JPH11106453A - Curable resin composition and repairing agent for concrete - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in surface curing property and resin strength and having effect without causing inhibition of curing due to an alkaline substance when used as a repairing agent for concretes by including specific three kinds of (meth)acrylates. SOLUTION: This resin composition is obtained by including 100 pts.wt. mixture of (A) 20-80 pts.wt. di(meth)acrylate having bisphenol skeleton of formula I [R1 and R1 ' are each H or methyl; R2 and R2 ' are each a 1-12C alkylene; (m) and (n) are each 1-20] with (B) 10-40 pts.wt. dicyclo-pentenyloxyalkylene (meth)acrylate of formula II [R3 is R1 ; R4 is R2 ; (p) is (n)] and (C) 10-40 pts.wt. hydroxyalkyl (meth)acrylate and as necessary, (D) 1-5 pts.wt. organic peroxide as a polymerization initiator and (E) 0.1-5 pts.wt. decomposition promoter. It is preferable that inorganic filler, a polymerization inhibitor or the like are further contained in the above composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an injection or an adhesive having a high resin strength of a cured product in the field of civil engineering and construction.

[0002]

2. Description of the Related Art Conventionally, when bonding or pouring is carried out in the field of civil engineering and construction, an epoxy-based room temperature-curable adhesive has been used. However, the epoxy-based room-temperature-curable adhesive has the disadvantage that it is inferior in low-temperature curability and that it causes mutagenicity and rash on the human body. In order to solve these drawbacks, adhesives and injections using an acrylic resin have been developed. Acrylic resins are gradually being used because they have a faster curing time than epoxy resins.

However, there is a drawback that the resin strength of the cured product is low, and its use in the field of civil engineering and construction has not progressed as compared with epoxy resins. Acrylic resins with improved resin strength of cured products include three-component curable resin compositions such as epoxy acrylate, dicyclopentenylethyl acrylate, and hydroxyalkyl methacrylate obtained by reacting a compound having an epoxy group with (meth) acrylic acid. (See JP-A-5-17545) and a curable resin composition containing bisphenol A diethylene glycol dimethacrylate and hydroxyalkyl methacrylate (see JP-A-8-127509).

[0004]

However, these curable resin compositions are not suitable for use in direct sunlight in summer.
Since the water resistance at high temperatures of up to 80 ° C. is insufficient, there has been a problem that the adhesiveness of the curable resin composition is reduced in high temperature and high humidity places such as direct sunlight after rain in summer. In addition, when used as an adhesive or a filler for concrete, there is a problem that the presence of an alkaline compound such as calcium hydroxide contained in the concrete makes it difficult for the acrylic resin composition to harden. As a result of intensive studies, the present inventors have obtained knowledge that can solve the above-mentioned problems by using a specific curable resin composition, and have completed the present invention.

[0005]

That is, the present invention provides (1)
A di (meth) acrylate having a bisphenol skeleton represented by the general formula (A),

Embedded image (2) dicyclopentenyloxyalkylene (meth) acrylate represented by the general formula (a),

Embedded image And (3) a curable resin composition containing a hydroxyalkyl (meth) acrylate, and (4)
The curable resin composition contains an organic peroxide and (5) a decomposition accelerator. And it is a concrete repair agent containing the curable resin composition. The present invention also provides a method for repairing concrete, characterized in that the curable resin composition is a cured product, and the curable resin composition is used.

[0006]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The (1) di (meth) acrylate having a bisphenol skeleton used in the present invention refers to a compound having an oxyalkylene glycol at the terminal of the bisphenol skeleton.
It refers to a di (meth) acrylate having two (meth) acryl groups and is represented by the following general formula (A).
Component (1) has the effects of improving water resistance, heat resistance, and resin strength. In addition, unlike the epoxy (meth) acrylate, the component (1) has an effect of not being inhibited from curing even when an alkaline compound such as calcium hydroxide is present.

[0008]

Embedded image

As the component (1), NK ester BPE
-100 (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK ester BPE-200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), NK ester BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.),
NK ester BPE-1300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), light ester BP-2EMBR-MA (Kyoeisha Chemical Co., Ltd.) and the like can be mentioned. One or two of these
More than one species can be used. Among them, BPE-200 (R ₁ , R
₁ 'is a methyl group, R _2, R _2' is an ethylene group, m + n = 4)
Is preferred. R ₁ and R ₁ ′ are preferably methyl groups from the viewpoint of improving durability by a fatigue test. R ₂ and R ₂ ′ are 1 to 4 in terms of water resistance at a high temperature, resin strength of a cured product and economy.
Preferred are alkylene groups having two carbon atoms, and more preferred are ethylene groups. m + n is preferably 3 to 8, and more preferably 4 in that the resin strength of the cured product is large.

