JP7164522B2 - Radically polymerizable resin composition and structural repair material - Google Patents

Description

TECHNICAL FIELD The present invention relates to a radically polymerizable resin composition that satisfies both physical properties of low-temperature curability and adhesive strength. Furthermore, the present invention relates to a structure repairing material containing the radically polymerizable resin composition suitable for repairing cracks generated due to deterioration of concrete structures.

Conventionally, methods using synthetic resins such as epoxy resins and acrylic syrups have been proposed as repair and reinforcement materials for concrete structures that have deteriorated over time. It is (Patent Documents 1 to 3).
In addition, for concrete structures that are constantly subject to vibration, such as balustrade walls of expressways and railways, the crack followability of the hardened material is required to prevent breakage after fixing and drying of the repair material. is raised as an issue. In response to such problems, for example, Patent Document 4 discloses a repair/reinforcement agent for concrete structures that uses an acrylic/styrene resin as an admixture. It is known to use polymers with temperatures below °C.
(Patent Documents 4 to 5).

Japanese Unexamined Patent Application Publication No. 2003-002948 JP-A-2001-247636 Japanese Patent Application Laid-Open No. 2000-154297 JP 2009-019354 A JP 2012-091985 A

However, even the methods described in Patent Documents 1 to 5 described above do not have sufficient adhesive strength for concrete structures that are constantly subject to vibration, and there is room for improvement for repairing cracks. rice field.
The present invention has been made in view of the above-mentioned conventional circumstances, and includes a radically polymerizable resin composition having low-temperature curability and exhibiting excellent adhesive strength, and a structure repair using the radically polymerizable resin composition. The purpose is to provide materials.

（一般式（Ｑ）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基、又は炭素数６～１８の芳香族基である。＊は、少なくとも１個のメルカプト基を有する任意の有機基に連結していることを示す。ａは０～２の整数である。）
［４]前記（Ｄ）成分が、下記一般式（Ｑ－１）で表わされる構造を有する化合物である、上記[１]～[３]のいずれかに記載のラジカル重合性樹脂組成物。

（一般式（Ｑ－１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基、又は炭素数６～１８の芳香族基である。＊＊は、少なくとも１個のメルカプト基を有する任意の有機基に連結していることを示す。ａは０～２の整数である。）
［５]前記（Ｄ）成分が、２～６官能の多官能チオール化合物から選ばれる少なくとも１種である、上記[１]～[４]のいずれかに記載のラジカル重合性樹脂組成物。
［６]前記（Ａ）成分と前記(Ｂ)成分の合計量を１００質量部としたときに、前記(Ａ)成分の含有量が５～９５質量部であり、前記(Ｂ)成分の含有量が５～９５質量部であり、前記成分(Ｃ)の含有量が０．０１～１０質量部であり、前記成分(Ｄ)の含有量が０．１～２０質量部である、上記[１]～[５]のいずれかに記載のラジカル重合性樹脂組成物。
［７]前記（Ｃ）成分が、Ｎ，Ｎ－ジメチルアニリン、Ｎ，Ｎ－ジメチル－ｐ－トルイジン、Ｎ，Ｎ－ビス（２－ヒドロキシエチル）－ｐ－トルイジン、Ｎ，Ｎ－ビス（２－ヒドロキシプロピル）－ｐ－トルイジン、Ｎ，Ｎ－ビス（２－ヒドロキシエチル）アニリンからなる群から選択される少なくとも１種を含有する、上記[１]～[６]のいずれかに記載のラジカル重合性樹脂組成物。
［８]さらにアミン系硬化促進剤以外の硬化促進剤として金属有機化合物を含有する、上記[１]～[７]のいずれかに記載のラジカル重合性樹脂組成物。
［９]前記（Ａ）成分と前記(Ｂ)成分の合計量を１００質量部としたときに、前記金属有機化合物の含有量が０．１～５質量部である、上記[８]に記載のラジカル重合性樹脂組成物。
［１０]前記金属有機化合物が、コバルト化合物、銅化合物からなる群から選択される少なくとも１種を含有する、上記[８]または[９]に記載のラジカル重合性樹脂組成物。
［１１]さらに（Ｅ）硬化剤を含有する、上記[１]～[１０]のいずれかに記載のラジカル重合性樹脂組成物。
［１２]前記（Ａ）成分と前記(Ｂ)成分の合計量を１００質量部としたときに、前記(Ｅ)成分の含有量が０．１～１０質量部である、上記[１１]に記載のラジカル重合性樹脂組成物。
［１３]前記（Ｅ）成分が、ジベンゾイルパーオキサイド、ベンゾイルｍ－メチルベンゾイルパーオキサイド、ｍ－トルオイルパーオキサイド、メチルエチルケトンパーオキサイド、クメンハイドロパーオキサイド、ｔ－ブチルパーオキシベンゾエートからなる群から選択される少なくとも１種を含有する、上記[１１]または[１２]に記載のラジカル重合性樹脂組成物。
［１４]上記[１]～[１３]のいずれかに記載のラジカル重合性樹脂組成物を含有する構造物修復材。
［１５]上記[１]～[１３]のいずれかに記載のラジカル重合性樹脂組成物及び（Ｆ）充填材を含有する構造物修復材。
［１６]前記（Ａ）成分と前記(Ｂ)成分の合計量を１００質量部としたときに、前記(Ｆ)成分の含有量が１～７００質量部である、上記[１５]に記載の構造物修復材。
［１７]前記（Ｆ）成分が、珪砂、炭酸カルシウム、タルク及びヒュームドシリカからなる群から選択される少なくとも１種である、上記[１５]または[１６]に記載の構造物修復材。
［１８]前記構造物修復材が、スラブ式軌道の構造物修復材である、上記[１４]～[１７]のいずれかに記載の構造物修復材。That is, the gist of the present invention is the following [1] to [18].
[1] Characterized by containing (A) a radically polymerizable resin, (B) a radically polymerizable unsaturated monomer, (C) an amine curing accelerator, and (D) a polyfunctional thiol compound A radically polymerizable resin composition.
[2] The radical according to [1] above, 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] above, wherein the component (D) is a compound having a structure represented by the following formula (Q).

(In general formula (Q), 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 at least one (a is an integer of 0 to 2.)
[4] The radically polymerizable resin composition according to any one of [1] to [3] above, wherein the component (D) is a compound having a structure represented by the following general formula (Q-1).

(In 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 [1] to [4] above, wherein the component (D) is at least one selected from difunctional to hexafunctional polyfunctional thiol compounds.
[6] 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 component (B) is contained The above [ 1] The radically polymerizable resin composition according to any one of [5].
[7] Component (C) is 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, the radical according to any one of [1] to [6] above. Polymerizable resin composition.
[8] The radically polymerizable resin composition according to any one of [1] to [7] above, further comprising a metal organic compound as a curing accelerator other than the amine-based curing accelerator.
[9] The above-mentioned [8], wherein the content of the metal organic compound is 0.1 to 5 parts by mass when the total amount of the components (A) and (B) is 100 parts by mass. Radically polymerizable resin composition of.
[10] The radically polymerizable resin composition according to [8] or [9] above, wherein the metal organic compound contains at least one selected from the group consisting of a cobalt compound and a copper compound.
[11] The radically polymerizable resin composition according to any one of [1] to [10] above, further comprising (E) a curing agent.
[12] In the above [11], wherein the content of the component (E) is 0.1 to 10 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. A radically polymerizable resin composition as described.
[13] The component (E) is selected from the group consisting of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate. The radically polymerizable resin composition according to the above [11] or [12], containing at least one of
[14] A structure repair material containing the radically polymerizable resin composition according to any one of [1] to [13] above.
[15] A structure repairing material comprising the radically polymerizable resin composition according to any one of [1] to [13] above and (F) a filler.
[16] The above-mentioned [15], wherein the content of component (F) is 1 to 700 parts by mass when the total amount of component (A) and component (B) is 100 parts by mass. Structural restoration material.
[17] The structure restoration material according to [15] or [16] above, 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-restoring material according to any one of [14] to [17] above, which is a structure-restoring material for a slab-type track.

