JPWO2018135654A1 - Radical polymerizable resin composition and injectable for structure repair - Google Patents

Abstract

(A) a radical polymerizable resin, (B) a radical polymerizable unsaturated monomer, and (C) an amine curing accelerator, and (B) the radical polymerizable unsaturated monomer is an oxyalkylene Radical polymerizable unsaturated monomer (b-1) having a structure and / or radical polymerizable unsaturated monomer (b-2) having a caprolactone ring-opening structure Composition.

Description

  The present invention relates to a radical polymerizable resin composition that satisfies both physical properties of low elastic modulus and high specific gravity. Furthermore, the present invention relates to a low-viscosity structure restoration injecting agent containing the radical polymerizable resin composition suitable for repairing cracks generated due to deterioration of concrete structures and the like.

Conventionally, with respect to the occurrence of cracks due to aging deterioration of concrete structures, repair by filling with an injecting agent has been performed as one of the repair methods for crack portions (Patent Document 1).
In particular, for concrete structures that constantly vibrate, such as high rail walls such as expressways and railways, in addition to the same adhesion strength as conventional injectants, use injectants that have predetermined elastic properties. Therefore, it is necessary to prevent the injection material from being broken after being fixed and dried (Patent Document 2).

JP 2005-002687 A JP 2009-019354 A

When the volume of the deteriorated portion of the concrete structure covers a wide range, it is common to use an injection compounded with an aggregate such as silica sand in order to ensure the strength of the repaired portion. However, it is difficult to sufficiently permeate the filler containing the aggregate into a narrow crack width, and a method of repairing by injecting only the resin composition without mixing the aggregate has been studied. . As in Patent Document 2, when trying to achieve a low elastic modulus with an injectable agent without an aggregate for repairing cracks always accompanied by vibration, the injecting agent tends to have a low specific gravity and a predetermined adhesion strength. The problem that cannot be obtained occurs. That is, when the concrete at the restoration site contains moisture, if the specific gravity of the injection agent is low, the injection agent floats due to the moisture at the restoration site, and good adhesion strength cannot be obtained.
The present invention has been made in view of the above-described conventional circumstances, and includes a radical polymerizable resin composition satisfying both physical properties of low elastic modulus and high specific gravity, and an injectable for structure repair using the radical polymerizable resin composition The purpose is to provide.

That is, the gist of the present invention is the following [1] to [10].
[1] It contains (A) a radical polymerizable resin, (B) a radical polymerizable unsaturated monomer, and (C) an amine-based curing accelerator, and (B) a radical polymerizable unsaturated monomer A radical polymerizable unsaturated monomer (b-1) having an oxyalkylene structure and / or a radical polymerizable unsaturated monomer (b-2) having a caprolactone ring-opening structure Polymerizable resin composition.
[2] The radical polymerizable resin composition according to [1], wherein the component (b-1) has a polyalkylene oxide (meth) acrylate structure having 1 to 30 moles of alkylene oxide added.
[3] The radical polymerizable resin composition according to the above [1] or [2], wherein the component (b-2) has a polycaprolactone (meth) acrylate structure having caprolactone addition mole number of 1 to 5.
[4] The total amount of the component (b-1) and the component (b-2) is 20 to 95% by mass in the component (B), according to any one of the above [1] to [3]. Radical polymerizable resin composition.
[5] In any one of the above [1] to [4], the component (A) is a urethane (meth) acrylate resin containing a polyol structure selected from polyester polyol, polyether polyol, and polyoxyalkylene bisphenol A ether. The radically polymerizable resin composition described.
[6] The radically polymerizable resin composition according to any one of [1] to [5], further including (D) a curing agent.
[7] The content of the component (b-1) with respect to the total amount of the component (b-1) and the component (b-2) is 40 to 100% by mass, according to the above [1] to [6] The radically polymerizable resin composition according to any one of the above.
[8] The content of the radical polymerizable resin (A) in the total amount of the radical polymerizable resin (A) and the radical polymerizable unsaturated monomer (B) is 5 to 60% by mass, [ The radically polymerizable resin composition according to any one of 1] to [7].
[9] The radical polymerizable resin composition according to any one of [1] to [8], wherein the viscosity of the radical polymerizable composition is 10 to 500 mPa · s / 25 ° C.
[10] An injecting agent for repairing a structure comprising the radical polymerizable resin composition according to any one of [1] to [9] above, and having a liquid specific gravity of 1.01 to 1.15.

  According to the present invention, a radical polymerizable resin composition having a low elastic modulus and a high specific gravity (specific gravity at 23 ° C. is greater than 1.00) can be provided. The injecting agent for repairing a structure containing a radically polymerizable composition having such characteristics has a high specific gravity, and thus penetrates into and adheres to a crack portion generated in the structure, and has a low elastic modulus. Breakage after injection fixed and dried. When the structural restoration injecting agent of the present invention is used, it is possible to satisfactorily repair a narrow crack portion with respect to a concrete structure always accompanied by vibration. That is, it is possible to provide an injecting agent for repairing a structure that can maintain the same adhesion strength as that in the past when it is fixed and does not cause breakage after fixing.

[Radically polymerizable resin composition]
The radical polymerizable resin composition of the present invention comprises (A) a radical polymerizable resin, (B) a radical polymerizable unsaturated monomer, and (C) an amine-based curing accelerator, and (B) a radical. The polymerizable unsaturated monomer is a radical polymerizable unsaturated monomer (b-1) having an oxyalkylene structure and / or a radical polymerizable unsaturated monomer (b-2) having a caprolactone ring-opening structure. It is a radically polymerizable resin composition characterized by containing.
In addition, (A) radical polymerizable resin may be called (A) component, (B) radical polymerizable unsaturated monomer may be called (B) component, and (C) amine type hardening accelerator ( C) component, and the radical polymerizable unsaturated monomer (b-1) having an oxyalkylene structure is sometimes referred to as (b-1) component, and the radical polymerizable unsaturated monomer having a caprolactone ring-opening structure. The monomer (b-2) may be referred to as the component (b-2).

