TW202138399A - Radical-polymerizable resin composition and cured object obtained therefrom - Google Patents

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

Free radical polymerizable resin composition and its hardened product

The present invention relates to a radical polymerizable resin composition and its cured product.

When a general liquid vinyl monomer is used for polymerization, large shrinkage occurs. When vinyl monomers are used in industrial products, deformation problems arise due to the shrinkage. Therefore, to create a resin with a small shrinkage rate during polymerization is of great industrial significance.

Radical polymerizable resin compositions such as unsaturated polyester resins or vinyl ester resins (epoxy acrylate) generally shrink when they are cured. Most of the monomers "styrene" or "methyl methacrylate" shown in Table 1 of Non-Patent Document 1 are used as monomers. Therefore, unsaturated polyester resins in general formulations are accompanied by 8 to The volume shrinkage of about 12%, vinyl ester resin will be accompanied by a volume shrinkage of about 8-10%. Even when compared with the so-called 3-6% volume shrinkage of general epoxy resins, this value is still quite large. Therefore, the use of unsaturated polyester resins or vinyl ester resins in industrial applications is prevented, or the entry into various industries and applications other than this is prevented.

As a method to solve this problem, Patent Document 1 uses polystyrene beads as a low-shrinkage material to try to reduce manufacturing man-hours or shorten manufacturing time, and it can be manufactured with excellent low-shrinkage, dimensional stability and surface Smooth, low-shrinkage unsaturated polyester resin composition.

In addition, in Patent Document 2, by blending an AB-type block copolymer into an unsaturated polyester resin composition, a low-shrinkage unsaturated polyester resin composition can be obtained, which can be produced with a low shrinkage upon curing. And it is a molded body with excellent heat resistance.

Furthermore, in Patent Document 3, by mixing an AB-type block copolymer (vinyl acetate-styrene series) composed of segments of A and B with an unsaturated polyester resin, and fine silicic acid at room temperature or medium During warm molding, it is possible to obtain a low-shrinkage unsaturated polyester resin composition with a large low-shrinkage effect and high water resistance.

In addition, in a conventional hydraulic composition (for example, cement containing Portland cement, etc.), concrete made by mixing an expansive material as a mixed material is sometimes referred to as "expandable concrete." According to the Japanese JIS standard, although the hydrate of the expansion material is formed by curing in water for 7 days to increase the volume, the expansion effect in the air cannot be confirmed. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-315198 [Patent Document 2] Japanese Patent No. 2794802 [Patent Document 3] Japanese Patent Laid-Open No. 05-222282 [Non-Patent Literature]

[Non-Patent Document 1] Takeshi Endo, Is volume shrinkage during polymerization unavoidable, Polymers, Vol. 27, February (1978), pages 108-111.

[The problem to be solved by the invention]

In the conventional radically polymerizable resin composition, in order to create a resin with a low shrinkage rate, a single formulation of a thermoplastic resin such as polystyrene, or a block copolymer of two or more types is used. Most of these functions as "anti-shrinkage materials". In addition, these resin compositions are based on the knowledge that offsets the thermal expansion of thermoplastic resins and the curing shrinkage of unsaturated polyester resins caused by curing heat, and their uses are mostly limited to sheet molding compounds (SMC) or blocks. The use of phantom plastic (BMC), etc., which can be heated and formed above the medium temperature range.

The present invention is an invention made in view of the above-mentioned past situation, and its object is to provide a radical polymerizable resin composition with a small shrinkage rate, which does not introduce an anti-shrinking material but an expansion material, thereby being not limited The molding method, use temperature, application, etc., the resin composition can expand at a certain ratio when it is cured, and then it is stable, so the shrinkage rate is small. In addition, an object is to provide a cured product of a radical polymerizable resin composition that does not cause a decrease in strength or the like after molding. [Means to solve the problem]

That is, the present invention is represented by the following [1] to [13].

[1]. A radical polymerizable resin composition containing: a radical polymerizable compound (A), an expansion material (B), a radical polymerization initiator (C) and aggregate (I), and does not contain free Water, wherein the aforementioned aggregate (I) contains bound water. [2]. The radical polymerizable resin composition according to [1], wherein the content of the aggregate (I) is 5 parts by mass to 500 parts by mass relative to 100 parts by mass of the radical polymerizable compound (A) share. [3]. The radical polymerizable resin composition according to [1] or [2], wherein the radical polymerizable compound (A) contains a vinyl ester resin and a radical polymerizable monomer. [4]. The radical polymerizable resin composition of any one of [1] to [3], wherein the expansion material (B) includes at least 1 selected from the group consisting of lime and calcium sulfoaluminate kind. [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], which further contains 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 expansion material (B) is 0.3 relative to 100 parts by mass of the radical polymerizable compound (A) Parts by mass ~ 30 parts by mass. [8]. The radical polymerizable resin composition according to any one of [1] to [7], wherein, with respect to 100 parts by mass of the radical polymerizable compound (A), the radical polymerization initiator ( C) is 0.1 parts by mass to 10 parts by mass. [9]. A cured product of the radical polymerizable resin composition according to any one of [1] to [8]. [10]. The cured product of [9], wherein the rate of change of the length of the cured product is 0～1000×10 ^-6 after 3000 hours after curing. [11]. A method for producing a radical polymerizable resin composition, including the following steps: mixing a radical polymerizable compound (A), an expansion material (B), a radical polymerization initiator (C), and aggregate The mixing step of (I), wherein the aforementioned aggregate (I) contains bound water. [12]. The method for producing a radical polymerizable resin composition as in [11], which does not include the step of adding water. [13]. A radically polymerizable resin composition, which is a radically polymerizable resin composition obtained by the method for producing a radically polymerizable resin composition such as [11] or [12], which contains free radical Base polymerizable compound (A), expansion material (B), radical polymerization initiator (C) and aggregate (I). [Effects of the invention]

According to the present invention, it is possible to provide a radical polymerizable resin composition and a cured product of the radical polymerizable resin composition. The radical polymerizability of the radical polymerizable resin composition and the cured product of the radical polymerizable resin composition is reduced by the reduction of the free volume of the liquid component during curing. Add an appropriate amount of expansion material to the resin composition, so that the strength can be maintained while suppressing shrinkage.

[Best form to implement the invention]

The present invention will be described in detail below.

(Free radical polymerizable resin composition) The radical polymerizable resin composition of one embodiment of the present invention contains: a radical polymerizable compound (A), an expansion material (B), a radical polymerization initiator (C), and an aggregate (I), and Does not contain free water. The aforementioned aggregate (I) contains bound water. Here, the so-called "bound water" is a concept used to distinguish it from free water. As described in the "Measuring Method of Water Content" described later, in the TG/DTA experiment, water calculated from the weight change rate (decrease rate) from 95°C to 105°C. For example, the crystal water contained in the aggregate (I), the adsorbed water strongly adsorbed to the internal micropores or the surface of the aggregate (I), etc. are mentioned. In addition, the so-called "free water" includes, for example, water added in the step of adding water in the step of producing a radically polymerizable resin composition. "The radical polymerizable resin composition does not contain free water, and the aggregate (I) contains bound water" means a radical polymerizable resin composition obtained by a production method that does not add water. It means that the aggregate (I) is preferably used in the production step of the radical polymerizable resin composition without pre-treatment under absolute drying conditions described later, and in the production step, by not including The meaning of the radical polymerizable resin composition obtained by the manufacturing method of the step of adding water. For example, the aggregate (I) etc. which are generally commercially available can be used as it is. Or in order to more stabilize the amount of bound water contained, a pretreatment of storing the aggregate (I) for a certain period of time under a certain temperature and humidity may also be performed. The moisture content of the bound water contained in the aggregate (I) can be confirmed by the measurement method described later, so the temperature can be appropriately determined according to the type of aggregate (I) used or the moisture content at the time of acquisition , Humidity and processing time.

＜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 radically polymerizable compound (A) refers to a compound that has an ethylenically unsaturated group in the molecule and undergoes a polymerization reaction by radicals. Examples of the radically polymerizable compound (A) include vinyl ester resins (epoxy (meth)acrylate resins), unsaturated polyester resins, polyester (meth)acrylate resins, and urethanes. (Meth)acrylate resins, (meth)acrylate resins, radically polymerizable unsaturated monomers, and mixtures of the aforementioned resins and radically polymerizable unsaturated monomers, etc., among which are selected from vinyl ester resins, One or more of unsaturated polyester resins and mixtures with these radically polymerizable unsaturated monomers are preferred. Among them, vinyl ester resins are more preferred. In addition, in this specification, the so-called "(meth)acrylate" means "acrylate or methacrylate".

[Vinyl Ester Resin] As the vinyl ester resin, what is obtained by reacting an epoxy resin and an unsaturated monobasic acid can be used.

