Radical polymerizable resin composition and cured product thereof

Abstract

The present invention provides a radical-polymerizable resin composition which can be inhibited from shrinking while retaining the strength by adding a proper amount of an expanding material to a radical-polymerizable resin composition which suffers curing shrinkage due to a decrease in the free volume of a liquid component during curing. This radical-polymerizable resin composition comprises a radical-polymerizable compound (A), an expanding material (B), a free-radical polymerization initiator (C), and an aggregate (I). The aggregate (I) contains bound water.

Description

Technical Field

[0001] 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 in Japan on December 26, 2019, and incorporates the content herein by reference.

Background Art

[0002] When polymerization is carried out using a general liquid vinyl monomer, a large shrinkage occurs. Due to this shrinkage, when using vinyl monomers for industrial products, distortion problems occur. Therefore, creating a resin with a small shrinkage rate during polymerization is very industrially significant.

[0003] Radically polymerizable resin compositions typified by unsaturated polyester resins and vinyl ester resins (epoxy acrylates) also usually undergo shrinkage during curing. Since "styrene" and "methyl methacrylate", which are monomers shown in Table 1 of Non-Patent Document 1, are often used as monomers, unsaturated polyester resins in general formulations involve a volume shrinkage of about 8 to 12%, and vinyl ester resins involve a volume shrinkage of about 8 to 10%. This value is quite large even when compared with the 3 to 6% volume shrinkage of general epoxy resins. Therefore, it has hindered the use of unsaturated polyester resins or vinyl ester resins in industrial applications or their entry into other industries and applications.

[0004] As a method for solving this problem, Patent Document 1 states that by using polystyrene beads as a low-shrinkage material, it is possible to reduce the man-hours of manufacturing or shorten the manufacturing time, and to produce a low-shrinkage unsaturated polyester resin composition having excellent low shrinkage, dimensional stability, and surface smoothness.

[0005] In Patent Document 2, it is stated that by blending an A-B type block copolymer into an unsaturated polyester resin composition, a low-shrinkage unsaturated polyester resin composition capable of producing a molded article with low shrinkage during curing and excellent heat resistance can be obtained.

[0006] Furthermore, in Patent Document 3, 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, 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.

[0007] In addition, there is a so-called "expansive concrete" which is a concrete obtained by mixing an expansive agent as an admixture into a conventional water-curable composition (for example, a composition containing cement such as Portland cement). According to the Japanese JIS standard, it is said that by curing in water for 7 days, a hydrate of the expansive agent is formed and the volume increases, but no expansion effect is recognized in the air.

Prior Art Documents

Patent Documents

[0008]

Patent Document 1

Patent Document 2

Patent Document 3

Non-Patent Documents

[0009]

Non-Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0010] In conventional radically polymerizable resin compositions, in order to create a resin with a low shrinkage rate, a single blend of a thermoplastic resin such as polystyrene or a block copolymer of two or more types has been used. These have mostly functioned as "shrinkage preventives." Moreover, 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 are often limited in use to applications such as sheet molding compounds (SMC) and bulk molding compounds (BMC) that are heat-molded at medium temperatures or higher.

[0011] The present invention has been made in view of the above conventional situation. Instead of using a shrinkage preventive, by incorporating an expanding material, the whole expands at a constant ratio during the curing of the resin composition without being limited by the molding method, use temperature, application, etc., and then stabilizes, thereby providing a radically polymerizable resin composition with a small shrinkage rate. Another object is to provide a cured product of a radically polymerizable resin composition that does not cause a decrease in strength after molding.

Means for Solving the Problems

[0012] That is, the present invention is represented by the following [1] to

[13] .

[0013] [1] A radically polymerizable resin composition containing a radically polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I), and not containing free water, The radically polymerizable resin composition in which the aggregate (I) contains bound water. [2] The radically polymerizable resin composition according to [1], wherein the content of the aggregate (I) is 5 parts by mass to 500 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A). [3] The radically polymerizable resin composition according to [1] or [2], wherein the radically polymerizable compound (A) contains a vinyl ester resin and a radically polymerizable monomer. [4] The radical polymerizable resin composition according to any one of [1] to [3], wherein the expanding agent (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 hydroperoxide (ROOH). [6] The radical polymerizable resin composition according to any one of [1] to [5], further containing 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 agent (B) is 0.3 parts by mass to 30 parts by mass with respect 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 with respect 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 change rate of the length of the cured product is 0 to 1000×10 after 3000 hours or more after curing. -6 The cured product according to [9].

[11] A method for producing a radical polymerizable resin composition, comprising a mixing step of mixing a radical polymerizable compound (A), an expanding agent (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 a 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] , The radical polymerizable resin composition containing a radical polymerizable compound (A), an expanding agent (B), a radical polymerization initiator (C), and an aggregate (I).

Advantages of the Invention

[0014] According to the present invention, for a radically polymerizable resin composition that causes curing shrinkage due to a decrease in the free volume of the liquid component during curing, by adding an appropriate amount of an expanding material, a radically polymerizable resin composition capable of suppressing shrinkage while maintaining strength, and a cured product of the radically polymerizable resin composition can be provided.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0016] The present invention will be described in detail below.

[0017] (Radically Polymerizable Resin Composition) The radical polymerizable resin composition according to one embodiment of the present invention contains a radical polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I), and does not contain free water. The aggregate (I) contains bound water. Here, "bound water" is a concept for distinguishing from free water. As described in the "method for measuring water content" described later, it is water calculated from the weight change rate (decrease rate) from 95°C to 105°C in a TG / DTA experiment. For example, it includes crystal water contained in the aggregate (I), adsorbed water strongly adsorbed on the internal micropores and surface of the aggregate (I), and the like. Further, "free water" includes, for example, water added in the step of adding water in the manufacturing 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" is the meaning of the radical polymerizable resin composition obtained by a manufacturing method that does not add water. Preferably, it means a radical polymerizable resin composition obtained by a manufacturing method that does not perform pretreatment on the aggregate (I) under the absolute dry conditions described later, is used in the manufacturing process of the radical polymerizable resin composition, and does not include a step of adding water in the manufacturing process. For example, commercially available aggregates (I) and the like can be used as they are. Alternatively, in order to make the content of bound water more stable, pretreatment of storing the aggregate (I) at a certain temperature and humidity for a certain time can also be performed. Since the water content of the bound water contained in the aggregate (I) can be confirmed by the measurement method described later, the temperature, humidity, and treatment time can be appropriately determined according to the type of the aggregate (I) used and the water content at the time of acquisition.

[0018] <Radical 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 having an ethylenically unsaturated group in the molecule and in which a polymerization reaction proceeds by radicals. 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 and radically polymerizable unsaturated monomers. Among these, one or more selected from vinyl ester resins, unsaturated polyester resins, and mixtures of these with radically polymerizable unsaturated monomers are preferred. Among these, vinyl ester resins are more preferred. In the present specification, “(meth)acrylate” means “acrylate or methacrylate”.

[0019] Vinyl ester resin As the vinyl ester resin, those obtained by reacting an unsaturated monobasic acid with an epoxy resin can be used.