ADVANTAGE OF THE INVENTION According to this invention, the radically polymerizable resin composition which has low-temperature curability and expresses the outstanding adhesive strength can be provided. Since the structural repair material containing the radically polymerizable composition having such properties has low-temperature curability, it can be rapidly cured even in a low-temperature environment, and has excellent adhesive strength. In addition, even when the shrinkage rate is large, breakage after fixing and drying and peeling of the interface between the repaired part and the repairing material are less likely to occur. By using the structure repair material of the present invention, it is possible to satisfactorily repair cracks in concrete structures that are constantly subject to vibration. That is, it is possible to provide a structural restoration material that exhibits excellent adhesion strength when fixed and that does not cause breakage or the like after being fixed.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a plan view and a lateral cross-sectional view of two cement mortar plates used to prepare a specimen for a bending load test using the structural restoration material of the present invention; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram showing a plan view and a lateral cross-sectional view of a specimen for a bending load test obtained using the structural restoration material of the present 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-based curing accelerator, and (D) a polyfunctional thiol compound. It is a radically polymerizable resin composition characterized by containing
Incidentally, (A) the radically polymerizable resin may be referred to as the (A) component, (B) the radically polymerizable unsaturated monomer may be referred to as the (B) component, and (C) the amine curing accelerator may be referred to as ( C) It may be called 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 that has an ethylenically unsaturated group in the resin and undergoes a polymerization reaction by radicals.
Examples of the radically polymerizable resin (A) include urethane (meth)acrylate resins, vinyl ester resins, unsaturated polyester resins, polyester (meth)acrylate resins, (meth)acrylate resins, etc. Among them, radically polymerizable resin compositions Urethane (meth)acrylate resins or tough vinyl ester resins are preferred from the viewpoint of the flexibility of the cured product. In addition, in this 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 into hydroxyl groups or isocyanato groups at both ends of a polyurethane obtained by reacting a polyhydric isocyanate and a polyhydric alcohol. Resin can be used.
As the polyhydric alcohol, compounds described as "polyhydroxy compounds" or "polyhydric alcohols" described in JP-A-2009-292890 and WO2016/171151 can be used without particular limitation.
Polyhydric alcohols are not particularly limited, but for example, polyester polyols, polyether polyols;
Dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol;
Dihydric alcohols such as adducts of dihydric alcohols typified by hydrogenated or non-hydrogenated bisphenol A and alkylene oxides typified by propylene oxide or ethylene oxide;
Trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol can be used.
Examples of the above-described adducts of dihydric alcohols and alkylene oxides include polyoxyalkylenebisphenol A ethers.
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 polyoxyalkylenebisphenol A ethers.
Among them, a urethane (meth)acrylate resin containing a polyol structure of polyether polyol is more preferable from the viewpoint of obtaining a low-viscosity radically polymerizable resin composition and flexibility when cured. As the polyether polyol, polyethylene glycol or polypropylene glycol is preferable because the production of the radically polymerizable resin composition can be facilitated.
The weight average molecular weight of the polyether polyol is preferably 500-5000, more preferably 500-3000. If the weight-average molecular weight is within the above range, a radically polymerizable resin composition obtained by blending the urethane (meth)acrylate resin with a radically polymerizable unsaturated monomer or the like described later will have low viscosity and compatibility. Good. The weight-average molecular weight is measured according to Examples.

Examples of polyvalent isocyanates include those described in JP-A-2009-292890 and those described in WO2016/171151. Examples include 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, Compounds such as hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, and triphenylmethane triisocyanate can be exemplified. Among these, diphenylmethane diisocyanate and isophorone diisocyanate are preferred from the viewpoint of reactivity when synthesizing a resin.
When 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 isocyanato group, or a method of reacting the terminal hydroxyl group with a 2-(meth) Examples include a method of reacting an isocyanato group-containing (meth)acrylic compound such as acryloyloxyethyl isocyanate, 2-(meth)acryloyloxypropyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate. Among these, from the viewpoint of reactivity when synthesizing the resin, the method of reacting a terminal isocyanato group 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 includes monofunctional (meth)acrylic compounds such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. ) 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 2,000 to 22,000, more preferably 3,000 to 19,000, and still more preferably 4,000 to 16,000. If the weight-average molecular weight is within the above range, a radically polymerizable resin composition obtained by blending the urethane (meth)acrylate resin with a radically polymerizable unsaturated monomer or the like described later will have low viscosity and compatibility. Good.

[Vinyl ester resin]
Vinyl ester resin is obtained by esterifying all or part of the epoxy group contained in the epoxy compound with an unsaturated monobasic acid, and has a radically reactive carbon-carbon double bond in the side chain. is doing. Since a representative example of the unsaturated monobasic acid is (meth)acrylic acid, it is called an epoxy (meth)acrylate resin.
As the epoxy compound, any monomer, oligomer, or polymer 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, tetramethylbisphenol F type epoxy resin; stilbene type epoxy Resins; novolac type epoxy resins such as phenol novolak type epoxy resins and cresol novolak type epoxy resins; polyfunctional epoxy resins such as triphenol methane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; phenol aralkyl type epoxy having a phenylene skeleton Resins, phenol aralkyl epoxy resins such as phenol aralkyl epoxy resins having a biphenylene skeleton; dihydroxynaphthalene epoxy resins, naphthol epoxy resins such as epoxy resins obtained by glycidyl-etherifying a dimer of dihydroxynaphthalene; triglycidyl isocyanate triazine nucleus-containing epoxy resins such as nurate and monoallyl diglycidyl isocyanurate; alicyclic polyepoxy compounds such as alicyclic diepoxyacetal, alicyclic diepoxyadipate, alicyclic diepoxycarboxylate, and vinylcyclohexene dioxide ; Bridged cyclic hydrocarbon compound-modified phenol-type epoxy resin such as dicyclopentadiene-modified phenol-type epoxy resin; Glycidyl ester-type epoxy resin obtained by reaction of polybasic acid such as dimer acid and epichlorohydrin; Examples include oxazolidone ring-containing epoxy resins obtained by reaction.
A well-known thing can be used as said unsaturated monobasic acid. Examples include (meth)acrylic acid, crotonic acid, cinnamic acid and the like. Among these, (meth)acrylic acid is preferred.
Moreover, as the unsaturated monobasic acid, a reaction product of a compound having one hydroxy group and one or more (meth)acryloyl groups and a polybasic acid anhydride may be used.
The polybasic acid anhydride is used to increase the molecular weight of the epoxy resin, and known ones can be used. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol/2 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 -ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyldodecane)dicarboxylic acid, and anhydrides such as carboxyl group-terminated butadiene-acrylonitrile copolymer (trade name: Hycar CTBN).
Among the above vinyl ester resins, bisphenol A-type epoxy (meth)acrylate resins are preferable from the viewpoints of imparting toughness, versatility, and cost.