[0010] The amount of component (1) used is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight based on 100 parts by weight of the total of (1), (2) and (3). If the amount is less than 20 parts by weight, the resin strength of the cured product may be reduced.
If the amount exceeds 0 parts by weight, the surface curability may decrease.

The (2) dicyclopentenyloxyalkylene (meth) acrylate used in the present invention is represented by the general formula (A). Component (2) has low odor, good water resistance, and has an effect as a reactive diluent.

[0012]

Embedded image

The component (2) includes dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxydiethylene glycol (meth) acrylate,
Examples include dicyclopentenyloxytriethylene glycol (meth) acrylate and dicyclopentenyloxypropylene glycol (meth) acrylate.
Among them, dicyclopentenyloxyethyl (meth) acrylate is preferred because it has good surface curability and is easily available. R ₃ is preferably a methyl group from the viewpoint of safety for the human body. R ₄ is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably an ethylene group, from the viewpoint of high resin strength. p is preferably 1 to 3, and more preferably 1 in that the resin strength of the cured product is large.

The amount of component (2) used is preferably from 10 to 40 parts by weight, more preferably from 15 to 35 parts by weight, per 100 parts by weight of the total of (1), (2) and (3). If the amount is less than 10 parts by weight, the surface curability and water resistance at high temperatures may be reduced, and if it exceeds 40 parts by weight, the resin strength of the cured product may be reduced.

The (3) hydroxyalkyl (meth) acrylate used in the present invention includes 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and glycerol mono ( (Meth) acrylate and the like. Component (3) has the effect of being less susceptible to curing inhibition by an alkaline compound such as calcium hydroxide.

Of these, the cured product has good resin strength and high water resistance at high temperatures, and is therefore represented by the general formula (C).
Hydroxyalkyl (meth) acrylate is preferred,
2-hydroxypropyl (meth) acrylate and 2-hydroxybutyl (meth) acrylate are more preferred.
2-Hydroxyethyl (meth) acrylate may have a low water resistance at high temperatures or a cured product may be deteriorated.

[0017]

Embedded image

R ₅ is preferably a methyl group from the viewpoint of safety for the human body. R ₆ is, the viewpoint of fast curing speed, 2-5
An alkyl group having two carbon atoms is preferable, and a methyl group and an ethyl group are more preferable.

The amount of component (3) used is preferably from 10 to 40 parts by weight, more preferably from 15 to 35 parts by weight, based on a total of 100 parts by weight of (1), (2) and (3). If the amount is less than 10 parts by weight, the resin strength of the cured product may be reduced.
If it exceeds 0 parts by weight, the water resistance may decrease.

Further, in the present invention, it is preferable to use (4) a polymerization initiator in order to cure at room temperature or lower. Examples of the polymerization initiator include the following organic peroxides.

(1) Ketone peroxides: methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide,
Methyl acetoacetate peroxide, acetylacetone peroxide and the like. (2) Peroxyketals: 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane, 2,2-bis ( Tert-butylperoxy) octane, normal butyl-4,4-
Bis (tert-butylperoxy) valerate and 2,2-bis (tert-butylperoxy) butane; (3) Hydroperoxides: tertiary butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide,
Paramenthane hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide and the like. (4) Dialkyl peroxides: ditertiary butyl peroxide, tertiary butyl cumyl peroxide, dicumyl peroxide, α, α′-bis (tertiary butylperoxy-meta-isopropyl) benzene, 2,5-dimethyl -2,5-di (tert-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3 and the like. (5) diacyl peroxides: acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, laurinoyl peroxide, 3,3,5-trimethylhexanoyl peroxide, succinic acid peroxide,
Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide and meta-toluoyl peroxide. (6) Peroxydicarbonates: diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, dinormal propylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2 -Ethoxyethyl peroxydicarbonate, dimethoxyisopropyl peroxydicarbonate, di (3-methyl-3
-Methoxybutyl) peroxydicarbonate and diallyl peroxydicarbonate. (7) Peroxyesters: tertiary butyl peroxyacetate, tertiary butyl peroxyisobutyrate, tertiary butyl peroxypivalate, tertiary butyl peroxy neodecanoate,
Cumyl peroxy neodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,3,5-trimethylhexanoate, tert-butyl peroxy laurate, tert-butyl peroxy Oxybenzoate, ditertiary butyl peroxyisophthalate, 2,5-dimethyl-2,5-di (benzoylperoxy) hexane, tertiary butylperoxymaleic acid, tertiary butylperoxyisopropyl carbonate,
Cumyl peroxy octoate, tertiary hexyl peroxy neodecanoate, tertiary hexyl peroxy pivalate, tertiary butyl peroxy neo hexanoate, tertiary hexyl peroxy neo hexanoate and cumyl peroxy neo hexanoate Eat and so on. (8) Other organic peroxides: acetylcyclohexylsulfonyl peroxide, tert-butylperoxyallyl carbonate, and the like.

