JP7707922B2 - Radical polymerizable resin composition and cured product thereof - Google Patents

Description

The present invention relates to a radically polymerizable resin composition and a cured product thereof.
This application claims priority based on Japanese Patent Application No. 2019-235910, filed on December 26, 2019, the contents of which are incorporated herein by reference.

When polymerization is carried out using typical liquid vinyl monomers, large shrinkage occurs. This shrinkage causes distortion problems when vinyl monomers are used in industrial products. Therefore, creating a resin with a small shrinkage rate during polymerization is of great industrial significance.

Radical polymerizable resin compositions such as unsaturated polyester resins and vinyl ester resins (epoxy acrylates) usually shrink during curing. Since "styrene" and "methyl methacrylate" are often used as monomers, which are shown in Table 1 of Non-Patent Document 1, unsaturated polyester resins in general formulations shrink in volume by 8 to 12%, and vinyl ester resins shrink in volume by 8 to 10%.
This figure is considerably larger than the 3-6% volume shrinkage that is typical for epoxy resins, and has prevented unsaturated polyester resins and vinyl ester resins from being used in industrial applications, or from being used in other industries and applications.

As a method for solving this problem, Patent Document 1 claims that by using polystyrene beads as a low-shrinkage material, it is possible to reduce the number of manufacturing steps or shorten the manufacturing time, and produce a low-shrinkage unsaturated polyester resin composition that has excellent low shrinkage properties, dimensional stability, and surface smoothness.

Furthermore, Patent Document 2 claims that by blending an A-B type block copolymer with an unsaturated polyester resin composition, it is possible to obtain a low-shrinkage unsaturated polyester resin composition that has low shrinkage during curing and can be used to produce molded articles with excellent heat resistance.

Furthermore, Patent Document 3 claims that by mixing an A-B type block copolymer (vinyl acetate-styrene type) consisting of A and B segments and fine silica particles with an unsaturated polyester resin, it is possible to obtain a low-shrinkage unsaturated polyester resin composition that has a large low-shrinkage effect during molding at room temperature or medium temperature and has high water resistance.

There is also a type of concrete called "expansive concrete" that is made by mixing an expansive material as an admixture with a conventional hydraulic composition (containing cement such as Portland cement, for example). According to the Japanese JIS standard, it is said that by curing in water for seven days, the expansive material forms a hydrate, which increases the volume, but the expansion effect in air is not recognized.

Japanese Patent Application Publication No. 11-315198 Patent No. 2794802 Japanese Patent Application Publication No. 05-222282

Endo, Tsuyoshi, Is Volume Shrinkage Inevitable During Polymerization?, Polymers, Vol. 27, February issue (1978), pp. 108-111.

In conventional radical polymerizable resin compositions, in order to create resins with low shrinkage, a single blend of thermoplastic resins such as polystyrene or a block copolymer of two or more types is used. In most cases, these function as "shrinkage prevention materials."
Furthermore, these resin compositions are based on the idea of offsetting the thermal expansion of the thermoplastic resin due to heat generation during curing and the curing shrinkage of the unsaturated polyester resin, and their applications have often been limited to applications in which hot molding is performed at medium temperatures or higher, such as sheet molding compounds (SMC) and bulk molding compounds (BMC).

The present invention has been made in consideration of the above-mentioned conventional situation, and aims to provide a radical polymerizable resin composition having a small shrinkage rate by incorporating an expansion agent instead of a shrinkage prevention agent, which is not limited by the molding method, use temperature, application, etc., and expands at a constant rate as a whole when the resin composition is cured and then stabilizes.
Another object of the present invention is to provide a cured product of the radical polymerizable resin composition that does not suffer from a decrease in strength after molding.

That is, the present invention is shown in the following [1] to [13].

[1] A radical polymerizable resin composition containing a radical polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I), and not containing free water,
The radical polymerizable resin composition, wherein the aggregate (I) contains bound water.
[2] The radical polymerizable resin composition according to [1], wherein the content of the aggregate (I) is 5 parts by mass to 500 parts by mass per 100 parts by mass of the radical polymerizable compound (A).
[3] The radical polymerizable resin composition according to [1] or [2], wherein the radical polymerizable compound (A) contains a vinyl ester resin and a radical polymerizable monomer.
[4] The radical polymerizable resin composition according to any one of [1] to [3], wherein the expanding material (B) contains at least one selected from the group consisting of lime and calcium sulfoaluminate.
[5] The radical polymerizable resin composition according to any one of [1] to [4], wherein the radical polymerization initiator (C) is a hydroperoxide (ROOH).
[6] The radical polymerizable resin composition according to any one of [1] to [5], further comprising a metal-containing compound (D) and a thiol compound (E).
[7] The radical polymerizable resin composition according to any one of [1] to [6], wherein the expanding material (B) is 0.3 parts by mass to 30 parts by mass relative to 100 parts by mass of the radical polymerizable compound (A).
[8] The radical polymerizable resin composition according to any one of [1] to [7], wherein the radical polymerization initiator (C) is 0.1 parts by mass to 10 parts by mass relative to 100 parts by mass of the radical polymerizable compound (A).
[9] A cured product of the radical polymerizable resin composition according to any one of [1] to [8].
[10] The cured product according to [9], wherein the rate of change in length of the cured product is 0 to 1000×10 ⁻⁶ after 3000 hours from curing.
[11] A method for producing a radical polymerizable resin composition, comprising a mixing step of mixing a radical polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I),
The method for producing a radical polymerizable resin composition, wherein the aggregate (I) contains bound water.
[12] The method for producing the radical polymerizable resin composition according to [11], which does not include a step of adding water.
[13] A radical polymerizable resin composition obtained by using the method for producing a radical polymerizable resin composition according to [11] or [12],
A radically polymerizable resin composition comprising a radically polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I).

According to the present invention, by adding an appropriate amount of an expanding agent to a radically polymerizable resin composition that causes cure shrinkage due to a decrease in the free volume of the liquid component during curing, it is possible to provide a radically polymerizable resin composition that can suppress shrinkage while maintaining strength, and a cured product of the radically polymerizable resin composition.

1 is a graph showing the results of Examples 1 to 3 and Comparative Examples 1 to 3. 1 is a graph showing the results of Example 4 and Comparative Example 4.

The present invention is described in detail below.

(Radically polymerizable resin composition)
The radical polymerizable resin composition of one embodiment of the present invention contains a radical polymerizable compound (A), an expanding agent (B), a radical polymerization initiator (C), and an aggregate (I), and does not contain free water. The aggregate (I) contains bound water. Here, the term "bound water" is a concept for distinguishing it from free water. As described in the "Method for measuring water content" below, the water is calculated from the weight change rate (reduction rate) from 95°C to 105°C in a TG/DTA experiment. For example, the water of crystallization contained in the aggregate (I) and the adsorbed water strongly adsorbed to the internal micropores or surface of the aggregate (I) can be mentioned. In addition, the "free water" can be, for example, water added in the step of adding water in the production process of the radical polymerizable resin composition. The meaning of "the radical polymerizable resin composition does not contain free water, and the aggregate (I) contains bound water" means a radical polymerizable resin composition obtained by a production method without adding water. Preferably, the term "radical polymerizable resin composition" refers to a radical polymerizable resin composition obtained by a manufacturing method that does not include a step of adding water in the manufacturing process, in which aggregate (I) is used in the manufacturing process of a radical polymerizable resin composition without pretreatment under bone dry conditions as described below. For example, a commercially available aggregate (I) can be used as is. Alternatively, in order to make the amount of bound water contained more stable, the aggregate (I) can be pretreated by storing it at a constant temperature and humidity for a certain period of time. The moisture content of bound water contained in the aggregate (I) can be confirmed by the measurement method described below, so the temperature, humidity, and processing time can be appropriately determined depending on the type of aggregate (I) used and the moisture content at the time of acquisition.