[Unsaturated polyester resin]
As the unsaturated polyester resin, one obtained by subjecting an unsaturated dibasic acid, and optionally a dibasic acid component containing a saturated dibasic acid, to an esterification reaction with a polyhydric alcohol component can be used. .
Examples of the unsaturated dibasic acid and the saturated dibasic acid include those described in WO2016/171151, and these may be used alone or in combination of two or more.
Although the polyhydric alcohol is not particularly limited, examples thereof include those described in WO2016/171151, as in the case of the urethane (meth)acrylate resin.

The unsaturated polyester may be modified with a dicyclopentadiene-based compound to the extent that the effects of the present invention are not impaired. Examples of the modification method with a dicyclopentadiene-based compound include known methods such as a method of obtaining a dicyclopentadiene and maleic acid addition product and then using this as a monobasic acid to introduce a dicyclopentadiene skeleton. be done.
An oxidatively polymerizable (air-curable) 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 containing an oxidation polymerizable group, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidylphenyl allyl ether, hydroxyl group and allyl ether. A method of adding a reaction product of a compound having a group and an acid anhydride can be used.
Incidentally, the oxidative polymerization (air curing) in the present invention refers to cross-linking associated with generation and decomposition of peroxide due to oxidation of a methylene bond between an ether bond and a double bond, which is found in, for example, an allyl ether group. .

[Polyester (meth)acrylate resin]
As the polyester (meth)acrylate resin, for example, a polyester obtained by reacting a polyhydric carboxylic acid and a polyhydric alcohol, specifically, for both terminal hydroxyl groups such as polyethylene terephthalate, (meth)acrylic acid can be used.

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

<Radical 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 the radically polymerizable unsaturated monomer is not particularly limited, those having a (meth)acryloyl group or a vinyl group are preferred.

Monomers having a (meth)acryloyl group include acrylic acid esters, methacrylic acid esters, and the like, and monofunctional monomers and polyfunctional monomers can be used. Specific examples of monofunctional monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, (meth)acrylic t-butyl acid, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, stearyl (meth)acrylate, tridecyl (meth)acrylate, phenoxy Ethyl (meth) acrylate, dicyclopentenyloxyethyl (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, Compounds such as diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, tricyclodecanyl acrylate, tricyclodecanyl methacrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate are exemplified. be able to.
Furthermore, compounds such as caprolactone-modified hydroxyalkyl (meth)acrylates and caprolactone-modified tris(acryloxyalkyl)isocyanurates can also be exemplified. From the viewpoint of reducing the viscosity of the radically polymerizable resin composition, a monomer having a polycaprolactone (meth)acrylate structure with a caprolactone addition mole number of 1 to 5 (m=1 to 5) can be exemplified. Further, a monomer having a polycaprolactone (meth)acrylate structure with 1 to 3 moles of caprolactone can be exemplified. Among them, caprolactone-modified hydroxyethyl (meth)acrylate is preferred.

Specific examples of polyfunctional monomers include neopentyl glycol di(meth)acrylate, PTMG dimethacrylate, 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-(methacryloxy-polyethoxy)phenyl]propane, tetraethylene glycol diacrylate, bisphenol AEO-modified (n = 2) diacrylate, isocyanuric acid EO-modified (n =3) diacrylate, pentaerythritol diacrylate monostearate, and the like.

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 meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate;
Polyoxyalkylene-glycol di(meth)acrylate 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, etc.) meth)acrylate;
Trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, allyl(meth)acrylate, diallyl fumarate;
Other compounds include tris(2-hydroxyethyl)isocyanurate and the like.

Specific examples of vinyl group-containing monomers include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, triallyl phthalate, triallyl isocyanurate vinylbenzyl butyl ether, vinylbenzylhexyl ether, vinylbenzyl octyl ether, vinylbenzyl-(2-ethylhexyl) ether, vinylbenzyl (β-methoxymethyl) ether, vinylbenzyl (n-butoxypropyl) ether, vinylbenzyl Cyclohexyl ether, vinylbenzyl-(β-phenoxyethyl) ether, vinylbenzyldicyclopentenyl ether, vinylbenzyldicyclopentenyloxyethyl ether, vinylbenzyldicyclopentenylmethyl ether, divinylbenzyl ether can be mentioned.
These may be used alone or in combination of two or more.

As the radical polymerizable unsaturated monomer (B) component, from the viewpoint of cost and dilution, methyl (meth)acrylate, phenoxyethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, (meth)acrylic Lauryl acid and styrene are preferred.

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

<Amine-based curing accelerator (C)>
As the amine-based curing accelerator (C) used in the present invention, known amines can be used without particular limitation. Specifically, aniline, N,N-dimethylaniline, N,N-diethylaniline, p- toluidine, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, 4-(N,N-dimethylamino)benzaldehyde, 4-[N,N-bis(2 -hydroxyethyl)amino]benzaldehyde, 4-(N-methyl-N-hydroxyethylamino)benzaldehyde, N,N-bis(2-hydroxypropyl)-p-toluidine, N-ethyl-m-toluidine, triethanolamine , m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N-bis(2-hydroxyethyl)aniline, diethanolaniline, 2,4,6-tris(dimethylaminomethyl)phenol, N,N-dimethyl Amines such as benzylamine and the like can be used. 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. Moreover, among these, a hydroxyl group-containing aromatic tertiary amine is 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-based curing accelerator (C) is preferably 0.01 to 10 parts by mass with respect to a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer, and more It is preferably 0.05 to 5.0 parts by mass, more preferably 0.1 to 3.0 parts by mass. When the content is within the above range, it is easy to adjust the curability.

<Polyfunctional 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). It is a compound that can be These may be used individually by 1 type, or may use 2 or more types together. From the viewpoint of storage stability and odor, secondary or tertiary thiol compounds are preferred.
Here, the term "primary thiol compound" refers to a compound having a mercapto group bonded to a primary carbon atom, and similarly, the term "secondary thiol compound" refers to a compound having a mercapto group bonded to a secondary carbon atom. A compound, also a "tertiary thiol compound", refers to a compound having a mercapto group attached to a tertiary carbon atom. In addition, in this invention, even if a secondary thiol compound has a mercapto group couple|bonded with a primary carbon atom, this compound is regarded as a secondary thiol compound (D2). Similarly, when the tertiary thiol compound has at least one or more 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) Consider.
Therefore, 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. 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.

上記一般式（Ｑ）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基、又は炭素数６～１８の芳香族基である。＊は、少なくとも１個のメルカプト基を有する任意の有機基に連結していることを示す。ａは０～２の整数である。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 general formula (Q) above, 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. * indicates attachment to any organic group having at least one mercapto group. a is an integer from 0 to 2;

上記一般式（Ｑ－１）において、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基、又は炭素数６～１８の芳香族基である。＊＊は、少なくとも１個のメルカプト基を有する任意の有機基に連結していることを示す。ａは０～２の整数である。Among the polyfunctional thiol compounds (D) represented by the above general formula (Q), those having a structure represented by the following general formula (Q-1) are preferred.