As the polymerization initiator other than the organic peroxide, the following azo compounds can be mentioned. (1) Azonitrile compounds: azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 1,1′-azobis (cyclohexane-1-carbonitrile), -[(1-cyano-1-methylethyl) azo] formamide and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile and the like. (2) Azoamidine compounds: 2,2′-azobis (2
-Methylpropionamidine) dihydrochloride and the like. (3) Cyclic azoamidine compounds: 2,2′-
Azobis [2- (2-imidazolin-2-yl) propane] and the like. (4) Azoamide compound: 2,2′-azobis {2-methyl-normal- [1,1-bis (hydroxymethyl)
-2-hydroxyethyl] propionamide} and 2,
2′-azobis {2-methyl-normal- [1,1-bis (hydroxymethyl) ethyl] propionamide}
etc. (5) Alkyl azo compounds: 2,2′-azobis (2,4,4-trimethylpentane) and the like.

One or more of these can be used. Among the polymerization initiators, organic peroxides are preferable in terms of adhesiveness and curability, and cumene hydroperoxide is more preferable.

The amount of component (4) used is preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, based on 100 parts by weight of the total of (1), (2) and (3). If the amount is less than 1 part by weight, there is a risk of poor curing. If the amount exceeds 5 parts by weight, the resin strength may be reduced.

Further, in the present invention, it is preferable to use (5) a decomposition accelerator in order to accelerate the decomposition of the polymerization initiator.

The following are examples of the decomposition accelerator. (1) Thiourea derivatives: diethylthiourea, dibutylthiourea, ethylenethiourea, tetramethylthiourea, mercaptobenzimidazole, benzoylthiourea and the like. (2) amines: N, N-diethyl-p-toluidine,
N, N-dimethyl-p-toluidine, N, N-diisopropanol-p-toluidine, triethylamine, tripropylamine, ethyldiethanolamine, N, N-
Dimethylaniline, ethylenediamine, triethanolamine and the like. (3) Metal salts of organic acids: cobalt naphthenate, copper naphthenate, zinc naphthenate, cobalt octylate and iron octylate. (4) Organic metal chelate compounds: copper acetylacetonate, titanium acetylacetonate, manganese acetylacetonate, chromium acetylacetonate, iron acetylacetonate, vanadyl acetylacetonate, cobalt acetylacetonate and the like. Other examples of the decomposition accelerator include a condensation reaction product of an aldehyde and an amine. One or more of these can be used.

Of these, amines, metal salts of organic acids and organic metal chelate compounds are preferred from the viewpoint of curability, and amines and amines are preferred because they can further improve the adhesion to the cement concrete surface in a wet state. It is more preferable to use a combination of an organic acid metal salt and / or an organic metal chelate compound.

The amount of the component (5) used is preferably 0.1 to 5 parts by weight, more preferably 1 to 3 parts by weight, based on 100 parts by weight of the total of (1), (2) and (3). If the amount is less than 0.1 part by weight, curing may be poor, and if it exceeds 5 parts by weight, storage stability may decrease.

Further, in the present invention, it is preferable to use an inorganic filler from the viewpoint of improving the workability by setting the thixotropy and viscosity of the curable resin composition of the present invention to an appropriate level.
In particular, the viscosity is 500 to 50,000 using an inorganic filler.
By adjusting the cps and the thixotropic coefficient to 4.0 to 5.0, workability can be improved. When the viscosity exceeds 50,000 cps or the thixotropy exceeds 5.0, the curable resin composition does not sufficiently penetrate into fine cracks in concrete when used as a concrete repair agent, and the repair effect is prolonged. There is a possibility that it cannot be held. If the viscosity is less than 500 cps or the thixo coefficient is less than 4.0, the curable resin composition flows out from the repaired part when used as a concrete repairing agent, and there is a possibility that the repair cannot be performed sufficiently. In addition, depending on the repair location, a large amount of a curable resin composition (particularly, a repair agent for concrete) may be required. At this time, if a predetermined strength can be achieved, the inorganic filler is increased and the component (1) is increased. ) ~
Since the organic component (3) can be reduced as much as possible, it is economically preferable.

