WO2019004125A1

WO2019004125A1 - Radical polymerizable resin composition and structure-repairing material

Info

Publication number: WO2019004125A1
Application number: PCT/JP2018/024008
Authority: WO
Inventors: 小林　健一; 絵梨畠山; 一博黒木
Original assignee: 昭和電工株式会社
Priority date: 2017-06-26
Filing date: 2018-06-25
Publication date: 2019-01-03
Also published as: CN110799558B; CN110799558A; TW201906952A; JP7164522B2; TWI754078B; JPWO2019004125A1

Abstract

The present invention provides a radical polymerizable resin composition which is curable at low temperature and exhibits superior adhesion strength, and a structure-repairing material using the radical polymerizable resin composition. The present invention pertains to: a radical polymerizable resin composition characterized by containing (A) a radical polymerizable resin, (B) a radical polymerizable unsaturated monomer, (C) an amine curing accelerator, and (D) a polyfunctional thiol compound; and a structure-repairing material using the radical polymerizable resin composition.

Description

Radically polymerizable resin composition and structure repair material

The present invention relates to a radically polymerizable resin composition satisfying both the low temperature curing property and the adhesive strength. Furthermore, the present invention relates to a structure restorative material containing the radically polymerizable resin composition suitable for repairing a crack generated due to deterioration of a concrete structure or the like.

Conventionally, methods using synthetic resins such as epoxy resin and acrylic syrup as repair / reinforcement materials due to aged deterioration of concrete structures etc. have been proposed, and improvement of low temperature curing property such as construction in winter is mentioned as one of the problems It is done. (Patent Documents 1 to 3).
In addition, for concrete structures that are always accompanied by vibrations, such as highway walls and railroad ramps, in order to prevent breakage after fixing and drying the repair material, the crack followability of the hardened material, etc. Has been mentioned as an issue. For such problems, for example, Patent Document 4 discloses a repair / reinforcement agent for a concrete structure using an acrylic / styrene resin as an admixture, and Patent Document 5 discloses a glass transition temperature of an acrylic resin or the like of -25. It is known to use polymers below ° C.
(Patent Documents 4 to 5).

JP 2003-002948 A JP 2001-247636 JP 2000-154297 A JP, 2009-019354, A JP 2012-091985 A

However, even the methods described in Patent Documents 1 to 5 described above have insufficient adhesive strength to concrete structures that always involve vibration, and there is room for improvement for repairing a cracked portion. The
The present invention has been made in view of the above-mentioned conventional circumstances, and has a low-temperature curing property and a radical polymerizable resin composition which exhibits excellent adhesive strength, and a structure repair using the radical polymerizable resin composition. The purpose is to provide materials.

That is, the present invention is summarized in the following [1] to [18].
[1] It is characterized by containing (A) radically polymerizable resin, (B) radically polymerizable unsaturated monomer, (C) amine-based curing accelerator and (D) polyfunctional thiol compound. Radically polymerizable resin composition.
[2] The radical according to the above [1], wherein the component (A) is at least one selected from vinyl ester resins, unsaturated polyester resins, polyester (meth) acrylate resins and urethane (meth) acrylate resins Polymerizable resin composition.
[3] The radically polymerizable resin composition according to [1] or [2], wherein the component (D) is a compound having a structure represented by the following formula (Q).

(In the general formula (Q), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. (A) is an integer of 0 to 2).
[4] The radically polymerizable resin composition according to any one of the above [1] to [3], wherein the component (D) is a compound having a structure represented by the following general formula (Q-1).

(In the general formula (Q-1), R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. ** is Indicates that it is linked to any organic group having at least one mercapto group, a is an integer of 0 to 2.)
[5] The radically polymerizable resin composition according to any one of the above [1] to [4], wherein the component (D) is at least one selected from a bifunctional to hexafunctional polyfunctional thiol compound.
[6] The content of the component (A) is 5 to 95 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass, and the content of the component (B) is [5 to 95 parts by mass, the content of the component (C) is 0.01 to 10 parts by mass, and the content of the component (D) is 0.1 to 20 parts by mass] The radically polymerizable resin composition according to any one of [1] to [5].
[7] The component (C) is N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2) The radical according to any one of the above [1] to [6], which contains at least one selected from the group consisting of -hydroxypropyl) -p-toluidine and N, N-bis (2-hydroxyethyl) aniline Polymerizable resin composition.
[8] The radically polymerizable resin composition according to any one of the above [1] to [7], further comprising a metal organic compound as a curing accelerator other than the amine curing accelerator.
[9] The composition according to the above [8], wherein the content of the metal organic compound is 0.1 to 5 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). Radically polymerizable resin composition.
[10] The radically polymerizable resin composition according to the above [8] or [9], wherein the metal organic compound contains at least one selected from the group consisting of cobalt compounds and copper compounds.
[11] The radically polymerizable resin composition according to any one of the above [1] to [10], which further comprises (E) a curing agent.
[12] When the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (E) is 0.1 to 10 parts by mass, in the above [11] The radically polymerizable resin composition as described.
[13] The component (E) is selected from the group consisting of dibenzoyl peroxide, benzoyl m-methyl benzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate The radically polymerizable resin composition as described in said [11] or [12] containing at least 1 sort (s).
[14] A structure restorative material containing the radically polymerizable resin composition according to any one of the above [1] to [13].
[15] A structure restorative material comprising the radically polymerizable resin composition according to any one of the above [1] to [13] and (F) a filler.
[16] The composition according to the above [15], wherein the content of the component (F) is 1 to 700 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. Structural restoration material.
[17] The structure restorative material according to the above [15] or [16], wherein the component (F) is at least one selected from the group consisting of silica sand, calcium carbonate, talc and fumed silica.
[18] The structure restorative material according to any one of the above [14] to [17], wherein the structure restorative material is a slab type track structure restorative material.

According to the present invention, it is possible to provide a radically polymerizable resin composition that has low-temperature curability and expresses excellent adhesive strength. A structure restorative material containing a radically polymerizable composition having such properties has low temperature curability, so that it can be rapidly cured even in a low temperature environment and has excellent adhesive strength, so it can be rapidly cured. And even in a scene where the shrinkage rate is large, it is difficult to cause breakage after adhesion and drying or peeling of the interface between the repaired portion and the restorative material. By using the structure restoration material of the present invention, a crack portion can be well repaired for a concrete structure which always involves vibration. That is, it is possible to provide a structure restorative material that can exhibit excellent adhesion strength at the time of fixing, and does not cause breakage or the like after the fixing.

It is a schematic diagram which shows the top view and transversal direction cross section of two cement mortar boards used in order to produce the test body for a bending load test using the structure repair material of this invention. It is a schematic diagram which shows the top view and horizontal direction sectional drawing of the test body for a bending load test obtained using the structure repair material of this invention of this invention.

[Radical Polymerizable Resin Composition]
The radically polymerizable resin composition of the present invention comprises (A) a radically polymerizable resin, (B) a radically polymerizable unsaturated monomer, (C) an amine curing accelerator, and (D) a polyfunctional thiol compound. It is a radically polymerizable resin composition characterized by containing.
In addition, (A) radically polymerizable resin may be called (A) component, (B) radically polymerizable unsaturated monomer may be called (B) component, (C) amine-based curing accelerator ( It may be called C component, and (D) polyfunctional thiol compound may be called (D) component.

<Radical Polymerizable Resin (A)>
In the present invention, the radically polymerizable resin (A) refers to a compound having an ethylenically unsaturated group in the resin and a polymerization reaction proceeds by a radical.
Examples of the radically polymerizable resin (A) include urethane (meth) acrylate resin, vinyl ester resin, unsaturated polyester resin, polyester (meth) acrylate resin, (meth) acrylate resin and the like, among which radically polymerizable resin composition Urethane (meth) acrylate resin or a vinyl ester resin having toughness is preferred from the viewpoint of the flexibility of the cured product of the above. In the present specification, "(meth) acrylate" means "acrylate or methacrylate".