In general formula (Q-1) above, 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. ** indicates attachment to any organic group having at least one mercapto group. a is an integer from 0 to 2;

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

（一般式（Ｓ）中、Ｒ^３は水素原子、炭素数１～１０のアルキル基、又は炭素数６～１８の芳香族基であり、Ｒ^４は炭素数１～１０のアルキル基又は炭素数６～１８の芳香族基である。ａは０～２の整数である。）

(In 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 an aromatic group of 6 to 18. a is an integer of 0 to 2.)

When the mercapto group-containing carboxylic acid represented by the general formula (S) is a compound derived from the secondary thiol compound (D2), specifically, 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto -3-phenylpropionic acid and the like.
Further, when the compound is derived from the tertiary thiol compound (D3), specific examples thereof include 2-mercaptoisobutyric acid, 3-mercapto-3-methylbutyric acid and the like.

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 alkylene oxide 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-hexane Diol, 2,4-hexanediol, 3,4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 9,9-bis[4-(2-hydroxyethyl ) dihydric alcohols such as phenyl]fluorene; glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl)isocyanurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, trihydric or higher alcohols such as sucrose and 2,2-bis(2,3-dihydroxypropyloxyphenyl)propane; other examples include polycarbonate diols and dimer acid polyester polyols.

Among these, dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol are preferred from the viewpoint of easy availability and exhibiting curing acceleration ability even under wet conditions. trivalent or higher such as glycerin, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis(2,3-dihydroxypropyloxyphenyl)propane Alcohol; polycarbonate diol, dimer acid polyester polyol are preferred, and from the viewpoint of number of functional groups and vapor pressure, 1,4-butanediol, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, polycarbonate More preferred are diols and dimer acid polyester polyols.

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

[Secondary thiol compound (D2)]
Specific examples of the secondary thiol compound (D2) include di(1-mercaptoethyl) 3-mercaptophthalate, di(2-mercaptopropyl) phthalate, di(3-mercaptobutyl) phthalate, and ethylene glycol. Bis(3-mercaptobutyrate), propylene glycol bis(3-mercaptobutyrate), diethylene glycol bis(3-mercaptobutyrate), butanediol bis(3-mercaptobutyrate), octanediol bis(3-mercaptobutyrate) ), trimethylolethane tris (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), Ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate), octanediol bis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol Bis(4-mercaptovalerate), diethylene glycol bis(4-mercaptovalerate), butanediol bis(4-mercaptovalerate), octanediol bis(4-mercaptovalerate), trimethylolpropane tris(4-mercaptovalerate rate), pentaerythritol tetrakis (4-mercaptovalerate), dipentaerythritol hexakis (4-mercaptovalerate), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis(3-mercaptovalerate), butanediol bis(3-mercaptovalerate), octanediol bis(3-mercaptovalerate), trimethylolpropane tris(3-mercaptovalerate), pentaerythritol tetrakis(3-mercapto valerate), 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-phenylpropionate ), dipentaerythritol hexakis(3-mercapto-3-phenylpropionate), 1,3,5-tris[2-(3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2, 4,6(1H,3H,5H)-trione and the like.

Among the secondary thiol compounds (D2), commercially available compounds having two or more secondary mercapto groups in the molecule include 1,4-bis(3-mercaptobutyryloxy)butane (manufactured by Showa Denko K.K. "Karens MT (registered trademark) BD1"), pentaerythritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko Co., Ltd. "Karens MT (registered trademark) PE1"), 1,3,5-tris[2-( 3-mercaptobutyryloxyethyl)]-1,3,5-triazine-2,4,6(1H,3H,5H)-trione ("Karenzu MT (registered trademark) NR1" manufactured by Showa Denko K.K.), Trimethylolethane tris (3-mercaptobutyrate) (manufactured by Showa Denko K.K. "TEMB"), trimethylolpropane tris (3-mercaptobutyrate) (manufactured by Showa Denko K.K. "TPMB") and the like are preferably used. be done.

[Tertiary thiol compound (D3)]
Specific examples of the tertiary thiol compound (D3) include di(2-mercaptoisobutyl) phthalate, 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, ethylene Glycol bis(3-mercapto-3-methylbutyrate), propylene glycol bis(3-mercapto-3-methylbutyrate), diethylene glycol bis(3-mercapto-3-methylbutyrate), butanediol bis(3-mercapto -3-methylbutyrate), octanediol bis (3-mercapto-3-methylbutyrate), trimethylolethane tris (3-mercapto-3-methylbutyrate), trimethylolpropane tris (3-mercapto-3- methyl butyrate), pentaerythritol tetrakis (3-mercapto-3-methylbutyrate), dipentaerythritol hexakis (3-mercapto-3-methylbutyrate) 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 of the total of (A) the radically polymerizable resin and (B) the 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 improved adhesion can be sufficiently exhibited. Moreover, if the content is 20 parts by mass or less, the strength of the cured resin composition can be sufficiently maintained, and it is suitable for use as a repairing material for structures.

<Curing agent (E)>
The radically polymerizable resin composition of the present invention may contain a curing agent (E). The (E) curing agent used in the present invention is not particularly limited, and known radical polymerization initiators can be used, and organic peroxides are preferably used.
Examples of organic peroxides include ketone peroxides, perbenzoates, hydroperoxides, diacyl peroxides, peroxyketals, hydroperoxides, diallyl peroxides, peroxyesters and peroxydicarbonates. More specifically, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl perbenzoate, dibenzoyl peroxide (also referred to as benzoyl peroxide), benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, dicumyl Peroxide, diisopropyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-dimethyl- 2,5-bis(t-butylperoxy)hexyne-3,3-isopropylhydroperoxide, t-butylhydroperoxide, dicumylhydroperoxide, acetylperoxide, bis(4-t-butylcyclohexyl)peroxide Oxydicarbonate, diisopropyl peroxydicarbonate, isobutyl peroxide, 3,3,5-trimethylhexanoyl peroxide, lauryl peroxide and the like can be used. Azo compounds and the like can also be used as curing agents, and specific examples include azobisisobutyronitrile and azobiscarbonamide. These organic peroxides and azo compounds can be used alone or in combination. Among them, from the viewpoint of easy availability, dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butyl peroxybenzoate is preferred. Dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, and m-toluoyl peroxide are more preferable from the viewpoint of being less susceptible to moisture during curing.

The 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 the total of 100 parts by mass of the components (A) and (B). 0.5 to 6 parts by weight is even more preferred. When the amount of the curing agent (E) is 0.1 parts by mass or more, desired curability can be easily obtained. On the other hand, when the amount of the curing agent (E) is 10 parts by mass or less, it is economically advantageous and a sufficient working time can be easily obtained.

<Other ingredients>
[Polymerization inhibitor]
The radically polymerizable resin composition of the present invention contains a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer and from the viewpoint of controlling the reaction rate. may contain.
Polymerization inhibitors include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-tert-butylcatechol.