Examples of the inorganic filler include silica powder such as crystalline silica powder, fused silica powder, spherical silica powder and fumed silica, silica sand, carbon black, wollastonite, clay, titanium oxide, magnesium oxide, and oxide. Iron, bentonite, mica, lead chromate, nickel slag, aluminum hydroxide, alumina powder including spherical powder, stainless steel powder, silicon carbide powder, silicon nitride powder, boron nitride powder, talc powder, calcium carbonate powder, glass beads , Shirasu balloon, aluminum powder, titanium powder and the like. One or more of these may be used in combination. Among these, calcium carbonate powder is preferred in terms of economy and high resin strength. The particle size of the inorganic filler is preferably 0.1 to 10 μm from the viewpoint that the curable resin composition easily penetrates into fine cracks in concrete when used as a repair agent for concrete.

The amount of the inorganic filler used is preferably 100 parts by weight or less, more preferably 0.1 to 50 parts by weight, based on 100 parts by weight of the total of (1), (2) and (3).
If the amount is less than 0.1 part by weight, there is a possibility that there is no effect.
If the amount exceeds the weight part, the resin strength of the cured product may be reduced.

Further, in the present invention, it is preferable to use a polymerization inhibitor from the viewpoint of improving storage stability. Examples of the polymerization inhibitor include methyl hydroquinone, hydroquinone, catechol, hydroquinone monomethyl ether, mono-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, p-benzoquinone, 2,5
-Diphenyl-p-benzoquinone, 2,5-ditert-butyl-p-benzoquinone, picric acid, citric acid, phenothiazine, tert-butyl catechol,
2-butyl-4-hydroxyanisole and 2,6-ditert-butyl-p-cresol and the like.
The amount of use of these polymerization inhibitors is preferably 0.001 to 3 parts by weight, more preferably 0.01 to 2 parts by weight, based on 100 parts by weight in total of (1), (2) and (3). .
If the amount is less than 0.001 part by weight, the storage stability is reduced. If the amount exceeds 3 parts by weight, the curing time may be prolonged or the curing may not be performed.

In addition, a silane coupling agent, a reactive diluent, a solvent, an antioxidant, NBR, a pigment, a dye, a plasticizer, an ultraviolet absorber, a thixotropic agent, a wax, and an antifoaming agent are added. be able to.

The curable resin composition of the present invention may be used as an adhesive or an injecting agent. However, the curable resin composition may be used as a concrete repair agent because it is hardly inhibited from hardening by an alkaline compound such as calcium hydroxide. And more preferably used as an adhesive for concrete or a filler for concrete.

The curable resin composition of the present invention is usually used by stirring and mixing components (1) to (5) at room temperature. At the time of stirring and mixing, an inorganic filler may be added. The curable resin composition of the present invention can be used as a one-pack type or a two-pack type. When used as a one-pack type, the components (1) to (4) are mixed in advance and, for example, a method of mixing the component (5) when used as a repair agent for concrete, or a method of mixing the components (1) to (4).
(3) and (5) are mixed in advance, and the component (4) is mixed when actually used. When used as a two-pack type, the mixture of components (1) to (3) is divided into two liquids, and component (4) is added to one liquid and component (5) is added to the other liquid. In addition, for example, when used as a repair agent for concrete, a method of mixing two liquids and the like can be mentioned.

[0036]

【Example】

Experimental Example 1 A curable resin composition was prepared using commercially available materials shown in Table 1, and each physical property was measured. The results are shown in Table 1.