[Urethane (Meth) Acrylate Resin]
The urethane (meth) acrylate resin is obtained, for example, by introducing a (meth) acryloyl group to hydroxyl groups or isocyanato groups at both ends of a polyurethane obtained by reacting a polyvalent isocyanate and a polyvalent alcohol. Resin can be used.
As the polyhydric alcohol, compounds described as “polyhydroxy compounds” or “polyhydric alcohols” described in JP-A-2009-292890 and WO 2016/171151 can be used without particular limitation.
The polyhydric alcohol is not particularly limited, but, for example, polyester polyol, polyether polyol;
Dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol;
A dihydric alcohol such as an adduct of a dihydric alcohol represented by hydrogenated or non-hydrogenated bisphenol A and the like with propylene oxide or an alkylene oxide represented by ethylene oxide;
Examples thereof include trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane and pentaerythritol.
Examples of the adduct of the above dihydric alcohol and alkylene oxide include polyoxyalkylene bisphenol A ether.
Among these, the urethane (meth) acrylate resin is preferably a urethane (meth) acrylate resin containing a polyol structure selected from polyester polyols, polyether polyols, and polyoxyalkylene bisphenol A ethers.
Among them, a urethane (meth) acrylate resin containing a polyol structure of a polyether polyol is more preferable from the viewpoint of flexibility when a low viscosity radically polymerizable resin composition is obtained and cured. As the polyether polyol, polyethylene glycol or polypropylene glycol is preferable because preparation of a radically polymerizable resin composition can be facilitated.
The weight average molecular weight of the polyether polyol is preferably 500 to 5,000, and more preferably 500 to 3,000. When the weight-average molecular weight is within the above range, a low viscosity and compatibility is obtained when a radically polymerizable resin composition in which a radically polymerizable unsaturated monomer or the like described later is blended with a urethane (meth) acrylate resin is used. It is good. The measuring method of a weight average molecular weight is measured according to an Example.

Examples of the polyvalent isocyanate include those described in JP-A-2009-292890 and those described in WO2016 / 171151, and examples thereof include 2,4-tolylene diisocyanate and its isomer, diphenylmethane diisocyanate, Examples thereof include compounds such as hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate and the like. Among these, diphenylmethane diisocyanate and isophorone diisocyanate are preferable from the viewpoint of reactivity at the time of synthesizing a resin.
In the case of introducing a (meth) acryloyl group, for example, a method of reacting a hydroxyl group-containing (meth) acrylic compound described in JP-A-2009-292890 with the terminal isocyanate group, or 2- (meth) Examples thereof include methods of reacting isocyanato group-containing (meth) acrylic compounds such as acryloyloxyethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, and 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Among these, from the viewpoint of reactivity at the time of synthesizing a resin, a method in which a terminal isocyanate group is reacted with a hydroxyl group-containing (meth) acrylic compound is preferable.
From the viewpoint of flexibility and adhesion of the radically polymerizable resin composition, the hydroxyl group-containing (meth) acrylic compound is a monofunctional (meth) acrylic compound, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) Acrylate, caprolactone modified hydroxyalkyl (meth) acrylate, hydroxyethyl acrylamide and the like are preferable, and among these, 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is more preferable.
The weight average molecular weight of the urethane (meth) acrylate resin is preferably 2000 to 22000, more preferably 3000 to 19000, and still more preferably 4000 to 16000. When the weight-average molecular weight is within the above range, a low viscosity and compatibility is obtained when a radically polymerizable resin composition in which a radically polymerizable unsaturated monomer or the like described later is blended with a urethane (meth) acrylate resin is used. It is good.

[Vinyl ester resin]
The vinyl ester resin is obtained by subjecting all or part of the epoxy group contained in the epoxy compound to an esterification reaction with an unsaturated monobasic acid, and has a radical reactive carbon-carbon double bond in the side chain. doing. As a representative example of the unsaturated monobasic acid is (meth) acrylic acid, it is referred to as an epoxy (meth) acrylate resin.
As the epoxy compound, monomers, oligomers and polymers in general having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure thereof are not particularly limited. For example, biphenyl type epoxy resin; bisphenol type epoxy resin such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin, tetramethyl bisphenol F type epoxy resin; stilbene type epoxy Resins; novolac epoxy resins such as phenol novolac epoxy resins and cresol novolac epoxy resins; polyfunctional epoxy resins such as triphenolmethane epoxy resins and alkyl-modified triphenolmethane epoxy resins; phenol aralkyl epoxy epoxides having a phenylene skeleton Resin, phenol aralkyl type epoxy resin such as phenol aralkyl type epoxy resin having a biphenylene skeleton; dihydroxy naphthalene type epoxy resin Naphthol type epoxy resin such as epoxy resin obtained by glycidyl etherification of a cis resin, a dimer of dihydroxy naphthalene; triazine nucleus-containing epoxy resin such as triglycidyl isocyanurate, monoallyl diglycidyl isocyanurate; Alicyclic polyepoxy compounds such as aryl cyclic diepoxy adipate, aryl cyclic diepoxy carboxylate and vinylcyclohexene dioxide; Bridged cyclic hydrocarbon compounds such as dicyclopentadiene modified phenolic epoxy resin modified phenolic epoxy resin A glycidyl ester type epoxy resin obtained by the reaction of a polybasic acid such as a dimer acid with epichlorohydrin; an oxazolide obtained by reacting the epoxy resin with a diisocyanate Ring-containing epoxy resins.
A well-known thing can be used as said unsaturated monobasic acid. For example, (meth) acrylic acid, crotonic acid, cinnamic acid and the like can be mentioned. Among these, (meth) acrylic acid is preferable.
Further, as the unsaturated monobasic acid, a reaction product of a compound having one hydroxy group and one or more (meth) acryloyl groups with a polybasic acid anhydride may be used.
The said polybasic acid anhydride is used in order to increase the molecular weight of the said epoxy resin, and can use a well-known thing. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol / two molar maleic anhydride adduct, polyethylene Glycol · 2 mol maleic anhydride adduct, propylene glycol · 2 mol maleic anhydride adduct, polypropylene glycol · 2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16- (6 And anhydrides such as -ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, and a carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name: Hycar CTBN).
Among the above-mentioned vinyl ester resins, bisphenol A epoxy (meth) acrylate resins are preferable from the viewpoint of toughness imparting, versatility and cost.

[Unsaturated polyester resin]
As the unsaturated polyester resin, those obtained by subjecting a polyhydric alcohol component to an esterification reaction of an unsaturated dibasic acid, and optionally a dibasic acid component containing a saturated dibasic acid can be used. .
Examples of the unsaturated dibasic acid and the saturated dibasic acid include those described in WO 2016/171151, which may be used alone or in combination of two or more.
Although there is no restriction | limiting in particular in the said polyhydric alcohol, For example, the thing of WO2016 / 171151 can be mentioned like the case of urethane (meth) acrylate resin.

As the unsaturated polyester, one modified with a dicyclopentadiene type compound may be used as long as the effects of the present invention are not impaired. As a modification method with a dicyclopentadiene type compound, for example, after obtaining dicyclopentadiene and a maleic acid addition product, a known method such as a method of introducing a dicyclopentadiene skeleton using this as a monobasic acid is mentioned Be
An oxidative polymerization (air curing) group such as an allyl group or a benzyl group can be introduced into the vinyl ester resin or unsaturated polyester resin used in the present invention. The introduction method is not particularly limited, but, for example, addition of a polymer having an oxidative polymerization group, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether, hydroxyl group and allyl ether A method of adding a reaction product of a compound having a group and an acid anhydride may, for example, be mentioned.
Incidentally, the oxidative polymerization (air curing) in the present invention means, for example, a crosslink associated with formation and decomposition of peroxide by oxidation of a methylene bond between an ether bond and a double bond, which is found in, for example, allyl ether group. .

[Polyester (meth) acrylate resin]
As polyester (meth) acrylate resin, for example, polyester obtained by reacting polyvalent carboxylic acid and polyvalent alcohol, specifically, (meth) acrylic acid to hydroxyl groups at both ends of polyethylene terephthalate and the like The resin obtained by reacting can be used.

[(Meth) acrylate resin]
As the (meth) acrylate resin, for example, a poly (meth) acrylic resin having one or more functional groups selected from a hydroxyl group, an isocyanate group, a carboxy group and an epoxy group, a monomer having the functional group A resin obtained by, for example, reacting a (meth) acrylic acid ester having a hydroxyl group with a functional group of a copolymer with an acrylate) can be used.

<Radically polymerizable unsaturated monomer (B)>
The radically polymerizable unsaturated monomer (B) used in the present invention is important for reducing the viscosity of the radically polymerizable resin composition and improving hardness, strength, chemical resistance, water resistance and the like.
Although there is no restriction | limiting in particular in the said radically polymerizable unsaturated monomer, What has a (meth) acryloyl group or a vinyl group is preferable.