<Radically polymerizable compound (A)>
The radical polymerizable resin composition of the present invention uses a radical polymerizable compound (A) as a base material. In the present invention, the radical polymerizable compound (A) refers to a compound that has an ethylenically unsaturated group in the molecule and undergoes a polymerization reaction by a radical.
Examples of the radically polymerizable compound (A) include vinyl ester resins (epoxy (meth)acrylate resins), unsaturated polyester resins, polyester (meth)acrylate resins, urethane (meth)acrylate resins, (meth)acrylate resins, radically polymerizable unsaturated monomers, and mixtures of the above resins with radically polymerizable unsaturated monomers, among which at least one selected from vinyl ester resins, unsaturated polyester resins, and mixtures of these with radically polymerizable unsaturated monomers are preferred. Of these, vinyl ester resins are more preferred. In this specification, "(meth)acrylate" means "acrylate or methacrylate".

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

Examples of the epoxy resin include bisphenol type epoxy resin, biphenyl type epoxy resin, novolac type epoxy resin, trisphenolmethane type epoxy resin, aralkyldiphenol type epoxy resin, naphthalene type epoxy resin, aliphatic type epoxy resin, etc. These may be used alone or in combination.

Examples of bisphenol-type epoxy resins include those obtained by reacting a bisphenol with epichlorohydrin and/or methylepichlorohydrin, and those obtained by reacting a glycidyl ether of bisphenol A with a condensate of the bisphenol 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.

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 or triscretholmethane with epichlorohydrin and/or methylepichlorohydrin.
Examples of aralkyldiphenol type epoxy resins include those obtained by reacting aralkylphenol with epichlorohydrin and/or methylepichlorohydrin.

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

Aliphatic epoxy resins include alicyclic epoxy resins, alicyclic diol diglycidyl ether epoxy resins, aliphatic diol diglycidyl ether epoxy resins, poly(oxyalkylene) glycol diglycidyl ether epoxy resins, etc.

Examples of alicyclic epoxy resins include alicyclic diepoxy acetal, alicyclic diepoxy adipate, and alicyclic diepoxy carboxylate.
Specific examples of alicyclic diol diglycidyl ethers include diglycidyl ethers of alicyclic diols having 3 to 20 carbon atoms (preferably 6 to 12 carbon atoms, more preferably 7 to 10 carbon atoms), such as cyclohexanedimethanol diglycidyl ether, dicyclopentenyl dialcohol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, and dihydroxyterpene diglycidyl ether. Of these, a commercially available product of cyclohexanedimethanol diglycidyl ether is "Denacol EX-216L" manufactured by Nagase ChemteX Corporation.

Specific examples of aliphatic diol diglycidyl ethers include 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. Commercially available products of 1,6-hexanediol diglycidyl ether include "Denacol EX-212L" from Nagase Chemtex Corporation, "SR-16H" and "SR-16HL" from Sakamoto Yakuhin Kogyo Co., Ltd., and "Epogosey (registered trademark) HD" from Yokkaichi Synthetic Co., Ltd. Commercially available products of 1,4-butanediol diglycidyl ether include "Denacol EX-214L" from Nagase Chemtex Corporation.

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, poly(tetramethylene) glycol diglycidyl ether, etc.

Preferred examples of aliphatic epoxy resins include 1,6-hexanediol diglycidyl ether, diglycidyl ether of polyethylene glycol, poly(tetramethylene) glycol diglycidyl ether, etc. Among these, those having a number average molecular weight of 150 to 1000 are more preferable.

The epoxy resin may be a diglycidyl ester such as diglycidyl ester of dimer acid or diglycidyl ester of hexahydrophthalic acid. The epoxy resin may be an epoxy resin having an oxazolidone ring obtained by reacting the epoxy resin with a diisocyanate. A specific example of an epoxy resin having an oxazolidone ring is Araldite (registered trademark) AER4152 manufactured by Asahi Kasei Epoxy.

The unsaturated monobasic acid may be a known one, such as (meth)acrylic acid, crotonic acid, cinnamic acid, etc. Also, 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 one or both of "acrylic acid and methacrylic acid", and "(meth)acryloyl group" means one or both of "acryloyl group and methacryloyl group".
The polybasic acid 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-2 mole maleic anhydride adduct, polyethylene glycol-2 mole maleic anhydride adduct, propylene glycol-2 mole maleic anhydride adduct, polypropylene glycol-2 mole maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16-(6-ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyldodecane)dicarboxylic acid, carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name: Hycar CTBN), and the like.

[Unsaturated polyester resin]
As the unsaturated polyester resin, a resin obtained by subjecting a dibasic acid component containing an unsaturated dibasic acid and, if necessary, a saturated dibasic acid, to an esterification reaction with a polyhydric alcohol component can be used.
Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc., which may be used alone or in combination of two or more kinds.
Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic 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 dialkyl esters thereof; and halogenated saturated dibasic acids. These may be used alone or in combination of two or more.

The polyhydric alcohol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2- 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 adducts of dihydric phenols such as hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A with alkylene oxides such as propylene oxide or ethylene oxide;
Examples of the alcohol include trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

The unsaturated polyester may be modified with a dicyclopentadiene compound within the scope of the present invention. The modification method with a dicyclopentadiene compound may include a known method in which an addition product of dicyclopentadiene and maleic acid (cydecanol monomaleate) is obtained and then the product is used as a monobasic acid to introduce a dicyclopentadiene skeleton.
An oxidative polymerization (air curing) group such as an allyl group or a benzyl group can be introduced into the vinyl ester resin or unsaturated polyester resin used in the present invention. There is no particular limitation on the method of introduction, but examples include the addition of a polymer containing an oxidative polymerization group, condensation of a compound having a hydroxyl group and an allyl ether group, and a method of 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-diglycidylphenyl allyl ether.
In the present invention, oxidative polymerization (air curing) refers to crosslinking that occurs with the generation and decomposition of peroxide due to the oxidation of a methylene bond between an ether bond and a double bond, as seen in, for example, an allyl ether group.

[Polyester (meth)acrylate resin, urethane (meth)acrylate resin, and (meth)acrylate resin]
The polyester (meth)acrylate resin in the present invention may be, for example, a polyester obtained by reacting a polyvalent carboxylic acid with a polyhydric alcohol, specifically, a resin obtained by reacting hydroxyl groups at both ends of polyethylene terephthalate or the like with (meth)acrylic acid.
Furthermore, as the urethane (meth)acrylate resin, for example, a resin obtained by reacting hydroxyl groups or isocyanato groups at both ends of a polyurethane obtained by reacting an isocyanate with a polyhydric alcohol with (meth)acrylic acid can be used.
Examples of the (meth)acrylate resin that can be used include poly(meth)acrylic resins having one or more substituents selected from a hydroxyl group, an isocyanato group, a carboxy group, and an epoxy group, and resins obtained by reacting a (meth)acrylic acid ester having a hydroxyl group with a substituent of a polymer of a monomer having the above-mentioned substituent and a (meth)acrylate.

[Radically polymerizable unsaturated monomer]
In the present invention, a radically polymerizable unsaturated monomer can be used as the radically polymerizable compound (A).
The radical polymerizable unsaturated monomer may be used alone, but it is preferable to use the radical polymerizable unsaturated monomer as a mixture with at least one of the vinyl ester resin and the unsaturated polyester resin.
The radical polymerizable unsaturated monomer is not particularly limited, but is preferably one having a vinyl group or a (meth)acryloyl group.
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.

Specific examples of monomers having a (meth)acryloyl group include (meth)acrylic acid esters. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-butyl (meth)acrylate, 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, acrylate, phenoxyethyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol monomethyl ether (meth)acrylate, ethylene glycol monoethyl ether (meth)acrylate, ethylene glycol monobutyl ether (meth)acrylate, ethylene glycol monohexyl ether (meth)acrylate, ethylene glycol mono 2-ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol 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, dimethacrylate of PTMG, 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 4-bis[4-(methacryloxy.diethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy.polyethoxy)phenyl]propane, tetraethylene glycol diacrylate, bisphenol AEO-modified (n=2) diacrylate, isocyanuric acid EO-modified (n=3) diacrylate, pentaerythritol diacrylate monostearate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl (meth)acrylate, tris(2-hydroxyethyl)isocyanuracrylate, and the like.