(Materials used) BPE-200: m + n = 4 in the general formula (D), NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.
Bisphenol A diethylene glycol dimethacrylate DCPEMA: dicyclopentenyloxyethyl methacrylate

[0038]

Embedded image

(Measurement method) Tensile breaking strength: The resin strength was indicated. A rectangular sheet having a width of 10 mm and a length of 80 mm was cut out from a silicon rubber sheet having a thickness of 1 mm, and used as a mold for preparing a test piece. After placing a PET film on a glass plate and further placing this mold, a curable resin composition was cast. Further, a PET film was placed thereon, and after curing for 4 weeks in an atmosphere of 25 ° C. and 60% humidity, a rectangular test specimen having a thickness of 1 mm × a width of 10 mm × a length of 80 mm was prepared. Using a universal testing machine,
At 20 ° C., a tensile test was performed at a grip interval of 20 mm and a tensile speed of 5 mm / min to determine the maximum load, and (tensile breaking strength) =
(Maximum load) / [(width) × (thickness)]. Tensile breaking strength: Resin strength was shown. A curable resin composition is formed on a glass plate so as to have a thickness of 1 mm.
After curing for 4 weeks in an atmosphere of 5 ° C. and a humidity of 60%, a strip test specimen having a thickness of 1 mm × a width of 10 mm × a length of 80 mm was prepared. Using a universal testing machine, the test specimen was subjected to a tensile test at 20 ° C. at a grip interval of 20 mm and a tensile speed of 5 mm / min to determine the maximum load, and (tensile breaking strength) = (maximum load)
/ [(Width) × (thickness)]. Surface curability: Shown by curing time. The time from the preparation of the curable resin composition in an atmosphere at 25 ° C. and a humidity of 60% until the stickiness disappeared by touching the surface of the curable resin composition with a finger was defined as the curing time.

[0040]

[Table 1]

Experimental Example 2 Curable resin compositions were prepared using commercially available materials shown in Table 2, and their physical properties were measured. The results are shown in Table 2.

(Material used) BPE-100: m + n = 2.6 in the general formula (D)
NK ester BPE-10 manufactured by Shin-Nakamura Chemical Co., Ltd.
0 BPE-500: m + n = 10 in the general formula (D), NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0043]

[Table 2]

Experimental Example 3 Curable resin compositions were prepared using commercially available materials shown in Table 3, and their physical properties were measured. The results are shown in Table 3.

(Materials used) DCPEA: dicyclopentenyloxyethyl acrylate

(Measurement method) Water absorption: Water resistance at high temperature was shown. The curable resin composition was cured in an atmosphere at 25 ° C. and a humidity of 60%, and cured for 48 hours to obtain a strip specimen having a thickness of 1 mm × a width of 10 mm × a length of 80 mm. After measuring the weight of the obtained cured product, it was immersed in water and left at 80 ° C. for 24 hours. Thereafter, the test piece was taken out and the surface of the test piece was wiped off, and the weight was measured immediately. (Water absorption) = [(weight after immersion) − (weight before immersion)] / (weight before immersion) × 100 (%). Appearance-1: The water absorption was tested at the same time, and the appearance of the cured product after immersion in water at 80 ° C. for 24 hours was visually observed.

[0047]

[Table 3]

Experimental Example 4 Curable resin compositions were prepared using commercially available materials shown in Table 4, and their physical properties were measured. The results are shown in Table 4.

[0049]

[Table 4]

Experimental Example 5 Curable resin compositions were prepared using commercially available materials shown in Table 5, and their physical properties were measured. Table 5 shows the results.

(Materials used) Saturated calcium hydroxide solution: concentration of about 1.9% by weight

(Measurement method) Curing time: Curing inhibition by an alkaline substance was shown. A mixture obtained by mixing 10 parts by weight of the curable resin composition and 0.5 part by weight of a saturated calcium hydroxide solution as needed was placed in a container, and covered with a styrene foam-based heat insulating material. A K-type thermocouple (0.3 × 1 PK-S, manufactured by Ninomiya Electric Cable Co., Ltd.) was inserted, and the temperature change was measured. The time from when the mixture was added to the container to when the exothermic peak was exhibited was defined as the curing time. The curing time when no saturated calcium hydroxide solution was used was designated as curing time-1, and the curing time when using a saturated calcium hydroxide solution was designated as curing time-2.

[0053]

[Table 5]

Experimental Example 6 A curable resin composition was prepared using commercially available materials shown in Table 6, and each physical property was measured. The results are shown in Table 6.

(Materials used) Calcium carbonate powder: particle size 1.7 μm

(Measurement Method) Viscosity: Measured at 25 ° C. and 10 rpm using a B-type viscometer. Thixotropic coefficient: a value obtained by dividing the viscosity at 25 ° C. and 1 rpm by the viscosity at 10 rpm.