Acrylic acid ester, methacrylic acid ester etc. are mentioned as a monomer which has a (meth) acryloyl group, A monofunctional monomer and a polyfunctional monomer can be used. Specific examples of monofunctional monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and (meth) acrylic Acid t-Butyl, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, phenoxy Ethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene glycol monobutyl ether (meth) acrylate, ethylene glycol monohexyl ether (Meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol monobutyl ether (meth) acrylate, diethylene glycol monohexyl ether (meth) acrylate And compounds such as diethylene glycol mono 2-ethylhexyl ether (meth) acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc. can do.
Furthermore, compounds such as caprolactone modified hydroxyalkyl (meth) acrylate and caprolactone modified tris (acryloxyalkyl) isocyanurate can also be exemplified. From the viewpoint of reducing the viscosity of the radically polymerizable resin composition, monomers having a polycaprolactone (meth) acrylate structure with 1 to 5 (m = 1 to 5) moles of caprolactone added can be exemplified. Further, the addition mole number of caprolactone can be exemplified by a monomer having a polycaprolactone (meth) acrylate structure of 1 to 3. Among them, caprolactone modified hydroxyethyl (meth) acrylate is preferable.

Specific examples of the polyfunctional monomer include neopentyl glycol di (meth) acrylate, PTMG dimetaacrylate, 1,3-butylene glycol di (meth) acrylate and 1,6-hexane. Diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 2-hydroxy 1,3 dimethacryloxypropane, 2,2-bis [4- (methacryloylethoxy) phenyl] propane, 2,2-bis [4 -(Methacryloxy diethoxy) phenyl] propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, tetraethylene glycol diacrylate, bisphenol AEO modified (n = 2) diacrylate, isocyanuric acid EO modified (n = 3) diacrylate, pentaerythritol Mention may be made of acrylate monostearate.

Furthermore, as polyfunctional monomers, ethylene glycol di (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butylene glycol di Alkanediol di- (meth) acrylates such as meta) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate;
Polyoxyalkylene-glycol di (such as diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate) Meta) acrylate;
Trimethylolpropane di (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol Tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, diallyl fumarate;
Examples of other compounds include tris (2-hydroxyethyl) isocyanuric acrylate and the like.

Specific examples of the monomer having a vinyl group include styrene, p-chlorostyrene, vinyl toluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl phthalate, Triallyl isocyanurate vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl ether, vinyl benzyl (2-ethylhexyl) ether, vinyl benzyl (β-methoxymethyl) ether, vinyl benzyl (n-butoxypropyl) ether, vinyl benzyl Cyclohexyl ether, vinyl benzyl (β-phenoxyethyl) ether, vinyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxyethyl ether, vinyl Nji distearate cyclopentenyl methyl ether, and divinyl benzyl ether.
These may be used alone or in combination of two or more.

From the viewpoint of cost and dilutability, as the above radically polymerizable unsaturated monomer (B) component, methyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, (meth) acrylic Preferred are lauryl acid and styrene.

In the radically polymerizable resin composition of the present invention, the content of component (A) is preferably 5 to 95% by mass, more preferably 15 to 85% by mass, based on the total amount of components (A) and (B). More preferably, it is 25 to 75% by mass. If the content of the component (A) with respect to the total amount of the components (A) and (B) is within the above range, good workability can be obtained.

<Amine-based accelerator (C)>
As the amine curing accelerator (C) used in the present invention, known amines can be used without particular limitation, and specifically, aniline, N, N-dimethylaniline, N, N-diethylaniline, p- Toluidine, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2) -Hydroxyethyl) amino] benzaldehyde, 4- (N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine , M-toluidine, diethylenetriamine, pyridine, phenylymorpholine, piperidine, N, N-bis (2-hydroxyethyl) Aniline, diethanol aniline, 2,4,6-tris (dimethylaminomethyl) phenol, N, the N- dimethylbenzylamine amines such like. Among them, aromatic tertiary amines are preferable from the viewpoint of facilitating curing. Specifically, N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl)- p-Toluidine and N, N-bis (2-hydroxyethyl) aniline are preferred. Among these, hydroxyl group-containing aromatic tertiary amines are more preferable. Specifically, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl) -p-toluidine, N, N-bis (2-hydroxyethyl) aniline preferable.

The content of the amine curing accelerator (C) is preferably 0.01 to 10 parts by mass, more preferably 100 parts by mass in total of the (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. The amount is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass. It is easy to adjust the curability if the content is within the above range.

<Multifunctional thiol compound (D)>
The polyfunctional thiol compound (D) used in the present invention is a compound having a plurality of mercapto groups, and is selected from primary thiol compound (D1), secondary thiol compound (D2) and tertiary thiol compound (D3). Compound. These may be used alone or in combination of two or more. From the viewpoint of storage stability and odor, secondary or tertiary thiol compounds are preferred.
Here, “primary thiol compound” refers to a compound having a mercapto group bonded to a primary carbon atom, and similarly, “secondary thiol compound” has a mercapto group bonded to a secondary carbon atom. The compound or “tertiary thiol compound” refers to a compound having a mercapto group bonded to a tertiary carbon atom. In the present invention, even if the secondary thiol compound has a mercapto group bonded to a primary carbon atom, the compound is regarded as a secondary thiol compound (D2). Similarly, when the tertiary thiol compound has at least one of at least one of a mercapto group bonded to a primary carbon atom and a mercapto group bonded to a secondary carbon atom, the compound is a tertiary thiol compound (D3). It is regarded as
Accordingly, the primary thiol compound (D1), secondary thiol compound (D2) and tertiary thiol compound (D3) used in the present invention are thiol compounds having a plurality of mercapto groups in the compound. The number of mercapto groups in the thiol compound is usually about 2 to 10, and in particular, by using a thiol compound having 2 to 6 mercapto groups, the odor after curing of the resin composition is reduced. be able to.

The polyfunctional thiol compound (D) used in the present invention is preferably a compound having a structure represented by the following general formula (Q).

In the above general formula (Q), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. * Indicates linking to any organic group having at least one mercapto group. a is an integer of 0 to 2;

Among the polyfunctional thiol compounds (D) represented by the general formula (Q), those having a structure represented by the following general formula (Q-1) are preferable.

In Formula (Q-1), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. ** represents linking to any organic group having at least one mercapto group. a is an integer of 0 to 2;

Among the polyfunctional thiol compounds (D) represented by the general formula (Q) and the general formula (Q-1), an ester of a mercapto group-containing carboxylic acid represented by the following general formula (S) and a polyhydric alcohol Compounds are more preferred. Such a compound is obtained by an esterification reaction of a mercapto group-containing carboxylic acid and a polyhydric alcohol in a known manner.

(In the general formula (S), R ³ 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 ⁴ is an alkyl group having 1 to 10 carbon atoms or the carbon number 6 to 18 aromatic groups, a is an integer of 0 to 2)

When the mercapto group-containing carboxylic acid represented by the general formula (S) is a derivative compound of the secondary thiol compound (D2), specifically, 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto -3-phenylpropionic acid and the like.
Further, when it is a compound derived from the tertiary thiol compound (D3), specifically, 2-mercaptoisobutyric acid, 3-mercapto-3-methylbutyric acid and the like can be mentioned.

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propanediol, 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecanedimethanol, 2,2-bis (2-hydroxyethoxyphenyl) propane, bisphenol A alkyleneoxy Adduct, bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-hexanediol, 2,3- Hexanediol, 1,4-Hexanediol, 2,4-Hexanediol, 3,4-Hexanediol, 1,5-Hexanediol, 2,5-Hexanediol, 1,6-Hexanediol, 9,9-bis Dihydric alcohols such as [4- (2-hydroxyethyl) phenyl] fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris (2-hydroxyethyl) isocyanurate, hexanetriol, sorbitol , Penta Risuritoru, dipentaerythritol, sucrose, 2,2-bis (2,3-dihydroxy propyloxy phenyl) trivalent or more alcohols such as propane and the like; polycarbonate diol, and dimer acid polyester polyol and the like.

Among them, dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol and the like from the viewpoint of exhibiting the curing accelerating ability even under easy availability and wet conditions Glycerin, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, trivalent or higher trivalent compounds such as 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane; Alcohol; polycarbonate diol, dimer acid polyester polyol is preferable, and from the viewpoint of functional group number and vapor pressure, 1,4-butanediol, trimethylol ethane, trimethylol propane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol Lumpur, polycarbonate diols, dimer acid polyester polyol is more preferred.

[Primary thiol compound (D1)]
Specific examples of the primary thiol compound (D1) include trimethylolpropane tristhiopropionate, tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate, pentaerythritol tetrakis (3-mercaptopropio) And tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate) and the like.
As a commercial item of a compound having two or more primary mercapto groups in the molecule among primary thiol compounds (D1), pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by SC Organic Chemical Co., Ltd., product Name: PEMP), trimethylolpropane tristhiopropionate (manufactured by Sakai Chemical Co., Ltd., product name: TMTP), etc. are preferably used.