[0020] Examples of the epoxy resin include bisphenol type epoxy resins, biphenyl type epoxy resins, novolac type epoxy resins, trisphenol methane type epoxy resins, aralkyl diphenol type epoxy resins, naphthalene type epoxy resins, aliphatic type epoxy resins, etc. These can be used alone or in combination of multiple types.

[0021] Examples of the bisphenol type epoxy resin include those obtained by reacting bisphenols with epichlorohydrin and / or methyl epichlorohydrin, and those obtained by reacting a glycidyl ether of bisphenol A with a condensate of the bisphenols and epichlorohydrin and / or methyl epichlorohydrin. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol S, and tetrabromobisphenol A. Examples of the biphenyl type epoxy resin include those obtained by reacting biphenol with epichlorohydrin and / or methyl epichlorohydrin.

[0022] Examples of novolac epoxy resins include those obtained by reacting phenol novolac or cresol novolac with epichlorohydrin and / or methyl epichlorohydrin, and the like. Examples of trisphenol methane type epoxy resins include those obtained by reacting trisphenol methane, triscresol methane with epichlorohydrin and / or methyl epichlorohydrin, and the like. Examples of aralkyl diphenol type epoxy resins include those obtained by reacting aralkyl phenol with epichlorohydrin and / or methyl epichlorohydrin, and the like.

[0023] Examples of naphthalene type epoxy resins include those obtained by reacting dihydroxynaphthalene with epichlorohydrin and / or methyl epichlorohydrin, and the like.

[0024] Examples of aliphatic epoxy resins include alicyclic epoxy resins, alicyclic diol diglycidyl ether type epoxy resins, aliphatic diol diglycidyl ether type epoxy resins, poly(oxyalkylene) glycol diglycidyl ether type epoxy resins, and the like.

[0025] Examples of alicyclic epoxy resins include alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, and the like. 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 alcohol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, and dihydroxyl terpene diglycidyl ether. Among these, a commercially available product of cyclohexanedimethanol diglycidyl ether is "Denacol EX-216L" from Nagase ChemteX Corporation.

[0026] Specific examples of the aliphatic diol diglycidyl ether 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, 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 Yakuhin Kogyo Co., Ltd., and "Epogosei (registered trademark) HD" from Yokkaichi Gosei Co., Ltd. Further, a commercially available product of 1,4 - butanediol diglycidyl ether is "Denacol EX - 214L" from Nagase ChemteX Corporation.

[0027] Specific examples of the poly(oxyalkylene) glycol diglycidyl ether include, for example, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, poly(tetramethylene) glycol diglycidyl ether, and the like.

[0028] Preferred examples of the aliphatic epoxy resin include 1,6 - hexanediol diglycidyl ether, diglycidyl ether of polyethylene glycol, poly(tetramethylene) glycol diglycidyl ether, and the like. Among them, those having a number average molecular weight of 150 to 1000 are more preferred.

[0029] The epoxy resin may be a diglycidyl ester such as diglycidyl dimer acid ester or diglycidyl hexahydrophthalate ester. Further, examples of the epoxy resin include an epoxy resin having an oxazolidone ring obtained by reacting the epoxy resin with a diisocyanate. Specific examples of the epoxy resin having an oxazolidone ring include Araldite (registered trademark) AER4152 manufactured by Asahi Kasei Epoxy Co., Ltd.

[0030] Known unsaturated monobasic acids can be used, and examples thereof include (meth)acrylic acid, crotonic acid, cinnamic acid, etc. Further, a reaction product of a compound having one hydroxy group and one or more (meth)acryloyl groups and 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. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol 2-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-terminated butadiene-acrylonitrile copolymer (trade name Hycar CTBN), etc. can be mentioned.

[0031] [Unsaturated polyester resin] As the unsaturated polyester resin, one obtained by subjecting a dibasic acid component containing an unsaturated dibasic acid and, if necessary, a saturated dibasic acid, and a polyhydric alcohol component to an esterification reaction can be used. Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc. These may be used alone or in combination of two or more. Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, 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 anhydride, 4,4'-biphenyldicarboxylic acid, and dialkyl esters thereof, halogenated saturated dibasic acids, etc. These may be used alone or in combination of two or more.

[0032] There is no particular limitation on the polyhydric alcohol. For example, dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5-pentanediol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2-cyclohexaneglycol, 1,3-cyclohexaneglycol, 1,4-cyclohexaneglycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol; Dihydric alcohols such as adducts of dihydric phenols represented by hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. and alkylene oxides represented by propylene oxide or ethylene oxide; Trihydric or higher alcohols such as 1,2,3,4 - tetrahydroxybutane, glycerin, trimethylolpropane, pentaerythritol, etc. can be mentioned.

[0033] The unsaturated polyester may be one modified with a dicyclopentadiene - based compound as long as the effects of the present invention are not impaired. Examples of the modification method with a dicyclopentadiene - based compound include known methods such as a method of obtaining a dicyclopentadiene - maleic acid adduct (isodecyl monomaleate) and then introducing a dicyclopentadiene skeleton using this as a monobasic acid. In the vinyl ester resin or unsaturated polyester resin used in the present invention, an oxidative polymerization (air - curing) group such as an allyl group or a benzyl group can be introduced. There is no particular limitation on the introduction method. For example, addition of an oxidative polymerization group - containing polymer, condensation of a compound having a hydroxyl group and an allyl ether group, a method of adding a reaction product of an allyl glycidyl ether, 2,6 - diglycidyl phenyl allyl ether with a compound having a hydroxyl group and an allyl ether group and an acid anhydride, etc. can be mentioned. Note that the oxidative polymerization (air - curing) in the present invention refers to cross - linking accompanying the generation and decomposition of peroxides due to the oxidation of the methylene bond between the ether bond and the double bond, such as that found in an allyl ether group.

[0034] 〔Polyester (meth) acrylate resin, urethane (meth) acrylate resin, and (meth) acrylate resin〕 As the polyester (meth) acrylate resin in the present invention, for example, a polyester obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, specifically, a resin obtained by reacting (meth) acrylic acid with the hydroxyl groups at both ends of polyethylene terephthalate, etc. can be used. In addition, as the urethane (meth) acrylate resin, for example, a resin obtained by reacting (meth) acrylic acid with hydroxyl groups or isocyanato groups at both ends of polyurethane obtained by reacting isocyanate and 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, isocyanato groups, carboxyl groups and epoxy groups, or a polymer of a monomer having the substituent and (meth) acrylate A resin obtained by reacting a (meth) acrylic acid ester having a hydroxyl group with respect to the substituent can be used.

[0035] [Radically polymerizable unsaturated monomer] In the present invention, a radically polymerizable unsaturated monomer can be used as the radically polymerizable compound (A). The radically polymerizable unsaturated monomer may be used alone, but is preferably used as a mixture of the radically polymerizable unsaturated monomer and at least one of the vinyl ester resin and the unsaturated polyester resin. The radically polymerizable unsaturated monomer is not particularly limited, but those having a vinyl group or a (meth) acryloyl group are preferred. Specific examples of the monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene, vinyl acetate, diallyl phthalate, triallyl isocyanurate and the like.

