen preparation was a steel mold. The test apparatus was a Shimadzu concrete compressive strength tester "CCM-1000kNI" (manufactured by Shimadzu Corporation). After each specimen was prepared, the test was carried out at 6 hours, 1 day, 3 days, and 7 days of curing.

[0184] <Method for measuring curing shrinkage> For the cured product of the second radically polymerizable resin composition of this embodiment, the shrinkage / expansion rate after curing (change rate: negative number is shrinkage rate, positive number is expansion rate) was measured in accordance with Japanese Standard JIS A 1129-3 (dial gauge method). The method for producing the molded body (cured product) was carried out by referring to Appendix A of Japanese Standard JIS A 1129. The mold used was a mold for specimens of 40×40×160 mm specified in Japanese Standard JIS R 5201. The specimens of the cured product were molded according to the method for making specimens for strength tests specified in 10 of JIS R 5201. After molding, they were left standing (cured) in a room at a temperature of 23 °C ± 2 °C and a humidity of 50% while still in the mold, and demolded approximately 24 hours after molding. Then, using the instrument shown in 3 of JIS A 1129-3, the measurement was started under the conditions shown in 4.3 of JIS A 1129-3 (time is set to 0).

[0185] Change amount (negative number: shrinkage amount, positive number: expansion amount) = long side length at elapsed time - long side length at start time (0 hour) (160 mm) (1)

[0186] Rate of change (negative number: shrinkage rate, positive number: expansion rate) = Amount of change / Long side length at the start (0 o'clock) (160 mm) (2)

[0187] The results are shown in Table 2.

[0188] <Combination of the first radically polymerizable compound and the second radically polymerizable composition> Hereinafter, the test method and results of the combination of the first radically polymerizable compound and the second radically polymerizable composition will be described.

[0189] (Examples 17 to 23, Comparative Examples 5 to 6) <Regarding the five-sided restraint test> For the concrete mold used in the five-sided restraint test, Zero Cube L (10 cm × 10 cm × height 9 cm) of Omi Chemical Co., Ltd. (RDE) was used. Since it is a pot for gardening, there is a hole with a diameter of about 2 cm at the bottom. When conducting the simple five-sided restraint test shown below, use an appropriate concrete plate and block the hole at the bottom before use.

[0190] The obtained first radically polymerizable resin compositions (primer compositions) PC-1, PC-2, PC-4, PC-6, cPC-1 and the second radically polymerizable resin compositions (resin mortar compositions) RC-1, RC-2, RC-7, RC-8, RC-9, RC-10, cRC-1 were used. First, apply the first radically polymerizable resin composition to the inner wall of the above concrete mold at an application rate of 0.3 kg / m 2The material was then coated. Next, the second radical polymerizable resin composition was packed tightly into the material, and the specimens were cured at 25°C for 24 hours to prepare the test specimens. The test specimens were evaluated according to the evaluation criteria below. Next, as a dry-wet cycle test, the test specimens were evaluated after 30 cycles, with one cycle consisting of dry conditions (temperature 15°C, humidity 60% for 4 days) and wet conditions (temperature 60°C, humidity 90% for 3 days), according to the evaluation criteria below. Similarly, as a hot-cold cycle test, the test specimens were evaluated after 30 cycles, with one cycle consisting of submersion conditions (temperature 25°C, curing in water for 18 hours), cooling conditions (temperature -20°C for 3 hours), and heating conditions (temperature 50°C for 3 hours), according to the evaluation criteria below. For each combination of Examples 17-23 and Comparative Examples 5-6 shown in Table 3, the five-sided restraint test was evaluated according to the method described above. The evaluation criteria are shown below. Cracks and peeling will be visually inspected, and lifting will be judged by tapping the surface and the pitch of the sound. (If lifting is present, the sound will be high pitched when tapped.)

[0191] ○: The resin mortar remains adhered to all five surfaces it is in contact with, and there are no cracks or delaminations on the concrete structure side. Also, no separation is observed between the resin mortar and the primer. △: The resin mortar remains adhered to all five surfaces, but cracks and delamination are visible on one surface of the concrete structure. ×: Cracks or lifting are observed on two or more of the five restraints (bonding) surfaces. Also, delamination is observed on one or more surfaces.

[0192] The results are shown in Table 3.

[0193] [Table 3]

[0194] (Reinforcement bar pull-out test) "Method for preparing test specimens" As shown in Figure 1, a formwork (2) with sides of 10 cm was prepared in accordance with JSTM C 2101T (Test method for adhesion strength between reinforcing bars and concrete by tensile test). Deformed reinforcing bars (1) D16 coated with the first radical polymerizable composition (curable primer) (3a) were placed inside the formwork (2). In that state, the second radical polymerizable composition (4a) was packed tightly into the formwork (2). After 24 hours of curing, the formwork (2) was removed to obtain the test specimens. The obtained test specimens were subjected to rebar pull-out tests according to the evaluation methods and criteria described below. Similarly, as a dry-wet cyclic test, rebar pull-out tests were also performed on the specimens after 30 cycles, with one cycle consisting of dry conditions (temperature 15°C, humidity 60% for 4 days) and wet conditions (temperature 60°C, humidity 90% for 3 days). Furthermore, as a hot-cold cyclic test, rebar pull-out tests were also performed on the specimens after 30 cycles, with one cycle consisting of submersion conditions (temperature 25°C, curing in water for 18 hours), cooling conditions (temperature -20°C for 3 hours), and heating conditions (temperature 50°C for 3 hours).