[Curing accelerator other than amine type]
The radically polymerizable resin composition of the present invention may contain a curing accelerator other than the amine-based curing accelerator described above. Curing accelerators other than amines are not particularly limited, 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 preferred. These metal organic compounds can be used alone or in combination.
Examples of β-diketones include acetylacetone, ethyl acetoacetate, α-acetyl-γ-butyrolactone, N-pyrosininoacetoacetamide, N,N-dimethylacetoacetamide and the like.
The amount of the metal organic compound compounded is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 3 parts by mass, with respect to the total of 100 parts by mass of components (A) and (B). is more preferable. When the blending amount of the metal organic compound is 0.1 parts by mass or more, the desired curing time and curing state can be easily obtained, and the drying properties are 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 are likely to be obtained.

[Photopolymerization initiator]
The radically polymerizable resin composition of the present invention may contain a photopolymerization initiator for the purpose of improving curability. Examples of photopolymerization initiators include photoradical polymerization initiators.
A photoradical polymerization initiator is used to promote polymerization of acrylic resins and monomers having double bonds and to improve curability.
Specifically, as photoradical polymerization initiators, benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl, methyl orthobenzoyl benzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy -Acetophenones such as 2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. Thioxanthone-based ones can be mentioned.
The photopolymerization initiator can be added in the range of 0.1 to 10 parts by mass with respect to a total of 100 parts by mass of (A) the radically reactive resin and (B) the 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 water is entrapped 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 preferred.

Examples of anionic surfactants include alkyl sulfate ester salts such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene alkyl salts such as sodium polyoxyethylene lauryl ether sulfate and triethanolamine polyoxyethylene alkyl ether sulfate; Ether sulfate ester salts; sulfonates such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and sodium dialkylsulfosuccinate; fatty acid salts such as sodium stearate soap, potassium oleate soap, and castor oil potassium soap ; naphthalenesulfonic acid formalin condensates, special polymer systems, and the like.
Among these, sulfonates are preferred, sodium dialkylsulfosuccinate is more preferred, and sodium dioctylsulfosuccinate is even more preferred.

Examples of nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene distyrenated phenyl ether, poly Polyoxyethylene derivatives such as oxyethylene tribenzylphenyl ether and polyoxyethylene polyoxypropylene glycol; Sorbitan fatty acid esters such as polyoxyalkylene alkyl ether, sorbitan monolaurylate, sorbitan monopalmitate and sorbitan monostearate; polyoxyethylene polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, and polyoxyethylene sorbitan monopalmitate; polyoxyethylene sorbitol fatty acid esters such as polyoxyethylene sorbit tetraoleate; glycerin monostearate; Glycerin fatty acid esters such as glycerin monooleate can be mentioned.

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

[Interface modifier]
The radically polymerizable resin composition of the present invention may contain a wet interface modifier, for example, as an interface modifier to improve permeability to a wet or submerged site to be repaired.
Wet interface modifiers include fluorine-based wetting interface modifiers, silicone-based wetting interface modifiers, and the like, and these may be used alone or in combination of two or more.
Commercially available fluorine-based wet interface modifiers include Megafac (registered trademark) F176, Megafac (registered trademark) R08 (manufactured by Dainippon Ink and Chemicals, Inc.), PF656, PF6320 (manufactured by OMNOVA), and Troisol. S-366 (manufactured by Troy Chemical Co., Ltd.), Florard FC430 (manufactured by 3M Japan Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Commercially available silicone-based wetting and dispersing agents include BYK (registered trademark)-322, BYK (registered trademark)-377, BYK (registered trademark)-UV3570, BYK (registered trademark)-330, and BYK (registered trademark)-302. , BYK (registered trademark)-UV3500, BYK-306 (manufactured by BYK-Chemie Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
Other commercially available wet interface modifiers include Pelex NBL, Pelex OT-P, and Pelex TR (manufactured by Kao Corporation).
When the radically polymerizable resin composition of the present invention contains an interfacial modifier, the content thereof is based on a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. and preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

[Thixotropic agent]
The radically polymerizable resin composition of the present invention may contain a thixotropic agent for the purpose of viscosity adjustment and the like for ensuring workability on vertical surfaces and ceiling surfaces.
Examples of thixotropic agents include inorganic thixotropic agents and organic thixotropic agents. Examples of organic thixotropic agents include hydrogenated castor oil, amide, polyethylene oxide, vegetable oil polymerized oil, and surfactants. Examples include agent systems and composite systems using these in combination, and specific examples include DISPARLON (registered trademark) 6900-20X (Kusumoto Kasei Co., Ltd.).
Examples of inorganic thixotropic agents include silica and bentonite. Hydrophobic ones include Reolosil (registered trademark) PM-20L (vapor-phase silica manufactured by Tokuyama Corp.) and Aerosil (registered trademark). AEROSIL R-106 (Nippon Aerosil Co., Ltd.) and the like, and hydrophilic ones 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 BYK-Chemie Japan Co., Ltd.), which are thixotropic modifiers, were added to hydrophilic pyrogenic silica. can also be preferably used.
When the radically polymerizable resin composition of the present invention contains a thixotropic agent, the content thereof is based on a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

[Wetting and dispersing agent]
The radically polymerizable resin composition of the present invention may contain a wetting and dispersing agent for the purpose of high filling, viscosity reduction, sedimentation prevention, etc. when mixing a filler. These may be used alone or in combination of two or more.
Commercially available wetting and dispersing agents 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 and dispersing agent, its content is based on a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. It is preferably 0.1 to 5.0 parts by mass, more preferably 0.3 to 3.0 parts by mass, and even more preferably 0.5 to 2.0 parts by mass.

[Cure retardant]
The radically polymerizable resin composition of the present invention may contain a curing retarder for the purpose of adjusting the curing time. Cure retarders include free radical cure retarders such as 2,2,6,6-tetramethylpiperidine 1-oxyl free radical (TEMPO), 4-hydroxy-2,2,6,6- TEMPO derivatives such as tetramethylpiperidine 1-oxyl free radical (4H-TEMPO) and 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical (4-Oxo-TEMPO). Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl free radical (4H-TEMPO) is preferred from the viewpoint 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 thereof is 100 parts by mass in total of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. On the other hand, each is preferably from 0.0001 to 10 parts by mass, more preferably from 0.001 to 10 parts by mass.

[Antifoaming agent]
The radically polymerizable resin composition of the present invention may contain an antifoaming agent for the purpose of improving the generation of bubbles during molding and the retention of bubbles in molded articles. Antifoaming agents include silicone antifoaming agents and polymer antifoaming agents.
The amount of the defoaming agent to be used is preferably in the range of 0.01 to 5 parts by weight per 100 parts by weight of the total of (A) the radically polymerizable resin and (B) the 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 adhesion to the base material to be repaired. Coupling agents include known silane-based coupling agents, titanate-based coupling agents, aluminum-based coupling agents, and the like.
Examples of such coupling agents include silane coupling agents represented by R ⁵ —Si(OR ⁶ ) ₃ . Examples of R ⁵ include an aminopropyl group, a glycidyloxy group, a (meth)acryloxy group, an N-phenylaminopropyl group, a mercapto group, and a vinyl group. Examples of R ⁶ include a methyl group. , an ethyl group, and the like.
When the radically polymerizable resin composition of the present invention contains a coupling agent, its content is based on a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. , preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass.