[Secondary thiol compound (D2)]
Specifically, as the secondary thiol compound (D2), 3-mercaptophthalic acid di (1-mercaptoethyl), phthalic acid di (2-mercaptopropyl), phthalic acid di (3-mercaptobutyl), ethylene glycol Bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate) ), Trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), Tylene glycol bis (2-mercapto propionate), propylene glycol bis (2- mercapto propionate), diethylene glycol bis (2- mercapto propionate), butanediol bis (2-mercapto propionate), octanediol bis (2-Mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol Bis (4-mercaptovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate), octanediol bis (4-mercaptovalerate) Tri) trimethylolpropane tris (4-mercaptovalerate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), Propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptovalerate), octanediol bis (3-mercaptovalerate), trimethylolpropane tris (3- 3- Mercaptovalerate), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexakis (3-mercaptovalerate), hydrogenated bisphenol A bis (3-mercapto) Butyrate), 4,4 ′-(9-fluorenylidene) bis (2-phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto) -3-phenylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto-3-phenylpropionate) ), Trimethylolpropane tris (3-mercapto-3-phenylpropionate), tris-2- (3-mercapto-3-phenylpropionate) ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phen) ), Dipentaerythritol hexakis (3-mercapto-3-phenyl propionate), 1,3,5-tris [2- (3-mercaptobutyryloxyethyl)]-1,3,5- And triazine-2,4,6 (1H, 3H, 5H) -trione and the like.

Among commercially available secondary thiol compounds (D2), compounds having two or more secondary mercapto groups in the molecule include 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK) “Kalens MT (registered trademark) BD1”), pentaerythritol tetrakis (3-mercaptobutyrate) (“Kalens MT (registered trademark) PE1” manufactured by Showa Denko KK), 1,3,5-tris [2- ( 3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione ("Kalens MT (registered trademark) NR1" manufactured by Showa Denko KK), Trimethylol ethane tris (3-mercaptobutyrate) ("SEMB" manufactured by Showa Denko KK), trimethylolpropane tris (3-mercaptobutyrate) (Showa Denko KK) "TPMB") or the like is preferably used.

[Third-order thiol compound (D3)]
Specific examples of the tertiary thiol compound (D3) include phthalic acid di (2-mercaptoisobutyl), ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), and diethylene glycol Bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2-mercaptoisobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane Tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), di (3-mercapto-3-methylbutyl) phthalate, Tyrene glycol bis (3-mercapto-3-methyl butyrate), propylene glycol bis (3-mercapto-3-methyl butyrate), diethylene glycol bis (3-mercapto-3-methyl butyrate), butanediol bis (3- Mercapto-3-methylbutyrate), octanediol bis (3-mercapto-3-methylbutyrate), trimethylolethane tris (3-mercapto-3-methylbutyrate), trimethylolpropane tris (3-mercapto-3) -Methyl butyrate), pentaerythritol tetrakis (3-mercapto-3-methyl butyrate), dipentaerythritol hexakis (3-mercapto 3-methyl butyrate) and the like.

The content of the polyfunctional thiol compound (D) is preferably 0.1 to 20 parts by mass, more preferably 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. Is 0.3 to 15 parts by mass. When the content is 0.1 parts by mass or more, effects such as low temperature curability and adhesion improvement can be sufficiently exhibited. Moreover, if content is 20 mass parts or less, the intensity | strength at the time of curing a resin composition can fully be maintained, and it is suitable as a repair material use of a structure.

<Hardener (E)>
The radically polymerizable resin composition of the present invention may contain a curing agent (E). The curing agent (E) used in the present invention is not particularly limited, and known radical polymerization initiators can be used, and it is preferable to use an organic peroxide.
Examples of the organic peroxide include ketone peroxide, perbenzoate, hydroperoxide, diacyl peroxide, peroxy ketal, hydroperoxide, diallyl peroxide, peroxy ester, peroxy dicarbonate and the like. More specifically, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl perbenzoate, dibenzoyl peroxide (also referred to as benzoyl peroxide), benzoyl m-methyl benzoyl peroxide, m-toluoyl peroxide, dicumyl peroxide Peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butylperoxybenzoate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,5-dimethyl- 2,5-Bis (t-butylperoxy) hexyne-3, 3-isopropylhydroperoxide, t-butylhydroperoxide, dicumyl hydroperoxide, acetylperoxide, bis (4-t-butylcyclohexene) ) Peroxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethyl hexanoyl peroxide, lauryl peroxide and the like can be used. Moreover, an azo compound etc. can also be used as a hardening | curing agent, Specifically, azobisisobutyronitrile, azobis carbonamide etc. are mentioned. These organic peroxides and azo compounds can be used alone or in combination. Among these, dibenzoyl peroxide, benzoyl m-methyl benzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate from the viewpoint of availability. Is preferred. More preferably, dibenzoyl peroxide, benzoyl m-methyl benzoyl peroxide, and m-tolu oil peroxide are preferable from the viewpoint of being hardly affected by moisture when curing.

The compounding amount of the curing agent (E) is preferably 0.1 to 10 parts by mass, more preferably 0.3 to 8 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). Even more preferred is 0.5 to 6 parts by weight. When the compounding amount of the curing agent (E) is 0.1 parts by mass or more, desired curability is easily obtained. On the other hand, it is economically advantageous that the compounding quantity of a hardening | curing agent (E) is 10 mass parts or less, and sufficient working time is easy to be obtained.

<Other ingredients>
[Polymerization inhibitor]
The radically polymerizable resin composition of the present invention is a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer, and from the viewpoint of controlling the reaction rate. May be included.
Examples of the polymerization inhibitor include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, 4-tert-butyl catechol and the like.

[Curing accelerators other than amines]
The radical polymerizable resin composition of the present invention may contain a curing accelerator other than the above-mentioned amine curing accelerator. There is no particular limitation on curing accelerators other than amine type, and known metal organic compounds and β-diketones can be used.
Examples of metal organic compounds include copper compounds such as copper naphthenate, cobalt compounds such as cobalt octylate, cobalt naphthenate and cobalt hydroxide, zinc compounds such as zinc hexoate, and manganese compounds such as manganese octylate. . Among these, cobalt naphthenate, cobalt octylate and copper naphthenate are preferable. These metal organic compounds can be used alone or in combination.
Examples of the β-diketones include acetylacetone, ethyl acetoacetate, α-acetyl-γ-butyrolactone, N-pyrrolininoacetoacetamide, N, N-dimethylacetoacetamide and the like.
The compounding amount of the metal organic compound is preferably 0.1 to 5 parts by mass, preferably 0.3 to 3 parts by mass, with respect to 100 parts by mass in total of the components (A) and (B). Is more preferred. When the amount of the metal organic compound is 0.1 parts by mass or more, a desired curing time and a cured state can be easily obtained, and the drying property is improved. On the other hand, when the blending amount of the metal organic compound is 5 parts by mass or less, desired pot life and storage stability can be easily obtained.

[Photopolymerization initiator]
The radically polymerizable resin composition of the present invention may contain a photopolymerization initiator for the purpose of improving the curability. As a photoinitiator, an optical radical polymerization initiator etc. are mentioned, for example.
The radical photopolymerization initiator is used to promote the polymerization of an acrylic resin or monomer having a double bond and to improve the curability.
Specifically, as a radical photopolymerization initiator, benzoin ether type such as benzoin alkyl ether, benzophenone type, benzophenone type such as benzyl, methyl ortho benzoyl benzoate, benzyl dimethyl ketal, 2, 2-diethoxyacetophenone, 2-hydroxy type Acetophenones such as -2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. The thing of a thioxanthone type is mentioned.
The photopolymerization initiator can be added in a range of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. .

[Surfactant]
The radically polymerizable resin composition of the present invention may contain a surfactant from the viewpoint of improving compatibility between the resin and water and facilitating curing in a state in which the water is embraced in the resin.
Surfactants include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. These surfactants may be used alone or in combination of two or more.
Among these surfactants, one or more selected from anionic surfactants and nonionic surfactants are preferable.