<Radically 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 undergoing a polymerization reaction by radicals.
Examples of the radical 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 them, radical polymerizable resin composition From the viewpoint of lowering the elastic modulus of the cured product, urethane (meth) acrylate resin is preferable. In the present specification, “(meth) acrylate” means “acrylate or methacrylate”.

[Urethane (meth) acrylate resin]
The urethane (meth) acrylate resin was obtained, for example, by introducing a (meth) acryloyl group into a hydroxyl group or an isocyanate group at both ends of a polyurethane obtained by reacting a polyvalent 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.
Although there is no restriction | limiting in particular in a polyhydric alcohol, For example, polyester polyol, polyether polyol;
Dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, cyclohexanedimethanol;
A dihydric alcohol such as an adduct of a dihydric phenol represented by hydrogenated bisphenol A and the like and an alkylene oxide represented by propylene oxide or ethylene oxide;
Examples include trivalent or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, and pentaerythritol.
Examples of the adduct of the dihydric phenol and alkylene oxide include polyoxyalkylene bisphenol A ether.
Among these, the urethane (meth) acrylate resin is a urethane (meth) acrylate resin containing one or more polyol structures selected from polyester polyol, polyether polyol, and polyoxyalkylene bisphenol A ether. preferable.
Among these, a urethane (meth) acrylate resin containing a polyol structure of a polyether polyol is more preferable from the viewpoint of lowering the modulus of elasticity when the radical polymerizable resin composition is cured. As the polyether polyol, polyethylene glycol or polypropylene glycol is preferable from the viewpoint of reducing the elastic modulus when the radical polymerizable resin composition is cured.
500-4000 are preferable and, as for the weight average molecular weight of polyether polyol, 500-3000 are more preferable. When the weight average molecular weight is within the above range, an appropriate elastic modulus and viscosity can be obtained as an injecting agent for structure repair. The method for measuring the weight average molecular weight is as described in the examples.

Examples of the polyvalent isocyanate include those described in JP2009-292890A and those described in WO2016 / 171151, and diphenylmethane diisocyanate is preferable from the viewpoint of reactivity when synthesizing the resin.
When introducing a (meth) acryloyl group, for example, a method of reacting a terminal isocyanate group with a hydroxyl group-containing (meth) acrylic compound described in JP-A-2009-292890, or a terminal hydroxyl group with 2- (meth) acryloyloxy. Examples include a method of reacting an isocyanato group-containing (meth) acrylic compound such as ethyl isocyanate, 2- (meth) acryloyloxypropyl isocyanate, 1,1-bis (acryloyloxymethyl) ethyl isocyanate. Among these, from the viewpoint of increasing the specific gravity of the radical polymerizable resin composition, a method in which a hydroxyl group-containing (meth) acrylic compound is reacted with a terminal isocyanate group is preferable.
From the viewpoint of increasing the specific gravity of the radical polymerizable resin composition, the hydroxyl group-containing (meth) acrylic compound is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, caprolactone-modified hydroxyalkyl (meth) acrylate. , Hydroxyethyl acrylamide and the like are preferable, among which 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is more preferable, and 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate is more preferable.
As a weight average molecular weight of urethane (meth) acrylate resin, Preferably it is 3000-20000, More preferably, it is 4000-11000. When the weight average molecular weight is within the above range, when the radical polymerizable resin composition is blended with the urethane (meth) acrylate resin described later, the radical polymerizable unsaturated monomer, the viscosity is low and the compatibility is high. It is good.

[Vinyl ester resin]
Vinyl ester resin is a resin sometimes called an epoxy (meth) acrylate resin.
As the vinyl ester resin, one obtained by reacting an unsaturated monobasic acid with an epoxy resin can be used.
Examples of the epoxy resin include bisphenol A diglycidyl ether and high molecular weight homologues thereof, novolak glycidyl ethers, and the like.
Specifically, the epoxy resin etc. which are described in WO2016 / 171151 are mentioned.
Known unsaturated monobasic acids can be used, and examples thereof include (meth) acrylic acid, crotonic acid, cinnamic acid and the like. Further, a reaction product of a compound having one hydroxy group and one or more (meth) acryloyl groups and a polybasic acid anhydride may be used. In the present specification, “(meth) acrylic acid” means one or both of “acrylic acid and methacrylic acid”, and “(meth) acryloyl group” means “acryloyl group and methacryloyl group”. Or one of both.
The polybasic acid is used to increase the molecular weight of the epoxy resin, and known ones such as those described in WO2016 / 171151 can be used.

[Unsaturated polyester resin]
As unsaturated polyester resin, what was obtained by esterifying the unsaturated dibasic acid and the dibasic acid component containing a saturated dibasic acid as needed, and a polyhydric alcohol component can be used. .
Examples of the unsaturated dibasic acid and the saturated dibasic acid include those described in WO2016 / 171151. These 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 as described in WO2016 / 171151 can be mentioned similarly to the case of urethane (meth) acrylate resin.

The unsaturated polyester may be modified with a dicyclopentadiene compound within a range not impairing the effects of the present invention. As for the modification method using a dicyclopentadiene compound, for example, after obtaining dicyclopentadiene and a maleic acid addition product (sidedecanol monomaleate), this is used as a monobasic acid to introduce a dicyclopentadiene skeleton. Known methods such as
An oxidation 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. For example, addition of an oxidation polymerization group-containing polymer, condensation of a compound having a hydroxyl group and an allyl ether group, allyl glycidyl ether, 2,6-diglycidyl phenyl allyl ether with a hydroxyl group and allyl ether And a method of adding a reaction product of a compound having a group and an acid anhydride.
Incidentally, the oxidative polymerization (air curing) in the present invention refers to cross-linking associated with the generation and decomposition of peroxide by oxidation of a methylene bond between an ether bond and a double bond, such as found in an allyl ether group. .

[Polyester (meth) acrylate resin]
As the polyester (meth) acrylate resin in the present invention, for example, a polyester obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol, specifically, with respect to hydroxyl groups at both ends such as polyethylene terephthalate, ) A resin obtained by reacting acrylic acid can be used.