[Light stabilizer]
A light stabilizer may be used in the radically polymerizable resin composition of the present invention for the purpose of improving the long-term durability of the molded article. Light stabilizers include ultraviolet absorbers and hindered amine light stabilizers. These may be used alone or in combination of two or more. Specific examples of UV absorbers include benzotriazole-based, triazine-based, benzophenone-based, cyanoacrylate-based, and salicylate-based light stabilizers. Hindered amine-based light stabilizers include NH type and N—CH ₃ type , NO alkyl type, and the like.
The amount of light stabilizer used is in the range of 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. It is preferably 0.05 to 2 parts by mass, more preferably 0.05 to 2 parts by mass.

〔wax〕
The radically polymerizable resin composition of the present invention may contain wax for the purpose of improving surface drying properties. As waxes, paraffin waxes, polar waxes, and the like can be used alone or in combination, and known waxes having various melting points can be used.
Polar waxes include those having both polar and non-polar groups in their structure. Specifically, NPS-8070, NPS-9125 (manufactured by Nippon Seiro Co., Ltd.), Emanone 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, preferably 0.1 to 2 It is more preferable to contain .0 parts by mass.

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

[Plasticizer]
The resin composition of the present invention may contain a plasticizer for the purpose of adjusting the viscosity and flexibility of the cured product. Plasticizers include epoxies, polyesters, phthalates, adipates, trimellitates, phosphates, citrates, sebacates, and azelaine. Acid ester type, maleic acid ester type, benzoic acid ester type and the like can be used alone or in combination, and known ones can be used.
The amount of the plasticizer added varies depending on its type, but it is 0.01 to 20 parts by mass with respect to a total of 100 parts by mass of (A) the radically polymerizable resin and (B) the radically polymerizable unsaturated monomer. preferably. More preferably, it is contained in an amount of 0.1 to 10 parts by mass.

The total content of 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 60 to 100% by mass, more preferably 90 to 100% by mass.
Further, when the radically polymerizable resin composition of the present invention contains (E) a curing agent, the (A) component, (B) component, (C) component, ( The total content of component D) and curing agent (E) 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 in inorganic structures and ease of mixing with fillers and the like. , more preferably 30 to 500 mPa·s/25°C, still more preferably 50 to 400 mPa·s/25°C. Here, the method for measuring the viscosity is as described in Examples.

<Method for Producing Radical Polymerizable Resin Composition>
In the method for producing the radically polymerizable resin composition of the present invention, the mixing order of each component is not particularly limited, but from the viewpoint of workability for obtaining a uniform mixture efficiently, the viscosity adjustment as a radically polymerizable composition, etc. , From the viewpoint of workability when adjusting the composition to the target physical property range, add and mix a part of the component (B) after synthesizing the component (A), reduce the viscosity of the component (A), and then add the remaining (B) component and other components are preferably added and mixed. Alternatively, part of the component (B) is used as a diluent during the synthesis of the component (A) to obtain a mixture of the component (A) and a part of the component (B), and then the remaining component (B) and other components. is preferably added and mixed. The mixing ratio of the component (A) and part of the component (B) when the viscosity is reduced is not particularly limited, but the mass ratio is preferably 95:5 to 20:80, more preferably 85:15 to 30:70. be.
The viscosity of the mixture of component (A) and part of component (B) is preferably 50 to 4000 mPa·s, more preferably 80 to 3000 mPa·s, still more preferably 100 to 2000 mPa·s. The method for measuring the viscosity is as described in Examples. By adjusting the viscosity within the above range in advance, the remaining components can be uniformly mixed in a short time when the radically polymerizable resin composition of the present invention is obtained.

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

<Filler (F)>
The structural repair material of the present invention can use the radically polymerizable resin composition of the present invention as a structural repair material. , as a structural repair material. The filler (F) is not particularly limited, and examples thereof include inorganic fillers and organic fillers.
Inorganic fillers include cement, quicklime, river gravel, river sand, sea gravel, sea sand, mountain gravel, crushed stone, crushed sand, sand containing silica as a main component such as silica sand, and artificial bones such as calcium carbonate, ceramics and glass scraps. Known materials such as talc, zeolite, and activated carbon can be used, but from the viewpoint of fluidity, material cost reduction, and material availability, a combination with silica sand, calcium carbonate, talc, and fumed silica is preferred. As silica sand, natural silica sand, Gairome silica sand, artificial silica sand, and the like can be used. As for the size of silica sand, sizes of about No. 3 to No. 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 within the range generally used can be used. Moreover, aluminum hydroxide can be used from the viewpoint of imparting flame retardancy. In addition, from the viewpoint of coloring, coloring agents such as titanium oxide and iron oxide, and inorganic pigments can also be used, and molecular sieves can also be used. The particle size of the inorganic filler is preferably 1 nm to 5000 μm, more preferably 10 nm to 3000 μm. When the particle size of the inorganic filler is within the above range, good workability and physical properties can be obtained.
Organic fillers such as amide waxes and water-absorbing polymers can also be used as the organic fillers.

Fibers can also be used as the filler (F). Specific examples of fibers include glass fiber, carbon fiber, basic magnesium sulfate fiber, vinylon fiber, nylon fiber, aramid fiber, polypropylene fiber, acrylic fiber, polyester fiber such as polyethylene terephthalate fiber, cellulose fiber, metal such as steel fiber. fibers, ceramic fibers such as alumina fibers, natural fibers such as basalt fibers, and the like. These fibers are selected from, for example, plain weave, satin weave, nonwoven fabric, mat, roving, chop, flake, knit, braid, and composite structures thereof, etc., biaxial mesh, triaxial mesh. It is preferred to use in For example, the fiber structure may be impregnated with a radically polymerizable composition and optionally prepolymerized to form a prepreg for use.
As the mesh, for example, biaxial mesh and triaxial mesh are used. The length (mesh) of one side of the square of the biaxial mesh and the length (mesh) of one side of the equilateral triangle of the triaxial mesh are each preferably 5 mm or more, more preferably 10 to 20 mm. By using biaxial mesh or triaxial mesh, it is possible to obtain a structural reinforcement material that is lightweight, economical, workable, and durable.
These fibers are preferably used for reinforcing structures.
In applications such as structural reinforcement, among fibers, glass fiber, cellulose fiber, and the like, which are excellent in strength and cost, are preferable from the viewpoint that deterioration of the substrate can be visually inspected from the outside. Carbon fiber is also preferable from the viewpoint of excellent 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 repair material of the present invention contains the filler (F), the amount thereof is preferably 1 to 700 parts by mass with respect to the total 100 parts by mass of the components (A) and (B). 10 to 600 parts by mass is more preferable, and 50 to 500 parts by mass is even more preferable. When fibers are used as the filler (F), the blending amount thereof is preferably 5 to 400 parts by mass, preferably 15 to 300 parts by mass, with respect to the total of 100 parts by mass of components (A) and (B). parts is more preferable, and 30 to 250 parts by mass is even more preferable. If the blending ratio of the filler is within the above range, the curability and workability are good, which is preferable.

The method of repairing a structure is not particularly limited, but for example, the structure repairing material of the present invention can be applied to a portion to be repaired of concrete, asphalt concrete, mortar, wood, metal, etc., dried and cured. can. The method of applying the structural restoration material is not particularly limited, but for example, a dipping application method, a spray application method, a roller application method, and an application method using an instrument such as a brush, brush or spatula can be applied.
The amount of the structural repair material to be applied is not particularly limited, but is appropriately adjusted in consideration of the size of the repaired portion, the adhesion of the structural repair material, the strength of the cured product of the structural repair material, and the like.
The drying method after applying the structural repair material is not particularly limited, but a method of natural drying or a method of heating within a range in which the properties of the cured structure repair material are not deteriorated are used.
Alternatively, the structure repair material of the present invention can be directly injected into the cracked portion of the structure, dried, and cured for repair.