Further, examples of polyfunctional (meth)acrylic acid esters include alkanediol 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. 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.

Furthermore, the following compounds can also be used as the radical polymerizable unsaturated monomer. Specific examples include divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl fumarate, allyl methacrylate, vinylbenzyl butyl ether, vinylbenzyl hexyl ether, vinylbenzyl octyl ether, vinylbenzyl (2-ethylhexyl) ether, vinylbenzyl (β-methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzyl cyclohexyl ether, vinylbenzyl (β-phenoxyethyl) ether, vinylbenzyl dicyclopentenyl ether, vinylbenzyl dicyclopentenyloxyethyl ether, vinylbenzyl dicyclopentenyl methyl ether, and divinylbenzyl ether.
In addition to the above, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc. may also be used.
These may be used alone or in combination of two or more.

The radically polymerizable unsaturated monomer can be used to reduce the viscosity of the radically polymerizable resin composition of the present invention and to improve hardness, strength, chemical resistance, water resistance, etc., but if the content is too high, it may lead to deterioration of the cured product or environmental pollution. Therefore, the content of the radically polymerizable unsaturated monomer in the radically polymerizable compound (A) is preferably 90 mass% or less.

The radical polymerizable compound (A) may contain residual catalysts or polymerization inhibitors used in synthesizing vinyl ester resins, unsaturated polyester resins, polyester (meth)acrylate resins, urethane (meth)acrylate resins, and (meth)acrylate resins. Examples of the catalyst include compounds containing tertiary nitrogen, such as triethylamine, pyridine derivatives, imidazole derivatives, and imidazole derivatives; amine salts, such as tetramethylammonium chloride and triethylamine; and phosphorus compounds, such as trimethylphosphine and triphenylphosphine.
Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, and phenothiazine.
When the catalyst or polymerization inhibitor remains in the radically polymerizable compound (A), the amount thereof is preferably 0.001 to 2 parts by mass, respectively, per 100 parts by mass of the vinyl ester resin and the unsaturated polyester resin in total.

The content of the radical polymerizable compound (A) in the radical polymerizable resin composition of the present invention is preferably 10 to 99.9% by mass, more preferably 15 to 80% by mass, even more preferably 20 to 60% by mass, and even more preferably 25 to 40% by mass. When the content of the radical polymerizable compound (A) in the radical polymerizable resin composition is within the above range, the hardness of the cured product is further improved.

<Expansion material (B)>
The expansive material (B) used in the present invention may be any expansive material that satisfies the standard of Japanese Industrial Standard JIS A 6202 "Expansive material for concrete" and is generally used as an expansive material for concrete. Specifically, any expansive material that produces calcium hydroxide or ettringite by hydration reaction may be used, and preferred expansive materials include (1) expansive materials containing free quicklime as an active ingredient (quicklime-based expansive materials), (2) expansive materials containing calcium sulfoaluminate as an active ingredient (ettringite-based expansive materials), and (3) quicklime-ettringite composite expansive materials.

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

The content of the expansion material (B) of the present invention is preferably 0.3 to 30 parts by mass, more preferably 0.5 to 25 parts by mass, even more preferably 0.7 to 20 parts by mass, and most preferably 1 to 16 parts by mass, relative to 100 parts by mass of the radical polymerizable compound (A). If the content of the expansion material (B) is 30 parts by mass or less, the expansion rate does not exceed the elongation amount of the resin when the radical polymerizable resin composition is cured. Conversely, if the content is 0.3 parts by mass or more, the expansion performance for the radical polymerizable compound (A) is not not expressed. In addition, these expansion materials (B) may be used alone or in a mixture of two or more types.

<Radical Polymerization Initiator (C)>
The radical polymerizable resin composition of the present invention contains a radical polymerization initiator (C) as a curing agent. Examples of the radical polymerization initiator (C) include a thermal radical polymerization initiator (C-1) and a photoradical polymerization initiator (C-2). Among them, the thermal radical polymerization initiator (C-1) is preferred.
Examples of the thermal radical polymerization initiator (C-1) include organic peroxides such as diacyl peroxides such as benzoyl peroxide, peroxy esters such as tert-butyl peroxybenzoate, hydroperoxides such as cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, and paramenthane hydroperoxide, dialkyl peroxides such as dicumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxy ketals, alkyl peresters, and percarbonates. Among these, hydroperoxide-based organic peroxides (ROOH) (also simply referred to as hydroperoxide (ROOH)) are preferred, and among these, cumene hydroperoxide (CHP) such as Percumyl (registered trademark) H-80 manufactured by NOF Corporation is preferred.

Examples of photoradical polymerization initiators (C-2) include benzoin ether-based initiators such as benzoin alkyl ethers, benzophenone-based initiators such as benzophenone, benzil, and methyl orthobenzoyl benzoate, acetophenone-based initiators such as benzil dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 1,1-dichloroacetophenone, and thioxanthone-based initiators such as 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isopropylthioxanthone.

Examples of photoradical polymerization initiators (C-2) that are sensitive from ultraviolet light to the visible light region include known initiators such as acetophenone, benzyl ketal, and (bis)acylphosphine oxide. Specifically, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) are mixed in a ratio of 75%/25% (trade name: Irgacure-1700, manufactured by Ciba Specialty Chemicals Co., Ltd.); 1-hydroxycyclohexyl phenyl Ketone (trade name: Irgacure 184, manufactured by Ciba Specialty Chemicals, Inc.) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals, Inc.) were mixed in a ratio of 75%/25% to produce Irgacure 1800 (manufactured by Ciba Specialty Chemicals, Inc.), and 50%/50% to produce Irgacure 1850 (manufactured by Ciba Specialty Chemicals, Inc.); bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide (trade name: Irgacure 819, manufactured by Ciba Specialty Chemicals, Inc.); 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Lucirin 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 Chiba Specialty Chemicals Corporation) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name: Lucirin TPO, manufactured by BASF Corporation) in a ratio of 50%/50%.

Examples of the photoradical polymerization initiator (C-2) having photosensitivity in the visible light region include camphorquinone, benzyltrimethylbenzoyldiphenylphosphinoxide, methylthioxanthone, and dicyclopentadiethyltitanium-di(pentafluorophenyl).
These radical polymerization initiators (C) may be used alone or in combination of two or more. In order to support the main reaction of the heat curing or photocuring, the other reaction may be introduced, and the heat radical polymerization initiator (C-1) and the photoradical polymerization initiator (C-2) may be used in combination as necessary.

Depending on the molding conditions, they can also be used in composite forms such as organic peroxide/dye system, diphenyl iodine salt/dye system, imidazole/keto compound, hexaarylbiimidazole compound/hydrogen donor compound, mercaptobenzothiazole/thiopyrylium salt, metal arene/cyanine dye, and hexaarylbiimidazole/radical generator.

When the radical polymerizable resin composition of the present invention contains a radical polymerization initiator (C), the amount thereof is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the radical polymerizable compound (A).

<Metal-containing compound (D)>
The radical polymerizable resin composition of the present invention may contain one or more metal-containing compounds (D) selected from a metal soap (D-1) and a metal complex (D-2) having a β-diketone skeleton as a curing accelerator. The metal soap (D-1) in the present invention refers to a salt of a long-chain fatty acid or an organic acid other than a long-chain fatty acid and a metal element other than potassium and sodium. The metal complex (D-2) having a β-diketone skeleton in the present invention refers to a complex in which a compound having a structure in which one carbon atom is between two carbonyl groups is coordinated to a metal element.

The content of the metal-containing compound (D) in the radical polymerizable resin composition in terms of the 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, relative to 100 parts by mass of the radical polymerizable compound (A) described above. When the content of the metal-containing compound (D) in terms of the metal component is within the above range, curing proceeds quickly even in water and in a humid atmosphere.

[Metal soap (D-1)]
The long-chain fatty acid in the metal soap (D-1) is not particularly limited, but is preferably, for example, a fatty acid having 6 to 30 carbon atoms. Specifically, preferred are linear or cyclic saturated fatty acids such as octanoic acids such as heptanoic acid and 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, and naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid.
Other examples include rosin acid, linseed oil fatty acid, soybean oil fatty acid, tall oil acid, and the like.