[0036] (Meth)acrylate monomers having a (meth)acryloyl group include, for example, (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, dicyclopentenyl oxyethyl (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, ethylene glycol monohexyl ether (meth)acrylate, ethylene glycol mono-2-ethylhexyl ether (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monohexyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, neopentyl glycol di(meth)acrylate, 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-bis[4-(methacryloxy diethoxy)phenyl]propane, 2,Examples include 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, dicyclopentenyl oxyethyl acrylate, tricyclodecanyl (meth)acrylate, tris(2-hydroxyethyl)isocyanurate acrylate, etc.

[0037] Furthermore, examples of polyfunctional (meth)acrylic acid esters include 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, 1,6-hexanediol di(meth)acrylate; polyoxyalkylene glycol di(meth)acrylates such as diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol (meth)acrylate; trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc.

[0038] Furthermore, the following compounds can also be used as the radically polymerizable unsaturated monomer. Specifically, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanurate, allyl (meth)acrylate, diallyl fumarate, allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl ether, 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 can be mentioned. In addition to the above, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, etc. can be mentioned. These may be used alone or in combination of two or more.

[0039] The radically polymerizable unsaturated monomer can be used to lower the viscosity of the radically polymerizable resin composition of the present invention and improve hardness, strength, chemical resistance, water resistance, etc. However, if its content is too high, it may lead to deterioration of the cured product and environmental pollution. Therefore, the content of the radically polymerizable unsaturated monomer is preferably 90% by mass or less in the radically polymerizable compound (A).

[0040] The radical polymerizable compound (A) may contain a catalyst or a polymerization inhibitor remaining from the synthesis of a vinyl ester resin, an unsaturated polyester resin, a polyester (meth)acrylate resin, a urethane (meth)acrylate resin, and a (meth)acrylate resin. 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, phenothiazine, and the like. When a catalyst or a polymerization inhibitor remains in the radical polymerizable compound (A), the amount thereof is preferably 0.001 to 2 parts by mass, respectively, based on 100 parts by mass in total of the vinyl ester resin and the unsaturated polyester resin.

[0041] 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, still 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.

[0042] <Expansion agent (B)> As the expansion agent (B) used in the present invention, any expansion agent may be used as long as it satisfies the standard of Japanese Industrial Standard JIS A 6202 "Expansion agent for concrete", which is generally used as an expansion agent for concrete. Specifically, those that generate calcium hydroxide or ettringite by a hydration reaction may be used. Preferred expansion agents include (1) an expansion agent having free quicklime as an active ingredient (quicklime-based expansion agent), (2) an expansion agent having calcium sulfoaluminate as an active ingredient (ettringite-based expansion agent), and (3) a quicklime-ettringite composite expansion agent.

[0043] Specific examples of the quicklime-based expansion material include, for example, Pacific Hyper Expand-K, Pacific Hyper Expand-M, Pacific Expand-K, Pacific Expand-M, Pacific N-EX, etc. manufactured by Pacific Material. Specific examples of the ettringite-based expansion material include Denka CSA #10, Denka CSA #20, etc. manufactured by Denka. Specific examples of the quicklime-ettringite composite expansion material include Denka Power CSA Type S, Denka Power CSA Type R, Denka Power CSA Type T, etc. manufactured by Denka.

[0044] 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, still more preferably 0.7 to 20 parts by mass, and most preferably 1 to 16 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A). If the content of the expansion material (B) is 30 parts by mass or less, when the radically polymerizable resin composition is cured, the expansion ratio will not exceed the elongation amount of the resin. Conversely, if it is 0.3 parts by mass or more, the expansion performance with respect to the radically polymerizable compound (A) will not fail to appear. Further, these expansion materials (B) may be used alone or in combination of two or more.

[0045] <Radical polymerization initiator (C)> The radically 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 photo radical polymerization initiator (C-2). Among them, the thermal radical polymerization initiator (C-1) is preferable. Examples of the thermal radical polymerization initiator (C-1) include diacyl peroxide-based initiators such as benzoyl peroxide; peroxy ester-based initiators such as tert-butyl peroxybenzoate; hydroperoxide-based initiators such as cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, and paramethane hydroperoxide; dialkyl peroxide-based initiators such as dicumyl peroxide; ketone peroxide-based initiators such as methyl ethyl ketone peroxide and acetylacetone peroxide; peroxyketal-based initiators; alkyl perester-based initiators; and organic peroxides such as percarbonate-based initiators. Among these, hydroperoxide-based organic peroxides (ROOH) (simply referred to as hydroperoxides (ROOH)) are preferred, and among them, cumene hydroperoxide (CHP) such as Parkmill (registered trademark) H-80 manufactured by NOF Corporation is particularly preferred.

[0046] Examples of the photo radical polymerization initiator (C-2) include benzoin ether-based initiators such as benzoin alkyl ether; benzophenone-based initiators such as benzophenone, benzyl, and methyl orthobenzoylbenzoate; acetophenone-based initiators such as benzyldimethyl 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.

[0047] Examples of the photo radical polymerization initiator (C-2) having photosensitivity 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, 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Inc.) and bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide (manufactured by Ciba Specialty Chemicals Inc.) are mixed at a ratio of 75% / 25% under the trade name Irgacure-1700 (manufactured by Ciba Specialty Chemicals Inc.); 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.) are mixed at a ratio of 75% / 25% under the trade name Irgacure 1800 (manufactured by Ciba Specialty Chemicals Inc.), and at a ratio of 50% / 50% under the trade name 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); 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur 1173, manufactured by Ciba Specialty Chemicals Inc.) and 2,4,6-trimethylbenzoyldiphenylphosphine oxide (trade name Lucirin TPO, manufactured by BASF Corporation) are mixed at a ratio of 50% / 50% under the trade name Darocur 4265, and the like.

[0048] Examples of the photo radical polymerization initiator (C-2) having photosensitivity in the visible light region include camphorquinone, benzyltrimethylbenzoyldiphenylphosphinoxide, methylthioxanthone, dicyclopentadienyltitanium - bis(pentafluorophenyl), and the like. These radical polymerization initiators (C) may be used alone or in combination of two or more. For the purpose of assisting the main reaction between thermal curing and photo-curing, the other reaction may be incorporated, and the thermal radical polymerization initiator (C-1) and the photo-radical polymerization initiator (C-2) may be used in combination as needed.

[0049] Also, depending on the molding conditions, they can be used in a composite form such as organic peroxide / dye system, diphenyliodonium salt / dye system, imidazole / ketone compound, hexaallylbiimidazole compound / hydrogen donor compound, mercaptobenzothiazole / thiopyrylium salt, metal arene / cyanine dye, hexaallylbiimidazole / radical generator, etc.

[0050] 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 still more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (A).

[0051] <Metal-containing compound (D)> The radical polymerizable resin composition of the present invention may contain at least one metal-containing compound (D) selected from metal soaps (D-1) and metal complexes (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 with one carbon atom between two carbonyl groups is coordinated to a metal element.

[0052] 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 still more preferably 0.005 to 3 parts by mass with respect 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 rapidly even in water and a humid atmosphere.

[0053] 〔Metal soap (D-1)〕 There is no particular limitation on the long-chain fatty acid in the metal soap (D-1), but for example, a fatty acid having 6 to 30 carbon atoms is preferred. Specifically, octanoic acid 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, naphthenic acid and other linear or cyclic saturated fatty acids, unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid are preferred. In addition, rosin acid, linseed oil fatty acid, soybean oil fatty acid, tall oil fatty acid and the like can also be mentioned.