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

<Synthesis example>
As will be described later, using the following raw materials, (A) urethane methacrylate resin (UM1), which is a radically polymerizable resin, was synthesized, and then (B) methyl methacrylate (Mitsubishi Rayon Co., Ltd.) was synthesized as a radically polymerizable unsaturated monomer. ), product name: Acrylic Ester M) was mixed to obtain a mixture of components (A) and (B).

Raw materials for the urethane methacrylate resin (UM1) are shown below.
(polyhydric alcohol)
Polypropylene glycol 1 (weight average molecular weight 1000), manufactured by Mitsui Chemicals, Inc., product name: Actcol D-1000
Polypropylene glycol 2 (weight average molecular weight 2000), manufactured by Mitsui Chemicals, Inc., product name: Actcol 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)
Diphenylmethane diisocyanate: 500 g (2.0 mol), Actcol D-1000 (manufactured by Mitsui Chemicals, Inc. polypropylene glycol 1: Weight average molecular weight 1000): 100 g (0.1 mol), Actcol D-2000 (manufactured by Mitsui Chemicals, Inc. polypropylene glycol 2: weight average molecular weight 2000): 1800 g (0.9 mol), and dibutyltin dilaurate: 0.2 g was charged and reacted with stirring at 60° C. for 4 hours. Next, 288 g (2.0 mol) of 2-hydroxypropyl methacrylate was added dropwise to the reactant over 2 hours while stirring, and after the dropwise addition was completed, the reaction was allowed to proceed by stirring for 5 hours to obtain a urethane methacrylate resin (UM1). . The weight average molecular weight of the obtained urethane methacrylate resin (UM1) was 9,055 as measured by the following method.
Next, 1035 g of methyl methacrylate was added to this urethane methacrylate resin (UM1) to obtain a mixture of components (A) and (B). The mixture had a viscosity of 300 mPa·s at 25° C. and a liquid specific gravity of 1.02 as determined by the following measurement method.

<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 room temperature (23° C.) under the following conditions and calculated in terms of polystyrene.
(Measurement condition)
Column: 2 LF-804 manufactured by Showa Denko Co., Ltd. Column temperature: 40°C
Sample: 0.4% by mass tetrahydrofuran solution of object to be measured Flow rate: 1 ml/min Eluent: tetrahydrofuran

<Measurement of viscosity>
Using a RE-85 type viscometer manufactured by Toki Sangyo Co., Ltd., cone plate type, cone rotor 1°34′×R24, the viscosity was measured at 25° C. and 100 rpm.

<Measurement of liquid specific gravity>
According to JIS K ^7112-1999 Annex 2 "Plastic-liquid resin-water replacement method", the liquid specific gravity at 23 ° C. was measured using an electronic hydrometer MD-200S manufactured by Alpha Mirage Co., Ltd.

Examples 1-17
As raw materials, the mixture obtained in Synthesis Example 1, and optionally the (B) radically polymerizable unsaturated monomer, the following (C) amine-based curing accelerator, (D) a polyfunctional thiol compound, (E) A curing agent was used as a raw material for 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 Co., Ltd., product name: Karenz MT PE1
(2) Trimethylolpropane-tris(3-mercaptobutyrate) trifunctional secondary thiol, manufactured by Showa Denko K.K., product name: TPMB
(3) 1,4-bis(3-mercaptobutyryloxy)butane, bifunctional secondary thiol, manufactured by Showa Denko K.K., product name: Karenz MT BD1
(4) Pentaerythritol tetrakis (3-mercaptopropionate), tetrafunctional primary thiol, manufactured by SC Organic Chemical Co., Ltd., product name: PEMP
(5) Trimethylolpropane tristhiopropionate, trifunctional primary thiol, manufactured by Yodo Chemical Co., Ltd., product name: TMTP
(E) Curing agent Dibenzoyl peroxide, manufactured by Kayaku Akzo Co., Ltd., product name: Perkadox CH-50L

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

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 included. Table 1 shows the content of each component in the radically polymerizable resin composition. The curability of the radically polymerizable resin composition thus obtained was measured and evaluated in the same manner. Table 1 shows the results.

<Curability measurement under 25°C environment>
Gelation time, curing temperature, and curing time were evaluated by the following evaluation methods.
Adjust the resin composition to 25 ° C., put it in a test tube (outer diameter 18 mm, length 165 mm) to a depth of 100 mm, place it in a constant temperature bath set at 25 ° C., and measure the temperature of the resin composition with a thermocouple. did. The time required for the temperature of the resin composition to rise from 25° C. to 35° C. was measured and defined as the gelation time (unit: minutes).
The time required for the resin composition to reach the maximum heat generation temperature was defined as the minimum curing time, and the heat generation temperature at that time was defined as the curing temperature, and measured according to JIS K- ^6901-2008 .
<Curability measurement under 10°C environment>
Evaluation was carried out in the same manner as for the above 25°C curability, except that the temperature of the resin composition and the ambient temperature for measurement were 10°C.

As shown in Tables 1 to 3, the radical polymerizable resin composition of the present invention containing a polyfunctional thiol compound has a gelling time and a minimum curing time even in an environment of 25°C and a low temperature of 10°C. , it was found that rapid curing can be obtained.
In particular, it was found that the examples in which the total amount of the polyfunctional thiol compound was 0.5 parts by mass or more had a faster curing speed. In addition, in the examples containing 0.3 parts by mass or more, due to the manifestation of the chain transfer agent effect, the time from the gelation time to the minimum curing time tends to increase, and a mild curing process was obtained, resulting in rapid curing. It has been found that contraction can be relieved.
On the other hand, the radically polymerizable resin composition of Comparative Example 1, which does not contain a polyfunctional thiol compound, has slow curability as compared with the resin compositions of Examples 1 to 22, from the gelling time to the minimum curing time. time was found to be short.

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

In the same manner as in Example 1, with respect to a total of 100 parts by mass of components (A) and (B) in the proportions shown in Tables 4 to 6, (C) an amine curing accelerator, (D) a polyfunctional thiol compound and (E) a curing agent were added in this order and stirred to obtain (F) a filler-free radically polymerizable resin composition. Furthermore, the filling material (F) was added in the proportions shown in Tables 4 to 6 and stirred to obtain a structural restoration material.
Tables 4 to 6 show the content of each component in the structural restoration material.
After that, using the obtained structure-restoring material, a specimen for an adhesion test was produced by the method described below.
Adhesiveness of the structural restoration material thus obtained was measured by the following method, and the adhesiveness was evaluated. The results are shown in Tables 4-6.

<Method for preparing specimen for adhesion test>
The structure restoration material obtained above was placed on one JIS K 5600 cement mortar plate of length × width × thickness = 70 mm × 70 mm × 20 mm used in the method for producing a specimen for bending load test described later. It was molded in a thickness of 3 mm at a temperature of 25° C. and a humidity of 50%, and cured with the upper portion sealed with a film. After that, it 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 the surface was cleaned by acetone degreasing. After that, a dolly with a diameter of 20 mm for the adhesion test was fixed with an epoxy adhesive, and fixed and cured for 5 hours in an environment of 25 ° C. and 50% humidity to develop the strength of the adhesive. did.