Examples of the aforementioned epoxy resins include bisphenol type epoxy resins, biphenyl type epoxy resins, novolac type epoxy resins, trisphenol methane type epoxy resins, aralkyl diphenol type epoxy resins, and naphthalene type epoxy resins. Epoxy resin, aliphatic epoxy resin, etc. These systems can be used alone or in combination of plural kinds.

Examples of phenolic epoxy resins include those obtained by reacting bisphenols with epichlorohydrin and/or methylepichlorohydrin; condensation of glycidyl ether of bisphenol A and the aforementioned bisphenols It is obtained by reacting with epichlorohydrin and/or methyl epichlorohydrin. Examples of bisphenols include bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, and the like. Examples of biphenyl type epoxy resins include those obtained by reacting biphenyl with epichlorohydrin and/or methyl epichlorohydrin.

Examples of novolak-type epoxy resins include those obtained by reacting phenol novolac or cresol novolac with epichlorohydrin and/or methylepichlorohydrin. Examples of the trisphenolmethane type epoxy resin include those obtained by reacting trisphenolmethane, tricresolmethane, epichlorohydrin and/or methylepichlorohydrin, and the like. As an aralkyl diphenol type epoxy resin, the thing obtained by reacting an aralkyl phenol with epichlorohydrin and/or methyl epichlorohydrin, etc. are mentioned, for example.

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

As aliphatic epoxy resins, alicyclic epoxy resins, alicyclic glycol diglycidyl ether epoxy resins, aliphatic glycol diglycidyl ether epoxy resins, poly(oxygen Alkyl) glycol diglycidyl ether type epoxy resin and the like.

As an alicyclic type epoxy resin, alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, etc. are mentioned, for example. Specific examples of alicyclic glycol diglycidyl ether include, for example, cyclohexane dimethanol diglycidyl ether, dicyclopentene glycol diglycidyl ether, diglycidyl ether of hydrogenated bisphenol A, and dihydroxy terpene Diglycidyl ethers of alicyclic glycols having 3 to 20 carbon atoms (preferably 6 to 12 carbon atoms, more preferably 7 to 10 carbon atoms) such as diglycidyl ether. Among these, "Denacol EX-216L" of Nagasechemtex Co., Ltd. is a commercially available product of cyclohexanedimethanol diglycidyl ether.

Specific examples of aliphatic glycol diglycidyl ether include 1,6-hexanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, ethylene glycol diglycidyl ether, and propylene glycol diglycidyl ether. Diglycidyl ethers of aliphatic diols such as glycidyl ether and the like 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). Among them, as commercial products of 1,6-hexanediol diglycidyl ether, there are "Denacol EX-212L" of Nagasechemtex Co., Ltd., "SR-16H" or "SR" of Sakamoto Pharmaceutical Co., Ltd. -16HL", "Epogosey (registered trademark) HD" of Yokkaichi Synthetic Co., Ltd., etc. In addition, as a commercially available product of 1,4-butanediol diglycidyl ether, there is "Denacol EX-214L" of Nagasechemtex Co., Ltd.

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

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

The aforementioned epoxy resin may also be a diglycidyl ester such as dimer acid diglycidyl ester and hexahydrophthalic diglycidyl ester. Moreover, as said epoxy resin, the epoxy resin which has the oxazolidone ring obtained by reacting the said epoxy resin and diisocyanate is mentioned. As a specific example of the epoxy resin having an oxazolidinone ring, Araldite (registered trademark) AER4152 manufactured by Asahi Kasei Epoxy and the like can be given.

Well-known ones can be used for the said unsaturated monobasic acid system, for example, (meth)acrylic acid, crotonic acid, cinnamic acid etc. are mentioned. In addition, a reaction product of a compound having one hydroxyl group and one or more (meth)acryloyl groups and a polybasic acid anhydride can also be used. In this specification, the so-called "(meth)acrylic acid" refers to one or both of "acrylic acid and methacrylic acid", and the so-called "(meth)acrylic acid group" refers to "acrylic acid group and methacrylic acid group". "Methacryl" means one or both parties. As the aforementioned polybasic acid, a known substance for increasing the molecular weight of the aforementioned epoxy resin can be used. Examples include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer Acid, ethylene glycol/2 mol maleic anhydride adduct, polyethylene glycol/2 mol maleic anhydride adduct, propylene glycol/2 mol maleic anhydride adduct, polypropylene glycol/2 mol horse Acid anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16-(6-ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyl Dodecane) dicarboxylic acid, carboxyl-terminal butadiene/acrylonitrile copolymer (trade name Hycar CTBN), etc.

[Unsaturated polyester resin] As the unsaturated polyester resin, an unsaturated dibasic acid and a dibasic acid component of a saturated dibasic acid contained as needed and a polyhydric alcohol component can be used. As said unsaturated dibasic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc. are mentioned, for example, These systems may be used individually or in combination of 2 or more types. As the aforementioned saturated dibasic acid, for example, aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, isosebacic acid, phthalic acid, phthalic anhydride, halogenated Phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid Aromatic dibasic acids such as carboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyldicarboxylic acid and these dialkyl esters, halogenated saturated dicarboxylic acids These systems may be used alone or in combination of two or more of them.

The aforementioned polyol is not particularly limited, and examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1 ,5-Pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl 1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5 -Pentylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexane Diols such as diol, 1,4-cyclohexanedimethanol, terephthalic methanol, dicyclohexyl-4,4'-diol, 2,6-naphthalenediol, 2,7-naphthalenediol, etc.; Dihydric phenol represented by hydrogenated bisphenol A, cyclohexane dimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. and epoxy represented by propylene oxide or ethylene oxide Dihydric alcohols such as adducts of alkanes; Trivalent or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.

As long as the effect of the present invention is not impaired, the unsaturated polyester series may be modified by a dicyclopentadiene series compound. Regarding the modification method by dicyclopentadiene-based compounds, for example, after obtaining the addition product of dicyclopentadiene and maleic acid (cydecanol monomalate), this is used as a monobasic acid and introduced into the dicyclopentadiene skeleton. Well-known methods such as the method. The vinyl ester resin or unsaturated polyester resin used in the present invention can introduce an oxidative polymerization (air curing) group such as an allyl group or a benzyl group. The method of introduction is not particularly limited, and for example, the addition of an oxidative polymer group-containing polymer or the condensation of a compound having a hydroxyl group and an allyl ether group, for allyl glycidyl ether, 2,6-diglycidyl benzene A method of adding a reaction product of a compound having a hydroxyl group and an allyl ether group and an acid anhydride to the base allyl ether, etc. In addition, the so-called oxidative polymerization (air curing) in the present invention refers to the peroxide formed by oxidation of the methylene bond between the ether bond and the double bond, which can be seen in, for example, allyl ether groups. Cross-links that accompany the formation and decomposition.

[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 (meth)acrylic acid with a polyhydric carboxylic acid and a polyhydric alcohol (specifically, such as polyethylene terephthalate) can be used. A resin obtained by reacting hydroxyl groups at both ends of a glycol ester, etc.). In addition, as the urethane (meth)acrylate resin, for example, the hydroxyl groups or isocyanate groups at both ends of the polyurethane obtained by reacting (meth)acrylic acid with an isocyanate and a polyol can be used. The resin obtained by the reaction. As the (meth)acrylate resin, for example, a poly(meth)acrylic resin having one or more substituents selected from a hydroxyl group, an isocyanate group, a carboxyl group, and an epoxy group, or a (meth)acrylic resin having a hydroxyl group can be used. Acrylics are resins obtained by reacting a monomer having the aforementioned substituent with the substituent of a (meth)acrylate polymer.

[Free radical 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 system may be used alone, but it is preferable to use a mixture of a radically polymerizable unsaturated monomer and at least one of the aforementioned vinyl ester resin and the aforementioned unsaturated polyester resin. . There are no particular restrictions on the aforementioned radically polymerizable unsaturated monomer, and those having a vinyl group or a (meth)acrylic acid group are preferred. Specific examples of monomers having vinyl groups include styrene, p-chlorostyrene, vinyl toluene, α-methylstyrene, dichlorostyrene, divinylbenzene, tert-butylstyrene , Vinyl acetate, diallyl phthalate, triallyl isocyanate, etc.