[0195] "Testing equipment" Measurements were performed using an Amsler universal testing machine (MR type) manufactured by Maekawa Testing Machine Manufacturing Co., Ltd.

[0196] "Test Method" The tensile load was measured using JSTM C 2101T, and the bond stress was calculated using the following formula (3). The tensile load used in calculating the bond stress was the value obtained when the free end slip was 0.002D (where D is the rebar diameter).

[0197] γ = P / (4πD) 2 ) × α (3)

[0198] γ: Adhesion stress (N / mm) 2 ) P: Tensile load (N) D: Diameter of the reinforcing bar (nominal diameter; 16mm for D16) α: Correction factor for the compressive strength of concrete (30 / σc) σc: Compressive strength (N / mm²) of cylindrical specimens fabricated simultaneously2 )

[0199] "Evaluation Method of Test Results" The adhesive stress of 2.0 N / mm² when the slip amount of the reinforcing bar, which is the pass value of JSTM C 2101T, is 0.002D (= 0.032 mm) 2 The above was regarded as ○. 2.0 N / mm² 2 Less than that was regarded as ×. Also, the maximum adhesive stress was shown numerically. The results are shown in Table 3.

[0200] In addition, in the above hole filling method, it was described as the hole filling material for the bolt box, but as an application, it can also be applied to the repair method for defective parts of concrete structures such as box culverts and water channels.

Explanation of Symbols

[0201] 1... Reinforcing bar 2... Formwork 3a... First radically polymerizable composition 3b... Cured product of the first radically polymerizable composition 4a... Second radically polymerizable composition 4b... Cured product of the second radically polymerizable composition 5... Container

Claims

1. A recess filler kit comprising a first radical polymerizable resin composition and a second radical polymerizable resin composition, 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 aforementioned 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 expansive agent (J), cement (P), and aggregate (K). The recess filler kit is characterized in that the water content of the second radical polymerizable resin composition is less than 0.25 parts by mass with respect to 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

2. The recess filler kit according to claim 1, wherein the first radical polymerizable compound (A-1) and the second radical polymerizable compound (A-2) each independently contain a vinyl ester resin.

3. The recess filler kit according to claim 1 or 2, wherein the expansive material (J) comprises at least one selected from the group consisting of quicklime and calcium sulfoaluminate.

4. The recess filler kit according to claim 1 or 2, wherein the first radical polymerization initiator (D-1) and the second radical polymerization initiator (D-2) are each independently hydroperoxides.

5. The first radical polymerizable resin composition further contains a first metal-containing compound (E-1) and a first thiol compound (F-1), The recess filler kit according to claim 1 or 2, wherein the second radical polymerizable resin composition further contains a second metal-containing compound (E-2) and a second thiol compound (F-2).

6. The amount of the expanding agent (J) is 0.3 to 30 parts by mass relative to a total of 100 parts by mass of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). The cement (P) is present in an amount of 20 to 200 parts by mass relative to a total of 100 parts by mass of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2). The recess filler kit according to claim 1 or 2, wherein the aggregate (K) is in an amount of 200 to 800 parts by mass per 100 parts by mass total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

7. The amount of the first radical polymerization initiator (D-1) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1), The recess filler kit according to claim 1 or 2, wherein the amount of the second radical polymerization initiator (D-2) is 0.1 to 10 parts by mass per 100 parts by mass of the total of the second radical polymerizable compound (A-2) and the second radical polymerizable unsaturated monomer (B-2).

8. The recess filler kit according to claim 1 or 2, wherein the acidic compound (C) is present in the first radical polymerizable resin composition in a total of 100 parts by mass of the first radical polymerizable compound (A-1) and the first radical polymerizable unsaturated monomer (B-1).

9. The recess filler kit according to claim 1 or 2, wherein the acidic compound (C) is an unsaturated monobasic acid.

10. The recess filler kit according to claim 1 or 2, wherein the first radical polymerization initiator (D-1) is a photo-radical polymerization initiator that is photosensitive from ultraviolet light to the visible light region.

11. A cured product of the recess filler kit according to claim 1 or 2, A cured product of a recess filler kit, characterized in that a first cured product, which is a cured product of the first radical polymerizable resin composition, is formed on the surface of the recess, and a second cured product of the second radical polymerizable resin composition is formed on the surface of the first cured product.

12. A method for filling a recess using the recess-filling material kit described in claim 1 or 2, A base layer formation step involves applying the first radical polymerizable resin composition to the surface of the recess to form a base layer, A method for filling a recess, characterized by comprising a filling step of filling the surface of the underlayer formed on the surface of the recess with the second radical polymerizable resin composition.

13. The recess filling method according to claim 12, wherein the recess is a bolt box.

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