The organic acid other than the long-chain fatty acid in the metal soap (D-1) is not particularly limited, but is preferably a weak acid compound having a carboxy group, a hydroxy group, or an enol group, which is soluble in an organic solvent.
Examples of compounds having a carboxy group include carboxylic acids such as formic acid, acetic acid, and oxalic acid; hydroxy acids such as citric acid, bile acid, sugar acid, 12-hydroxystearic acid, hydroxycinnamic acid, and folic acid; amino acids such as alanine and arginine; and aromatic acids such as benzoic acid and phthalic acid.
Examples of compounds having a hydroxy group or an enol group include ascorbic acid, alpha acid, imido acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, and phosphonic acid.
Among these, long-chain fatty acids are preferred, linear or cyclic saturated fatty acids having 6 to 16 carbon atoms, or unsaturated fatty acids having 6 to 16 carbon atoms are more preferred, octanoic acid, 2-ethylhexanoic acid, and naphthenic acid are even more preferred, and of these, 2-ethylhexanoic acid and naphthenic acid are preferred.

Examples of the metal element constituting the metal soap (D-1) include metal elements of Groups 1 and 2, such as lithium, magnesium, calcium, and barium (excluding potassium and sodium), metal elements of Groups 3 to 12, such as titanium, zirconium, vanadium, manganese, iron, ruthenium, cobalt, rhodium, nickel, palladium, platinum, copper, silver, gold, and zinc, metal elements of Groups 13 and 14, such as aluminum, indium, tin, and lead, rare earth metal elements, such as neodymium and cerium, and bismuth.
In the present invention, metal elements of 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.

Specific examples of metal soap (D-1) include zirconium octylate, manganese octylate, cobalt octylate, bismuth octylate, calcium octylate, zinc octylate, vanadium octylate, lead octylate, tin octylate, cobalt naphthenate, copper naphthenate, barium naphthenate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate. Of these, zirconium octylate, manganese octylate, cobalt octylate, bismuth octylate, calcium octylate, lead octylate, tin octylate, bismuth naphthenate, calcium naphthenate, lead naphthenate, and tin naphthenate are more preferred. Of these, manganese octylate and cobalt octylate are particularly preferred. A specific example of cobalt octylate is cobalt hexoate (cobalt content in the total product: 8% by mass, molecular weight: 345.34) manufactured by Toei Kako Co., Ltd. A specific example of manganese octylate is manganese hexoate (manganese content in the total product: 8% by mass, molecular weight: 341.35) manufactured by Toei Kako Co., Ltd.

[Metal Complex Having a β-Diketone Skeleton (D-2)]
Metal complex (D-2) having a β-diketone skeleton (hereinafter also referred to as "metal complex (D-2)"). Examples of the metal complex (D-2) include those in which a metal is complexed with acetylacetone, ethyl acetoacetate, benzoylacetone, or the like, and these metal complexes (D-2) also exhibit the same functions as the metal soap (D-1).
Examples of the metal element constituting the metal complex (D-2) include the same metal elements as those in the metal soap (D-1).

Specific examples of metal complexes (D-2) that are preferred include zirconium acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis(acetylacetonate), iron acetylacetonate, and cobalt acetoacetate acetate, with zirconium acetylacetonate, titanium acetylacetonate, and titanium dibutoxybis(acetylacetonate) being more preferred.

<Thiol compound (E)>
The radical polymerizable resin composition of the present invention may contain one or more thiol compounds (E) selected from a secondary thiol compound (E-1) and a tertiary thiol compound (E-2). In the present invention, the thiol compound (E) functions as a curing accelerator and is presumed to coordinate in the vicinity of the metal of the metal-containing compound (D) and to have a function of preventing the deactivation of the metal by water.
The thiol compound (E) used in the present invention is not particularly limited as long as it is a compound having one or more mercapto groups bonded to a secondary or tertiary carbon atom in the molecule (hereinafter, each may be referred to as a "secondary mercapto group" and a "tertiary mercapto group", respectively), but from the viewpoint of rapidly progressing curing even in water and from the viewpoint of preventing the metal of the metal-containing compound (D) from being deactivated by water, a polyfunctional thiol which is a compound having two or more secondary or tertiary mercapto groups in the molecule is preferred, and among them, a bifunctional thiol which is a compound having two secondary or tertiary mercapto groups in the molecule is preferred. Moreover, the secondary thiol compound (E-1) is more preferred than the tertiary thiol compound (E-2).
As used herein, the term "polyfunctional thiol" refers to a thiol compound having two or more mercapto groups as functional groups, and the term "bifunctional thiol" refers to a thiol compound having two mercapto groups as functional groups.

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

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

[Secondary thiol compound (E-1)]
When the thiol compound (E) having a structure represented by the formula (Q) is a secondary thiol compound (F1), specific examples thereof include 3-mercaptobutyric acid, di(1-mercaptoethyl) 3-mercaptophthalate, di(2-mercaptopropyl) phthalate, di(3-mercaptobutyl) phthalate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptobutyrate), and the like. captobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), pentaerythritol tetrakis(2-mercaptopropionate), dipentaerythritol hexakis(2-mercaptopropionate), ethylene glycol bis(4-mercaptovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane tris(4-mercapto bis(3-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) Examples of the mercaptobutyrate include bis(2-phenoxyethyl(3-mercaptobutyrate)), ethylene glycol bis(3-mercapto-3-phenylpropionate), propylene glycol bis(3-mercapto-3-phenylpropionate), diethylene glycol bis(3-mercapto-3-phenylpropionate), butanediol bis(3-mercapto-3-phenylpropionate), octanediol bis(3-mercapto-3-phenylpropionate), trimethylolpropane tris(3-mercapto-3-phenylpropionate), tris-2-(3-mercapto-3-phenylpropionate)ethyl isocyanurate, pentaerythritol tetrakis(3-mercapto-3-phenylpropionate), and dipentaerythritol hexakis(3-mercapto-3-phenylpropionate).

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

[Tertiary thiol compound (E-2)]
When the thiol compound (E) having the structure represented by the formula (Q) is a tertiary thiol compound (E-2), specific examples thereof 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), trimethylolethane tris(2-mercaptoisobutyrate), trimethylolpropane tris(2-mercaptoisobutyrate), pentaerythritol tetrakis(2-mercaptoisobutyrate), dipentaerythritol hexakis(2-mercaptoisobutyrate), and tetrakis(2-mercaptoisobutyrate). phthalate), di(3-mercapto-3-methylbutyl), 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), trimethylolethane tris(3-mercapto-3-methylbutyrate), trimethylolpropane tris(3-mercapto-3-methylbutyrate), pentaerythritol tetrakis(3-mercapto-3-methylbutyrate), dipentaerythritol hexakis(3-mercapto-3-methylbutyrate), and the like.

The total amount of thiol compound (E) in the radical polymerizable resin composition of the present invention 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, relative to 100 parts by mass of the radical polymerizable compound (A) described above. When the amount of thiol compound (E) is 0.01 parts by mass or more, a sufficient curing function can be obtained, and when it is 10 parts by mass or less, curing proceeds quickly.

In addition, the total molar ratio [(E)/(D)] of the thiol compound (E) to the metal component of the metal-containing compound (D) is preferably 0.1 to 15, more preferably 0.3 to 10 in one embodiment of the present invention, even more preferably 0.6 to 8, even more preferably 0.8 to 5, and in another embodiment of the present invention, more preferably 0.5 to 15, even more preferably 1 to 12, even more preferably 1.5 to 10, and even more preferably 2 to 9. When the molar ratio [(E)/(D)] is 0.1 or more, the thiol compound (E) can be sufficiently coordinated in the vicinity of the metal of the metal-containing compound (D), and by setting the molar ratio to 15 or less, the balance between production costs and effects is improved.