As a specific example of the monomer which has a (meth)acryl group, (meth)acrylate etc. are mentioned. Specifically, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, iso-butyl (meth)acrylate, tert-(meth)acrylate Butyl ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate Ester, tridecyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentene oxide (meth)acrylate Ethyl ethyl, 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 Base ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol monobutyl ether (meth)acrylate, diethylene glycol monohexyl ether (meth) Acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, neopentyl glycol di(meth)acrylate, PTMG dimethacrylate, 1,3-butanediol di( Meth) acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2-hydroxy-1,3-dimethylpropeneoxypropane, 2,2-Bis[4-(methacryloylethoxy)phenyl]propane, 2,2-bis[4-(methacryloyloxy·diethoxy)phenyl]propane, 2 ,2-Bis[4-(methacryloxy·polyethoxy)phenyl]propane, tetraethylene glycol diacrylate, bisphenol AEO modified (n=2) diacrylate, isocyanurea Acid EO modification (n=3) diacrylate, pentaerythritol diacrylate monostearate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecyl (meth)acrylate, Ginseng (2-hydroxyethyl) isocyanuric acid acrylate and so on.

Furthermore, as polyfunctional (meth)acrylates, for example, ethylene glycol di(meth)acrylate, 1,2-propylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, Base) acrylate, 1,4-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, etc. Alcohol di(meth)acrylate; diethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, triethylene glycol (meth)acrylate, tetraethylene glycol di(meth)acrylate ) Polyoxyalkylene glycol di(meth)acrylate such as acrylate, polyethylene glycol (meth)acrylate; trimethylolpropane di(meth)acrylate, glycerol di(meth) Acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerol tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate Esters, dipentaerythritol hexa(meth)acrylate, etc.

Furthermore, the following compounds can also be used as a radically polymerizable unsaturated monomer. Specifically, divinylbenzene, diallyl phthalate, triallyl phthalate, triallyl cyanurate, triallyl isocyanate, (meth)acrylic acid Allyl ester, diallyl fumarate, allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl ether, vinyl benzyl (2- Ethylhexyl) ether, vinylbenzyl (β-methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzylcyclohexyl ether, vinylbenzyl (β-methoxymethyl) ether -Phenoxyethyl) ether, vinylbenzyl biscyclopentenyl ether, vinylbenzyl biscyclopentenyloxy ethyl ether, vinylbenzyl biscyclopentenyl methyl ether, divinylbenzyl ether . Moreover, in addition to the above, dicyclopentenyl (meth)acrylate, dicyclopentenoxyethyl (meth)acrylate, and the like can be mentioned. These systems may be used alone or in combination of two or more kinds.

Although the radically polymerizable unsaturated monomer can be used to reduce the viscosity of the radically polymerizable resin composition of the present invention, and improve the hardness, strength, chemical resistance, water resistance, etc., if the content is too large, it will cause hardened products. Circumstances of degradation or environmental pollution. Therefore, the content of the radically polymerizable unsaturated monomer is preferably 90% by mass or less in the radically polymerizable compound (A).

The radically polymerizable compound (A) can remain synthetic vinyl ester resin, unsaturated polyester resin, polyester (meth)acrylate resin, urethane (meth)acrylate resin and (meth) Catalyst or polymerization inhibitor used in acrylic 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; trimethylphosphine, Phosphorus compounds such as triphenylphosphine, etc. As a polymerization inhibitor, hydroquinone, methylhydroquinone, phenothiazine, etc. are mentioned, for example. When the catalyst or polymerization inhibitor remains in the radically polymerizable compound (A), the amount is preferably 0.001 to 2 parts by mass relative to 100 parts by mass of the total of the vinyl ester resin and the unsaturated polyester resin.

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, and more preferably 20 to 60% by mass %, and more preferably 25-40% by mass. When the content of the radical polymerizable compound (A) in the radical polymerizable resin composition is within the aforementioned range, the hardness of the cured product will further increase.

＜Expansion material (B)＞ The expansive material (B) used in the present invention may be any expansive material that satisfies the Japanese Industrial Standards JIS A 6202 "Expansive Material for Concrete", which is generally used as an expansive material for concrete. Any expansion can be used. Material. Specifically, calcium hydroxide or entringite can be produced by a hydration reaction. As a preferable expansion material, (1) an expansion material that uses free quicklime as an effective ingredient (quicklime-based expansion Material), (2) Expansive material (ettringite-based expansive material) using calcium sulfoaluminate as an effective ingredient, (3) Quicklime-Ettringite composite expansive material, etc.

As specific examples of the quicklime-based expansion material, Pacific HYPER EXPAN-K, Pacific HYPER EXPAN-M, Pacific Expan-K, Pacific Expan-M, and Pacific N-EX manufactured by TAIHEIYO MATERIALS can be mentioned. Specific examples of ettringite-based expansion materials include Denca CSA #10 and Denca CSA #20 manufactured by Denca. Specific examples of the quicklime-ettringite composite expansion material include Denca power CSA Type S, Denca power CSA Type R, and Denca power CSA Type T manufactured by Denca.

With respect to 100 parts by mass of the radically polymerizable compound (A), the content of the expandable material (B) of the present invention is preferably 0.3-30 parts by mass, more preferably 0.5-25 parts by mass, and more preferably 0.7- 20 parts by mass, most preferably 1-16 parts by mass. When the content of the expansion material (B) is 30 parts by mass or less, when the radical polymerizable resin composition is cured, the expansion rate will not exceed the elongation of the resin. Conversely, if it is 0.3 parts by mass or more, the radical polymerizable compound (A) will exhibit swelling performance. In addition, these expansion materials (B) may be used alone, or two or more of them may be mixed and used.

＜Free radical polymerization initiator (C)＞ The radical polymerizable resin composition of the present invention contains a radical polymerization initiator (C) as a curing agent. Examples of the radical polymerization initiator (C) include a thermal radical polymerization initiator (C-1) and a photo radical polymerization initiator (C-2). Among them, the thermal radical polymerization initiator (C-1) is preferred. Examples of the thermal radical polymerization initiator (C-1) include diacyl peroxide systems such as benzyl peroxide, peroxy ester systems such as tert-butyl peroxybenzoate, Hydroperoxides such as cumene hydroperoxide (CHP), diisopropylbenzene hydroperoxide, tert-butyl hydroperoxide, p-menthane hydroperoxide, dicumyl peroxide Dialkyl peroxides, methyl ethyl ketone peroxides, methyl ethyl ketone peroxides such as acetone peroxide, peroxide ketals, alkyl peroxide esters, and percarbonic acid Organic peroxides such as esters. Among them, hydroperoxide-based organic peroxides (ROOH) (also referred to as hydroperoxides (ROOH)) are preferred, among which PERCUMYL (registered trademark) H-80 manufactured by NOF Corporation Cumene hydroperoxide (CHP) is preferred.

Examples of the photoradical polymerization initiator (C-2) include benzoin-based ethers such as benzoin alkyl ether, benzophenone, benzyl, and methyl phthalate. The benzophenone series, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2- Acetophenone series such as methylpropiophenone and 1,1-dichloroacetophenone, thioxanthone series such as 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Wait.

Examples of photoradical polymerization initiators (C-2) having photosensitivity from ultraviolet light to visible light range include acetophenone series, benzyl ketal series, and (bis)phosphine oxide series. Well-known initiators include, specifically, the combination of 2-hydroxy-2-methyl-1-phenylpropan-1-one (trade name: Darocur1173, manufactured by Ciba Specialty Chemicals (stock)) and bis(2,6- Dimethoxybenzyl)-2,4,4-trimethylpentyl phosphine oxide (manufactured by Ciba Specialty Chemicals Co., Ltd.) is a trade name of Irgacure -1700 (Ciba Specialty Chemicals (stock); 1-hydroxycyclohexyl phenyl ketone (trade name: Irgacure-184, Ciba Specialty Chemicals (stock)) and bis(2,6-dimethoxybenzyl)- 2,4,4-Trimethylpentyl phosphine oxide (manufactured by Ciba Specialty Chemicals (stock)) is mixed with a trade name of Irgacure-1800 (manufactured by Ciba Specialty Chemicals (stock)) at a ratio of 75%/25%, and 50% %/50% to mix the trade name Irgacure-1850 (manufactured by Ciba Specialty Chemicals (stock)); bis(2,4,6-trimethylbenzyl)phenylphosphine oxide (trade name: Irgacure -819, Ciba Specialty Chemicals (stock)); 2,4,6-trimethylbenzyl diphenylphosphine oxide (trade name Lucirin TPO, BASF (stock)); 2-hydroxy-2 -Methyl-1-phenylpropan-1-one (trade name: Darocur1173, manufactured by Ciba Specialty Chemicals (Stock)) and 2,4,6-trimethylbenzyl diphenylphosphine oxide (trade name Lucirin TPO, BASF (shares) system) are mixed with a 50%/50% trade name Darocur4265, etc.

As the photoradical polymerization initiator (C-2) having photosensitivity in the visible light region, camphorquinone, benzyltrimethylbenzyldiphenylphosphine oxide, methylthioxanthone, and Cyclopentyl diethyl titanium-bis(pentafluorophenyl) and the like. These radical polymerization initiators (C) may be used alone or in combination of two or more kinds. For the purpose of assisting the main reaction of the thermal curing and light curing, the other reaction can be used, and the thermal radical polymerization initiator (C-1) and the photo radical polymerization initiator (C -2).