[0054] There is no particular limitation on the organic acid other than the long-chain fatty acid in the metal soap (D-1), but a weak acid compound having a carboxy group, a hydroxy group or an enol group and soluble in an organic solvent is preferred. Examples of the compound 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; aromatic acids such as benzoic acid and phthalic acid. Examples of the compound having a hydroxy group or an enol group include ascorbic acid, α-acid, imidic acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, tycoic acid, dehydroacetic acid, delta-acid, uric acid, hydroxamic acid, humic acid, fulvic acid, phosphonic acid and the like. Among these, long-chain fatty acids are preferred, 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 among them, 2-ethylhexanoic acid and naphthenic acid are preferred.

[0055] Examples of the metal element constituting the metal soap (D-1) 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 the present invention, Group 2-12 metal elements 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 still more preferred, and zirconium, manganese, cobalt, bismuth, and calcium are even more preferred.

[0056] Specific examples of the 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. Among them, 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. Among these, manganese octylate and cobalt octylate are particularly preferred. Specific examples of cobalt octylate include cobalt hexoate manufactured by Toei Chemical Industry Co., Ltd. (cobalt content in the total product amount: 8% by mass, molecular weight: 345.34). Specific examples of manganese octylate include manganese hexoate manufactured by Toei Chemical Industry Co., Ltd. (manganese content in the total product amount: 8% by mass, molecular weight: 341.35).

[0057] 〔Metal complex (D-2) having a β-diketone skeleton〕 A 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 formed by complexation of metals with acetylacetone, ethyl acetoacetate, benzoylacetone, etc. 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 of the metal soap (D-1).

[0058] Specific metal complexes (D-2) include zirconium acetylacetonate, vanadium acetylacetonate, cobalt acetylacetonate, titanium acetylacetonate, titanium dibutoxybis(acetylacetonate), iron acetylacetonate, and ethyl acetoacetate cobalt. Among them, zirconium acetylacetonate, titanium acetylacetonate, and titanium dibutoxybis(acetylacetonate) are more preferable.

[0059] <Thiol compound (E)> The radical polymerizable resin composition of the present invention may contain one or more thiol compounds (E) selected from secondary thiol compounds (E-1) and tertiary thiol compounds (E-2). In the present invention, it is presumed that the thiol compound (E) has a function as a curing accelerator and also has a function of coordinating to the vicinity of the metal of the metal-containing compound (D) to prevent 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 (hereinafter sometimes referred to as "secondary mercapto group" and "tertiary mercapto group", respectively) bonded to a secondary or tertiary carbon atom in the molecule. However, from the viewpoints of allowing rapid curing to proceed even in water and preventing the deactivation of the metal of the metal-containing compound (D) by water, polyfunctional thiols which are compounds having two or more secondary or tertiary mercapto groups in the molecule are preferable. Among them, difunctional thiols which are compounds having two secondary or tertiary mercapto groups in the molecule are preferable. Also, the secondary thiol compound (E-1) is more preferable than the tertiary thiol compound (E-2). Here, the "polyfunctional thiol" means a thiol compound having two or more mercapto groups as functional groups, and the "bifunctional thiol" means a thiol compound having two mercapto groups as functional groups.

[0060] There is no particular limitation on the compound having two or more secondary or tertiary mercapto groups in the molecule. 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 groups in the structure represented by the following formula (Q) is preferred.

[0061] [Chemical formula]

[0062] (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.)

[0063] [Secondary thiol compound (E-1)] When the thiol compound (E) having the structure represented by the formula (Q) is a secondary thiol compound (F1), specific examples thereof include 3-mercaptobutyric acid, bis(1-mercaptoethyl) 3-mercaptophtalate, bis(2-mercaptopropyl) phthalate, bis(3-mercaptobutyl) phthalate, ethylene glycol bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate), trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakis(3-mercaptobutyrate), dipentaerythritol hexakis(3-mercaptobutyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane tris(2-mercaptopropionate), 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-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), butanediol bis(3-mercapto-3-phenylpropionate), octanediol bis(3-mercapto-3-phenylpropionate), trimethylolpropane tris(3-mercapto-3-phenylpropionate), tris-2-(3-mercapto-3-phenylpropionate)ethyl isocyanurate, pentaerythritol tetrakis(3-mercapto-3-phenylpropionate), dipentaerythritol hexakis(3-mercapto-3-phenylpropionate) and the like can be mentioned.

[0064] Among the secondary thiol compounds (E-1), as commercially available products of compounds having two or more secondary mercapto groups in the molecule, 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), trimethylolpropane tris(3-mercaptobutyrate) (manufactured by Showa Denko K.K., TPMB) and the like can be mentioned, and it is preferable to use one or more of these. Among them, 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Showa Denko K.K., Karenz MT (registered trademark) BD1) is preferable.

[0065] 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), 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), 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.

[0066] The total amount of the 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, still more preferably 0.1 to 5 parts by mass, and even more preferably 0.2 to 4 parts by mass with respect to 100 parts by mass of the radical polymerizable compound (A) described above. When the amount of the thiol compound (E) is 0.01 part by mass or more, the curing function can be sufficiently obtained, and when it is 10 parts by mass or less, curing proceeds rapidly.

[0067] 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 from 0.1 to 15, more preferably from 0.3 to 10, still more preferably from 0.6 to 8, even more preferably from 0.8 to 5 in one embodiment of the present invention, and more preferably from 0.5 to 15, further preferably from 1 to 12, even more preferably from 1.5 to 10, even more preferably from 2 to 9 in another embodiment of the present invention. 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 the production cost and the effect is improved.

[0068] The thiol compound (E) may be used alone or in combination of two or more. When the secondary thiol compound (E-1) and the tertiary thiol compound (E-2) are used in combination, the molar ratio [(E-1) / (E-2)] between the two is preferably from 0.001 to 1000, more preferably from 1 to 10. When the molar ratio [(E-1) / (E-2)] is within the above range, in the radical polymerizable resin composition, the metal-containing compound (D) and the thiol compound (E) are stable, and no disulfide compound due to the bonding of the thiol compounds (E) to each other is generated as a by-product. From the viewpoint of storing the radical polymerizable resin composition in a stable state with the metal-containing compound (D) and the thiol compound (E), it is preferable to use the secondary thiol compound (E-1) or the tertiary thiol compound (F2) alone.

[0069] <Curing accelerator (F)> The radical 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-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, diethanolaniline, and other N,N-substituted anilines, N,N-substituted-p-toluidines, 4-(N,N-substituted amino)benzaldehydes, and other amines can be used. 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 with respect to 100 parts by mass of the radical-polymerizable compound (A).

[0070] <Polymerization inhibitor (G)> The radical-polymerizable resin composition of the present invention may contain a polymerization inhibitor from the viewpoints of suppressing excessive polymerization of the radical-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.

[0071] <Curing 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-based curing retarders, such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), and TEMPO derivatives such as 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 preferable in terms 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, respectively, based on 100 parts by mass of the radical polymerizable compound (A).

