JPH08295864A - Setting agent for building structure - Google Patents

Abstract

PURPOSE: To obtain a setting agent for a building structure usable under a wide range of circumstances, excellent in stability, and useful for setting fixing members such as anchor bolts, comprising a curing agent and the chief agent, i.e., an adduct of an unsaturated monobasic acid and an epoxy resin, diluted with a reactive monomer. CONSTITUTION: This setting agent comprises the chief agent, an organic peroxide as a curing agent, and, as a curing promoter, a t-aromatic amine bearing a hydroxyl group in the nitrogen-substituted group such as N,N-dihydroxypropyl-p- toluidine. The chief agent is an adduct (a polyfunctional ester) of an unsaturated monobasic acid and an epoxy resin such as methacrylic type epoxyacrylate resin where one or both of them contain a reactive double bond, diluted with a reactive monomer, i.e., an ester of a carboxylic acid such as (meth)acrylic acid and an alcohol such as allyl alcohol (the amount of the reactive monomer to be used is pref. 30-70wt.% based on the adduct).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fixing agent for a building structure for perforating a base material such as concrete or rock and fixing a fixing member such as an anchor bolt in the perforation.

[0002]

2. Description of the Related Art Conventionally, as a method of fixing a fixing member such as an anchor bolt to a base material by using a fixing agent in a hole,
There are capsule type and injection type.

The former capsule type is fixed by inserting a capsule containing a fixing agent into a perforation, crushing the capsule while hitting and rotating an anchor bolt or the like, and mixing the main agent of the fixing agent and a hardening agent. This is a method of fixing members. As the capsules used in this method, Japanese Patent Publication No. 62-37076 discloses "fixing material for fixing anchor bolts having excellent corrosion resistance", and Japanese Patent Laid-Open Publication No. 61-243876 discloses "adhesive mainly containing acrylic compound". , JP-A-61
The "fixing agent composition and the fixing agent composition for anchor bolts using the same" of JP-A-254681 is known.

Next, the latter injection type is classified into a field type and a cartridge type. In the case of the on-site formulation type, the main agent and the curing agent contained in each container are mixed and injected into the perforations to fix the fixing member. In the case of the cartridge type, the main agent and the curing agent in the cartridge are discharged by an appropriate amount with the force of a hand gun or hydraulic pressure, and the fixing agent mixed by a mixer such as a static mixer is injected into the perforation and fixed. Fix the member. The "two-component mortar material" disclosed in JP-A-59-24714 is known as a material used in this method.

The main components used for these fixing agents are all mixed with reactive monomers and diluted to an appropriate viscosity. Many of the reactive monomers are styrene monomers, and are widely used in general. However, styrene monomer is a dangerous substance (4th petroleum class 2),
Moreover, it is a substance classified as an organic solvent in the Industrial Safety and Health Law. Therefore, a non-styrene type resin that does not use a styrene monomer has been earnestly desired, and as a capsule using the resin of this type, "capsule for fixing bolts" of JP-A-4-27528 is known.

[0006]

In the radical curable resin used for the fixing agent, a styrene monomer is generally used as the reactive monomer. Is a hazardous material and a substance related to the Industrial Safety and Health Act.

Therefore, the adoption of a non-styrene resin has been earnestly desired and tried, but it could not be adjusted to an appropriate curability, and it was only used under a limited condition as a fixing agent.
The environment used is high temperature (low latitude area and summer), low temperature (high latitude area and winter), and water (rainy weather, river, sea), and it hardens within a predetermined time even in those environments. However, the fixing member must be fixed securely. Furthermore, the stability of the resin before the use of the fixing agent is also required.

The present invention solves these problems, is less harmful, and can exhibit a stable fixing force in a wide range of environments.
Moreover, it is an object to provide a fixing agent for a building structure, which is excellent in resin stability.

[0009]

The present inventor has accomplished the present invention as a result of extensive studies to solve the above problems. That is, the invention according to claim 1 of the present invention is a fixing agent for a building structure comprising a main agent and a curing agent, the main agent being an epoxy resin diluted with a reactive monomer and an unsaturated monobasic acid. An addition reaction product of the above, the reactive monomer is an ester of a carboxylic acid and an alcohol, and at least one of them is a polyfunctional ester having a reactive double bond, and the curing agent is It is an organic peroxide and is characterized in that the curing accelerator is a tertiary aromatic amine having a hydroxyl group in the nitrogen substituent.