Examples of anionic surfactants include alkyl sulfate ester salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate; and polyoxyethylene alkyl such as polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene alkyl ether sulfate triethanolamine Ether sulfuric acid ester salts; sulfonic acid salts such as sodium dodecyl benzene sulfonic acid, sodium dodecyl benzene sulfonic acid, sodium alkylnaphthalene sulfonic acid, sodium dialkyl sulfosuccinate; fatty acid salts such as sodium stearate soap, potassium oleate soap, castor oil potassium soap etc Naphthalenesulfonic acid formalin condensates, special polymer systems, etc. may be mentioned.
Among these, sulfonates are preferable, sodium dialkyl sulfosuccinate is more preferable, and sodium dioctyl sulfosuccinate is still more preferable.

Examples of nonionic surfactants include polyoxyethylene alkyl ether such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc., polyoxyethylene di-styrenated phenyl ether, poly Polyoxyethylene derivatives such as oxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, etc .; Sorbitan fatty acid esters such as polyoxyalkylene alkyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate; polyoxyethylene Sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate Etc. polyoxyethylene sorbitan fatty acid esters; polyoxyethylene sorbit tetraoleate and the like of the polyoxyethylene sorbitol fatty acid esters; glycerol monostearate, glycerine fatty acid esters such as glycerol monooleate.

Among these nonionic surfactants, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene alkyl ether are preferable. Further, HLB (Hydrophile-Lipophil Balance) of the nonionic surfactant is preferably 5 to 15, and more preferably 6 to 12.
When the radically polymerizable resin composition of the present invention contains a surfactant, the content thereof is 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. The amount is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 7 parts by mass, and still more preferably 0.1 to 5 parts by mass.

[Interface regulator]
The radically polymerizable resin composition of the present invention may contain, for example, a wet interface conditioner as an interface regulator in order to improve the permeability to a wet or submerged site to be repaired.
Examples of the wet interface conditioner include fluorine-based wet interface conditioners and silicone-based wet interface conditioners, and these may be used alone or in combination of two or more.
Commercially available products of fluorine-based wet interface conditioners are Megafac® F176, Megafac® R08 (Dainippon Ink and Chemicals, Inc.), PF656, PF6320 (OMNOVA), Troysol. S-366 (manufactured by Troy Chemical Co., Ltd.), Florard FC 430 (manufactured by 3M Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Commercial products of silicone-based wetting and dispersing agents include BYK (R) -322, BYK (R) -377, BYK (R) -UV3570, BYK (R) -330, BYK (R) -302 And BYK (registered trademark) -UV 3500, BYK-306 (manufactured by Bick Chemie Japan Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Other commercial products of the wet interface conditioner include Perex NBL, Perex OT-P, Perex TR (manufactured by Kao Corporation), and the like.
When the radically polymerizable resin composition of the present invention contains a surface conditioner, the content thereof is 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. Preferably, it is 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

[Modifier]
The radically polymerizable resin composition of the present invention may contain a thixotropic agent for the purpose of viscosity adjustment and the like for securing workability on a vertical surface and a ceiling surface.
As thixotropic agents, inorganic thixotropic agents and organic thixotropic agents can be mentioned, and as organic thixotropic agents, hydrogenated castor oil type, amide type, polyethylene oxide type, vegetable oil polymerized oil type, surface activity Agent systems and complex systems using these in combination, and specific examples thereof include DISPARLON (registered trademark) 6900-20X (Kushimoto Chemical Co., Ltd.) and the like.
Further, examples of inorganic thixotropic agents include silica and bentonite, and as hydrophobic ones, Reoroseal (registered trademark) PM-20L (gas phase method silica manufactured by Tokuyama Corporation), Aerosil (registered trademark) AEROSIL R-106 (Nippon Aerosil Co., Ltd.) and the like can be mentioned, and examples of hydrophilic substances include Aerosil (registered trademark) AEROSIL-200 (Nippon Aerosil Co., Ltd.) and the like. From the viewpoint of further improving thixotropy, BYK (registered trademark) -R605 and BYK (registered trademark) -R606 (manufactured by Bick Chemie Japan Ltd.), which are thixotropic modifiers, were added to hydrophilic calcined silica. Those can also be suitably used.
When the radically polymerizable resin composition of the present invention contains a thixotropic agent, the content thereof is 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. And preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass

[Wet dispersant]
The radically polymerizable resin composition of the present invention may contain a wetting and dispersing agent for the purpose of high filling at the time of filler mixing, viscosity reduction, sedimentation prevention and the like. These may be used alone or in combination of two or more.
Commercial products of the wetting and dispersing agent include BYK-W909, BYK-W985, BYK-W966, BYK-W980, BYK-W969, BYK-W996, BYK-W9010, BYK-W940 and the like.
When the radically polymerizable resin composition of the present invention contains a wetting dispersant, the content thereof is based on 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. Preferably, it is 0.1 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass, and still more preferably 0.5 to 2.0 parts by mass.

[Curing retarder]
The radically polymerizable resin composition of the present invention may contain a curing retarder for the purpose of adjusting the curing time. The curing retarder includes free radical curing retarder, for example, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6- Examples include TEMPO derivatives such as tetramethylpiperidine 1-oxyl free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4-Oxo-TEMPO). Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4H-TEMPO) is preferable in terms of cost and ease of handling.
When the radically polymerizable resin composition of the present invention contains a polymerization inhibitor and a curing retarder, the amount is 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. On the other hand, the amount is preferably 0.0001 to 10 parts by mass, and more preferably 0.001 to 10 parts by mass.

[Defoamer]
The radically polymerizable resin composition of the present invention may contain an antifoaming agent in order to improve the generation of foam during molding and the foam residue of the molded article. As an antifoamer, a silicone type antifoamer, a polymer type antifoamer etc. are mentioned.
The amount of the antifoaming agent used is preferably in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the (A) radically polymerizable resin and the (B) radically polymerizable unsaturated monomer. More preferably, it is 0.1 to 1 part by mass.

[Coupling agent]
The radically polymerizable resin composition of the present invention may contain a coupling agent for the purpose of improving the adhesion to a substrate to be repaired. Examples of the coupling agent include known silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like.
As such a coupling agent, for example, a silane coupling agent represented by R ⁵ -Si (OR ⁶ ) ₃ can be mentioned. Examples of R ⁵ include, for example, aminopropyl group, glycidyloxy group, (meth) acryloxy group, N-phenylaminopropyl group, mercapto group, vinyl group and the like, and as R ⁶ , for example, methyl group And ethyl groups.
When the radically polymerizable resin composition of the present invention contains a coupling agent, the content thereof is 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. Preferably, it is 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass.

[Light stabilizer]
The radically polymerizable resin composition of the present invention may use a light stabilizer in order to improve the long-term durability of the molded article. Examples of the light stabilizer include ultraviolet light absorbers and hindered amine light stabilizers. These may be used alone or in combination of two or more. Specific examples of the ultraviolet absorber include benzotriazole, triazine, benzophenone, cyanoacrylate and salicylate. Examples of the hindered amine light stabilizer include NH type and NCH ₃ type. And N—O alkyl type.
The amount of the light stabilizer used is in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. Preferably, it is 0.05 to 2 parts by mass.

〔wax〕
The radically polymerizable resin composition of the present invention may contain a wax for the purpose of improving surface drying. As the wax, paraffin waxes, polar waxes and the like can be used alone or in combination, and known ones having various melting points can be used.
Polar waxes include those having a combination of polar and nonpolar groups in the structure. Specifically, NPS-8070, NPS-9125 (manufactured by Nippon Seiwa Co., Ltd.), Emmonon 3199, 3299 (manufactured by Kao Corporation), BYK (registered trademark)-S740, BYK (registered trademark)-S750N, BYK (registered trademark) ) -S760, BYK (registered trademark)-S780, BYK (registered trademark)-S781, BYK (registered trademark)-S782 and the like.
The wax is preferably contained in an amount of 0.05 to 4 parts by mass with respect to 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. More preferably, it is contained in an amount of 0.

〔Flame retardants〕
The radically polymerizable resin composition of the present invention may contain a flame retardant. As the flame retardants, bromine flame retardants, chlorine flame retardants, phosphorus flame retardants, inorganic flame retardants, intumescent flame retardants, silicone flame retardants and the like can be used alone or in combination, and known flame retardants Can be used.
In addition, a halogen-based flame retardant such as a bromine-based flame retardant can be used in combination with antimony trioxide for the purpose of further improving the flame retardancy.
Although the addition amount of the flame retardant varies depending on the system and type of the flame retardant, it is 1 to 100 parts by mass with respect to a total of 100 parts by mass of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. It is preferable to contain part.