In addition, depending on the molding conditions, organic peroxides/colorants, diphenyliodonium salts/colorants, imidazole/ketone compounds, hexaallylbiimidazole compounds/hydrogen-donating compounds, mercaptobenzothiazole/thiol It is used in a composite form of pyridinium salt, metal aromatic hydrocarbon/cyanine pigment, hexaallyl biimidazole/radical generator, etc.

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

＜Compounds containing metals (D)＞ The radical polymerizable resin composition of the present invention may contain one or more metal-containing compounds (D ) As a hardening accelerator. Furthermore, 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. In addition, the metal complex (D-2) having a β-diketone skeleton in the present invention refers to a complex formed by coordination of a metal element with a compound having a structure in which one carbon atom exists between two carbonyl groups Things.

The content of the metal-containing compound (D) in the radical polymerizable resin composition in terms of metal components is preferably 0.0001 to 5 parts by mass relative to 100 parts by mass of the aforementioned radical polymerizable compound (A), and Preferably it is 0.001 to 4 parts by mass, more preferably 0.005 to 3 parts by mass. When the content of the metal-containing compound (D) in terms of the metal component is within the aforementioned range, it hardens quickly even in water and in a humid environment.

[Metal soap (D-1)] The long-chain fatty acid in the metal soap (D-1) is not particularly limited. For example, fatty acids having 6 to 30 carbon atoms are preferred. Specifically, it is octanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, and octadecanoic acid such as heptanoic acid and 2-ethylhexanoic acid. Chain or cyclic saturated fatty acids, oils such as alkanoic acid, arachidic acid, behenic acid, tetracosanoic acid, hexadecanoic acid, octadecanoic acid, triacontanic acid, naphthenic acid, etc. Unsaturated fatty acids such as acid, linoleic acid and hypolinoleic acid are preferred. Moreover, rosin acid, linseed oil fatty acid, soybean oil acid, tall oil acid, etc. can also be mentioned.

In addition, there are no particular restrictions on the organic acids other than the long-chain fatty acids in the metal soap (D-1), as long as they are weak acid compounds having a carboxyl group, a hydroxyl group, or an enol group and are soluble in an organic solvent. Examples of compounds having a carboxyl group include carboxylic acids such as formic acid, acetic acid, and oxalic acid; hydroxy acids such as citric acid, bile acid, sugar acid, 12-hydroxystearate, hydroxycinnamic acid, and folic acid; Amino acids such as amino acids; aromatic acids such as benzoic acid and phthalic acid. In addition, examples of compounds having a hydroxyl group and enol group include ascorbic acid, alpha acid, imidic acid, erythorbic acid, crotonic acid, kojic acid, squaric acid, sulfinic acid, teichoic acid, dehydroacetic acid, Delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, phosphonic acid, etc. Among them, long-chain fatty acids are preferred, chain or cyclic saturated fatty acids with 6 to 16 carbon atoms, or unsaturated fatty acids with 6 to 16 carbon atoms are more preferred, and caprylic acid, 2 -Ethylhexanoic acid and naphthenic acid are more preferable, and among them, 2-ethylhexanoic acid and naphthenic acid are more preferable.

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

As specific metal soaps (D-1), zirconium octoate, manganese octoate, cobalt octoate, bismuth octoate, calcium octoate, zinc octoate, vanadium octoate, lead octoate, tin octoate, cobalt naphthenate, copper naphthenate, naphthenate Barium octoate, bismuth octoate, calcium naphthenate, lead naphthenate, and tin naphthenate are preferred. Among them, zirconium octoate, manganese octoate, cobalt octoate, bismuth octoate, calcium octoate, lead octoate, tin octoate, Bismuth naphthenate, calcium naphthenate, lead naphthenate and tin naphthenate are more preferred. Among them, manganese octoate and cobalt octoate are particularly preferred. As a specific example of cobalt octoate, Hexoate Cobalt manufactured by Toei Chemical Co., Ltd. (the content of cobalt in the total amount of the product is 8% by mass, and the molecular weight is 345.34). In addition, as a specific example of manganese octoate, Hexoate Manganese manufactured by Toei Chemical Co., Ltd. (manganese content of 8% by mass and molecular weight of 341.35 in the entire product) can be cited.

[Metal complex with β-diketone skeleton (D-2)] A metal complex (D-2) having a β-diketone skeleton (hereinafter also referred to as "metal complex (D-2)"). Examples of metal complexes (D-2) include those formed by complexation with metals such as acetone, ethyl acetate, benzylacetone, etc., and these metal complexes (D-2) It also exhibits the same function as the aforementioned metal soap (D-1). Examples of the metal element constituting the metal complex (D-2) include the same metal elements as the aforementioned metal soap (D-1).

As specific metal complexes (D-2), zirconium acetone, vanadium acetone, cobalt acetone, titanium acetone, dibutoxy bis(acetone) titanium, iron acetone And ethyl cobalt acetylacetone are preferred, among which zirconium acetylacetonate, titanium acetylacetonate, and titanium dibutoxybis(acetacetone) are more preferred.

＜Thiol compound (E)＞ The radically polymerizable resin composition of the present invention may contain one or more thiol compounds (E) selected from a secondary thiol compound (E-1) and a tertiary thiol compound (E-2). In the present invention, it is presumed that the thiol compound (E) has a function as a hardening accelerator, and also has a function of coordinating near the metal of the metal-containing compound (D) to prevent passivation of the metal due to water. The thiol compound (E) used in the present invention, as long as it has one or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule (hereinafter, sometimes referred to as "secondary mercapto" and "tertiary mercapto", respectively) Sulfhydryl ") is sufficient, and there is no particular limitation. However, from the viewpoint of rapid hardening even in water and the viewpoint of preventing the passivation of the metal of the metal-containing compound (D) due to water, the molecular Among them, polyfunctional thiols of compounds having two or more secondary or tertiary mercapto groups are preferred, and among them, bifunctional thiols of compounds having two secondary or tertiary mercapto groups in the molecule are preferred. In addition, the secondary thiol compound (E-1) is more preferable than the tertiary thiol compound (E-2). Here, the "multifunctional thiol" refers to a thiol compound in which the functional group has two or more mercapto groups, and the so-called "difunctional thiol" refers to a sulfur compound having two or more functional groups. The meaning of alcohol compound.

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

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

[Level 2 mercaptan compound (E-1)] When the thiol compound (E) having the structure represented by the aforementioned formula (Q) is a secondary thiol compound (F1), as the specific example, 3-mercaptobutyric acid and 3-mercaptophthalic acid can be mentioned. (1-mercaptoethyl) ester, 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 ginseng (3-mercaptobutyrate), Trimethylolpropane ginseng (3-mercaptobutyrate), pentaerythritol 4 (3-mercaptobutyrate), dipentaerythritol (3-mercaptobutyrate) Butyrate), ethylene glycol bis(2-mercaptopropionate), propylene glycol bis(2-mercaptopropionate), diethylene glycol bis(2-mercaptopropionate), butanediol bis(2-mercaptopropionate) Mercaptopropionate), octanediol bis(2-mercaptopropionate), trimethylolpropane (2-mercaptopropionate), pentaerythritol 4 (2-mercaptopropionate), dipentaerythritol (2 -Mercaptopropionate), ethylene glycol bis(4-mercaptovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol Bis (4-mercaptovalerate), trimethylolpropane (4-mercaptovalerate), pentaerythritol 4 (4-mercaptovalerate), dipentaerythritol (4-mercaptovalerate), ethylene disulfide Alcohol bis(3-mercaptovalerate), propylene glycol bis(3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), caprylic acid Diol bis(3-mercaptovalerate), trimethylolpropane (3-mercaptovalerate), pentaerythritol 4 (3-mercaptovalerate), dipentaerythritol (3-mercaptovalerate), Hydrogenated bisphenol A bis(3-mercaptobutyrate), bisphenol A dihydroxy ethyl ether-3-mercaptobutyrate, 4,4'-(9-fluorenylene) bis(2-phenoxyethyl) Bis(3-mercaptobutyrate)), ethylene glycol bis(3-mercapto-3-phenylpropionate), propylene glycol bis(3-mercapto-3-phenylpropionate), diethylene glycol bis(3-mercapto-3-phenylpropionate) (3-mercapto-3-phenylpropionate), butanediol bis(3-mercapto-3-phenylpropionate), octanediol bis(3-mercapto-3-phenylpropionate), Trimethylolpropane ginseng (3-mercapto-3-phenylpropionate), ginseng-2-(3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol four (3- Mercapto-3-phenylpropionate), dipentaerythritol (3-mercapto-3-phenylpropionate) and the like.