The invention according to claim 2 is characterized in that the addition reaction product of the epoxy resin and the unsaturated monobasic acid is a methacrylic epoxy acrylate resin.

According to a third aspect of the invention, the accelerator is N,
It is characterized by being N-dihydroxypropyl-p-toluidine.

The invention according to claim 4 is characterized in that the reactive monomer is an ester comprising methacrylic acid and / or acrylic acid and a divalent and / or trivalent alcohol.

The invention according to claim 5 is characterized in that the reactive monomer is an ester composed of allyl alcohol and / or methacrylic alcohol and a divalent and / or trivalent carboxylic acid.

The invention according to claim 6 is characterized in that the reactive monomer is 30 wt% or more and 70 wt% or less with respect to the addition reaction product of the epoxy resin and the unsaturated monobasic acid.

The main component which can be used in the present invention is an addition reaction product of an epoxy resin and an unsaturated monobasic acid, and an unsaturated polyester resin or an epoxy resin may be added to such an extent that its effect is not lost.

The epoxy resin is bisphenol A.
Type, bisphenol AD type, bisphenol S type, bisphenol F type, novolac type, biphenyl type, naphthalene type, phthalic acid type, hexahydrophthalic acid type, benzoic acid type diglycidyl ether, glycol type diglycidyl ether, etc., Bisphenol A type is generally used.

Unsaturated monobasic acids are acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, sorbic acid, hydroxyethyl methacrylate maleate, hydroxyethyl acrylate maleate, hydroxypropyl methacrylate maleate, hydroxypropyl acrylate.
Malate, dicyclopentadiene / malate, etc.
Generally, a methacrylic epoxy acrylate resin using methacrylic acid, hydroxymethacrylate / malate, hydroxypropylmethacrylate / malate or the like, which is excellent in alkali resistance, is preferable.

The reactive monomer that can be used in the present invention is an ester of carboxylic acid and alcohol, and one or both of the carboxylic acid and the alcohol has a reactive double bond. Erthels, such as ethylene glycol dimethacrylate,
Diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate,
There are trimethylolpropane trimethacrylate, diallyl phthalate, triallyl trimetate, and dicyclopentadiene compounds represented by the following formula (1) or (2), which are excellent in alkali resistance and include esters of methacrylic acid and methallyl alcohol. Is preferable. Further, these reactive monomers may be used alone or in a mixture. Furthermore, a monofunctional ester can be mixed in a small amount. In the following formula, R ₁ = hydrogen atom,
It is a methyl group. R ₂ and R ₃ are lower alkylene groups having 2 to 5 carbon atoms such as ethylene and butylene. n, m = 0-5
Is an integer.

The mixing ratio of the reactive monomer to the epoxy acrylate resin is not particularly limited, but is 10 to 70 wt.
%, More preferably 30 to 70 wt%, most preferably 40 to 60 wt%. The resin viscosity is 0.1 to 200 poise (E type viscometer, 25 ° C)
It is desirable to mix so that

[0020]

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[0021]

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Curing agents that can be used in the present invention include diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides,
Organic peroxides such as peroxyketals, alkylperesters and peroxycarbonates, for example, benzoyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, dicumyl peroxide, cumene hydroperoxide, etc., Most commonly benzoyl peroxide is used.
The curing agent is generally diluted with a diluent before use.

The diluent for the curing agent that can be used in the present invention includes inorganic substances such as calcium sulfate and calcium carbonate, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, aliphatic hydrocarbons, aromatic hydrocarbons and silicone oils. , Liquid paraffin polymerizable monomers, water, etc.

The curing accelerator that can be used in the present invention may be any tertiary aromatic amine having a hydroxyl group in the nitrogen substituent, such as N, N-dihydroxypropyl-p-toluidine and N-phenyl. Diethanolamine,
There are N-p-tolyldiethanolamine, N, N-bishydroxybutyl-p-toluidine and the like, and N, N-bishydroxypropyl-p-toluidine which is effective in a small amount is preferable. Further, the curing accelerator may be placed separately from the main agent and mixed with the main agent at the time of use so as to avoid direct contact with the curing agent, or may be preliminarily mixed and placed in the resin. The content may be about 0.1 to 5 wt%, but preferably 0.5 to 1.5 wt%.

These hardening accelerators may be used alone or in a mixture of two or more kinds, and further, hardening of N, N-dimethylaniline, cobalt naphthenate and the like which have been generally used in the past. It may be used in combination with an accelerator.