[0072] <Aggregate (I)> The radical polymerizable resin composition of the present invention contains an aggregate (I). The aggregate (I) contains bound water. The water content of the bound water in the aggregate (I) is not particularly limited, but for example, it is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, still more preferably 0.30% by mass or more, and most preferably 0.40% by mass or more. Also, the water content of the bound water in the aggregate (I) is preferably 5.0% by mass or less, more preferably 2.5% by mass or less, still more preferably 1.5% by mass or less, and most preferably 1.0% by mass or less. The water content of the bound water in the aggregate (I) is not particularly limited, but for example, it is preferably 0.2 parts by mass or more, more preferably 0.5 parts by mass or more, still more preferably 1.0 parts by mass or more, and most preferably 1.5 parts by mass or more with respect to 100 parts by mass of the radical polymerizable compound (A). Also, 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, still more preferably 2.5 parts by mass or less, and most preferably 2.0 parts by mass or less with respect to 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 those used in mortar or concrete can be used. The aggregate is not particularly limited, and examples thereof include calcium carbonate, crushed stone, sandstone, gypsum stone, marble, quartz, limestone, silica sand, silica stone, river sand, etc. However, cement is not included in the aggregate (I). Also, from the viewpoint of weight reduction, lightweight aggregates such as sintered shale, silicate balloons, and non-silicate balloon perlite can also be used.

[0073] The radical polymerizable resin composition of the present invention preferably does not substantially contain cement. The meaning of "not substantially containing" is that it contains 3% by mass or less, preferably 2% by mass or less, more preferably 1% by mass or less, and still more preferably 0.5% by mass or less with respect to the radical polymerizable resin composition.

[0074] Here, examples of the cement include Portland cement, other blended cements, super-fast-setting cements, etc. Examples of Portland cement include various types such as low-heat, moderate-heat, ordinary, early-strength, super-early-strength, and sulfate-resistant Portland cements. Examples of blended cements include blast-furnace cement, fly-ash cement, silica cement, etc.

[0075] Calcium carbonate functions as an extender pigment that is present in the coating film, transparent, and does not conceal the coated surface (substrate surface), and has functions such as filling properties in recesses and reduction of paint costs. Examples of commercially available calcium carbonate include, for example, TM-2 (manufactured by Uko Mining Co., Ltd.). Calcium carbonate has a specific particle size distribution, excellent dispersibility, and is also porous, so it can reduce the specific gravity of the aggregate itself to make it less likely to sag and improve the film-forming property.

[0076] Examples of silicate balloons include shirasu balloons, perlite, glass (silica) balloons, fly-ash balloons, etc. Examples of non-silicate balloons include alumina balloons, zirconia balloons, carbon balloons, etc.

[0077] The content of the aggregate in the composition of the present invention is not particularly limited, but is preferably 5 parts by mass to 500 parts by mass, more preferably 10 parts by mass to 450 parts by mass, based on 100 parts by mass of the radically polymerizable compound (A). In particular, if the content of the aggregate is 5 parts by mass or more, practical fluidity can be ensured. Also, if the content of the aggregate is 500 parts by mass or less, the amount of sticking to the trowel decreases, and a decrease in workability can be prevented.

[0078] <Fiber (J)> The radical polymerizable composition of the present invention may contain fibers, if necessary. Specific examples of the 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, ceramic fibers such as alumina fibers, and the like. Among them, for example, polyolefin fibers can be used as the thixotropic agent. The thixotropic agent (thixotropy-imparting agent) is compounded for the purpose of imparting thixotropy.

[0079] As commercially available polyolefin fibers, there are products with trademark names such as Chemvest (registered trademark) FDSS-2 (average fiber length 0.6 mm), Chemvest (registered trademark) FDSS-5 (average fiber length 0.1 mm), Chemvest (registered trademark) FDSS-25 (average fiber length 0.6 mm, hydrophilized product), Chemvest (registered trademark) FDSS-50 (average fiber length 0.1 mm, hydrophilized product), etc. (all are manufactured by Mitsui Petrochemical Industries, Ltd.).

[0080] The carbon fibers are not particularly limited, and any known carbon fibers can be used. Examples thereof include polyacrylonitrile-based (PAN-based) carbon fibers, rayon-based carbon fibers, pitch-based carbon fibers, and the like. The carbon fibers may be used alone or in combination of two or more. From the viewpoints of low cost and good mechanical properties, it is preferable to use PAN-based carbon fibers. Such carbon fibers are commercially available. Carbon fiber reinforced plastic (CFRP) may be used as the carbon fibers.

[0081] The diameter of the carbon fibers is preferably 3 to 15 μm, more preferably 5 to 10 μm. The length of the carbon fibers is usually 5 to 100 mm. In the present invention, the carbon fibers may be cut particularly to 10.0 mm to 100.0 mm, and further to 12.5 mm to 50.0 mm for use.

[0082] These fibers are preferably used in the form of a fiber structure selected from, for example, plain weave, twill weave, non-woven fabric, mat, roving, chop, knitted fabric, woven fabric, and composite structures thereof, biaxial mesh, and triaxial mesh. For example, the fiber structure can be impregnated with a radically polymerizable composition and, optionally, prepolymerized to form a prepreg for use. As the mesh, for example, a biaxial mesh or a triaxial mesh is used. The length of one side (mesh size) of the square of the biaxial mesh and the length of one side (mesh size) of the equilateral triangle of the triaxial mesh are each preferably 5 mm or more, more preferably 10 to 20 mm. By using a biaxial mesh or a triaxial mesh, a curable material for preventing concrete spalling that is lightweight, economical, easy to construct, and excellent in durability can be obtained. These fibers are preferably used when reinforcing coating film properties such as concrete spalling prevention and FRP waterproofing, or manufacturing FRP molded products. In applications such as preventing concrete spalling, glass fibers, cellulose fibers, etc., which are excellent in transparency among fibers, are preferable because the deterioration state of the base can be visually inspected from the outside.

[0083] The content of such fibers is preferably 0.3 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and still more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A).

[0084] <Water reducing agent (K)> The radically polymerizable resin composition of the present invention may contain a usable water reducing agent (K) that can impart water reducing properties, if necessary. As the water reducing agent, known water reducing agents used in concrete such as liquid or powder water reducing agents, AE water reducing agents, high-performance water reducing agents, and high-performance AE water reducing agents can be applied without limitation. The polycarboxylic acid-based water reducing agent can suppress the decrease in the fluidity of concrete accompanying the addition of the above-described swellable aluminosilicate, and is also suitable from the viewpoint of maintaining good fluidity and improving workability. In addition, as the water reducing agent, known water reducing agents used in concrete such as liquid or powdered water reducing agents, AE water reducing agents, high-performance water reducing agents, and high-performance AE water reducing agents can be applied without limitation. The water reducing agent is preferably contained in the radically polymerizable resin composition in an amount of 0.1 to 3.0 parts by mass.

[0085] 〔Solvent〕 A solvent can be blended in the radically polymerizable resin composition of the present invention as needed. Examples of solvents that can be blended include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, amyl acetate, and cellosolve acetate; and ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, and diisobutyl ketone. These solvents may be used during the production of the polymer.