Among the secondary mercaptan compounds (E-1), commercially available products of compounds having two or more secondary mercapto groups in the molecule include 1,4-bis(3-mercaptobutanoyloxy)butane (Manufactured by Showa Denko Corporation, Karenz MT (registered trademark) BD1), pentaerythritol 4 (3-mercaptobutyrate) (manufactured by Showa Denko Corporation, Karenz MT (registered trademark) PE1), 1,3,5- Ginseng [2-(3-mercaptobutyroxyethyl)]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) NR1), trimethylolethane ginseng (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd., TEMB), trimethylolpropane ginseng (3-mercaptobutyrate) (Showa) It is preferable to use one or more of these, manufactured by Denko Corporation, TPMB). Among them, 1,4-bis(3-mercaptobutoxy)butane (manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) BD1) is preferred.

[Level 3 mercaptan compound (E-2)] When the thiol compound (E) having the structure represented by the aforementioned formula (Q) is a tertiary thiol compound (E-2), as the specific example, phthalic acid bis(2-mercaptoisopropyl) ) Ester, ethylene glycol bis(2-mercaptoisobutyrate), propylene glycol bis(2-mercaptoisobutyrate), diethylene glycol bis(2-mercaptoisobutyrate), butanediol bis(2 -Mercaptoisobutyrate), octanediol bis(2-mercaptoisobutyrate), trimethylolethane ginseng (2-mercaptoisobutyrate), trimethylolpropane ginseng (2-mercaptoisobutyrate) Butyrate), pentaerythritol 4 (2-mercaptoisobutyrate), dipentaerythritol (2-mercaptoisobutyrate), phthalic acid bis(3-mercapto-3-methylbutyl), ethylenedi Alcohol bis(3-mercapto-3-methylbutyl ester), propylene glycol bis(3-mercapto-3-methylbutyl ester), diethylene glycol bis(3-mercapto-3-methylbutyl ester), butane two Alcohol bis (3-mercapto-3-methyl butyl ester), octanediol bis (3-mercapto-3-methyl butyl ester), trimethylol ethane (3-mercapto-3-methyl butyl ester) ), trimethylolpropane (3-mercapto-3-methylbutyl ester), pentaerythritol four (3-mercapto-3-methylbutyl ester), dipentaerythritol (3-mercapto-3-methylbutyl ester) )Wait.

The total amount of the thiol compound (E) in the radically polymerizable resin composition of the present invention is preferably 0.01-10 parts by mass, and more preferably, relative to 100 parts by mass of the aforementioned radically polymerizable compound (A) It is 0.1-7 parts by mass, more preferably 0.1-5 parts by mass, and still more preferably 0.2-4 parts by mass. When the amount of the thiol compound (E) is 0.01 parts by mass or more, the curing function can be sufficiently obtained, and when the amount is 10 parts by mass or less, curing will proceed quickly.

In addition, the total molar ratio [(E)/(D)] of the thiol compound (E) relative to the metal component of the metal-containing compound (D) is preferably 0.1-15, which is the same aspect of the present invention Among them, 0.3-10 is more preferable, 0.6-8 is more preferable, 0.8-5 is still more preferable, in other aspects of the present invention, 0.5-15 is more preferable, and 1-12 More preferably, it is more preferably from 1.5 to 10, and even more preferably from 2 to 9. When the molar ratio [(E)/(D)] is 0.1 or more, the thiol compound (E) can be sufficiently coordinated near the metal of the metal-containing compound (D), and by setting the molar ratio If it is 15 or less, the balance between manufacturing cost and effect will be improved.

The thiol compound (E) system may be used individually by 1 type, and may use 2 or more types together. When the secondary thiol compound (E-1) and the tertiary thiol compound (E-2) are used together, the molar ratio of the two [(E-1)/(E-2)] is 0.001～1000 Preferably, 1-10 is more preferable. When the molar ratio [(E-1)/(E-2)] is within the aforementioned range, in the radical polymerizable resin composition, the metal-containing compound (D) and the thiol compound (E) are stable, and neither As a by-product, a disulfide compound due to the bonding of thiol compounds (E) to each other is produced. From the viewpoint of maintaining the radical polymerizable resin composition in a stable state in which the metal-containing compound (D) and the thiol compound (E) are stable, the secondary thiol compound (E-1) or 3 is used alone Grade thiol compound (F2) is preferred.

＜Curing accelerator (F)＞ The radical polymerizable resin composition of the present invention may contain a metal-containing compound (D) and a curing accelerator (F) other than the thiol compound (E) for the purpose of improving the curability. Examples of hardening accelerators (F) other than the metal-containing compound (D) and the thiol compound (E) include amines. Specifically, aniline, N,N-dimethylaniline, and N,N- Diethylaniline, p-toluidine, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N,N-dimethyl Amino)benzaldehyde, 4-[N,N-bis(2-hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethylamino)benzaldehyde, N,N -Bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorphine, piperidine, N,N-substituted aniline such as N,N-bis(hydroxyethyl)aniline, diethanolaniline, N,N-substituted-p-toluidine, 4-(N,N-substituted amino)benzaldehyde, etc. Amines and so on. When the radical polymerizable resin composition of the present invention contains the hardening accelerator (F), the amount is preferably 0.01-10 parts by mass, preferably 0.05--10 parts by mass relative to 100 parts by mass of the radical-polymerizable compound (A). 5 parts by mass is more preferable, and 0.1 to 3 parts by mass is more preferable.

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

＜Hardening retarder (H)＞ The radical polymerizable resin composition of the present invention may contain a hardening retarder for the purpose of delaying the hardening of the radical polymerizable compound (A). Examples of the curing retarder include radical-based curing retarders, such as 2,2,6,6-tetramethylpiperidine 1-oxy radical (TEMPO), 4-hydroxy-2,2,6 ,6-Tetramethylpiperidine 1-oxy radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxy radical (4-Oxo-TEMPO) And other TEMPO derivatives. Among them, in terms of cost and ease of handling, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxy radical (4H-TEMPO) is preferred. When the radically polymerizable resin composition contains a polymerization inhibitor and a hardening retarder, the amount is preferably 0.0001 to 10 parts by mass, and more preferably 0.001 to 100 parts by mass of the radically polymerizable compound (A). 1 part by mass.

＜Aggregate (I)＞ The radical polymerizable resin composition of the present invention contains aggregate (I). The aggregate (I) contains bound water. The water content of the bound water of the aggregate (I) is not particularly limited. For example, 0.10% by mass or more is preferable, 0.20% by mass or more is more preferable, 0.30% by mass or more is more preferable, and 0.40% by mass The above is the best. In addition, the water content of the bound water of the aggregate (I) is preferably 5.0% by mass or less, more preferably 2.5% by mass or less, more preferably 1.5% by mass or less, and most preferably 1.0% by mass or less. good. The water content of the bound water of the aggregate (I) is not particularly limited. For example, relative to 100 parts by mass of the radical polymerizable compound (A), 0.2 parts by mass or more is preferable, and 0.5 parts by mass or more is more preferable. , More preferably 1.0 part by mass or more, and most preferably 1.5 part by mass or more. In addition, relative to 100 parts by mass of the radically polymerizable compound (A), the water content of the bound water of the aggregate (I) is preferably 7 parts by mass or less, more preferably 5 parts by mass or less, and 2.5 parts by mass. Part by mass or less is more preferable, and 2.0 parts by mass or less is most preferable. The method for measuring the water content of the bound water of the aggregate (I) is as described in the examples. The aggregate (I) is not particularly limited, and aggregates used in mortar or concrete can be used. The aggregate is not particularly limited, and examples thereof include calcium carbonate, crushed stone, sandstone, white stone rainforest, marble, quartz, limestone, silica sand, silica sand, and river sand. However, cement is not included in aggregate (I). In addition, from the viewpoint of weight reduction, lightweight aggregates such as sintered shale, silicic acid-based microspheres, and non-silicic acid-based microsphere perlite can also be used.

The radical polymerizable resin composition of the present invention preferably does not substantially contain cement. "Substantially not included" means that the content is 3% by mass or less relative to the radical polymerizable resin composition, preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5 It means less than mass%.

Here, as the cement, Portland cement, other mixed cements, super-rapid cement, etc. can be cited. As Portland cement, various Portland cements such as low heat, medium heat, normal, fast hardening, ultra fast hardening, and sulfate resistance can be cited. In addition, examples of the mixed cement include blast furnace cement, fly ash cement cement, silica cement, and the like.