Further, a polymerization inhibitor, a colorant, a pigment, an ultraviolet absorber, a surfactant, an aggregate, a filler, a thixotropic agent and the like can be added to and mixed with the main component as needed. In addition, if necessary for the curing agent component, aggregate,
Fillers, thixotropic agents, diluents, plasticizers and the like can be added and mixed.

The polymerization inhibitors used in the present invention include quinones, hydroquinones, phenols and the like. Examples thereof include benzoquinone, p-benzoquinone, p-toluquinone, p-xyloquinone, naphthoquinone, 2,6-dichloroquinone and hydroquinone. , Pt-butylcatechol, 2,5-di-t-butylhydroquinone, monomethylhydroquinone, p-methoxyphenol, 2,6-
Di-t-butyl-p-cresol, hydroquinone monomethyl ether and the like can be added in a necessary amount, but it is preferable to add hydroquinones and phenols because quinones may change with amines such as coloring.
The most effective are cresols.

The colorant, pigment and ultraviolet absorber which can be used in the present invention are added as necessary as a light resistance stabilizer for preventing gelation of the resin due to sunlight. These additives include lake pigments, azo pigments, phthalocyanine pigments, higher organic pigments and inorganic pigments, singly or in mixtures thereof.

For example, "toner yellow", "toner brown", "toner green" (manufactured by Takeda Pharmaceutical Co., Ltd.),
"Colortex Brown", "Colortex Orange", "Colortex Maron" (manufactured by Sanyo Pigment Co., Ltd.)
And "Oplus Yellow" (manufactured by Orient Chemical Co., Ltd.)
Can be added.

The surfactant which can be used in the present invention includes anionic type, cationic type, nonionic type and amphoteric type, and anionic type which is effective in stabilizing tensile strength in water is preferable. Anionic surfactants include alkyl ether carboxylates (“Beaulite EAC” manufactured by Sanyo Kasei Co., Ltd.) as carboxylic acid salts, and examples of sulfonates include dialkyl sulfosuccinates (“Sansepara 100” manufactured by Sanyo Kasei Co., Ltd.). )), Alkylallyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, etc.
Examples of the alkyl ether sulfates and phosphoric acid ester salts include alkyl ether phosphates.

Particularly preferably, when a surfactant is added to the resin, it is desirable to use a dialkylsulfosuccinate or an alkylallylsulfosuccinate which does not promote gelation of the resin. These anionic surfactants are 1
Monovalent and divalent metal salts or ammonium salts are preferable, and sodium salts are particularly preferable.

Although these surfactants may be arranged anywhere, it is preferable to mix them in the resin. The amount used is not particularly limited, but it is preferably suppressed to 30 wt% or less in terms of strength. The surfactant may be used by dissolving it in a reactive monomer or a solvent.

The aggregates that can be used in the present invention include artificial aggregates such as magnesia clinker, glass beads, ceramics and hard plastics, and natural aggregates such as silica stone, marble, granite, silica sand and quartz sand. Further, fibers such as glass fiber, carbon fiber and steel fiber can be used.

The filler which can be used in the present invention is quartz sand, silica sand, silica powder, calcium carbonate, gypsum, glass flake, mica, volcanic ash, shirasu, shirasu microballoon, concrete powder, foam concrete powder, glass micbal balloon. , Hollow glass, fly ash, carbon black, alumina, iron, aluminum, silica and the like.

The thixotropic agent which can be used in the present invention includes finely divided silica (trade name: Erosil), non-powdered alumina, talc, asbestos and colloidal hydrous aluminum silicate / organic composite (trade name: Orben), bentonite,
Castor oil derivatives and the like.

However, when the above-mentioned diluent, aggregate, filler, thixotropic agent, etc. are mixed with the curing agent, it is necessary to add and mix them in consideration of the inhibition of the stability of the organic peroxide.

The container that can be used in the present invention may be any container that does not break during transportation or storage and can be sealed so that the adhesive does not leak, and is made of glass, ceramics, synthetic resin, paper, metal or the like. There are things such as capsules, cartridges, cans, and packs. In this case, the shape and material of the container may be appropriately selected depending on the application of the capsule type and the injection type. Further, it is desirable to select the curing agent container in consideration of safety according to the characteristics of the curing agent.

[0038]

[Function] The resin, which is the main agent, does not contain a styrene monomer, and can be used as a fixing agent in a wide range of environments, and is excellent in resin stability.

[0039]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described below with reference to Examples.