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

<Radically polymerizable unsaturated monomer (B)>
The radically polymerizable unsaturated monomer (B) used in the present invention is important as a role of lowering the viscosity of the radically polymerizable resin composition and achieving both a low elastic modulus and a high specific gravity. The radical polymerizable unsaturated monomer (B) includes a radical polymerizable unsaturated monomer (b-1) having an oxyalkylene structure and / or a radical polymerizable unsaturated monomer having a caprolactone ring-opening structure (b -2). By using these (b-1) component and / or (b-2) component, the low elastic modulus and high specific gravity of a radically polymerizable composition can be made compatible.

The oxyalkylene structure is a structure represented by — (— O—R—) _n — (R represents an alkylene group, and n is an integer). As for carbon number of an alkylene group, 2-6 are preferable. n is preferably an integer of 1 to 30.
(B-1) The radical polymerizable unsaturated monomer having an oxyalkylene structure includes (meth) acrylate having an oxyalkylene structure, and the number of carbon atoms in the alkylene group is more preferably 2-6.
The component (b-1) is preferably a monomer having a polyalkylene oxide (meth) acrylate structure having 1 to 30 moles of alkylene oxide added. More preferably, the added mole number of alkylene oxide is 1-20. When the added mole number of the alkylene oxide is within the above range, a good balance is obtained from the viewpoint of the viscosity and specific gravity of the radical polymerizable resin composition.
Specifically, alkylene oxide modified (meth) acrylate of phenol such as phenoxyethyl (meth) acrylate, alkylene oxide modified di (meth) acrylate of bisphenol A such as ethoxybisphenol A dimethacrylate, alkylene oxide modified di (bisphenol F) Alkyl group-terminated polyalkylene glycol (meth) acrylates such as meth) acrylate, isocyanuric acid alkylene oxide-modified tri (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, and trimethylolpropane alkylene oxide-modified tri (meth) acrylate Can be mentioned. These may be used alone or in combination of two or more. Among these, from the viewpoint of reducing the viscosity of the radical polymerizable resin composition, alkyl groups such as alkylene oxide modified di (meth) acrylate of bisphenol A, alkylene oxide modified (meth) acrylate of phenol, and methoxypolyethylene glycol (meth) acrylate. A terminal polyalkylene glycol (meth) acrylate is preferable, and an alkylene oxide-modified di (meth) acrylate of bisphenol A and an alkylene oxide-modified (meth) acrylate of phenol are more preferable.
The component (b-1) contains an alkylene oxide-modified di (meth) acrylate of bisphenol A from the viewpoint of the low viscosity, low elastic modulus, and high specific gravity balance of the radical polymerizable resin composition of the present invention. It is more preferable that it contains two kinds of alkylene oxide-modified di (meth) acrylate of bisphenol A and alkylene oxide-modified (meth) acrylate of phenol. From the same viewpoint, the total content of these two types in the component (b-1) is preferably 60% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and still more preferably. 100% by mass. From the same viewpoint, the content of the bisphenol A alkylene oxide-modified di (meth) acrylate in the component (b-1) is preferably 50 to 100% by mass, more preferably 60 to 90% by mass, and still more preferably. It is 65-80 mass%. In the component (b-1), the content of the alkylene oxide-modified (meth) acrylate of phenol is preferably 0 to 50% by mass, more preferably 10 to 40% by mass, and further preferably 20 to 35% by mass. .
The number of moles of alkylene oxide added in the alkylene oxide-modified di (meth) acrylate of bisphenol A is preferably 1 from the viewpoint of the low viscosity, low elastic modulus and high specific gravity balance of the radical polymerizable resin composition of the present invention. -30, more preferably 4-30, still more preferably 4-20, and even more preferably 8-20.
From the same viewpoint, the number of moles of alkylene oxide added in the phenol-modified (meth) acrylate of phenol is preferably 1 to 10, more preferably 1 to 4, more preferably 1 to 2, and still more preferably 1. .

(B-2) The radical polymerizable unsaturated monomer having a caprolactone ring-opening structure is an unsaturated monomer having a structure represented by — (— C ₅ H ₁₀ COO—) _m —. m is preferably an integer of 1 to 10. Specific examples include (meth) acrylates having a caprolactone ring-opening structure. The radically polymerizable unsaturated monomer (b-2) having a caprolactone ring-opening structure is a monomer having a caprolactone addition mole number of 1 to 5 (m = 1 to 5) and a polycaprolactone (meth) acrylate structure. Preferably there is. The number of added moles of caprolactone is more preferably 1 to 3. When the number of added moles is within the above range, it is possible to satisfactorily balance the reduction in elastic modulus and the increase in specific gravity of the radical polymerizable resin composition, and it is possible to reduce the viscosity. More specifically, caprolactone-modified hydroxyalkyl (meth) acrylate, caprolactone-modified tris (acryloxyalkyl) isocyanurate and the like can be mentioned. From the viewpoint of reducing the viscosity, caprolactone-modified hydroxyethyl (meth) acrylate is preferable.
Moreover, it is preferable to use together the component (b-1) and the component (b-2) from the viewpoint of lowering the elastic modulus and increasing the specific gravity of the radical polymerizable resin composition of the present invention.
The content of the component (b-1) relative to the total amount of the component (b-1) and the component (b-2) is preferably 40 to 100% by mass, more preferably 55 to 90% by mass, and still more preferably 60 to 75%. It is mass%, More preferably, it is 60-70 mass%.

Specific examples of the other radical polymerizable unsaturated monomer include those described in JP-A-2009-292890, and lauryl (meth) acrylate, 2-ethylhexyl ( (Meth) acrylate and methyl (meth) acrylate are preferred.
The total amount of the component (b-1) and the component (b-2) in the radical polymerizable unsaturated monomer (B) is preferably 20 to 95% by mass, more preferably 30 to 95% by mass. If the content is within the above range, a good balance between low elastic modulus and high specific gravity can be achieved, and the viscosity can be further reduced. As one aspect, the total amount of the component (b-1) and the component (b-2) in the radical polymerizable unsaturated monomer (B) is preferably 20 to 95% by mass, more preferably 40 to 90% by mass. %, More preferably 65 to 85% by mass. Moreover, 75-95 mass% or 80-95 mass% may be sufficient as one aspect | mode.
The content of the radical polymerizable unsaturated monomer having a caprolactone ring-opening structure in the total amount of the radical polymerizable resin (A) and the radical polymerizable unsaturated monomer (B) is preferably 5 to 50% by mass. -40 mass% is more preferable, and 15-35 mass% is especially preferable. If it is in this range, the balance between low elastic modulus and high specific gravity can be improved.