The thiol compound (E) may be used alone or in combination of two or more. When a secondary thiol compound (E-1) and a tertiary thiol compound (E-2) are used in combination, the molar ratio of the two [(E-1)/(E-2)] is preferably 0.001 to 1000, more preferably 1 to 10. When the molar ratio [(E-1)/(E-2)] is within the above range, the metal-containing compound (D) and the thiol compound (E) are stable in the radical polymerizable resin composition, and disulfide compounds formed by bonding between the thiol compounds (E) as by-products are not generated. From the viewpoint of storing the radical polymerizable resin composition with the metal-containing compound (D) and the thiol compound (E) in a stable state, it is preferable to use the secondary thiol compound (E-1) or the tertiary thiol compound (F2) alone.

<Curing Accelerator (F)>
The radically polymerizable resin composition of the present invention may contain a curing accelerator (F) other than the metal-containing compound (D) and the thiol compound (E) for the purpose of improving the curability.
Examples of the curing accelerator (F) other than the metal-containing compound (D) and the thiol compound (E) 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-methyl-N-hydroxyphenyl) ... Examples of the amines that can be used include N,N-substituted anilines such as N,N-bis(hydroxyethylamino)benzaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N-bis(hydroxyethyl)aniline and diethanolaniline, N,N-substituted-p-toluidines, and 4-(N,N-substituted amino)benzaldehyde.
When the radical polymerizable resin composition of the present invention contains the curing accelerator (F), the amount thereof is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, and still more preferably 0.1 to 3 parts by mass, relative to 100 parts by mass of the radical polymerizable compound (A).

<Polymerization Inhibitor (G)>
The radically polymerizable resin composition of the present invention may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of the radically polymerizable compound (A) and controlling the reaction rate.
Examples of the polymerization inhibitor include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-tert-butylcatechol.

<Cure Retarder (H)>
The radical polymerizable resin composition of the present invention may contain a curing retarder for the purpose of delaying the curing of the radical polymerizable compound (A). Examples of the curing retarder include free radical curing retarders, such as TEMPO derivatives, such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), 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 from the standpoint of cost and ease of handling.
When the radical polymerizable resin composition contains a polymerization inhibitor and a curing retarder, the amount thereof is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 1 part by mass, each relative to 100 parts by mass of the radical polymerizable compound (A).

<Aggregate (I)>
The radical polymerizable resin composition of the present invention includes an aggregate (I). The aggregate (I) includes bound water. The water content of the bound water of the aggregate (I) is not particularly limited, but is preferably 0.10 mass% or more, more preferably 0.20 mass% or more, even more preferably 0.30 mass% or more, and most preferably 0.40 mass% or more. The water content of the bound water of the aggregate (I) is preferably 5.0 mass% or less, more preferably 2.5 mass% or less, even more preferably 1.5 mass% or less, and most preferably 1.0 mass% or less. The water content of the bound water of the aggregate (I) is not particularly limited, but is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, more preferably 1.0 mass% or more, and most preferably 1.5 mass% or more, relative to 100 mass parts of the radical polymerizable compound (A). The water content of the bound water in the aggregate (I) is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 2.5 parts by mass or less, and most preferably 2.0 parts by mass or less, based on 100 parts by mass of the radical polymerizable compound (A). The method for measuring the water content of the bound water in the aggregate (I) is as described in the Examples.
The aggregate (I) is not particularly limited, and can be one used in mortar or concrete. The aggregate is not particularly limited, and can be, for example, calcium carbonate, crushed stone, sandstone, kansui stone, marble, quartz, limestone, silica sand, silica stone, river sand, etc. However, cement is not included in the aggregate (I). In addition, from the viewpoint of weight reduction, lightweight aggregates such as sintered shale, silicate balloon, and non-silica balloon perlite can also be used.

It is preferable that the radical polymerizable resin composition of the present invention is substantially free of cement. "Substantially free" means that the radical polymerizable resin composition contains 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

Cement here includes Portland cement, other blended cements, ultra-fast hardening cements, etc. Portland cement includes various types of Portland cement such as low heat, moderate heat, normal, early strength, ultra-fast strength, and sulfate resistant. Blended cement includes blast furnace cement, fly ash cement, silica cement, etc.

Calcium carbonate functions as an extender pigment in the coating film, being transparent and not hiding the coated surface (substrate surface), and has the effect of filling recesses, reducing paint costs, etc. An example of this calcium carbonate on the market is TM-2 (manufactured by Yukou Mining Co., Ltd.).
Calcium carbonate has a specific particle size distribution, is highly dispersible, and is porous, so that it can reduce the specific gravity of the aggregate itself, making it less likely to sag, and improve film-forming properties.

Examples of silicate balloons include shirasu balloons, perlite, glass (silica) balloons, fly ash balloons, etc. Examples of non-silica balloons include alumina balloons, zirconia balloons, carbon balloons, etc.

The content of aggregate in the composition of the present invention is not particularly limited, but is preferably 5 to 500 parts by mass, and more preferably 10 to 450 parts by mass, per 100 parts by mass of the radically polymerizable compound (A). In particular, if the content of aggregate is 5 parts by mass or more, practical fluidity can be ensured. Furthermore, if the content of aggregate is 500 parts by mass or less, the amount of adhesion with the trowel is reduced, and a decrease in workability can be prevented.

<Fiber (J)>
The radical polymerizable composition of the present invention may contain fibers as necessary. Specific examples of fibers that can be used in the present invention include glass fibers, carbon fibers, vinylon fibers, nylon fibers, aramid fibers, polyolefin fibers, acrylic fibers, polyester fibers such as polyethylene terephthalate fibers, cellulose fibers, metal fibers such as steel fibers, and ceramic fibers such as alumina fibers. Among them, for example, polyolefin fibers can be used as a thixotropic agent. A thixotropic agent (a thixotropic agent) is a compound that is blended for the purpose of imparting thixotropy.

Polyolefin fibers currently on the market include polyethylene-based products with trade names such as Chemivest (registered trademark) FDSS-2 (average fiber length 0.6 mm), Chemivest (registered trademark) FDSS-5 (average fiber length 0.1 mm), Chemivest (registered trademark) FDSS-25 (average fiber length 0.6 mm, hydrophilized product), and Chemivest (registered trademark) FDSS-50 (average fiber length 0.1 mm, hydrophilized product) (all manufactured by Mitsui Petrochemical Industries, Ltd.).

The carbon fiber is not particularly limited, and any of the known carbon fibers can be used. Examples include polyacrylonitrile (PAN) carbon fiber, rayon carbon fiber, pitch carbon fiber, etc. The carbon fibers may be used alone or in combination 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 commercially available. Carbon fiber reinforced plastic (CFRP) may be used as the carbon fiber.

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 the present invention, the carbon fiber may be cut to a length of 10.0 mm to 100.0 mm, or even 12.5 mm to 50.0 mm, for use.

These fibers are preferably used in the form of a fiber structure, biaxial mesh, or triaxial mesh selected from plain weave, satin weave, nonwoven fabric, mat, roving, chop, knit, braid, and composite structures thereof, etc. For example, the fiber structure can be impregnated with a radical polymerizable composition, and optionally prepolymerized to form a prepreg, before use.
As the mesh, for example, a biaxial mesh or a triaxial mesh is used. The length of one side of a square of the biaxial mesh (mesh size) and the length of one side of an equilateral triangle of the triaxial mesh (mesh size) are each preferably 5 mm or more, more preferably 10 to 20 mm. By using a biaxial mesh or a triaxial mesh, a hardening material for preventing spalling of concrete can be obtained that is lightweight and has excellent economical efficiency, workability, and durability.
These fibers are preferably used when reinforcing coating properties such as concrete spalling prevention and FRP waterproofing, and when producing FRP molded products.
For applications such as preventing concrete spalling, glass fibers and cellulose fibers, which have excellent transparency among fibers, are preferred because they allow the deterioration state of the base to be visually inspected from the outside.

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, per 100 parts by mass of the radically polymerizable compound (A).