[0086] 〔Polyisocyanate compound〕 The radically polymerizable resin composition of the present invention may contain a polyisocyanate compound. The polyisocyanate compound reacts with the hydroxyl group of the radically polymerizable compound (A) to form a cured coating film. The polyisocyanate compound contains two or more isocyanate groups in the molecule, and the isocyanate 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; cycloaliphatic 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 like lysine triisocyanate, and adducts of each of these polyisocyanates with polyhydric alcohols, low molecular weight polyester resins, or water, cyclopolymerization products of the above-mentioned diisocyanates with each other (e.g., isocyanurate), biuret-type adducts, etc. Among them, isocyanurate of hexamethylene diisocyanate is preferred. These polyisocyanate compounds may be used alone or in combination of two or more.

[0087] When the radical-polymerizable resin composition contains a polyisocyanate compound, the amount thereof is preferably 0.1 part by mass to 50 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 2 to 20 parts by mass with respect to 100 parts by mass of the radical-polymerizable compound (A).

[0088] The blocked polyisocyanate compound is obtained by blocking the isocyanate group of the above polyisocyanate compound with a blocking agent. Examples of the blocking agent include phenolic compounds such as phenol, cresol, and xylenol; ε-caprolactam; lactam compounds such as δ-valerolactam, γ-butyrolactam, and β-propiolactam; alcohol compounds 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 compounds such as formamidoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, benzophenone oxime, and cyclohexanone oxime; and active methylene compounds such as dimethyl malonate, diethyl malonate, ethyl acetoacetate, methyl acetoacetate, and acetylacetone. By mixing the polyisocyanate and the blocking agent, the isocyanato group of the polyisocyanate can be easily blocked.

[0089] When the polyisocyanato compound is a non-blocked polyisocyanato compound, if the radically polymerizable compound (A) and the polyisocyanato compound in the radically polymerizable resin composition of the present invention are mixed, the two will react. Therefore, it is preferable to separate the radically polymerizable compound (A) and the polyisocyanato compound until use and mix them at the time of use. In addition, a curing catalyst can be used to react the radically polymerizable compound (A) with the polyisocyanato compound. Examples of suitable curing catalysts include organometallic catalysts such as tin octylate, dibutyltin bis(2-ethylhexanoate), dioctyltin bis(2-ethylhexanoate), dioctyltin diacetate, dibutyltin dilaurate, dibutyltin oxide, dioctyltin oxide, and lead 2-ethylhexanoate. When the radical polymerizable resin composition contains the above-mentioned amount of 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 radical polymerizable compound (A).

[0090] <Other components> The radical polymerizable resin composition of the present invention may contain components other than the above-mentioned components, as long as it does not particularly hinder the strength development property and acid resistance of the cured product. Examples of the components that can be contained include, for example, hydraulic inorganic substances such as calcium sulfate and pozzolanic substances, and, for example, admixtures that can impart properties such as setting adjustment, curing acceleration, curing delay, thickening, water retention, defoaming, water repellency, and waterproofing, which can be used in mortar or concrete; fibers made of materials such as metals, polymers, and carbon; pigments; extenders; foaming agents; and admixtures that can be used in mortar or concrete, such as clay minerals such as zeolites.

[0091] <Method for producing radical 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 a metal-containing compound (D) as necessary, and further blending and mixing the radical polymerization initiator (C), the expansion material (B), and the aggregate (I). In the method for producing the radical polymerizable resin composition, it is preferably not to 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 deteriorates. However, the bound water contained in raw materials such as the aggregate (I) has little effect on the compressive strength of the cured product, unlike the added free water. One embodiment of the method for producing a radically polymerizable resin composition of the present invention includes a step (S1) of mixing a radically 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 expansion material (B) with the obtained curable resin product to obtain a radically polymerizable resin composition.

[0092] In the step (S1) of obtaining the resin product (which may also be simply referred to as "step (S1)"), in addition to mixing the metal-containing compound (D) with the radically polymerizable compound (A), a polymerization inhibitor (G), a curing retarder (H), a thiol compound (E), etc. may be further mixed as necessary. In the step (S3) of obtaining the radically polymerizable resin composition (which may also be simply referred to as "step (S3)"), in addition to mixing the expansion material (B) with the curable resin product obtained in the step (S2) of obtaining the curable resin product (which may also be simply referred to as "step (S2)"), an aggregate (I), a water reducing agent (K), a fiber (J), etc. may be further mixed as necessary. As specific examples of the aggregate (I), for example, early strength Portland cement, N90 silica sand, calcium carbonate TM-2, N50 silica sand, N40 silica sand, etc. can be used.

[0093] The radically polymerizable resin composition produced in this way can be cured at room temperature and is excellent in workability, early strength development, and curability. Since it has the expansion material (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.

[0094] <Cured product of the radically polymerizable resin composition> The cured product of the radically polymerizable resin composition of the present invention is obtained by curing the above-mentioned radically polymerizable resin composition. The rate of change in the length of the cured product is not particularly limited and can be adjusted with each component of the radically polymerizable resin composition used. For example, the rate of change in the length of the cured product is preferably 0 to 1000×10 -6 after 3000 hours or more after curing.

[0095] [Method for curing radical polymerizable resin composition] When the radical polymerizable resin composition of the present invention contains a thermal radical polymerization initiator (C-1), as an example of the method for curing the radical polymerizable resin composition of the present invention, a curing 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 can be mentioned. For example, the radical polymerizable resin composition of the present invention is used as a cross-sectional repair material for inorganic structures. Since the radical polymerizable resin composition of the present invention contains the swelling material (B), the obtained cured product does not shrink significantly as in the prior art even after a certain period of time. Examples of the material of the substrate include concrete, asphalt concrete, mortar, brick, wood, metal, and 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.

[0096] When the radical polymerizable resin composition of the present invention contains a photo radical polymerization initiator (C-2), as the timing of photocuring, there are methods such as photocuring after applying the radical polymerizable resin composition to a substrate, and a method of preparing a sheet in which the radical polymerizable resin composition is preliminarily prepolymerized (also referred to as B-stage or prepreg) and then photocuring after sticking the sheet to the substrate.

[0097] As the light source, any light source having a spectral distribution in the photosensitive wavelength range of the photo radical polymerization initiator (C-2) may be used. For example, sunlight, ultraviolet lamps, near-infrared lamps, sodium lamps, halogen lamps, fluorescent lamps, metal halide lamps, LEDs, etc. can be used. Also, two or more photo radical polymerization initiators (C-2) can be used in combination, and a wavelength cut filter can be used for the light source, or a specific wavelength of an LED can be utilized to properly use the wavelengths required for prepolymerization and main polymerization. The wavelength used for prepolymerization is preferably a long wavelength with a low energy level, and in particular, when using near-infrared light, it is easy to control the degree of polymerization. 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 prepolymerization 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. For example, it may be irradiated for 0.01 hour or more, preferably 0.05 hour or more.

Examples

[0098] Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the examples at all.

[0099] <Method for Measuring Curing Shrinkage> For the cured product of the radical polymerizable resin composition of the present invention, 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 preparing the molded body (cured product) was carried out with reference to Appendix A of Japanese Standard JIS A 1129. As the mold, a mold for a specimen of 40×40×160 mm specified in Japanese Standard JIS R 5201 was used. The specimen of the cured product was molded according to the method for making a specimen for strength test specified in 10 of JIS R 5201. After molding, it was 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 about 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 (the start time is set to 0).