  The content of the component (A) in the total amount of the component (A) and the component (B) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, further preferably 10 to 45% by mass, and even more. Preferably it is 15-45 mass%, More preferably, it is 20-45 mass%, More preferably, it is 25-45 mass%, More preferably, it is 30-40 mass%. If the content is within the above range, the balance between the low elastic modulus and the high specific gravity of the radical polymerizable resin composition can be improved.

<Amine-based curing accelerator (C)>
As the amine 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 (hydroxyethyl) a Phosphorus, N, such as diethanol aniline, N- substituted aniline, N, N- substituted -p- toluidine, 4-(N, N- disubstituted amino) amines, such as benzaldehyde can be used. Among these, N, N-bis (2-hydroxyethyl) -p-toluidine or N, N-bis (2-hydroxypropyl) -p-toluidine is preferable from the viewpoint of facilitating curing.
The content of the amine curing accelerator is preferably 0.01 to 3.0 parts by mass, more preferably 100 parts by mass with respect to a total of 100 parts by mass of the (A) radical polymerizable resin and (B) radical polymerizable unsaturated monomer. Is 0.1 to 1.0 part by mass. If the content is within the above range, the curability can be easily adjusted.

<Curing agent (D)>
The radically polymerizable resin composition of the present invention may contain a curing agent (D). The (D) curing agent used in the present invention is not particularly limited, and a known radical polymerization initiator can be used, and an organic peroxide is preferably used.
Examples of organic peroxides include dibenzoyl peroxide (also called benzoyl peroxide), ketone peroxide, perbenzoate, hydroperoxide, diacyl peroxide, peroxyketal, hydroperoxide, diallyl peroxide, peroxy Examples thereof include esters and peroxydicarbonates, and azo compounds can also be used. More specifically, methyl ethyl ketone peroxide, cumene hydroperoxide, t-butylperbenzoate, dibenzoyl peroxide, dicumyl 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-isopropyl hydroperoxide , T-butyl hydroperoxide, dicumyl hydroperoxide, acetyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, isobutyl peroxide, 3,3,5-tri Chill hexanoyl peroxide, lauryl peroxide, azobisisobutyronitrile and azo-bis-carboxylic amide and the like can be used. These organic peroxides can be used alone or in combination. Of these, dibenzoyl peroxide is preferable from the viewpoints of cost, availability, and stability.

  0.1-8 mass parts is preferable with respect to a total of 100 mass parts of the said (A) component and (B) component, and, as for the compounding quantity of a hardening | curing agent (D), 0.5-5 mass parts is more preferable. When the blending amount of the curing agent (D) is 0.1 parts by mass or more, desired curability is easily obtained. On the other hand, when the blending amount of the curing agent (D) is 8 parts by mass or less, it is economically advantageous and sufficient working time is easily obtained.

<Other ingredients>
(Polymerization inhibitor)
The radical polymerizable resin composition of the present invention comprises a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of (A) radical polymerizable resin and (B) radical polymerizable unsaturated monomer, and controlling the reaction rate. May be included.
Examples of the polymerization inhibitor include known ones such as hydroquinone, methylhydroquinone, phenothiazine, catechol, and 4-tert-butylcatechol.
[Curing accelerators other than amines]
The radical polymerizable resin composition of the present invention may contain a curing accelerator other than the amine-based curing accelerator described above. It does not specifically limit as hardening accelerators other than an amine type | system | group, A well-known organometallic salt can be used. Examples of the organic metal salt include copper naphthenate, cobalt octylate, cobalt naphthenate, cobalt hydroxide, zinc hexate, manganese octylate and the like. Among these, cobalt naphthenate and cobalt octylate are preferable. These organometallic salts can be used alone or in combination.

The compounding amount of the organic metal salt is preferably 0.02 to 10 parts by mass, and 0.1 to 3.0 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). More preferably. When the compounding amount of the organic metal salt is 0.02 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 compounding amount of the organic metal salt is 10 parts by mass or less, desired pot life and storage stability are easily obtained.
(Photopolymerization initiator)
The resin composition of this embodiment may contain a photopolymerization initiator for the purpose of improving curability. As a photoinitiator, radical photopolymerization initiator etc. are mentioned, for example.
A radical photopolymerization initiator is used to improve the curability of an acrylic resin or monomer having a double bond.
Specifically, photo radical polymerization initiators include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, and 2-hydroxy. 2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, acetophenone series such as 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc. A thioxanthone type is mentioned.
A photoinitiator can be added in 0.1-10 mass parts with respect to 100 mass parts in total 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 the compatibility between the resin and water and facilitating curing in a state where water is embraced in the resin.
Examples of the surfactant include an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. 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 the anionic surfactant include alkyl sulfate esters such as sodium lauryl sulfate and triethanolamine lauryl sulfate; polyoxyethylene alkyl such as polyoxyethylene lauryl ether sodium sulfate and polyoxyethylene alkyl ether sulfate triethanolamine. Ether sulfate salts; sulfonates such as dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium alkylnaphthalene sulfonate, sodium dialkylsulfosuccinate; fatty acid salts such as sodium stearate soap, potassium oleate soap, castor oil potassium soap A naphthalene sulfonic acid formalin condensate, a special polymer system and the like.
Among these, sulfonates are preferable, sodium dialkylsulfosuccinate is more preferable, and sodium dioctylsulfosuccinate is still more preferable.
Nonionic surfactants include, for example, polyoxyethylene alkyl ethers such as polyoxylauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene distyrenated phenyl ether, polyoxyethylene Polyoxyethylene derivatives such as oxyethylene tribenzylphenyl ether and polyoxyethylene polyoxypropylene glycol; sorbitan fatty acid esters such as polyoxyalkylene alkyl ether, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate; polyoxyethylene Sorbitan monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate 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, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and polyoxyethylene alkyl ether are preferable. Moreover, 5-15 are preferable and, as for HLB (Hydrophile-Lipophil Balance) of a nonionic surfactant, 6-12 are more preferable.
When the radical polymerizable resin composition contains a surfactant, the amount thereof is preferably 0 with respect to a total of 100 parts by mass of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. 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.