The calcium carbonate system functions as a filler pigment that is transparent in the coating film and does not hide the coated surface (substrate surface), and has functions such as filling properties of recesses and reduction of coating costs. As the calcium carbonate, one listed is, for example, TM-2 (manufactured by Heng Mining Co., Ltd.). Since calcium silicate has a specific particle size distribution, is excellent in dispersibility and is porous, it can reduce the specific gravity of the aggregate itself to make it difficult to sag and improve film formation.

Examples of silicic acid-based microspheres include Shirasu microspheres, pearlite, glass (silica) microspheres, fly ash cement microspheres, and the like. Examples of non-silicic acid-based microspheres include alumina microspheres, zirconium microspheres, and carbon microspheres.

The content of the aggregate in the composition of the present invention is not particularly limited, and it is preferably 5 parts by mass to 500 parts by mass, and more preferably 10 parts by mass to 100 parts by mass of the radical polymerizable compound (A). 450 parts by mass. In particular, when the aggregate content is 5 parts by mass or more, practical fluidity can be ensured. In addition, when the content of the aggregate is 500 parts by mass or less, the amount of the trowel attached is reduced, so that the decrease in workability can be prevented.

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

As polyolefin fibers, currently commercially available ones include: polyethylene-based KEMIBESTO (registered trademark) FDSS-2 (average fiber length 0.6 mm), KEMIBESTO (registered trademark) FDSS-5 (average fiber length 0.1 mm), KEMIBESTO (registered trademark) Trademark) FDSS-25 (average fiber length 0.6mm, hydrophilic chemical product), KEMIBESTO (registered trademark) FDSS-50 (average fiber length 0.1mm, hydrophilic chemical product) and other brand name products (all are Mitsui Petrochemical Industrial (shares) system).

The carbon fiber is not particularly limited, and any known carbon fiber can be used. As this example, polyacrylonitrile-based (PAN-based) carbon fibers, rayon-based carbon fibers, pitch-based carbon fibers, and the like can be cited. The carbon fiber system may be used alone, or two or more of them may be mixed and used. From the viewpoint of low cost and good mechanical properties, it is better to use PAN-based carbon fiber. Such a carbon fiber system can be commercially available. As the carbon fiber system, carbon fiber reinforced plastic (CFRP) can be used.

The diameter of the carbon fiber is preferably 3-15 μm, and more preferably 5-10 μm. The length of the carbon fiber is usually 5 to 100 mm. In the present invention, in particular, the carbon fiber can be cut into 10.0 mm to 100.0 mm, and further cut into 12.5 mm to 50.0 mm for use.

The fibers are selected from, for example, plain weave, satin weave, non-woven fabric, mat, roving, chopped cut, knitted fabric, assembly, and composite structures such as fibrous structures, biaxial meshes, and triaxial meshes. It is better to use. For example, the radical polymerizable composition is impregnated in the aforementioned fiber structure, and if necessary, prepolymerization may be performed to form a prepreg for use. As the meshes, for example, biaxial meshes and triaxial meshes can be used. The length of one side of the square of the biaxial screen (mesh size) and the length of the side of the regular triangle of the triaxial screen (mesh size) are preferably 5 mm or more, and more preferably 10-20 mm. By using biaxial mesh or triaxial mesh, it is possible to obtain a hardening material for preventing concrete spalling that is lightweight and excellent in economy, workability, and durability. These fibers are preferably used to reinforce coating film performance such as concrete spalling prevention properties and FRP water resistance, or to manufacture FRP molded products. For applications such as prevention of concrete spalling, in terms of visually inspecting the deterioration state of the substrate from the outside, among the fibers, glass fibers or cellulose fibers having excellent transparency are preferred.

The content of such fibers is preferably 0.3 to 200 parts by mass, more preferably 0.5 to 100 parts by mass, and 1.0 to 50 parts by mass relative to 100 parts by mass of the radical polymerizable compound (A) Better.

＜Water reducing agent (K)＞ The radically polymerizable resin composition of the present invention may contain a usable water reducing agent (K) capable of imparting a water reducing state as required. As the water reducing agent, well-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. From the viewpoint of suppressing the decrease in the fluidity of concrete caused by the addition of the aforementioned swellable aluminosilicate, maintaining good fluidity and improving workability, polycarboxylic acid-based water-reducing agents are also suitable . In addition, as the water reducing agent, well-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. In the radical polymerizable resin composition, it is preferable to contain 0.1 to 3.0 parts by mass of the water reducing agent.

[Solvent] In the radical polymerizable resin composition of the present invention, a solvent can be prepared according to needs. Examples of solvents that can be formulated include aromatic hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate, butyl acetate, pentyl acetate, cellosolve acetate, etc.; methyl ethyl ketone, methyl ethyl ketone, methyl ethyl ketone, and methyl ethyl ketone. Ketone-based solvents such as methyl isobutyl ketone and diisobutyl ketone. These solvent systems can be used in the production of polymers.

[Polyisocyanate-based compound] The radically polymerizable resin composition of the present invention may contain a polyisocyanate-based compound. The polyisocyanate-based compound reacts with the hydroxyl group of the radical polymerizable compound (A) to form a cured coating film. The aforementioned polyisocyanate-based compound system has two or more isocyanate groups in the molecule, and the isocyanate group can be blocked by a blocking agent or the like. Examples of polyisocyanate-based compounds that are not blocked with a blocking agent include aliphatic diisocyanates such as lysine diisocyanate, hexamethylene diisocyanate, and trimethylhexane diisocyanate; hydrogenated extension Stubby diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4 (or 2,6)-diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), 1,3-( Isocyanatomethyl) cyclohexane and other cyclic aliphatic diisocyanates; toluene diisocyanate, stubbing diisocyanate, diphenylmethane diisocyanate, and other aromatic diisocyanates; lysine triisocyanate, etc. Polyisocyanates such as polyisocyanates with trivalent or higher valence and adducts of these polyisocyanates with polyols, low-molecular-weight polyester resins or water, and cyclized polymers of the above-mentioned diisocyanates (e.g., isocyanurate) Acid esters), biuret-type adducts, etc. Among them, the isocyanurate of hexamethylene diisocyanate is preferred. These polyisocyanate-based compounds may be used alone or in combination of two or more kinds.

When the radical polymerizable resin composition contains a polyisocyanate group compound, the amount is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the radical polymerizable compound (A) Parts, more preferably 2-20 parts by mass.

The blocked polyisocyanate-based compound is a compound obtained by blocking the isocyanate group of the above-mentioned polyisocyanate-based compound with a blocking agent. Examples of the blocking agent include phenols such as phenol, cresol, and xylenol; ε-caprolactam; δ-valerolactam, γ-butyrolactam, β-propiolactin, etc. Internal amine series; methanol, ethanol, n- or iso-propanol, n-, iso- or tert-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Alcohols such as ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, benzyl alcohol, etc.; formamide oxime, acetaldoxime, acetoxime, methyl ethyl ketone Oxime, diacetyl monooxime, benzophenone oxime, cyclohexane oxime and other oxime systems; dimethyl malonate, diethyl malonate, ethyl acetylacetate, methyl acetylacetate, acetone Active methylene-based blocking agents such as acetone. By mixing the polyisocyanate and the blocking agent, the isocyanate group of the polyisocyanate can be easily blocked.

When the polyisocyanate-based compound is an unblocked polyisocyanate-based compound, mixing the radical polymerizable compound (A) and the polyisocyanate-based compound in the radical polymerizable resin composition of the present invention may cause both For the reaction, it is preferable to separate the radical polymerizable compound (A) and the polyisocyanate-based compound before use, and to mix the two before use. Furthermore, in order to react the radical polymerizable compound (A) with the polyisocyanate-based compound, a curing catalyst can be used. Examples of suitable hardening catalysts include tin octoate, dibutyltin bis(2-ethylhexanoate), dioctyltin bis(2-ethylhexanoate), dioctyltin diacetate, and dilaurin. Organic metal catalysts such as dibutyl tin oxide, dibutyl tin oxide, dioctyl tin oxide, lead 2-ethylhexanoate, etc. When the radical polymerizable resin composition contains the aforementioned curing catalyst amount, the amount is preferably 0.01 parts by mass to 5 parts by mass, and more preferably 0.05 to 4 parts by mass relative to 100 parts by mass of the radically polymerizable compound (A). Mass parts.

＜Other ingredients＞ The radically polymerizable resin composition of the present invention may contain components other than the aforementioned components as long as it does not particularly hinder the strength development or acid resistance of the cured body. As the components that can be contained, in addition to hydraulic inorganic substances such as calcium sulfate or pozzolanic substances, for example, they can provide setting adjustment, hardening promotion, hardening delay, thickening, water retention, defoaming, water repellency, waterproofing, etc. It can be used as a mixture of mortar or concrete; fibers, pigments, extenders, foaming materials, zeolite and other clay minerals made of metals, polymers, or carbon can be used in mortar or Mixed materials for concrete.