[0100] Change amount (negative number: shrinkage amount, positive number: expansion amount) = long side length at elapsed time - long side length at start (0 hour) (160 mm) (1)

[0101] Change rate (negative number: shrinkage rate, positive number: expansion rate) = change amount / long side length at start (0 hour) (160 mm) (2)

[0102] The raw materials used for the production of each radical polymerizable resin composition in the examples and comparative examples are as follows.

[0103] <Radical polymerizable compound (A)> (Synthesis Example 1) "Synthesis of radical polymerizable compound (A-1)" To a 1 L four-neck separable flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, 150.4 g of AER-2603 (bisphenol A type epoxy resin manufactured by Asahi Kasei Corporation: epoxy equivalent 189), 188.4 g of SR-16H (1,6-hexanediol diglycidyl ether manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.), 0.255 g of methylhydroquinone, and 1.5 g of DMP-30 (manufactured by Tokyo Chemical Industry Co., Ltd.: 2,4,6-tris(dimethylaminomethyl)phenol) were added, and the temperature was raised to 110°C. After raising the temperature to 110°C, 172 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) was added dropwise over about 30 minutes and then reacted for about 4 hours. The reaction was terminated when the acid value reached 10 mgKOH / g, and a vinyl ester compound was obtained. Next, as radical polymerizable unsaturated monomers, 256.3 g of dicyclopentenyl oxyethyl 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 to obtain a non-styrene type radical polymerizable compound (A-1) having a viscosity of 280 mPa·s at 25°C and an ester compound component ratio of 60% by mass.

[0104] <Expansion material (B)> As a quicklime-ettringite composite expansion material, Denka Power CSA Type S manufactured by Denka Co., Ltd. was used.

[0105] <Radical polymerization initiator (C)> As the thermal radical polymerization initiator (C-1), cumene hydroperoxide (CHP), manufactured by NOF Corporation, Perk Mill (registered trademark) H-80 was used.

[0106] <Metal-containing compound (D)> As the metal soap (D-1), manganese octylate (manufactured by Toei Chemical Industry Co., Ltd., manganese hexoate, manganese content in the total product amount: 8 mass%, molecular weight: 341.35) was used.

[0107] <Thiol compound (E)> As the secondary thiol compound (E-1), a bifunctional secondary thiol, Karenz MT (registered trademark) BD1 (1,4-bis(3-mercaptobutyryloxy)butane, molecular weight: 299.43) manufactured by Showa Denko K.K. was used.

[0108] <Polymerization inhibitor (G)> Tertiary butyl catechol was used.

[0109] <Curing retarder (H)> 4-H-TEMPO was used.

[0110] <Aggregate (I)> N90 silica sand Calcium carbonate TM-2 Perlite FL-0 N50 silica sand N40 silica sand N70 silica sand

[0111] <Fiber (J)> Chemvest (registered trademark) FDSS-5 A polyolefin multi-branched fiber manufactured by Mitsui Petrochemical Industries, Ltd.

[0112] <Epoxy resin> Bond E208S (main agent) Bond E208S (hardener)

[0113] (Example 1) "Adjustment of Radical Polymerizable Resin Composition" (1) Step (S1): To the radical polymerizable compound (A-1) obtained in Synthesis Example 1, a metal-containing compound (D), a thiol compound (E), a polymerization inhibitor (G), and a curing retarder (H) were thoroughly mixed in the compounding amounts shown in Table 1 to prepare a resin product. (2) Step (S2): To the resin product obtained in Step (S1), a radical polymerization initiator (C) was mixed in the compounding amount shown in Table 1 to prepare a curable resin product. (3) Step (S3): To the curable resin product obtained in Step (S2), an expansion material (B), an aggregate (I), and a fiber (J) were thoroughly mixed in the respective components and compounding amounts shown in Table 1 to obtain the radical polymerizable resin composition of this example.

[0114] The mixing conditions in each step are as follows. Stirrer: HOMOGENIZING DISPER Model 2.5 (manufactured by Primix Corporation) Stirring rotation speed: 3000 - 5000 rpm Temperature: 25 °C

[0115] "Preparation of Cured Product of Radical Polymerizable Resin Composition" The obtained radical polymerizable resin composition was poured into a mold of 40 × 40 × 160 mm, and 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. A cured product of the radical polymerizable resin composition of this example was obtained.

[0116] "Evaluation of Shrinkage / Expansion Properties of Cured Product" Using the above evaluation method, the shrinkage / expansion properties of the cured product of the obtained radical polymerizable resin composition were evaluated. The results are shown in Table 2 and Figure 1.

[0117] (Example 2) A radical polymerizable resin composition was obtained in the same manner as in Example 1, except that 8.0 g of the expansion material (B) was used. Further, a cured product of the radical polymerizable resin composition was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the shrinkage and expansion properties of the obtained cured products were evaluated. The results are shown in Table 2 and FIG. 1.

[0118] (Example 3) A radical polymerizable resin composition was obtained in the same manner as in Example 1, except that 12.0 g of the expansion material (B) was used. Further, a cured product of the radical polymerizable resin composition was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the shrinkage and expansion properties of the obtained cured products were evaluated. The results are shown in Table 2 and FIG. 1.

[0119] "Test of Compressive Strength" For the cured product prepared in Example 3, a test of compressive strength was conducted, and the results are shown in Table 3. The specimens used for the compressive strength were prepared in accordance with JIS A 1138 (Method of Making Concrete in the Laboratory) and JIS A 1132 (Method of Making Specimens for Concrete Strength Tests). Using a mold of φ5 cm × 10 cm, the time until demolding from the mold was set to 24 hours to obtain specimens. The compressive strength of the produced specimens was measured in accordance with JIS A 1108 (Method of Testing Compressive Strength of Concrete) using an Amslab-type concrete compressive strength testing machine (CCM-1000kNI, manufactured by Shimadzu Corporation). The age of the material is as described in Table 3.

[0120] (Comparative Example 1) A radical polymerizable resin composition was obtained in the same manner as in Example 1, except that the expansion material (B) was not used. Further, a cured product of the radical polymerizable resin composition was produced in the same manner as in Example 3. Then, in the same manner as in Example 1, the shrinkage and expansion properties of the obtained cured products were evaluated. The results are shown in Table 2 and FIG. 1. Also, a test of compressive strength was conducted in the same manner as in Example 3, and the results are shown in Table 3.

[0121] (Comparative Example 2) Instead of the radical polymerizable compound (A-1), an epoxy resin composition was obtained in the same manner as in Example 1, except that Bond E208S (main agent), an epoxy resin, and Bond E208S (hardener) (manufactured by Konishi Co., trade name: epoxy resin for civil engineering and construction, main agent: bisphenol A type epoxy resin, hardener: a mixture of modified polyamide amine and polyamide amine) were used. Also, a cured product of the epoxy resin composition was prepared 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 2 and Figure 1. Also, a compression strength test was conducted in the same manner as in Example 3, and the results are shown in Table 3.