[Dispersant]
The radically polymerizable resin composition of the present invention may contain a wetting and dispersing agent, for example, in order to improve the permeability to a repaired site that has been wetted or submerged.
Examples of the wetting and dispersing agent include a fluorine-based wetting and dispersing agent and a silicone-based wetting and dispersing agent, and these may be used alone or in combination of two or more.
Commercially available fluorine-based wetting and dispersing agents include MegaFac (registered trademark) F176, MegaFac (registered trademark) R08 (manufactured by Dainippon Ink & Chemicals, Inc.), PF656, PF6320 (manufactured by OMNOVA), Troisol S- 366 (manufactured by Troy Chemical Co., Ltd.), Florard FC430 (manufactured by 3M Japan Co., Ltd.), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.
Commercially available products of the silicone-based wetting and dispersing agent 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 Japan), polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like.
When the radical polymerizable resin composition of the present invention contains a dispersant, the amount thereof is 100 parts by mass in total of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. Preferably, it is 0.01-10 mass parts, More preferably, 0.1-5 mass parts is preferable.

[Thixotropic agent]
The radical polymerizable resin composition of the present invention may contain a thixotropic agent for the purpose of adjusting the viscosity for ensuring workability on a vertical surface or a ceiling surface.
Examples of thixotropic agents include inorganic thixotropic agents and organic thixotropic agents. Examples of organic thixotropic agents include hydrogenated castor oil-based, amide-based, polyethylene oxide-based, vegetable oil-polymerized oil-based, and surface activity. An agent system and a composite system using these in combination are exemplified. Specifically, DISPARLON (registered trademark) 6900-20X (Enomoto Kasei Co., Ltd.) and the like can be mentioned.
In addition, examples of the inorganic thixotropic agent include silica and bentonite, and hydrophobic ones such as Leolosil (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, and examples of hydrophilic ones include Aerosil (registered trademark) AEROSIL-200 (Nippon Aerosil Co., Ltd.). From the viewpoint of further improving thixotropic properties, those obtained by adding BYK (registered trademark) -R605 or BYK (registered trademark) -R606 (made by Big Chemie Japan Co., Ltd.) as a thixotropic modifier to hydrophilic calcined silica. Can also be suitably used.
When the radical polymerizable resin composition of the present invention contains a thixotropic agent, the amount thereof is based on 100 parts by mass in total of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. The amount is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass.

(Curing retarder)
The radical polymerizable resin composition of the present invention may contain a curing retardant for the purpose of adjusting the curing time. Examples of the curing retarder include free radical curing retarders such as 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) 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 preferable in terms of cost and ease of handling.
When the radical polymerizable resin composition contains a polymerization inhibitor and a curing retarder, the amount thereof is 100 parts by mass in total of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. Preferably each is 0.0001-10 parts by mass, more preferably 0.001-10 parts by mass.

[Defoamer]
The radical polymerizable resin composition of the present invention may contain an antifoaming agent for the purpose of improving foam generation during molding and foam residue of the molded product. Examples of antifoaming agents include silicone-based antifoaming agents and polymer-based antifoaming agents.
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) radical polymerizable resin and the (B) radical polymerizable unsaturated monomer. More preferably, it is 0.1-1 mass part.

[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 that is a restoration target. Examples of the coupling agent include known silane coupling agents, titanate coupling agents, aluminum coupling agents, and the like.
An example of such a coupling agent is a silane coupling agent represented by R ³ —Si (OR ⁴ ) ₃ . Examples of R ³ include an aminopropyl group, a glycidyloxy group, a methacryloxy group, an N-phenylaminopropyl group, a mercapto group, and a vinyl group. Examples of R ⁴ include a methyl group and an ethyl group. Etc.
When the radical polymerizable resin composition contains a coupling agent, the amount thereof is preferably 0 with respect to 100 parts by mass in total of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.

(Light stabilizer)
The radically polymerizable resin composition of the present invention may use a light stabilizer for the purpose of improving the long-term durability of the molded product. Examples of the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. These may be used alone or in combination of two or more. Specifically, as the ultraviolet absorber, benzotriazole-based, triazine-based, benzophenone-based, cyanoacrylate, salicylate, and the like, as the hindered amine light stabilizer, N-H-type, N-CH ₃ type , N-O alkyl type and the like.
The amount of the light stabilizer used may be in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of (A) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer. Preferably, it is 0.05-2 mass parts.

〔wax〕
The radical polymerizable resin composition of the present invention may contain a wax. 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.
Examples of polar waxes include those having both a polar group and a nonpolar group in the structure. Specific examples include NPS-8070, NPS-9125 (manufactured by Nippon Seiwa Co., Ltd.), Emanon 3199, 3299 (manufactured by Kao Corporation), 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) the radical polymerizable resin and (B) the radical polymerizable unsaturated monomer, It is more preferable to contain 0.0 part by mass.

〔Flame retardants〕
The radical 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 intimate flame retardant, a silicone flame retardant, or the like can be used alone or in combination, and publicly known Things can be used.
In addition, 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.
Although the addition amount of a flame retardant changes with systems, it may contain 1-100 mass parts with respect to a total of 100 mass parts of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. preferable.

[Plasticizer]
The resin composition of the present invention may contain a plasticizer for the purpose of adjusting viscosity and elastic modulus. Plasticizers include epoxies, polyesters, phthalates, adipates, trimellitic esters, phosphate esters, citrate esters, sebacate esters, azelain Acid esters, maleates, benzoates and the like can be used alone or in combination, and known ones can be used.
Although the addition amount of a plasticizer changes with systems, it contains 0.01-20 mass parts with respect to a total of 100 mass parts of (A) radically polymerizable resin and (B) radically polymerizable unsaturated monomer. It is preferable. More preferably, it is preferable to contain 0.1-10 mass parts.
In the radically polymerizable composition of the present invention, the total content of the component (A), the component (B), and the component (C) is preferably 30 to 100% by mass, more preferably 60 to 100% by mass, More preferably, it is 90-100 mass%.
Moreover, when the radically polymerizable composition of the present invention contains (D) a curing agent, the (A) component, the (B) component, the (C) component, and (D) in the radically polymerizable composition of the present invention. The total amount of the 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.