<Adhesion test>
The adhesive strength of the adhesion test specimen obtained above was measured in a test environment of 23° C. temperature and 50% humidity using an adhesion tester manufactured by Elcometer, measuring range 0 to 7.0 MPa, manual type. . The adhesive force was measured twice for each specimen for the adhesion test. Then, the average value of the two measurement results was used to evaluate the adhesive strength.

Comparative example 2
(D) A structure restoration material was obtained in the same manner as in Example 18, except that the polyfunctional thiol compound was not included. After that, in the same manner as in Example 18, an adhesion test specimen was prepared and an adhesion test was conducted. The curability of Comparative Example 2 was similarly adjusted with a polymerization inhibitor so as to be similar to that of Example 18, and the gelation time was set to 7.0 min to eliminate the influence of the difference in curability. Table 4 shows the results.

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 exhibited strong adhesion.
On the other hand, Comparative Example 2 had lower adhesiveness than the specimens for adhesion test of Examples 18-34.

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

In the same manner as in Example 1, (C) an amine curing accelerator, (D) a polyfunctional thiol compound and ( E) A curing agent was added in this order in the proportions shown in Table 7 and stirred to obtain (F) a filler-free radically polymerizable resin composition. Furthermore, the filling material (F) was added at the ratio shown in Table 7 and stirred to obtain a structural restoration material.
Table 7 shows the content of each component in the structure-restoring material.
After that, using the obtained structure-restoring material, a specimen for a bending load test was produced by the method described below.
Using the structural restoration material thus obtained, a specimen for a bending load test was measured for bending load by the following method, and the bending strength of the restored structure was evaluated. Table 7 shows the results.

<Method for preparing specimen for bending load test>
As shown in Fig. 1, two JIS K 5600 cement mortar plates (A, B) of length x width x thickness = 70 mm x 70 mm x 20 mm were arranged on a plane with a space of 20 mm wide and sanded with #240 sandpaper. The side surface (the surface in contact with the structural restoration material) was roughened, and the surface was cleaned with an air blow. The structural restoration material obtained above was injected into the resulting space of length x width x thickness = 70 mm x 20 mm x 20 mm at an environmental temperature of 25°C and a humidity of 50%, and the top was sealed with a film. Hardened in condition. Then, it was cured under the same environment for 24 hours to obtain a specimen for bending load test shown in FIG.

<Bending load test>
For the bending load test specimen obtained above, in a test environment with a temperature of 23 ° C. and a humidity of 50%, Tensilon UTC-1T manufactured by Orientec Co., Ltd. was used at a distance between fulcrums of 40 mm and a test speed of 1 mm / min. , Bending load was measured by applying a load to the center surface linear portion (70 mm in length) of the hardened portion of the structural restoration material of the specimen for bending load test. A load was applied until the specimen for the load test broke, and the maximum load until the specimen broke was measured. The measurement of the bending load was performed twice for each specimen for the bending load test. Then, the average value of the two measurement results was used to evaluate the bending load. Higher bending load test (N) values indicate better bending strength of the repaired structure.

Comparative example 3
(D) A structure-restoring resin composition was obtained in the same manner as in Example 35, except that the polyfunctional thiol compound was not included. Further, the curability of Comparative Example 3 was adjusted with a polymerization inhibitor so as to be similar to that of Example 37, and the gelation time was set to 7.0 min to eliminate the influence of the difference in curability.

As shown in Table 7, the bending load test specimens of the present invention containing the polyfunctional thiol compounds of Examples 35 to 41 have excellent adhesion between the repair material and the mortar board, and therefore have high bending strength. It was found that On the other hand, Comparative Example 3 had lower bending strength than the bending load test specimens of Examples 35-41. This is because the bending load test specimens of Examples 35 to 41 have better adhesion between the structural restoration material and the cement mortar board than the bending load test specimen of Comparative Example 3. It is a thing.

In Tables 1 to 7, the same composition number indicates that the same radically polymerizable resin composition [(A) component to (E) component] is used.

INDUSTRIAL APPLICABILITY The radically polymerizable resin composition and the structural repair material of the present invention have low-temperature curability and excellent adhesive strength. It can be rapidly cured even in a low-temperature environment and has excellent adhesive strength, so that breakage after fixing and drying and separation between the repaired part and the repair material interface are less likely to occur. Therefore, by using the structure repair material of the present invention, it is possible to satisfactorily repair cracks in concrete structures that are constantly subject to vibration. That is, it can exhibit excellent adhesion strength when fixed, and can be suitably used for repairing cracks in concrete structures and the like.

Claims (14)

(A) a radically polymerizable resin;
(B) a radically polymerizable unsaturated monomer;
(C) an amine-based curing accelerator; and (D) a polyfunctional thiol compound.
The (A) radically polymerizable resin is a urethane (meth)acrylate resin,
The (C) amine curing accelerator is N,N-dimethylaniline, N,N-dimethyl-p-toluidine, N,N-bis(2-hydroxyethyl)-p-toluidine, N,N-bis( 2-hydroxypropyl)-p-toluidine, at least one selected from the group consisting of N,N-bis(2-hydroxyethyl)aniline,
A radically polymerizable resin composition, wherein the (D) polyfunctional thiol compound is an ester compound of a mercapto group-containing carboxylic acid represented by the following general formula (S) and a polyhydric alcohol.

(In 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 an aromatic group of 6 to 18. a is an integer of 0 to 2.) 2. The radically polymerizable resin composition according to claim 1 , wherein the component (D) is at least one selected from difunctional to hexafunctional polyfunctional thiol compounds. 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 parts by mass. 95 parts by mass, the content of component (C) is 0.01 to 10 parts by mass, and the content of component (D) is 0.1 to 20 parts by mass. The radically polymerizable resin composition according to . 4. The radically polymerizable resin composition according to any one of claims 1 to 3 , further comprising a metal organic compound as a curing accelerator other than the amine-based curing accelerator. 5. The radically polymerizable compound according to claim 4 , wherein the content of the metal organic compound is 0.1 to 5 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. Resin composition. 6. The radically polymerizable resin composition according to claim 4 , wherein the metal organic compound contains at least one selected from the group consisting of cobalt compounds and copper compounds. 7. The radically polymerizable resin composition according to any one of claims 1 to 6 , further comprising (E) a curing agent. The radical polymerization according to claim 7 , wherein the content of the component (E) is 0.1 to 10 parts by mass when the total amount of the component (A) and the component (B) is 100 parts by mass. elastic resin composition. At least the component (E) is selected from the group consisting of dibenzoyl peroxide, benzoyl m-methylbenzoyl peroxide, m-toluoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, and t-butyl peroxybenzoate. The radically polymerizable resin composition according to claim 7 or 8 , containing one. A structure repair material containing the radically polymerizable resin composition according to any one of claims 1 to 9 . A structure repair material comprising the radically polymerizable resin composition according to any one of claims 1 to 9 and (F) a filler. The structure repair material according to claim 11 , 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. . The structure repair material according to claim 11 or 12 , wherein the component (F) is at least one selected from the group consisting of silica sand, calcium carbonate, talc and fumed silica. The structure restoration material according to any one of claims 10 to 13 , wherein the structure restoration material is a slab-type track structure restoration material.

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