<Water Reducing Agent (K)>
The radical polymerizable resin composition of the present invention may contain a usable water reducing agent (K) capable of imparting water reducibility, if necessary. As the water reducing agent, any known water reducing agent used in concrete, such as a liquid or powder water reducing agent, an air-entraining water reducing agent, a high-performance water reducing agent, or a high-performance air-entraining water reducing agent, may be used without limitation.
Polycarboxylic acid-based water-reducing agents are capable of suppressing the decrease in fluidity of concrete that accompanies the addition of the above-mentioned swelling aluminosilicate, and are also suitable from the viewpoint of maintaining good fluidity and improving workability.
As the water reducing agent, any known water reducing agent used in concrete, such as liquid or powder water reducing agents, air-entraining water reducing agents, high-performance water reducing agents, and high-performance air-entraining water reducing agents, can be used without any restrictions.
The water reducing agent is preferably contained in the radical polymerizable resin composition in an amount of 0.1 to 3.0 parts by mass.

〔solvent〕
The radical polymerizable resin composition of the present invention can be mixed with a solvent as necessary. Examples of the solvent that can be mixed 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 be used when producing the polymer.

[Polyisocyanato Compound]
The radical polymerizable resin composition of the present invention may contain a polyisocyanate compound. The polyisocyanate compound reacts with the hydroxyl group of the radical polymerizable compound (A) to form a cured coating film.
The polyisocyanato compound contains two or more isocyanato groups in the molecule, and the isocyanato groups may be blocked with a blocking agent or the like.
Examples of polyisocyanate compounds that are not blocked with a blocking agent include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; cyclic aliphatic diisocyanates such as hydrogenated xylylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6)-diisocyanate, 4,4'-methylenebis(cyclohexylisocyanate), and 1,3-(isocyanatomethyl)cyclohexane; aromatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, and diphenylmethane diisocyanate; polyisocyanates having three or more valences such as lysine triisocyanate, and adducts of each of these polyisocyanates with polyhydric alcohols, low molecular weight polyester resins, water, or the like, cyclic polymers of the above-mentioned diisocyanates (for example, isocyanurates), and biuret-type adducts. Among these, the isocyanurate of hexamethylene diisocyanate is preferred.
These polyisocyanate compounds may be used alone or in combination of two or more kinds.

When the radical polymerizable resin composition contains a polyisocyanato compound, the amount thereof 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, per 100 parts by mass of the radical polymerizable compound (A).

The blocked polyisocyanato compound is a compound obtained by blocking the isocyanato groups of the above polyisocyanato compound with a blocking agent.
Examples of blocking agents include phenol-based agents such as phenol, cresol, and xylenol; ε-caprolactam; lactam-based agents such as δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol-based 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-based agents such as formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monooxime, benzophenone oxime, and cyclohexane oxime; and active methylene-based agents such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone. By mixing the polyisocyanate with the blocking agent, the isocyanato group of the polyisocyanate can be easily blocked.

When the polyisocyanato compound is an unblocked polyisocyanato compound, a reaction between the radical polymerizable compound (A) in the radical polymerizable resin composition of the present invention and the polyisocyanato compound occurs when they are mixed. Therefore, it is preferable to separate the radical polymerizable compound (A) and the polyisocyanato compound until use and mix the two at the time of use.
In addition, a curing catalyst can be used to react the radical polymerizable compound (A) with the polyisocyanate compound. Suitable curing catalysts include, for example, organometallic catalysts such as tin octylate, dibutyltin di(2-ethylhexanoate), dioctyltin di(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, and lead 2-ethylhexanoate.
When the radical polymerizable resin composition contains the curing catalyst in an amount of the above-mentioned, the amount thereof 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 radical polymerizable compound (A).

<Other ingredients>
The radical polymerizable resin composition of the present invention may contain components other than the above-mentioned components, so long as they do not significantly impair the strength expression or acid resistance of the cured product. Examples of the components that can be contained include hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, as well as admixtures that can be used in mortar or concrete and can impart properties such as setting adjustment, hardening acceleration, hardening retardation, thickening, water retention, defoaming, water repellency, and waterproofing, fibers made of materials such as metals, polymers, and carbon, pigments, extenders, foaming agents, and clay minerals such as zeolites.

<Method for producing radically polymerizable resin composition>
The method for producing the radical polymerizable resin composition of the present invention is not particularly limited, and a method known in the art can be used. Examples include a method including a mixing step of mixing the radical polymerizable compound (A), the expansion material (B), the radical polymerization initiator (C), and the aggregate (I). The aggregate (I) contains bound water. For example, the radical polymerizable resin composition can be produced by mixing the radical polymerizable compound (A) with the metal-containing compound (D) as necessary, and further blending and mixing the radical polymerization initiator (C), the expansion material (B), and the aggregate (I). It is preferable that the method for producing the radical polymerizable resin composition does not include a step of adding water. When water is added, the radical polymerizable resin composition contains free water, and the compressive strength of the cured product of the radical polymerizable resin composition is deteriorated. However, the bound water contained in the raw material such as the aggregate (I) is less likely to affect the compressive strength of the cured product, unlike the added free water.
One embodiment of the method for producing a radical polymerizable resin composition of the present invention includes a step (S1) of mixing a radical polymerizable compound (A) with a metal-containing compound (D) as necessary to obtain a resin product, a step (S2) of mixing a radical polymerization initiator (C) with the obtained resin product to obtain a curable resin product, and a step (S3) of mixing an expander (B) with the obtained curable resin product to obtain a radical polymerizable resin composition.

In the step (S1) of obtaining the resin product (sometimes simply referred to as "step (S1)"), in addition to mixing the metal-containing compound (D) with the radical polymerizable compound (A), a polymerization inhibitor (G), a curing retarder (H), a thiol compound (E), or the like may be further mixed, if necessary.
In the step (S3) (sometimes simply referred to as "step (S3)") of obtaining a radical polymerizable resin composition, in addition to mixing the expanding agent (B) with the curable resin product obtained in the step (S2) (sometimes simply referred to as "step (S2)") of obtaining a curable resin product, aggregate (I), a water reducing agent (K), fiber (J), etc. may be further mixed, if necessary. Specific examples of the aggregate (I) that can be used include high-early-strength Portland cement, N90 silica sand, calcium carbonate TM-2, N50 silica sand, and N40 silica sand.

The radically polymerizable resin composition produced in this manner can be cured at room temperature and has excellent workability, early strength development, and curing properties. Because it contains an expansion agent (B), the shrinkage rate during curing is small, and depending on the conditions, the expansion rate of the cured product can be made greater than 0.

<Cured Product of Radically Polymerizable Resin Composition>
The cured product of the radical polymerizable resin composition of the present invention can be obtained by curing the above-mentioned radical polymerizable resin composition.
The rate of change in length of the cured product is not particularly limited and can be adjusted by adjusting each component of the radical polymerizable resin composition used. For example, the rate of change in length of the cured product is preferably 0 to 1000× ¹⁰ after 3000 hours from curing.

[Method for curing radically polymerizable resin composition]
When the radical polymerizable resin composition of the present invention contains a thermal radical polymerization initiator (C-1), an example of a method for curing the radical polymerizable resin composition of the present invention is a method in which the radical polymerizable resin composition of the present invention is applied to the surface of a substrate and cured at room temperature. For example, the radical polymerizable resin composition of the present invention is used as a cross-section repair material for inorganic structures. Since the radical polymerizable resin composition of the present invention contains an expansion agent (B), the obtained cured product does not shrink significantly even after a certain period of time, as in the past.
Examples of materials for the substrate 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.

When the radical polymerizable resin composition of the present invention contains a photoradical polymerization initiator (C-2), the timing of photocuring can be, for example, a method in which the radical polymerizable resin composition is applied to a substrate and then photocured, or a method in which a sheet is prepared by prepolymerizing the radical polymerizable resin composition in advance (also called B-stage or prepreg), and the sheet is attached to a substrate and then photocured.