<Physical property value of radical polymerizable composition>
The viscosity of the radical polymerizable composition is preferably from 10 to 500 mPa · s / 25 ° C., more preferably from 10 to 350 mPa · s / 25 ° C., more preferably from the viewpoint of ease of injection into the cracks of the inorganic structure. Is 10 to 250 mPa · s / 25 ° C. The measuring method of a viscosity is as having described in the Example.
The liquid specific gravity of the radical polymerizable composition is preferably 1.01 to 1.15, more preferably 1.03 to 1.15, from the viewpoint of improving adhesion. Particularly preferred is 1.15. The method for measuring the liquid specific gravity is as described in the examples.
The volume shrinkage of the radical polymerizable composition is preferably 3 to 12%, more preferably 4 to 11%, and still more preferably 5 to 10% from the viewpoint of adhesiveness after injection into the crack of the inorganic structure. is there. The method for measuring the volumetric shrinkage is as described in the examples.
The elastic modulus of the radically polymerizable composition is preferably 1 to 900 N / mm ² , more preferably 3 to 600 N / mm ² , and still more preferably 5 to 200 N / mm ² from the viewpoint of durability against vibration. The measuring method of the elastic modulus is as described in the examples.

<Method for producing radically polymerizable composition>
The order of mixing the components is not particularly limited, but from the viewpoint of workability for efficiently obtaining a uniform mixture, and workability when adjusting the composition within the target physical property range such as liquid specific gravity as a radical polymerizable composition. From the viewpoint of (A), after synthesizing the component (A), a part of the component (B) is added and mixed. After the viscosity of the component (A) is reduced, the remaining component (B) and other components are added and mixed. Is preferred. Alternatively, a 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. It is preferable to add and mix. The mixing ratio (mass ratio) of the component (A) and the part (B) component at the time of reducing the viscosity is not particularly limited, but is preferably 95: 5 to 20:80, more preferably 85:15 to 30:70. It is.
The viscosity of the mixture of the component (A) and the component (B) is preferably 100 to 2000 mPa · s, more preferably 100 to 1500 mPa · s, and still more preferably 100 to 1000 mPa · s. The measuring method of a viscosity is as having described in the Example. If the viscosity is adjusted in the above range in advance, the remaining components can be mixed uniformly in a short time when the radical polymerizable resin composition of the present invention is mixed.
The liquid specific gravity of the mixture of the component (A) and the component (B) is preferably 0.95 to 1.15, more preferably 1.00 to 1.10. By adjusting the liquid specific gravity within the above range to mix the remaining components into the radical polymerizable resin composition of the present invention, the target liquid is adjusted by adjusting the type and amount of component (B). It becomes easy to adjust the specific gravity.

[Injection for structural repair]
The radical polymerizable resin composition of the present invention is preferably used as an injecting agent for repairing a structure containing the radical polymerizable resin composition.
Examples of the structure include inorganic structures such as concrete, asphalt concrete, mortar, wood, and metal.
The injecting agent for repairing a structure may be produced only from the radical polymerizable resin composition, or may contain an optional additive such as aggregate separately in the radical polymerizable composition.
Examples of the aggregate include silica sand, silica, talc, alumina, aluminum hydroxide, calcium carbonate, aluminum, and titanium. Among these, silica sand, silica, and calcium carbonate are preferable from the viewpoint of cost and material availability.
In addition, since the permeability of the injecting agent for structure repair may be reduced when the aggregate is contained, it is preferable that the injecting agent for structure repair of the present invention does not contain an aggregate. In particular, when repairing concrete with a narrow crack width using an injecting agent for structural restoration, an injecting agent containing aggregate is poorly permeable and difficult to adhere to the object to be repaired. Even if it is not contained, the injectable for repairing a structure of the present invention having a high specific gravity can be used particularly preferably.
The liquid specific gravity of the injecting agent for repairing a structure is preferably 1.01 to 1.15, more preferably 1.03 to 1.15, from the viewpoint of improving adhesion. It is especially preferable that it is -1.15. The method for measuring the liquid specific gravity is as described in the examples.

The method for repairing the structure is not particularly limited. For example, the structure repairing injecting agent according to the present invention is applied to a repair site such as concrete, asphalt concrete, mortar, wood, metal, etc., and dried and cured. be able to. The method for applying the injecting agent for repairing a structure is not particularly limited. For example, a coating method by dipping, a spraying method, a roller coating method, a coating method using a tool such as a brush, a brush or a spatula can be applied. .
The application amount of the injecting agent for structure repair is not particularly limited, but is appropriately determined in consideration of the size of the repaired part, the adhesion of the injecting agent for repairing the structure, the strength of the cured product of the injecting agent for structure repair, and the like. adjust.
Although the drying method after apply | coating the injection for structure restoration is not specifically limited, The method of heating naturally and the method of heating in the range which the characteristic of the hardening body of the injection for structure restoration does not deteriorate are used.

  EXAMPLES Hereinafter, although this invention is demonstrated based on an Example, this invention is not restrict | limited by an Example.

<Synthesis example>
As will be described later, (A) urethane (meth) acrylate resins (UM1) to (UM8), which are radical polymerizable resins, are synthesized using the following raw materials, and then (B) radical polymerizable unsaturated monomer. Methyl methacrylate (Mitsubishi Rayon Co., Ltd.) as one kind was mixed to obtain a mixture (U-1) to (U-8) of the component (A) and the component (B).