<Manufacturing method of 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 technical field can be used. A method including a mixing step of mixing a radical polymerizable compound (A), an expansion material (B), a radical polymerization initiator (C), and an aggregate (I) can be mentioned. Aggregate (I) contains bound water. For example, the radical polymerizable compound (A) is mixed with the metal-containing compound (D) according to the need, and then the radical polymerization initiator (C), the expansion material (B) and the aggregate are prepared and mixed (I), and a radical polymerizable resin composition can be produced. In the method for producing the radical polymerizable resin composition, it is preferable that the step not including the addition of water is included. When water is added, free water will be contained in the radical polymerizable resin composition, so the compressive strength of the cured product of the radical polymerizable resin composition will deteriorate. However, unlike the addition of free water, the bound water contained in raw materials such as aggregate (I) has less influence on the compressive strength of the hardened product. One embodiment of the method for producing the radical polymerizable resin composition of the present invention has the following step: the radical polymerizable compound (A) is mixed with the metal-containing compound (D) as needed to obtain Resin product step (S1); mixing the obtained resin product with the radical polymerization initiator (C) to obtain a curable resin product (S2); and combining the obtained curable resin product with an expansion material (B) Step (S3) of mixing to obtain a radical polymerizable resin composition.

In the aforementioned step (S1) of obtaining resin products (sometimes referred to as "step (S1)"), in addition to mixing the radically polymerizable compound (A) and the metal-containing compound (D), it is also necessary Furthermore, a polymerization inhibitor (G), or a hardening retarder (H), or a thiol compound (E), etc. can be mixed. In the step (S3) for obtaining a radical polymerizable resin composition (sometimes also referred to as "step (S3)"), in addition to the step (S2) for obtaining a curable resin product (sometimes also referred to as "step (S2)" In addition to mixing the curable resin product obtained in ") and the expansion material (B), aggregate (I), water reducing agent (K), fiber (J), etc. may be further mixed as required. As a specific example of the aggregate (I), for example, quick-hardening Portland cement, N90 silica sand, calcium carbonate TM-2, N50 silica sand, N40 silica sand, etc. can be used.

The radical polymerizable resin composition produced in this way can be cured at room temperature, and is excellent in workability, early strength development, and curability. Due to the expansion material (B), the shrinkage rate during hardening is small, and the expansion rate of the hardened product can be greater than 0 depending on the conditions.

<The cured product of a radically polymerizable resin composition> The cured product of the radically polymerizable resin composition of the present invention can be obtained by curing the above-mentioned radically polymerizable resin composition. The rate of change of the length of the cured product is not particularly limited, and can be adjusted according to the components of the radical polymerizable resin composition used. For example, the rate of change of the length of the cured product is preferably ^{0 to 1000×10 -6 after 3000 hours after curing.}

[Curing method of radical polymerizable resin composition] When the radical polymerizable resin composition of the present invention contains the thermal radical polymerization initiator (C-1), as an example of the curing method of the radical polymerizable resin composition of the present invention, the A curing method in which a radical polymerizable resin composition is coated on the surface of a substrate and cured at room temperature. For example, the radical polymerizable resin composition of the present invention is used as a cross-section restoration material of an inorganic structure. Since the radically polymerizable resin composition of the present invention contains the expansion material (B), the cured product obtained does not shrink as much as before even after a certain period of time. As the material of the base material, in addition to concrete, asphalt concrete, mortar, brick, wood, metal, phenol resin, epoxy resin, melamine resin, urea resin, unsaturated polyester resin, vinyl ester resin, alcohol Thermosetting resins such as acid resin, polyurethane, polyimide, etc.; polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyvinyl acetate, polyurethane, TEFLON (registered Trademark), ABS resin, AS resin, acrylic resin and other thermoplastic resins.

When the radical polymerizable resin composition of the present invention contains the photo-radical polymerization initiator (C-2), as the timing of photocuring, there is the following method: coating the radical polymerizable resin composition on the substrate Later, it is photocured, or the radical polymerizable resin composition is pre-polymerized (also called B-stage or prepreg) to make a sheet, and the sheet is pasted A method of photocuring after being attached to a base material, etc.

As the light source, as long as it is a light source having a spectral distribution in the photosensitive wavelength region of the photoradical polymerization initiator (C-2), for example, sunlight, ultraviolet light, near-infrared light, sodium light, halogen light, fluorescent light can be used. Lamps, metal halide lamps, LEDs, etc. In addition, two or more photo radical polymerization initiators (C-2) may be used in combination, and a wavelength filter may be used for the light source, or the specific wavelength of the LED may be used to distinguish the wavelengths required for pre-polymerization and main polymerization. The wavelength used for the pre-polymerization is preferably a long wavelength with a low energy level, especially when using near-infrared light, the degree of polymerization can be easily controlled. In the present invention, ultraviolet light (ultraviolet light) refers to 280 to 380 nm, visible light (visible light) refers to 380 to 780 nm, and near infrared light (near infrared) refers to light in the wavelength region of 780 to 1200 nm. The light irradiation time required for prepolymerization is affected by the effective wavelength range of the light source, output, irradiation distance, thickness of the composition, etc., so it cannot be specified uniformly, but for example, it is 0.01 hours or more, preferably as long as the irradiation is 0.05 hours or more. Can. [Example]

Hereinafter, the present invention will be explained in more detail through examples, but the present invention is not limited by the examples at all.

＜Measurement method of hardening shrinkage＞ According to the Japanese standard JIS A 1129-3 (dial gauge method), for the cured product of the radical polymerizable resin composition of the present invention, the shrinkage and expansion rate after curing (the rate of change: a negative number is the shrinkage rate) , A positive number is the expansion rate). The manufacturing method of the molded body (hardened product) is molded with reference to the appendix A of the Japanese standard JIS A 1129. The template is a template for specimens of 40×40×160mm specified in the Japanese standard JIS R 5201. The specimen of the hardened product is formed by the method of making the specimen for the strength test specified in JIS R 5201-10. After the forming, the template is directly left (cured) in a room with a temperature of 23°C±2°C and a humidity of 50%. And demoulding is carried out about 24 hours after forming. In addition, use the appliance shown in JIS A 1129-3, 3, and start the measurement under the conditions shown in JIS A 1129-3, 4.3 (set the start time to 0).

The amount of change (negative number: shrinkage, positive number: expansion) = the length of the long side when passing-the length of the long side at the beginning (0 o'clock) (160mm) (1)

Change rate (negative number: shrinkage rate, positive number: expansion rate) = change amount/length of the long side at the beginning (0 o'clock) (160mm) (2)

The raw material systems used for the production of each radical polymerizable resin composition in the examples and comparative examples are as follows.

＜Radical polymerizable compound (A)＞ (Synthesis example 1) "Synthesis of radical polymerizable compound (A-1)" Add 150.4 g of AER-2603 (bisphenol A epoxy resin manufactured by Asahi Kasei Co., Ltd.: epoxy equivalent 189), SR -16H (manufactured by Sakamoto Pharmaceutical Co., Ltd.: 1,6 hexanediol diglycidyl ether) 188.4 g, methylhydroquinone 0.255 g, DMP-30 (manufactured by Tokyo Chemical Industry Co., Ltd.: 2,4,6-ginseng (dimethyl (Aminomethyl) phenol) 1.5g, and the temperature was raised to 110°C. After the temperature was raised to 110°C, 172 g of methacrylic acid (manufactured by Mitsubishi Rayon Co., Ltd.) was dropped in about 30 minutes, and the reaction was allowed to react for about 4 hours. The reaction was terminated when the acid value became 10 mgKOH/g, and vinyl ester was obtained. Compound. Next, 256.3 g of dicyclopentenyloxyethyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., FA-512MT) as a radically polymerizable unsaturated monomer, and dicyclopentyl methacrylate (Hitachi Chemical Co., Ltd. make, FA-513M) 85.4g, and obtained a non-styrene type radical polymerizable compound (A-1) having a viscosity at 25°C of 280 mPa·s and an ester compound component ratio of 60% by mass.

＜Expansion material (B)＞ As the quicklime-ettringite composite expansion material, Denca power CSA Type S manufactured by Denca was used.

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

＜Compounds containing metals (D)＞ As the metal soap (D-1), manganese octoate (Hexoate Manganese manufactured by Toei Chemical Co., Ltd., manganese content in the entire product: 8% by mass and molecular weight 341.35) was used.

＜Thiol compound (E)＞ As the secondary thiol compound (E-1), a bifunctional secondary thiol manufactured by Showa Denko Co., Ltd., Karenz MT (registered trademark) BD1 (1,4-bis(3-mercaptobutoxy)butan Alkane, molecular weight 299.43).