The light source may be any light source having a spectral distribution in the photosensitive wavelength range of the photoradical polymerization initiator (C-2), and may be, for example, sunlight, an ultraviolet lamp, a near-infrared lamp, a sodium lamp, a halogen lamp, a fluorescent lamp, a metal halide lamp, or an LED. In addition, two or more types of photoradical polymerization initiator (C-2) may be used in combination, and a wavelength cut filter may be used as the light source, or a specific wavelength of an LED may be used to selectively use the wavelengths required for preliminary polymerization and main polymerization. The wavelengths used for preliminary polymerization are preferably long wavelengths with low energy levels, and the degree of polymerization is particularly easy to control when near-infrared light is used. In the present invention, ultraviolet light (ultraviolet rays) refers to light rays in the wavelength range of 280 to 380 nm, visible light (visible rays) refers to light rays in the wavelength range of 380 to 780 nm, and near-infrared light (near-infrared rays) refers to light rays in the wavelength range of 780 to 1200 nm. The irradiation time of the lamp required for preliminary polymerization cannot be generally specified because it is affected by the effective wavelength range, output, irradiation distance, thickness of the composition, etc. of the light source, but it is sufficient to irradiate for, for example, 0.01 hours or more, preferably 0.05 hours or more.

The present invention will be explained in more detail below with reference to examples, but the present invention is not limited to these examples in any way.

<Method of measuring cure shrinkage>
The post-curing shrinkage and expansion rates (change rates: negative numbers are shrinkage rates, positive numbers are expansion rates) of the cured product of the radical polymerizable resin composition of the present invention were measured in accordance with Japanese Standard JIS A 1129-3 (dial gauge method). The molding (cured product) was prepared by referring to Appendix A of Japanese Standard JIS A 1129. A mold for a specimen of 40 x 40 x 160 mm specified in Japanese Standard JIS R 5201 was used. The cured product specimen was molded according to the method for preparing specimens for strength tests specified in JIS R 5201-10, and after molding, the mold was left to stand (cure) in a room at a temperature of 23°C ± 2°C and a humidity of 50% and demolded about 24 hours after molding. Then, the measurement was started using the equipment specified in JIS A 1129-3, Section 3, under the conditions specified in JIS A 1129-3, Section 4.3 (the start time was set to 0).

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

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

The raw materials used in the production of each radical polymerizable resin composition in the examples and comparative examples are as follows:

<Radically polymerizable compound (A)>
(Synthesis Example 1)
"Synthesis of radically polymerizable compound (A-1)"
A 1L four-necked separable flask equipped with a stirrer, reflux condenser, gas inlet tube and thermometer was charged with 150.4 g of AER-2603 (Asahi Kasei Corporation bisphenol A type epoxy resin: epoxy equivalent 189), 188.4 g of SR-16H (Sakamoto Yakuhin Kogyo Co., Ltd. 1,6-hexanediol diglycidyl ether), 0.255 g of methyl hydroquinone, and 1.5 g of DMP-30 (Tokyo Kasei Kogyo Co., Ltd.: 2,4,6-tris (dimethylaminomethyl) phenol), and the temperature was raised to 110 ° C. After raising the temperature to 110 ° C., 172 g of methacrylic acid (Mitsubishi Rayon Co., Ltd.) was added dropwise over about 30 minutes and then reacted for about 4 hours, and the reaction was terminated when the acid value reached 10 mg KOH / g, to obtain a vinyl ester compound.
Next, 256.3 g of dicyclopentenyloxyethyl methacrylate (FA-512MT, manufactured by Hitachi Chemical Co., Ltd.) and 85.4 g of dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) were added as radically polymerizable unsaturated monomers to obtain a non-styrene type radically polymerizable compound (A-1) having a viscosity of 280 mPa·s at 25° C. and an ester compound component ratio of 60 mass%.

<Expansion material (B)>
As the quicklime-ettringite composite expanding material, Denka Power CSA Type S manufactured by Denka was used.

<Radical Polymerization Initiator (C)>
As the thermal radical polymerization initiator (C-1), cumene hydroperoxide (CHP), Percumyl (registered trademark) H-80 manufactured by NOF Corporation, was used.

<Metal-containing compound (D)>
Manganese octylate (manganese hexoate, manufactured by Toei Kako Co., Ltd., manganese content in the total amount of the product is 8% by mass, molecular weight is 341.35) was used as the metal soap (D-1).

<Thiol compound (E)>
As the secondary thiol compound (E-1), Karenz MT (registered trademark) BD1 (1,4-bis(3-mercaptobutyryloxy)butane, molecular weight 299.43), a bifunctional secondary thiol manufactured by Showa Denko K.K., was used.

<Polymerization Inhibitor (G)>
Tertiary butyl catechol was used.

<Cure Retarder (H)>
4-H-TEMPO was used.

<Aggregate (I)>
N90 Silica Sand Calcium Carbonate TM-2
Perlite FL-0 N50 Silica sand N40 Silica sand N70 Silica sand

<Fiber (J)>
Chemivest (registered trademark) FDSS-5
Polyolefin hyperbranched fiber manufactured by Mitsui Petrochemical Industries, Ltd.

<Epoxy resin>
Bond E208S (main agent)
Bond E208S (hardener)

Example 1
"Preparation of radically polymerizable resin composition"
(1) Process (S1):
The radical polymerizable compound (A-1) obtained in Synthesis Example 1 was thoroughly mixed with the metal-containing compound (D), the thiol compound (E), the polymerization inhibitor (G), and the curing retarder (H) in the amounts shown in Table 1 to prepare a resin product.
(2) Process (S2):
The resin product obtained in the step (S1) was mixed with the radical polymerization initiator (C) in the blending amount shown in Table 1 to prepare a curable resin product.
(3) Process (S3):
The curable resin product obtained in step (S2) was thoroughly mixed with the expandable material (B), aggregate (I), and fiber (J) in the amounts of each component shown in Table 1 to obtain a radical polymerizable resin composition of this example.

The mixing conditions in each step were as follows.
Agitator: HOMOGENIZING DISPER Model 2.5 (manufactured by Primix Corporation)
Stirring rotation speed: 3000 to 5000 rpm
Temperature: 25℃

"Preparation of cured product of radically polymerizable resin composition"
The obtained radical polymerizable resin composition was poured into a 40×40×160 mm mold, and left to stand (cure) in a room at a temperature of 23° C.±2° C. and a humidity of 50% to cure, and then demolded about 24 hours after molding to obtain a cured product of the radical polymerizable resin composition of this example.

"Evaluation of shrinkage and expansion of cured materials"
The shrinkage and expansion properties of the cured product of the obtained radical polymerizable resin composition were evaluated by the above-mentioned evaluation method. The results are shown in Table 2 and FIG.

Example 2
A radical polymerizable resin composition was obtained in the same manner as in Example 1, except that 8.0 g of the expanding agent (B) was used. A cured product of the radical polymerizable resin composition was also prepared in the same manner as in Example 1. The shrinkage and expansion properties of each of the cured products obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2 and FIG. 1.

Example 3
A radical polymerizable resin composition was obtained in the same manner as in Example 1, except that 12.0 g of the expanding agent (B) was used. A cured product of the radical polymerizable resin composition was also prepared in the same manner as in Example 1. The shrinkage and expansion properties of each of the cured products obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2 and FIG. 1.

"Compressive strength test"
The hardened product prepared in Example 3 was subjected to a compressive strength test. The results are shown in Table 3.
The specimens used for the compressive strength test were prepared in accordance with JIS A 1138 (Laboratory concrete preparation) and JIS A 1132 (Preparation of concrete strength test specimens). A formwork of φ5 cm × 10 cm was used, and the time from removal from the formwork was set to 24 hours to prepare the specimens.
The compressive strength of the manufactured specimens was measured using an Amsler type concrete compressive strength tester (CCM-1000kNI, manufactured by Shimadzu Corporation) in accordance with JIS A 1108 (Method of testing compressive strength of concrete). The material ages are as shown in Table 3.

(Comparative Example 1)
A radical polymerizable resin composition was obtained in the same manner as in Example 1, except that the expanding agent (B) was not used. A cured product of the radical polymerizable resin composition was produced in the same manner as in Example 3. The shrinkage and expansion properties of each of the cured products obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2 and FIG. 1. A compressive strength test was also performed in the same manner as in Example 3, and the results are shown in Table 3.