The raw materials of urethane (meth) acrylate resins (UM1) to (UM8) are shown below.
(Polyhydric alcohol)
(1) Polypropylene glycol 1 (weight average molecular weight 1000), manufactured by Mitsui Chemicals, Inc., product name: Actcol D-1000
(2) Polypropylene glycol 2 (weight average molecular weight 2000), manufactured by Mitsui Chemicals, Inc., product name: Actcol D-2000
(3) Polyethylene glycol 1 (weight average molecular weight 600), manufactured by Toho Chemical Industry Co., Ltd., product name: Toho polyethylene glycol 600
(4) Polyethylene glycol 2 (weight average molecular weight 1540), manufactured by Toho Chemical Co., Ltd., product name: Toho polyethylene glycol 1540
(5) Polyester polyol (weight average molecular weight 2000), manufactured by DIC Corporation, product name: Polylite OD-X-2420
(6) Polyoxyalkylene bisphenol A ether 1 (weight average molecular weight 800), manufactured by ADEKA Corporation, product name: BPX-55
(7) Polyoxyalkylene bisphenol A ether 2 (weight average molecular weight 2000), manufactured by ADEKA Corporation, product name: BPX-2000
(Polyvalent isocyanate)
Diphenylmethane diisocyanate (hydroxyl group-containing (meth) acrylate)
2-Hydroxyethyl methacrylate 2-Hydroxypropyl methacrylate Next, each synthesis example will be described in detail.

(Synthesis Example 1)
In a 3 L four-necked flask equipped with a stirrer, reflux condenser, gas inlet tube and thermometer, diphenylmethane diisocyanate: 500 g (2.0 mol), Actol D-1000 (Mitsui Chemicals, Inc., polypropylene glycol 1: Weight average molecular weight 1000): 500 g (0.5 mol), Toho Polyethylene Glycol 1540 (Toho Chemical Industries, Ltd. polyethylene glycol 2: Weight average molecular weight 1540): 700 g (0.5 mol), and Dibutyltin dilaurate: 0.2 g Was stirred and reacted at 60 ° C. for 4 hours. Subsequently, 2-hydroxyethyl methacrylate: 260 g (2.0 mol) was added dropwise to the reaction product over 2 hours, and the reaction product was stirred and reacted for 5 hours after completion of the addition to obtain a urethane methacrylate resin (UM1). . The raw materials used for the production of the urethane methacrylate resin (UM1) are shown in Table 1.
Subsequently, 850 g of methyl methacrylate was added to the urethane methacrylate resin (UM1) to obtain a mixture (U-1) of the component (A) and the component (B).
The weight average molecular weight of the urethane methacrylate resin (UM1) was 7300. Moreover, the viscosity in 25 degreeC of a mixture (U-1) was 990 mPa * s, and liquid specific gravity was 1.08.
For the measurement of the 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 Column temperature: 40 ° C
Sample: 0.4 mass% tetrahydrofuran solution of the object to be measured Flow rate: 1 ml / min Eluent: Tetrahydrofuran Further, the measurement conditions for the viscosity and liquid specific gravity are the same as those for the samples in the examples described later.

(Synthesis Examples 2 to 8)
About the synthesis examples 2-8, it synthesize | combined similarly to the synthesis example 1 except having changed the used raw material as Table 1, and obtained urethane methacrylate resin (UM2)-(UM8). Moreover, as shown in Table 2, with respect to each urethane methacrylate resin (UM2)-(UM8) 70 mass part, methyl methacrylate is added so that it may become 30 mass parts, and mixture (U-2)-(U -8) was obtained. The weight average molecular weights of the urethane methacrylate resins (UM2) to (UM8) are shown in Table 1. In addition, Table 2 shows the liquid specific gravity and viscosity values of the mixtures (U-2) to (U-8).

<Examples 1 to 16>
As raw materials, mixtures (U-1) to (U-8) obtained in each synthesis example, the following (B) radical polymerizable unsaturated monomer, (C) amine-based curing accelerator, and (D) A curing agent was used.
((B) radical polymerizable unsaturated monomer)
[(B-1) component]
(1) Ethoxybisphenol A dimethacrylate (number of moles of ethylene oxide added 10), manufactured by Shin-Nakamura Chemical Co., Ltd., product name: NK ester BPE-500
(2) Methoxypolyethylene glycol methacrylate, manufactured by NOF Corporation: BLEMMER PME-400 (number of moles of ethylene oxide added 9)
(3) Phenoxyethyl methacrylate (number of moles of ethylene oxide added 1), manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Ester PO
(4) Phenoxyethyl acrylate (ethylene oxide addition mole number 1), manufactured by Kyoeisha Chemical Co., Ltd., product name: Light acrylate PO-A
[(B-2) component]
(5) Caprolactone-modified (addition mole number 1) hydroxyethyl methacrylate, manufactured by Daicel Corporation, product name: Plaxel FM1
In Table 3, it was expressed as caprolactone-modified (1 mol) methacrylate.
(6) Caprolactone-modified (addition mole number 2) hydroxyethyl methacrylate, manufactured by Daicel Corporation, product name: Plaxel FM2D
In Table 3, it was expressed as caprolactone-modified (2 mol) methacrylate.
(7) Caprolactone-modified (added mole number 2) hydroxyethyl acrylate, manufactured by Daicel Corporation, product name: Plaxel FA2D
In Table 3, it was expressed as caprolactone-modified (2 mol) acrylate.
[Other radical polymerizable unsaturated monomers]
(8) Lauryl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Ester L
(9) 2-ethylhexyl methacrylate, manufactured by Kyoeisha Chemical Co., Ltd., product name: Light Ester EH
(10) Methyl methacrylate, manufactured by Mitsubishi Rayon Co., Ltd., product name: Acryester M

((C) amine curing accelerator)
(1) N, N-bis (2-hydroxyethyl) -p-toluidine, manufactured by Wako Pure Chemical Industries, Ltd., product name: Accelerator A
(2) N, N-bis (2-hydroxypropyl) -p-toluidine, manufactured by Morin Chemical Industry Co., Ltd., product name: PT-2HE
((D) curing agent)
Dibenzoyl peroxide, manufactured by Kayaku Akzo Co., Ltd., product name: Perkadox CH-50L

(B) radical polymerizable unsaturated monomer shown in Table 3 is added to each mixture (U-1) to (U-8) obtained in the synthesis example as necessary, and the component (A) and A preliminary sample consisting of component (B) was obtained. Next, with respect to 100 parts by mass of this preliminary sample, that is, 100 parts by mass of the component (A) and the component (B), (C) amine-based curing accelerator and (D) curing agent are listed in Table 3 in this order It added in the ratio shown and stirred, and the radically polymerizable resin composition was obtained.
In the column of methyl methacrylate in Table 3, the content of methyl methacrylate previously contained in the above mixtures (U-1) to (U-8) and (B) radical polymerizable non-polymerization added as necessary. The methyl methacrylate content as a saturated monomer was added and described.
In the column of (A) radical polymerizable resin in Table 3, only (A) radical polymerizable resin calculated from the amount of raw materials used in the production of mixtures (U-1) to (U-8) The content of was described. (A) Content of radically polymerizable resin was computed considering that the raw material used for manufacture of mixture (U-1)-(U-8) reacted 100%.