[Plasticizer]
The resin composition of the present invention may contain a plasticizer for the purpose of viscosity adjustment and flexibility adjustment of the cured product. As a plasticizer, epoxys, polyesters, phthalic acid esters, adipic acid esters, trimellitic acid esters, phosphoric acid esters, citric acid esters, sebacic acid esters, azeline Acid esters, maleic acid esters, benzoic acid esters, etc. can be used alone or in combination, and known ones can be used.
Although the addition amount of the plasticizer varies depending on the type, it is contained in 0.01 to 20 parts by mass with respect to 100 parts by mass in total of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. It is preferable to do. More preferably, the content is 0.1 to 10 parts by mass.

The total content of the components (A), (B), (C) and (D) in the radically polymerizable resin composition of the present invention is preferably 30 to 100% by mass, more preferably It is 60 to 100% by mass, more preferably 90 to 100% by mass.
When the radically polymerizable resin composition of the present invention contains (E) a curing agent, the (A) component, the (B) component, the (C) component, and the (C) component in the radically polymerizable resin composition of the present invention The total content of the D) component and the (E) curing agent is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, and still more preferably 90 to 100% by mass.

<Viscosity of Radically Polymerizable Resin Composition>
The viscosity of the radically polymerizable resin composition of the present invention is preferably 10 to 1000 mPa · s / 25 ° C. from the viewpoint of ease of injection into cracks of the inorganic structure and ease of mixing into fillers and the like. More preferably, the viscosity is 30 to 500 mPa · s / 25 ° C., further preferably 50 to 400 mPa · s / 25 ° C. Here, the method of measuring the viscosity is as described in the examples.

<Method of producing radically polymerizable resin composition>
The method for producing the radically polymerizable resin composition of the present invention is not particularly limited to the order of mixing of the components, but from the viewpoint of workability for efficiently obtaining a homogeneous mixture, viscosity adjustment as a radically polymerizable composition, etc. From the viewpoint of workability when adjusting the composition to the target physical property range, a part of the component (B) is added and mixed after synthesis of the component (A), and the viscosity of the component (A) is reduced, It is preferable to add and mix the (B) component of and other components. Alternatively, a part of the component (B) is used as a diluent at the time of synthesis of the component (A) to obtain a mixture of the component (A) and the part (B), and then the remaining component (B) and other components are obtained. Is preferably added and mixed. The mixing ratio of the component (A) to the component (B) at the time of lowering the viscosity is not particularly limited, but it is preferably 95: 5 to 20:80, more preferably 85:15 to 30:70 by mass ratio. is there.
The viscosity of the mixture of the component (A) and the partial component (B) is preferably 50 to 4000 mPa · s, more preferably 80 to 3000 mPa · s, and still more preferably 100 to 2000 mPa · s. The method of measuring the viscosity is as described in the examples. If the viscosity is adjusted in advance to the above-mentioned range, the remaining components can be mixed uniformly to form the radically polymerizable resin composition of the present invention in a short time.

[Structure restoration material]
The radically polymerizable resin composition of the present invention can be used as a structure repair material containing the radically polymerizable resin composition.
Examples of the structure include inorganic structures such as concrete, asphalt concrete, mortar, metal and the like, and wood. Particularly preferably, it can be used as a structural restoration material for slab type tracks such as expressways and railways.

<Filler (F)>
Although the structure restorative material of the present invention can use the radically polymerizable resin composition of the present invention as a structure restorative material, the filler (F) is contained in the radically polymerizable resin composition of the present invention , Can be a structural restoration material. The filler (F) is not particularly limited, and examples thereof include inorganic fillers and organic fillers.
As the inorganic filler, cement, quicklime, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, artificial bone such as calcium carbonate, ceramic, glass waste, etc. containing silica as a main component Known materials such as wood, talc, zeolite and activated carbon can be used, but from the viewpoint of flowability, material cost saving and material availability, a combination with silica sand, calcium carbonate, talc and fumed silica is preferred. As silica sand, natural silica sand, square grain silica sand, artificial silica sand etc. can be used. As the size of silica sand, those of about 3 to 8 can be used. As calcium carbonate, synthetic calcium carbonate, light calcium carbonate and ground calcium carbonate can be used. The average particle size of calcium carbonate is not particularly limited, and those in a generally used range can be used. Moreover, aluminum hydroxide can be used from a viewpoint of providing a flame retardance. Further, from the viewpoint of coloring, colorants such as titanium oxide and iron oxide and inorganic pigments can be used, and molecular sieves can also be used. The particle size of the inorganic filler is preferably 1 nm to 5000 μm, and more preferably 10 nm to 3000 μm. When the particle size of the inorganic filler is in the above range, good workability and physical properties can be obtained.
As the organic filler, an organic filler such as an amide wax or a water absorbing polymer can also be used.

Moreover, a fiber can also be used as said filler (F). Specific examples of the fibers include glass fibers, carbon fibers, basic magnesium sulfate fibers, vinylon fibers, nylon fibers, aramid fibers, polypropylene fibers, polyester fibers such as acrylic fibers and polyethylene terephthalate fibers, metals such as cellulose fibers and steel fibers Fibers, ceramic fibers such as alumina fibers, natural fibers such as basalt fibers, and the like can be mentioned. These fibers are, for example, in the form of a fiber structure selected from plain weave, satin weave, non-woven fabric, mat, roving, chops, flakes, knits, composites, composite structures thereof, etc., biaxial mesh, triaxial mesh It is preferable to use in For example, the fiber structure may be impregnated with a radically polymerizable composition, and in some cases, it may be prepolymerized to be used as a prepreg.
As a mesh, for example, a biaxial mesh or a triaxial mesh is used. The length of one side (gross) of the square of the biaxial mesh and the length (gross) of one side of the regular triangle of the triaxial mesh are preferably 5 mm or more, and more preferably 10 to 20 mm. By using a biaxial mesh or a triaxial mesh, it is possible to obtain a structural reinforcement material that is lightweight and is excellent in economy, workability, and durability.
These fibers are preferably used when reinforcing a structure.
Among the fibers, in applications such as structure reinforcement, glass fibers, cellulose fibers and the like, which are excellent in strength and cost, are preferable in that the deterioration state of the substrate can be visually inspected from the outside. In addition, carbon fiber is also preferable from the viewpoint of strength and weight reduction. The said filler (F) may be used individually by 1 type, and may use 2 or more types together.

When the structure restoration material of the present invention contains a filler (F), the compounding amount thereof is preferably 1 to 700 parts by mass with respect to 100 parts by mass in total of the component (A) and the component (B), The amount is more preferably 10 to 600 parts by mass, further preferably 50 to 500 parts by mass. When fibers are used as the filler (F), the blending amount is preferably 5 to 400 parts by mass, and 15 to 300 parts by mass with respect to 100 parts by mass in total of the components (A) and (B). It is more preferably part, and still more preferably 30 to 250 parts by mass. If the compounding ratio of the filler is within the above range, curability and workability are good, which is preferable.

Although the method of repairing the structure is not particularly limited, for example, the method of the present invention may be carried out by applying the structure restorative material of the present invention to a restoration site such as concrete, asphalt concrete, mortar, wood, metal, etc., drying and curing. it can. The method of applying the structure restoration material is not particularly limited, but, for example, a coating method by dipping, a coating method by spray, a coating method by roller, a coating method using an instrument such as a brush, brush or spatula, and the like can be applied.
The application amount of the structure restoration material is not particularly limited, but is appropriately adjusted in consideration of the size of the restoration portion, the adhesion of the structure restoration material, the strength of the cured product of the structure restoration material, and the like.
Although the drying method after applying a structure restorative material is not particularly limited, a method of natural drying or a method of heating within a range in which the properties of the cured product of the structure restorative material do not deteriorate are used.
Alternatively, the structure restoration material of the present invention can be restored by directly injecting it into a cracked part of the structure, and drying and hardening it.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited by the examples.

<Composition example>
As described later, a urethane methacrylate resin (UM1), which is a radically polymerizable resin, is synthesized using the following raw materials, and then methyl methacrylate (Mitsubishi Rayon (stock) is used as a radically polymerizable unsaturated monomer (B) Product name: Acrylic ester M) was mixed to obtain a mixture of the component (A) and the component (B).

The raw material of urethane methacrylate resin (UM1) is shown below.
(Polyhydric alcohol)
Polypropylene glycol 1 (weight average molecular weight 1000), manufactured by Mitsui Chemicals, Inc., product name: Actocal D-1000
Polypropylene glycol 2 (weight average molecular weight 2000), manufactured by Mitsui Chemicals, Inc., product name: Actocal D-2000
(Polyvalent isocyanate)
Diphenylmethane diisocyanate (hydroxyl group containing (meth) acrylate)
2-Hydroxypropyl Methacrylate Next, a synthesis example of the urethane methacrylate resin (UM1) will be specifically described.