[0122] (Comparative Example 3) An epoxy resin composition was obtained in the same manner as in Comparative Example 2, except that the swelling agent (B) was not used. Also, a cured product of the epoxy composition was prepared in the same manner as in Comparative 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 2 and Figure 1. Also, a compression strength test was conducted in the same manner as in Example 3, and the results are shown in Table 3.

[0123]

Table 1

[0124]

Table 2

[0125]

Table 3

[0126] (Example 4) A radical polymerizable resin composition was obtained in the same manner as in Example 3 except that the aggregate (I) shown in Table 4 was used. Also, a cured product of the radical polymerizable resin composition was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the shrinkage and expansion properties of each of the obtained cured products were evaluated. The results are shown in Table 4 and Figure 2. Also, a compression strength test was conducted in the same manner as in Example 3, and the results at the time points of 24 hours and 672 hours are shown in Table 4. Regarding the aggregate (I) and fiber (J) used in Example 4, before mixing with the resin product, the moisture content contained in the aggregate (I) and fiber (J) was measured. The results are shown in Table 4.

[0127] "Method for Measuring Moisture Content" For the aggregate (I) and fiber (J) to be mixed in the radical polymerizable resin composition of the present invention, the measurement of the moisture content contained in the aggregate and fiber was carried out by the following method. (1) Aggregate and fiber mixed at the same mass ratio as the mass ratio of the aggregate (I) and fiber (J) shown in Table 4 were weighed out in a total amount of 20 mg and set in a TG / DTA (TA7000 series simultaneous thermal analyzer STA7200RV, manufactured by Hitachi High-Technologies Corporation). (2) The temperature was raised from 30 °C to 105 °C at a rate of 10 °C / min and held at 105 °C for 60 min. (3) The weight change rate (decrease rate) from 95 °C to 105 °C was calculated.

[0128]

Table 4

[0129] (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 dried under the following absolute dry conditions and then used. Also, a cured product of the radical polymerizable resin composition was produced in the same manner as in Example 1. Then, in the same manner as in Example 1, the shrinkage and expansion properties of each of the obtained cured products were evaluated. The results are shown in Table 4 and Figure 2. Also, a compression strength test was conducted in the same manner as in Example 3, and the results at the 24-hour and 672-hour time points are shown in Table 4. Regarding the aggregate (I) used in Comparative Example 4, in the same manner as in Example 4, before mixing with the resin product, the water content contained in the aggregate was measured. The results are shown in Table 4.

[0130] "Absolutely dry condition" For the aggregate before mixing with the radically polymerizable resin composition, in order to create an absolutely dry aggregate in which the water contained in the aggregate was completely evaporated, the following operations were added. (1) 400 g of the aggregate was placed in an aluminum tray, spread thinly and evenly, and dried in an oven at 105°C. (2) After 48 hours had passed, it was taken out of the oven and used.

[0131] (Comparative Example 5) After mixing the aggregate (I) with the resin product, a radically polymerizable resin composition was obtained in the same manner as in Comparative Example 4, except that 5.00 g of water was added. Also, in the same manner as in Example 1, a cured product of the radically polymerizable resin composition was produced. The compression strength tests were carried out at the 24-hour and 672-hour time points in the same manner as in Example 3, and the results are shown in Table 4. Regarding the aggregate (I) used in Comparative Example 5, in the same manner as in Example 4, before mixing with the resin product, the water content contained in the aggregate was measured. The results are shown in Table 4.

[0132] (Discussion) From the results in Table 2 and Figure 1, according to the radically polymerizable resin composition of the present invention having the expanding agent (B), for the cured product, in Example 1, the shrinkage rate during curing was significantly suppressed, and for the cured products of Examples 2 and 3, it was found that they expanded from the start of curing to a reference length (160 mm) after 24 hours of curing.

[0133] The cured product of the radically polymerizable resin composition of Example 3 had an expansion amount (expansion rate) of +40 μm (+250×10 -6 ) to +131 μm (+819×10 -6 ). However, since the radically polymerizable resin composition of Comparative Example 1 did not contain the expanding agent (B), for the cured product thereof, -48 μm (-300×10 -6) to -80 μm (-500×10 -6 ) of the amount of shrinkage (shrinkage rate) was observed. In Comparative Example 2 using an epoxy resin composition, although it contained the expansion material (B), a large amount of shrinkage almost the same as that of Comparative Example 3 which did not contain it was observed.

[0134] From the results in Table 4 and Figure 2, in Comparative Example 4 where the water content of the aggregate (I) pretreated under absolute dry conditions was 0.00 g, for the cured product, instead of expansion, -250×10 -6 to -350×10 -6 ) of the shrinkage rate was observed. Also, in Comparative Example 5 where water was added after mixing the aggregate (I) into the resin product, the compressive strength of the cured product deteriorated as compared with Example 1 and Comparative Example 4.

Claims

1. A radically polymerizable resin composition containing a radically polymerizable compound (A), an expanding agent (B), a radical polymerization initiator (C), and an aggregate (I), and containing no free water, wherein the expanding agent (B) generates ettringite by a hydration reaction, the aggregate (I) contains bound water, and the radically polymerizable resin composition.

2. The radically polymerizable resin composition according to claim 1, wherein the content of the aggregate (I) is 5 parts by mass to 500 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A).

3. The radically polymerizable resin composition according to claim 1 or 2, wherein the radically polymerizable compound (A) contains a vinyl ester resin and a radically polymerizable monomer.

4. The radically polymerizable resin composition according to any one of claims 1 to 3, wherein the expanding agent (B) contains calcium sulfoaluminate.

5. The radically polymerizable resin composition according to any one of claims 1 to 3, wherein the expanding agent (B) contains at least one selected from the group consisting of an ettringite-based expanding agent and a quicklime-ettringite composite expanding agent, the ettringite-based expanding agent is an expanding agent having calcium sulfoaluminate as an active ingredient, the quicklime-ettringite composite expanding agent is a composite expanding agent containing a quicklime-based expanding agent and an ettringite-based expanding agent, and the quicklime-based expanding agent is an expanding agent having free quicklime as an active ingredient.

6. The radically polymerizable resin composition according to any one of claims 1 to 5, wherein the radical polymerization initiator (C) is a hydroperoxide (ROOH).

7. The radically polymerizable resin composition according to any one of claims 1 to 6, further containing a metal-containing compound (D) and a thiol compound (E).

8. The radically 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 with respect to 100 parts by mass of the radically polymerizable compound (A).

9. The radically polymerizable resin composition according to any one of claims 1 to 8, wherein the radical polymerization initiator (C) is 0.1 parts by mass to 10 parts by mass with respect to 100 parts by mass of the radically polymerizable compound (A).

10. A cured product of the radically polymerizable resin composition according to any one of claims 1 to 9.

11. The change rate of the length of the cured product is 0 to 1000×10 after 3000 hours from the curing －６ The cured product according to claim 10, which is such.

12. A method for producing a radically polymerizable resin composition, comprising a mixing step of mixing a radically polymerizable compound (A), an expanding material (B), a radical polymerization initiator (C), and an aggregate (I). The expanding material (B) produces ettringite by a hydration reaction. The method for producing a radically polymerizable resin composition, wherein the aggregate (I) contains bound water.

13. The method for producing a radically polymerizable resin composition according to claim 12, which does not include a step of adding water.

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