(Comparative Example 2)
An epoxy resin composition was obtained in the same manner as in Example 1, except that the epoxy resins Bond E208S (base) and Bond E208S (curing agent) (manufactured by Konishi Co., Ltd., product name: epoxy resin for civil engineering and construction, base: bisphenol A type epoxy resin, curing agent: mixture of modified polyamidoamine and polyamidoamine) were used instead of the radical polymerizable compound (A-1). A cured product of the epoxy resin composition was also prepared in the same manner as in Example 1. The shrinkage and expansion properties of each of the cured products obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2 and FIG. 1. A compressive strength test was also performed in the same manner as in Example 3, and the results are shown in Table 3.

(Comparative Example 3)
An epoxy resin composition was obtained in the same manner as in Comparative Example 2, except that the expanding agent (B) was not used. A cured product of the epoxy composition was also prepared in the same manner as in Comparative Example 1. The shrinkage and expansion properties of each of the cured products obtained were evaluated in the same manner as in Example 1. The results are shown in Table 2 and FIG. 1. A compressive strength test was also performed in the same manner as in Example 3, and the results are shown in Table 3.

Example 4
Radical polymerizable resin compositions were obtained in the same manner as in Example 3, except that aggregate (I) shown in Table 4 was used. Furthermore, cured products of the radical polymerizable resin compositions were produced in the same manner as in Example 1. Then, the shrinkage and expansion properties of the obtained cured products were evaluated in the same manner as in Example 1. The results are shown in Table 4 and FIG. 2. Furthermore, compressive strength tests were performed in the same manner as in Example 3, and the results at 24 hours and 672 hours are shown in Table 4.
The moisture contents of the aggregate (I) and the fiber (J) used in Example 4 were measured before mixing with the resin product. The results are shown in Table 4.

"Method of measuring moisture content"
For the aggregate (I) and fiber (J) to be mixed with the radically polymerizable resin composition of the present invention, the moisture contents in the aggregate and fiber were measured by the following method.
(1) A total of 20 mg of aggregate and fiber mixed in the same mass ratio as that of aggregate (I) and fiber (J) shown in Table 4 was weighed out and set in a TG/DTA (TA7000 series differential thermal/thermogravimetric simultaneous measurement apparatus STA7200RV, manufactured by Hitachi High-Tech Science Corporation).
(2) The temperature was increased from 30° C. to 105° C. at a rate of 10° C./min, and then held at 105° C. for 60 minutes.
(3) The weight change rate (weight loss rate) from 95°C to 105°C was calculated.

(Comparative Example 4)
A radical polymerizable resin composition was obtained in the same manner as in Example 4, except that the aggregate (I) of Example 4 was used after being dried under the following bone-dry conditions. A cured product of the radical polymerizable resin composition was also produced in the same manner as in Example 1. The shrinkage and expansion properties of each of the obtained cured products were evaluated in the same manner as in Example 1. The results are shown in Table 4 and FIG. 2. A compressive strength test was also performed in the same manner as in Example 3, and the results at 24 hours and 672 hours are shown in Table 4.
For the aggregate (I) used in Comparative Example 4, the moisture content in the aggregate was measured before mixing with the resin product in the same manner as in Example 4. The results are shown in Table 4.

"Extremely dry conditions"
The following procedure was carried out on the aggregate before it was mixed with the radical polymerizable resin composition in order to create bone-dry aggregate in which the moisture contained in the aggregate had been completely evaporated.
(1) 400 g of aggregate was placed in an aluminum tray, spread evenly, and dried in an oven at 105°C.
(2) After 48 hours, the product was removed from the oven and used.

(Comparative Example 5)
A radical polymerizable resin composition was obtained in the same manner as in Comparative Example 4, except that after mixing the aggregate (I) with the resin product, 5.00 g of water was added. In addition, a cured product of the radical polymerizable resin composition was produced in the same manner as in Example 1. Compressive strength tests were carried out at 24 hours and 672 hours in the same manner as in Example 3, and the results are shown in Table 4.
For the aggregate (I) used in Comparative Example 5, the moisture content in the aggregate was measured before mixing with the resin product in the same manner as in Example 4. The results are shown in Table 4.

(Consideration)
From the results in Table 2 and FIG. 1, it was found that, in the case of the radical polymerizable resin composition of the present invention containing the expanding agent (B), the shrinkage rate during curing of the cured product was significantly suppressed in Example 1, while the cured products of Examples 2 and 3 expanded from the reference length (160 mm) 24 hours after curing from the start of curing.

The cured product of the radical polymerizable resin composition of Example 3 was observed to have an expansion amount (expansion rate) of +40 μm (+250×10 ⁻⁶ ) to +131 μm (+819×10 ⁻⁶ ).
However, since the radical polymerizable resin composition of Comparative Example 1 did not contain the expanding agent (B), a shrinkage amount (shrinkage rate) of −48 μm (−300×10 ⁻⁶ ) to −80 μm (−500×10 ⁻⁶ ) was observed for the cured product.
In addition, in Comparative Example 2 using an epoxy resin composition, a large amount of shrinkage was observed, almost the same as that in Comparative Example 3, which did not contain the expanding agent (B), despite the fact that the expanding agent (B) was contained.

2, in Comparative Example 4, in which the moisture content of aggregate (I) pretreated under bone dry conditions was 0.00 g, a shrinkage rate of -250 x 10 ^-6 to -350 x 10 ^-6 was observed for the hardened product, rather than expansion. In Comparative Example 5, in which aggregate (I) was mixed with the resin product and then water was added, the compressive strength of the hardened product was worse than in Example 1 and Comparative Example 4.

Claims (13)

A radical polymerizable resin composition containing a radical polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I), and not containing free water,
The expanding material (B) generates ettringite by hydration reaction,
The radical polymerizable resin composition, wherein the aggregate (I) contains bound water. The radical polymerizable resin composition according to claim 1, wherein the content of the aggregate (I) is 5 to 500 parts by mass per 100 parts by mass of the radical polymerizable compound (A). The radical polymerizable resin composition according to claim 1 or 2, wherein the radical polymerizable compound (A) contains a vinyl ester resin and a radical polymerizable monomer. The radical polymerizable resin composition according to any one of claims 1 to 3, wherein the expanding agent (B) contains calcium sulfoaluminate. The expanding material (B) contains at least one selected from the group consisting of an ettringite-based expanding material and a quicklime-ettringite composite-based expanding material,
The ettringite-based expanding material is an expanding material containing calcium sulfoaluminate as an active ingredient,
The quicklime-ettringite composite expanding material is a composite expanding material containing a quicklime-based expanding material and an ettringite-based expanding material,
4. The radical polymerizable resin composition according to claim 1, wherein the quicklime-based expanding material is an expanding material containing free quicklime as an active ingredient . The radical polymerizable resin composition according to any one of claims 1 to 5, wherein the radical polymerization initiator (C) is a hydroperoxide (ROOH). The radical polymerizable resin composition according to any one of claims 1 to 6, further comprising a metal-containing compound (D) and a thiol compound (E). The radical polymerizable resin composition according to any one of claims 1 to 7, wherein the expanding agent (B) is 0.3 parts by mass to 30 parts by mass per 100 parts by mass of the radical polymerizable compound (A). The radical polymerizable resin composition according to any one of claims 1 to 8, wherein the radical polymerization initiator (C) is 0.1 to 10 parts by mass per 100 parts by mass of the radical polymerizable compound (A). A cured product of the radical polymerizable resin composition according to any one of claims 1 to 9. The cured product according to claim 10, wherein the rate of change in length of the cured product is 0 to 1000×10 ⁻⁶ after 3000 hours from curing. A method for producing a radical polymerizable resin composition, comprising a mixing step of mixing a radical polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I),
The expanding material (B) generates ettringite by hydration reaction,
The method for producing a radical polymerizable resin composition, wherein the aggregate (I) contains bound water. The method for producing the radical polymerizable resin composition according to claim 12, which does not include a step of adding water.