Synthesis Example 1
In a 3 L four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube and a thermometer, 500 g (2.0 mol) of diphenylmethane diisocyanate, Actocol D-1000 (Mitsui Chemical Co., Ltd. polypropylene glycol 1: Weight average molecular weight 1000): 100 g (0.1 mol), Actocol D-2000 (Mitsui Chemical Co., Ltd. polypropylene glycol 2: weight average molecular weight 2000): 1800 g (0.9 mol), and dibutyltin dilaurate: 0.2 g Were reacted at 60.degree. C. for 4 hours with stirring. Subsequently, the reaction product was stirred while adding 2-hydroxypropyl methacrylate: 288 g (2.0 mol) dropwise over 2 hours, and after completion of the dropwise addition, the reaction was stirred for 5 hours to be reacted to obtain a urethane methacrylate resin (UM 1) . The weight average molecular weight of the obtained urethane methacrylate resin (UM1) according to the following measurement method was 9055.
Next, 1035 g of methyl methacrylate was added to the urethane methacrylate resin (UM1) to obtain a mixture of the component (A) and the component (B). Moreover, the viscosity at 25 degrees C of the mixture by the following measuring method was 300 mPa * s, and the liquid specific gravity was 1.02.

<Measurement of weight average molecular weight>
Gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) was used. The weight average molecular weight was measured at normal temperature (23 ° C.) under the following conditions, and calculated in terms of polystyrene.
(Measurement condition)
Column: Showa Denko LF-804, 2 columns Column temperature: 40 ° C
Sample: 0.4% by mass solution of the substance to be measured in tetrahydrofuran Flow rate: 1 ml / min Eluent: tetrahydrofuran

<Measurement of viscosity>
The viscosity under a 25 ° C. environment was measured at a rotational speed of 100 rpm using a Toki Sangyo Co., Ltd. RE-85 viscometer, a cone-plate type, and a cone rotor 1 ° 34 ′ × R24.

<Measurement of liquid specific gravity>
The liquid specific gravity at 23 ° C. was measured using an electronic gravimeter MD-200S manufactured by Alpha Mirage Co., Ltd. according to JIS K 7112 ^-1999 , Annex 2, “Plastic-liquid resin-substitution method in water”.

Examples 1 to 17
As a raw material, the mixture obtained in Synthesis Example 1 and, if necessary, the (B) radically polymerizable unsaturated monomer, the following (C) amine-based curing accelerator, (D) polyfunctional thiol compound, (E) The curing agent was used as a raw material of the radically polymerizable resin composition.
(C) Amine curing accelerator N, N-bis (2-hydroxypropyl) -p-toluidine, manufactured by Wako Pure Chemical Industries, Ltd., Product name: Accelerator A
(D) Polyfunctional thiol compound (1) Pentaerythritol tetrakis (3-mercaptobutyrate), tetrafunctional secondary thiol, manufactured by Showa Denko KK, product name: Karenz MT PE1
(2) Trimethylolpropane-tris (3-mercaptobutyrate) trifunctional secondary thiol, manufactured by Showa Denko KK, product name: TPMB
(3) 1,4-bis (3-mercaptobutyryloxy) butane, bifunctional secondary thiol, manufactured by Showa Denko KK, product name: Kalens MT BD 1
(4) Pentaerythritol tetrakis (3-mercaptopropionate), tetrafunctional primary thiol, SC Organic Chemical Co., Ltd. product name: PEMP
(5) Trimethylolpropane tristhiopropionate, trifunctional primary thiol, Sakai Chemical Co., Ltd. product name: TMTP
(E) Hardening agent Dibenzoyl peroxide, Kayaku Akzo Co., Ltd. product name: Percadox CH-50L

(B) A radically polymerizable unsaturated monomer is added to the mixture of the (A) component and the (B) component so that the mass ratio of the (A) component / (B) component becomes 65/35. Then, a preliminary sample consisting of the (A) component and the (B) component was obtained. Then, (C) an amine-based curing accelerator, (D) a polyfunctional thiol compound, and (E) curing, per 100 parts by mass of this preliminary sample, that is, 100 parts by mass in total of the components (A) and (B) The agents were added in this order at the ratio shown in Tables 1 to 3 and stirred to obtain a radically polymerizable resin composition. With respect to the radically polymerizable resin composition thus obtained, the curability was measured and evaluated by the following method. The results are shown in Tables 1 to 3.

Comparative Example 1
(D) A radically polymerizable resin composition was obtained in the same manner as in Example 1 except that the polyfunctional thiol compound was not contained. The content of each component of the radically polymerizable resin composition is shown in Table 1. With respect to the radically polymerizable resin composition thus obtained, the curability was similarly measured and evaluated. The results are shown in Table 1.

<Curableness measurement under 25 ° C. environment>
The gelation time, the curing temperature and the curing time were evaluated by the evaluation methods shown below.
The resin composition is adjusted to 25 ° C., placed in a test tube (outer diameter 18 mm, length 165 mm) to a depth of 100 mm, placed in a thermostatic chamber set at 25 ° C., and the temperature of the resin composition is measured by a thermocouple. did. The time taken for the temperature of the resin composition to reach 25 ° C. to 35 ° C. was measured and used as the gelation time (unit: minute).
The minimum cure time the time until the resin composition to reach the maximum exothermic temperature, defines a heating temperature at that time as a curing temperature was measured according to JIS K-6901 ^-2008.
<Curableness measurement under 10 ° C. environment>
Evaluation was performed in the same manner as the 25 ° C. curability except that the temperature of the resin composition and the measurement environmental temperature were set to 10 ° C.

As shown in Tables 1 to 3, the radically polymerizable resin composition of the present invention containing a multifunctional thiol compound is as shown by the gelation time and the minimum curing time even in a 10 ° C. environment at 25 ° C. and a low temperature. It was found that fast curing was obtained.
In particular, it was found that in the examples where the total amount of polyfunctional thiol compounds was 0.5 parts by mass or more, the curing rate became faster. Moreover, in the examples of 0.3 parts by mass or more, the chain transfer agent effect shows a tendency to extend the time from gelation time to the minimum curing time, and a rapid curing process is obtained because a mild curing process is obtained. It has been found that the contraction can be alleviated.
On the other hand, the radically polymerizable resin composition of Comparative Example 1 which does not contain a polyfunctional thiol compound is slower in curing than the resin composition of Examples 1 to 22, and from the gelation time to the minimum curing time. It turned out that the time of was short.

Examples 18 to 34
The mixture of (A) component / (B) component by mass ratio of 65/35 used in Example 1 and the above-mentioned (C) amine curing accelerator, (D) polyfunctional thiol compound, (E) curing agent and The filler (F) described below was used.
(F) Filler (1) Silica sand, manufactured by Takeori Works, product name: Silica sand No. 8 (2) calcium carbonate, Nitto Powder Co., Ltd., product name: S light # 1200, average particle size Diameter: 2.6 μm

In the same manner as in Example 1, (C) an amine-based curing accelerator and (D) a multifunctional thiol compound with respect to a total of 100 parts by mass of the (A) component and the (B) component in the proportions shown in Tables 4 to 6 And (E) A hardening | curing agent was added in this order and it stirred, and obtained the radically polymerizable resin composition which does not contain the (F) filler. Further, (F) filler was added at a ratio shown in Tables 4 to 6 and stirred to obtain a structure restorative material.
The contents of each component of the structure restoration material are shown in Tables 4 to 6.
Then, the test body for adhesion tests was produced by the method shown below using the obtained structure restorative material.
The adhesiveness of the structure restorative material thus obtained was measured by the following method to evaluate the adhesiveness. The results are shown in Tables 4 to 6.

<Method of preparing test specimen for adhesion test>
The structure restoration material obtained above is environment-friendly on one JIS K 5600 cement mortar board of length × width × thickness = 70 mm × 70 mm × 20 mm used in the method for preparing a test specimen for bending load test described later. It was molded with a thickness of 3 mm under a temperature of 25 ° C. and a 50% humidity environment, and was cured with the upper part sealed with a film. Then, I was cured for 24 hours under the same environment. Next, the film on the surface was peeled off, the surface was roughened with # 240 sandpaper, the surface was air blown and washed by acetone degreasing. After that, a dolly with a diameter of 20 mm for adhesion test is fixed with an epoxy adhesive, and it is fixed for 5 hours to cure the adhesive in an environment temperature of 25 ° C and humidity 50% environment. did.