[0057]

[Table 6]

Example 7 Curable resin compositions were prepared using commercially available materials shown in Table 7, and their physical properties were measured. The results are shown in Table 7. (Materials used) 3000M: epoxy acrylate in which R ₇ is a methyl group in the general formula (e), epoxy ester 3000M manufactured by Kyoeisha Chemical Co., Ltd., bisphenol A diethylene glycol diglycidyl ether dimethacrylate

[0059]

Embedded image

[0060]

[Table 7]

Example 8 Curable resin compositions were prepared using commercially available materials shown in Table 8, and each physical property was measured. The results are shown in Table 8.

(Materials used) 3000A: epoxy acrylate represented by the general formula (E) wherein R ₇ is hydrogen, epoxy ester 3000A manufactured by Kyoeisha Chemical Co., Ltd., bisphenol A diethylene glycol diglycidyl ether diacrylate

(Measurement Method) Adhesive Strength-1: To evaluate whether the curable resin composition can be used as an adhesive or a filler between concretes,
The adhesive strength between mortar and mortar was shown. JIS A
According to 4.7 “Adhesive strength” of 6024 (1992),
The measurement was carried out under standard conditions and environmental conditions during repeated drying and drying. Adhesive strength-2: In order to evaluate whether the curable resin composition can be used as an adhesive between concrete and metal, the adhesive strength between the concrete sidewalk plate and the metal plate was shown. The curable resin composition is applied to the concrete sidewalk board surface, and the width is 40 m.
mx 40 mm long x 3 mm thick cold rolled steel sheet (JIS
G 3141 SPCC DD) was attached and bonded to prepare a test body. Further, using a commercially available adhesive (DK-355, manufactured by Denki Kagaku Kogyo Co., Ltd.), a tensile strength jig was attached to the cold-rolled steel sheet, and the adhesive strength was measured using a Kenken-type tensile strength tester. Destruction state: In the measurement of the adhesive strength-2, the state in which the test piece was broken was visually observed. Appearance-2: Durability by fatigue test was shown. 50m diameter
For a cured product of a curable resin composition having a mx height of 22.65 mm, a minimum stress of repetition of 40 kg / cm ^{2 at} room temperature was obtained.
Maximum stress of repetition 240 kg / cm ² , average stress 14
A sine wave load was applied under the conditions of 0 kg / cm ² and a repetition frequency of 3 Hz, and after 2 million cycles, the appearance of the test specimen was visually observed. Evaluation of crack injection property: The following test was performed to evaluate whether the curable resin composition can be used as a crack repair injection agent for concrete. A curable resin composition was injected into a cracked portion formed on a concrete floor of a reinforced concrete building for repair, and after 6 months, the appearance of the repaired portion was observed. The mark ○ indicates that there was no abnormality, the mark △ indicates that some cracks were present at the interface between the curable resin composition and the concrete, and the mark × indicates peeling at the interface between the curable resin composition and the cracked portion. Is what was seen.

[0064]

[Table 8]

[0065]

The curable resin composition according to the present invention has excellent surface curability and resin strength. In particular, when used as a repair agent for concrete (adhesive or filler), it has the following excellent effects, and its industrial applicability is great. (1) It is not affected by hardening inhibition by an alkaline substance such as calcium hydroxide in concrete. (2) It is excellent in water resistance and adhesiveness at a high temperature of 40 to 80 ° C. Therefore, it can be used to repair concrete under conditions such as direct sunlight after summer rainfall. (3) Excellent adhesion between concrete and adhesion between metal plate and concrete. Because of its high adhesive strength during repeated wet and dry cycles, it can be used to repair concrete that is constantly exposed to groundwater and rainwater. (4) Since the durability in the fatigue test is large, it can be filled in the gap between the lower bearing shoe and the shoe portion of the bridge bearing portion of the bridge pier having the steel bearing. (5) Because the adhesive strength is high even without a primer,
Work steps for applying the primer can be omitted, and workability is good.

Claims (5)

[Claims] 1. A di (meth) acrylate having a bisphenol skeleton represented by the following general formula (A): (2) dicyclopentenyloxyalkylene (meth) acrylate represented by the general formula (a): And (3) a curable resin composition containing a hydroxyalkyl (meth) acrylate. 2. The curable resin composition according to claim 1, further comprising (4) an organic peroxide and (5) a decomposition accelerator. 3. A concrete repair agent comprising the curable resin composition according to claim 1 or 2. 4. A cured product of the curable resin composition according to claim 1 or 2. 5. A method for repairing concrete, comprising using the repair agent for concrete according to claim 3.