<Comparative Examples 1-9>
A radical polymerizable resin composition was obtained in the same manner as in the example except that the component (b-1) and the component (b-2) were not included. Table 3 shows the content of each component of the radical polymerizable resin composition.
The radical polymerizable resin composition thus obtained was measured and evaluated for viscosity, liquid specific gravity, volume shrinkage, and elastic modulus by the following methods. The results are shown in Table 3.

<Viscosity measurement>
Using a RE-85 type viscometer, cone plate type, cone rotor 1 ° 34 ′ × R24 manufactured by Toki Sangyo Co., Ltd., the viscosity under an environment of 25 ° C. was measured at a rotation speed of 100 rpm.
<Liquid specific gravity measurement>
Annex 2 of JIS K 7112 ^-1999 according to "Plastics - - Liquid Resin underwater substitution method", using an electronic densimeter MD-200S manufactured by Alpha Mirage Co., were measured liquid density at 23 ° C..
<Volume shrinkage>
A test piece of length × width × thickness = 40 mm × 40 mm × 3 mm was produced as follows. That is, the radical polymerizable resin composition was poured into a mold of length × width × thickness = 200 mm × 200 mm × 3 mm in a normal temperature (23 ° C.) environment to prepare a test body (solid). Then, after curing for 12 hours in a normal temperature (23 ° C.) environment, curing was performed at 80 ° C. for 3 hours. From the prepared specimen, a specimen of length × width × thickness = 40 mm × 40 mm × 3 mm was cut out and used for measurement. Using the specimen, in accordance with the underwater substitution method JIS ^{K 7112 -1999,} the same tester liquid density measurement was measured solid density. The solid specific gravity was measured twice for each specimen. And the average value of the measurement result of 2 times was used for calculation of volume shrinkage. And calculate the volume shrinkage by using a formula of JIS K 6901 ^-2008 described.
<Elastic modulus>
The radical polymerizable resin composition was made solid as follows. That is, the radical polymerizable resin composition was poured into a mold of length × width × thickness = 200 mm × 200 mm × 3 mm under a normal temperature environment to prepare a test body (solid). Then, after curing for 12 hours in a room temperature environment, post-curing was performed at 80 ° C. for 3 hours.
Then, JIS ^{K 7113 -1995,} to produce a test body in accordance with No. 2 test piece. The prepared test specimen was tested in a test environment of a temperature of 23 ° C. and a humidity of 50% using an Instron 5900R at a grip length of 120 mm and a test speed of 50 mm / min. The elastic modulus was measured three times for each specimen. And the average value of the measurement result of 3 times was used for evaluation of an elasticity modulus.

As shown in Table 3, it contains a radically polymerizable unsaturated monomer (b-1) having an oxyalkylene structure and / or a radically polymerizable unsaturated monomer (b-2) having a caprolactone ring-opening structure. The radical polymerizable resin composition of the present invention was found to have a high specific gravity and a low elastic modulus.
In particular, Examples 8 and 10 having a large total amount of the component (b-1) and the component (b-2) were found to have extremely high high specific gravity and low elastic modulus.
On the other hand, the comparative example 1 which does not contain both the radically polymerizable unsaturated monomer (b-1) which has an oxyalkylene structure, and the radically polymerizable unsaturated monomer (b-2) which has a caprolactone ring-opening structure. It was found that the radically polymerizable resin compositions of 9 to 9 cannot achieve both high specific gravity and low elastic modulus as compared with the resin compositions of Examples 1-16.

Since the radical polymerizable resin composition and the structure repairing injecting agent of the present invention have a high specific gravity and a low elastic modulus, they can be suitably used for repairing cracks in concrete structures and the like.

Claims (10)

(A) a radical polymerizable resin;
(B) a radically polymerizable unsaturated monomer;
(C) an amine-based curing accelerator, and (B) a radically polymerizable unsaturated monomer (b-1) and / or caprolactone ring-opening having an oxyalkylene structure. A radical polymerizable resin composition comprising a radical polymerizable unsaturated monomer (b-2) having a structure.   The radically polymerizable resin composition according to claim 1, wherein the component (b-1) has a polyalkylene oxide (meth) acrylate structure having 1 to 30 moles of alkylene oxide added.   The radically polymerizable resin composition according to claim 1 or 2, wherein the component (b-2) has a polycaprolactone (meth) acrylate structure having 1 to 5 moles of caprolactone added.   The radically polymerizable resin composition according to any one of claims 1 to 3, wherein a total amount of the component (b-1) and the component (b-2) is 20 to 95% by mass in the component (B). object.   The radically polymerizable resin according to claim 1, wherein the component (A) is a urethane (meth) acrylate resin having a polyol structure selected from polyester polyol, polyether polyol, and polyoxyalkylene bisphenol A ether. Composition.   Furthermore, (D) The radically polymerizable resin composition in any one of Claims 1-5 containing a hardening | curing agent.   The radical in any one of Claims 1-6 whose content of the said (b-1) component with respect to the total amount of the said (b-1) component and the said (b-2) component is 40-100 mass%. Polymerizable resin composition.   The content of the radical polymerizable resin (A) in the total amount of the radical polymerizable resin (A) and the radical polymerizable unsaturated monomer (B) is 5 to 60% by mass. The radical polymerizable resin composition according to any one of the above.   The radical polymerizable resin composition according to any one of claims 1 to 8, wherein the radical polymerizable composition has a viscosity of 10 to 500 mPa · s / 25 ° C.   An injecting agent for repairing a structure comprising the radical polymerizable resin composition according to claim 1 and having a liquid specific gravity of 1.01 to 1.15.