<Adhesive test>
The adhesion of the test specimen for adhesion test obtained above was measured in a test environment of temperature 23 ° C. and humidity 50% using an adhesion tester made by Elcometer, measurement range 0 to 7.0 MPa, using a manual method. . The adhesion was measured twice for each of the adhesion test specimens. And the average value of two measurement results was used for evaluation of adhesive force.

Comparative example 2
(D) A structure restorative material was obtained in the same manner as in Example 18 except that the polyfunctional thiol compound was not contained. Thereafter, in the same manner as in Example 18, a test sample for adhesion test was produced and an adhesion test was conducted. Further, the curability of Comparative Example 2 was adjusted with a polymerization inhibitor so as to be similar to Example 18 as described above, and the influence of the difference in curability was eliminated by setting the gelation time to 7.0 min. The results are shown in Table 4.

As shown in Tables 4 to 6, it was found that the adhesion test specimens of the present invention containing the polyfunctional thiol compounds of Examples 18 to 34 can obtain strong adhesiveness.
On the other hand, Comparative Example 2 had lower adhesion as compared with the adhesion test specimens of Examples 18 to 34.

Examples 35 to 41
The mixture of (A) component / (B) component by mass ratio of 65/35 used in Example 1 and the above-mentioned (C) amine curing accelerator, (D) polyfunctional thiol compound, (E) curing agent and The filler (F) described below was used.
(F) Filler (1) Silica sand, manufactured by Takeori Works, product name: Silica sand No. 8 (2) calcium carbonate, Nitto Powder Co., Ltd., product name: S light # 1200, average particle size Diameter: 2.6 μm

In the same manner as in Example 1, (C) an amine-based curing accelerator, (D) a polyfunctional thiol compound, and (C) based on 100 parts by mass of the mixture of the (A) component and the (B) component in the proportions shown in Table 7 E) A curing agent was added in this order at a ratio shown in Table 7 and stirred to obtain a radically polymerizable resin composition (F) containing no filler. Further, (F) filler was added at a ratio shown in Table 7 and stirred to obtain a structure restorative material.
The content of each component of the structure restorative material is shown in Table 7.
Then, the test body for a bending load test was produced by the method shown below using the obtained structure restorative material.
With respect to the test body for a bending load test obtained using the structure restoration material obtained in this manner, the bending load was measured by the following method, and the bending strength of the restored structure was evaluated. The results are shown in Table 7.

<Method of preparing test specimen for bending load test>
As shown in FIG. 1, two JIS K 5600 cement mortar boards (A, B) of length × width × thickness = 70 mm × 70 mm × 20 mm are arranged in a plane with a space of 20 mm wide and # 240 sandpaper The side (surface in contact with the structure restoration material) was roughened and the surface was cleaned by air blow. The structure restorative material obtained above was injected into the space of length x width x thickness = 70 mm x 20 mm x 20 mm at an environment temperature of 25 ° C and a humidity of 50%, and the upper part was sealed with a film. It was cured in the state. Thereafter, it was aged for 24 hours under the same environment to obtain a specimen for a bending load test shown in FIG.

<Bending load test>
With respect to the test specimen for bending load test obtained above, in a test environment with a temperature of 23 ° C. and a humidity of 50%, using Tensilon UTC-1T manufactured by ORIENTEC Co., Ltd., the distance between supporting points is 40 mm and the test speed is 1 mm / min The bending load was measured by applying a load to a central surface portion (length 70 mm) of the central portion of the cured structure of the structure-repairing material of the test sample for bending load test. A load was applied until the test specimen for load test broke, and the maximum load before breaking was measured. The measurement of the bending load was performed twice for each of the test specimens for bending load test. And the average value of the measurement result of 2 times was used for evaluation of bending load. The higher the value of the bending load test (N), the better the bending strength of the repaired structure.

Comparative example 3
(D) A resin composition for structure repair was obtained in the same manner as in Example 35 except that the polyfunctional thiol compound was not contained. The curability of Comparative Example 3 was adjusted with a polymerization inhibitor so as to be similar to Example 37, and the influence of the difference in curability was eliminated by setting the gelation time to 7.0 min.

As shown in Table 7, the test sample for a bending load test of the present invention containing the multifunctional thiol compound of Examples 35 to 41 has high adhesion between the repair material and the mortar board, so that high bending strength is obtained. Was found to be obtained. On the other hand, Comparative Example 3 had lower bending strength as compared with the test specimens for bending load test of Examples 35-41. This is because the test pieces for bending load test of Examples 35 to 41 have better adhesion between the structure restoration material and the cement mortar board as compared with the test pieces for bending load test of Comparative Example 3. It is a thing.

In Tables 1 to 7, when the composition numbers in the tables are the same, it indicates that the same radical polymerizable resin composition [(A) component to (E) component] is used.

The radically polymerizable resin composition and the structure restorative material of the present invention have low temperature curability and have excellent adhesive strength. Since the resin composition can be rapidly cured even in a low temperature environment and has excellent adhesive strength, it is difficult to cause breakage after adhesion / drying or peeling of the interface between the repaired portion and the restorative material. Therefore, by using the structure restoration material of the present invention, the crack portion can be well repaired with respect to a concrete structure that always involves vibration. That is, when adhering, it is possible to develop excellent adhesion strength, and it can be suitably used for repairing cracks in concrete structures and the like.

Claims

(A) radically polymerizable resin,
(B) radically polymerizable unsaturated monomer,
A radically polymerizable resin composition comprising (C) an amine-based curing accelerator and (D) a polyfunctional thiol compound.
The radically polymerizable resin composition according to claim 1, wherein the component (A) is at least one selected from vinyl ester resins, unsaturated polyester resins, polyester (meth) acrylate resins, and urethane (meth) acrylate resins. object.
The radically polymerizable resin composition according to claim 1 or 2, wherein the component (D) is a compound having a structure represented by the following general formula (Q).

(In the general formula (Q), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. (A) is an integer of 0 to 2).
The radically polymerizable resin composition according to any one of claims 1 to 3, wherein the component (D) is a compound having a structure represented by the following general formula (Q-1).

(In the general formula (Q-1), R 1 and R 2 are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic group having 6 to 18 carbon atoms. ** is Indicates that it is linked to any organic group having at least one mercapto group, a is an integer of 0 to 2.)
The radically polymerizable resin composition according to any one of claims 1 to 4, wherein the component (D) is at least one selected from a bifunctional to hexafunctional polyfunctional thiol compound.
When the total amount of the component (A) and the component (B) is 100 parts by mass, the content of the component (A) is 5 to 95 parts by mass, and the content of the component (B) is 5 The component (C) is contained in an amount of 0.01 to 10 parts by mass, and the content of the component (D) is contained in an amount of 0.1 to 20 parts by mass. The radically polymerizable resin composition as described in any one of the above.
The component (C) is N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-bis (2-hydroxyethyl) -p-toluidine, N, N-bis (2-hydroxypropyl) The radically polymerizable resin composition according to any one of claims 1 to 6, which contains at least one selected from the group consisting of -p-toluidine and N, N-bis (2-hydroxyethyl) aniline.
The radically polymerizable resin composition according to any one of claims 1 to 7, further comprising a metal organic compound as a curing accelerator other than the amine curing accelerator.
9. The radically polymerizable compound according to claim 8, wherein the content of the metal organic compound is 0.1 to 5 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). Resin composition.
The radically polymerizable resin composition according to claim 8 or 9, wherein the metal organic compound contains at least one selected from the group consisting of cobalt compounds and copper compounds.
The radically polymerizable resin composition according to any one of claims 1 to 10, further comprising (E) a curing agent.
The radical polymerization according to claim 11, wherein the content of the component (E) is 0.1 to 10 parts by mass, based on 100 parts by mass of the total amount of the components (A) and (B). Resin composition.
The component (E) is at least selected from the group consisting of dibenzoyl peroxide, benzoyl m-methyl benzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate The radically polymerizable resin composition of Claim 11 or 12 containing 1 type.
A structure restorative comprising the radically polymerizable resin composition according to any one of claims 1 to 13.
A structure restorative material comprising the radically polymerizable resin composition according to any one of claims 1 to 13 and (F) a filler.
The structure restorative material according to claim 15, wherein a content of the component (F) is 1 to 700 parts by mass when a total amount of the component (A) and the component (B) is 100 parts by mass. .
The structure restorative material according to claim 15 or 16, wherein the component (F) is at least one selected from the group consisting of silica sand, calcium carbonate, talc and fumed silica.
The structure restorative material according to any one of claims 14 to 17, wherein the structure restorative material is a slab type track structure restorative material.