＜Polymerization inhibitor (G)＞ Use tert-butylcatechol.

＜Hardening retarder (H)＞ Use 4-H-TEMPO.

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

＜Fiber (J)＞ KEMIBESTO (registered trademark) FDSS-5 Multi-branched fiber made by Mitsui Petrochemical Industry Co., Ltd. and polyolefin

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

(Example 1) "Adjustment of radical polymerizable resin composition" (1) Step (S1): Combine the metal-containing compound (D), the thiol compound (E), the polymerization inhibitor (G), and the hardening retarder (H) according to the compounding amount shown in Table 1 and the radical polymerizable compound obtained in Synthesis Example 1 (A-1) Mix thoroughly to prepare a resin product. (2) Step (S2): The radical polymerization initiator (C) was mixed with the resin product obtained in step (S1) according to the compounding amount shown in Table 1 to prepare a curable resin product. (3) Step (S3): The swelling material (B), aggregate (I), fiber (J), and the curable resin product obtained in step (S2) were thoroughly mixed according to the components and blending amounts shown in Table 1 to obtain this embodiment The radical polymerizable resin composition.

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

"Production of a cured product of a radical polymerizable resin composition" The obtained radical polymerizable resin composition is injected into a 40×40×160mm template, and the template is directly allowed to stand (cured) in a room with a temperature of 23°C±2°C and a humidity of 50% to harden it, and then form it. After about 24 hours, demoulding is carried out. The cured product of the radical polymerizable resin composition of this example was obtained.

"Assessment of shrinkage and expansion of hardened products" According to the above-mentioned evaluation method, the shrinkage and expansion properties of the cured product of the obtained radical polymerizable resin composition were evaluated. The results are shown in Table 2 and Fig. 1.

(Example 2) The radical polymerizable resin composition was obtained in the same manner as in Example 1 except for using the expansion material (B) in a compounding amount of 8.0 g. In addition, according to the same method as in Example 1, a cured product of the radical polymerizable resin composition was produced. In addition, according to the same method 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.

(Example 3) The radical polymerizable resin composition was obtained in the same manner as in Example 1, except that the expansion material (B) was used in a compounding amount of 12.0 g. In addition, according to the same method as in Example 1, a cured product of the radical polymerizable resin composition was produced. In addition, according to the same method 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.

"Test of Compressive Strength" The compression strength test was performed on the cured product produced in Example 3, and the results are shown in Table 3. The specimens used for compressive strength are 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 test), using a φ5cm×10cm template, from the template to the The time until demolding was set to 24 hours to prepare a specimen. In accordance with JIS A 1108 (Test Method for Compressive Strength of Concrete), an Amsler concrete compressive strength tester (manufactured by CCM-1000kNI Shimadzu Corporation) was used to measure the compressive strength of the manufactured specimens. The material age (material age) is as described in Table 3.

(Comparative example 1) The radical polymerizable resin composition was obtained in the same manner as in Example 1 except that the expansion material (B) was not used. In addition, according to the same method as in Example 3, a cured product of the radical polymerizable resin composition was produced. In addition, according to the same method 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. In addition, the compressive strength test was performed in the same manner as in Example 3, and the results are shown in Table 3.

(Comparative example 2) In addition to using Bond E208S (main agent) and Bond E208S (hardener) as epoxy resins (manufactured by Konishi, trade name: epoxy resin for civil engineering and construction, main agent: bisphenol A epoxy resin, hardener: modified Except for replacing the radical polymerizable compound (A-1) with a mixture of polyamide amine and polyamide amine), the epoxy resin composition was obtained in the same manner as in Example 1. In addition, according to the same method as in Example 1, a cured product of the epoxy resin composition was produced. In addition, according to the same method 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. In addition, the compressive strength test was performed in the same manner as in Example 3, and the results are shown in Table 3.

(Comparative example 3) The epoxy resin composition was obtained in the same manner as in Comparative Example 2 except that the expansion material (B) was not used. In addition, according to the same method as in Comparative Example 1, a cured product of the epoxy composition was produced. In addition, according to the same method 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. In addition, the compressive strength test was performed in the same manner as in Example 3, and the results are shown in Table 3.

(Example 4) The 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. In addition, according to the same method as in Example 1, a cured product of the radical polymerizable resin composition was produced. In addition, according to the same method as in Example 1, the shrinkage and expansion properties of the obtained cured products were evaluated. The results are shown in Table 4 and Fig. 2. In addition, the compressive strength test was performed according to the same method as in Example 3, and the results at the time points of 24 hours and 672 hours are shown in Table 4. Before mixing with the resin product, with respect to the aggregate (I) and the fiber (J) used in Example 4, the water content contained in the aggregate (I) and the fiber (J) was measured. The results are shown in Table 4.

"Measurement method of water content" With regard to the aggregate (I) and the fiber (J) mixed in the radical polymerizable resin composition of the present invention, the measurement of the water content contained in the aggregate and the fiber is carried out according to the following method. (1) Mix the aggregate and fiber at the same mass ratio as the mass ratio of aggregate (I) and fiber (J) shown in Table 4, and measure the total amount of the mixed aggregate and fiber 20mg and place it in TG /DTA (TA7000series differential thermal thermogravimetry simultaneous measuring device STA7200RV, manufactured by Hitachi High-Tech Science Co., Ltd.). (2) From 30°C to 105°C, operate at a temperature increase rate of 10°C/min, and maintain at 105°C for 60 minutes. (3) Calculate the weight change rate (decrease rate) from 95°C to 105°C.

(Comparative Example 4) Except that the aggregate (I) of Example 4 was dried and used according to the following absolute drying conditions, the radical polymerizable resin composition was obtained in the same manner as in Example 4. In addition, according to the same method as in Example 1, a cured product of the radical polymerizable resin composition was produced. In addition, according to the same method as in Example 1, the shrinkage and expansion properties of the obtained cured products were evaluated. The results are shown in Table 4 and Fig. 2. In addition, the compressive strength test was performed according to the same method as in Example 3, and the results at the time of 24 hours and 672 hours are shown in Table 4. According to the same method as in Example 4, before mixing with the resin product, for the aggregate (I) used in Comparative Example 4, the water content contained in the aggregate was measured. The results are shown in Table 4.

"Absolutely dry conditions" In order to create an absolutely dry aggregate that completely evaporates the water contained in the aggregate, the following operations are added to the aggregate before mixing with the radical polymerizable resin composition. (1) Put 400g of aggregate in an aluminum tray, flatten it to a thin shape, and dry it in an oven at 105°C. (2) Take it out of the oven after 48 hours and use it.

(Comparative Example 5) After mixing the aggregate (I) in the resin product, the radical polymerizable resin composition was obtained in the same manner as in Comparative Example 4 except that 5.00 g of water was added. In addition, according to the same method as in Example 1, a cured product of the radical polymerizable resin composition was produced. According to the same method as in Example 3, tests of the compressive strength at 24 hours and 672 hours were performed, and the results are shown in Table 4. According to the same method as in Example 4, before mixing with the resin product, with respect to the aggregate (I) used in Comparative Example 5, the water content contained in the aggregate was measured. The results are shown in Table 4.

(Survey) According to the results in Table 2 and FIG. 1, it can be seen that by the radical polymerizable resin composition of the present invention having the expansion material (B), in Example 1, the shrinkage rate of the cured product during curing is significantly reduced Suppressed, the hardened products of Examples 2 and 3 swelled from the reference length (160 mm) after hardening 24 hours from the start of hardening.

In the cured product of the radical polymerizable resin composition of Example 3, the swelling amount (expansion rate) of ^{+40 μm (+250×10 -6} ) to +131 μm (+819×10 ^{-6) was observed.} However, since the radical polymerizable resin composition of Comparative Example 1 does not contain the expandable material (B), the cured product was observed to be -48μm (-300×10 ^-6 ) to -80μm (-500×10 ^-6 ) The amount of shrinkage (shrinkage rate). In addition, in Comparative Example 2 using the epoxy resin composition, even if the expansion material (B) was included, a large amount of shrinkage was almost the same as in Comparative Example 3, which was not included.

According to the results in Table 4 and Fig. 2, it can be seen that in Comparative Example 4 where the water content of the aggregate (I) pretreated under absolute dry conditions is 0.00 g, the hardened product is -250× 10 ^-6 ～-350×10 ^-6 shrinkage, not expansion. In addition, in Comparative Example 5 in which the aggregate (I) was mixed with the resin product and water was added, the compressive strength of the cured product was inferior to that of Example 1 and Comparative Example 4.

[Fig. 1] A graph showing the results of Examples 1 to 3 and Comparative Examples 1 to 3. [Fig. 2] A graph showing the results of Example 4 and Comparative Example 4.

Claims (13)

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

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