Example 1 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
As a curing accelerator, N, N-
5 g of dihydroxypropyl-p-toluidine, 2,6-di-t-butyl-p-cresol (B
HT) 0.5 g and the surfactant dioctyl sodium sulfosuccinate 5 g were mixed. Using the resin prepared here, the curing characteristics were measured at 5, 15 and 30 ° C. at a resin / curing agent ratio of 100: 5 according to JIS K 6901 room temperature curing characteristics. Berezoyl peroxide (40% diluted with calcium sulfate) was used as a curing agent. Furthermore, the 60 degreeC heating test was done. In the 60 ° C. heating test, 18 g of the resin was enclosed in a glass container (outer diameter: 17 mm, length: 120 mm), placed in a constant temperature bath at 60 ° C., and the number of days until the resin gelled was measured.

Next, 50 g of the resin prepared as described above was mixed with 50 g of silica sand No. 8 and 1 g of Aerosil to prepare the main ingredient, and 10 g of benzoyl peroxide paste (40% concentration) was prepared.
5 g of silica sand No. 8 and 0.01 g of Aerosil were mixed to prepare a curing agent. The tensile load was measured as follows using the main agent and the curing agent prepared here.

First, size 500 × 500 × 1000 m
18 mm x 100 mm using an electric hammer drill on a concrete block with m ³ and compressive strength of 210 kg / cm ^2.
A hole of (diameter x length) was punched, the swarf was removed with a blower, the swarf on the hole wall was removed with a nylon brush, and the swarf was removed with a blower again to clean the inside of the hole. Next, 3 g of the curing agent was stirred and mixed with 30 g of the main ingredient prepared above, and the mixture was injected into the hole,
After inserting the M16 (material SNB7) bolt, the tensile load was measured one day after curing. Incidentally, the concrete block, the main agent, the curing agent and the bolt were set to the measurement temperature in a large-sized constant temperature tank in advance, and then the bolt was embedded, cured and measured in the constant temperature tank. The measurement is the tensile tester A for anchor bolts.
It was performed using NSER-5-III (manufactured by Asahi Kasei Corporation).

The above results are shown in Table 1.

Example 2 65 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 3 of diethylene glycol dimethacrylate as a reactive monomer.
As a curing accelerator, N, N-
5 g of dihydroxypropyl-p-toluidine, 2,6-di-t-butyl-p-cresol (B
HT) 0.5 g and the surfactant dioctyl sodium sulfosuccinate 5 g were mixed. Using the resin prepared here, the curing characteristics, 60 ° C. heating test and tensile load were measured in the same manner as in Example 1. Table 1 shows the results.

Example 3 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
N-p- as a curing accelerator was added to 500 g of 5 wt% resin.
Triyldiethanolamine 5 g, 2,6-di-t-butyl-p-cresol (BHT) as a polymerization inhibitor
0.5g and surfactant 5g of sodium dioctyl sulfosuccinate were mixed. Using the resin prepared here, the curing characteristics, 60 ° C. heating test and tensile load were measured in the same manner as in Example 1. Table 1 shows the results.

Example 4 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
To 100 g of 5 wt% resin, Np-
1 g of triaryldiethanolamine, 2,6-di-t-butyl-p-cresol (BHT) as a polymerization inhibitor
Add 0.05 g. Using the resin prepared here 60
A ℃ heating test was performed. The results are shown in Table 2.

Example 5 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
To 100 g of 5 wt% resin, Np-
1 g of triaryldiethanolamine and 0.05 g of hydroquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 6 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
To 100 g of 5 wt% resin, Np-
Triaryldiethanolamine 1g, p as polymerization inhibitor
-Add 0.05 g of benzoquinone. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 7 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
As a curing accelerator, N, N-
1 g of dihydroxypropyl-p-toluidine, 2,6-di-t-butyl-p-cresol as a polymerization inhibitor 0.
Add 05 g. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 8 55 wt% of epoxy acrylate resin obtained by adding methacrylic acid to bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
As a curing accelerator, N, N-
1 g of dihydroxypropyl-p-toluidine and 0.05 g of hydroquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 9 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
As a curing accelerator, N, N-
1 g of dihydroxypropyl-p-toluidine and 0.05 ppm of p-benzoquinone as a polymerization inhibitor are added.
A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 10 55 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin and 45 of diethylene glycol dimethacrylate as a reactive monomer.
100 wt% of resin, 1 g of N, N-dihydroxypropyl-p-toluidine as a curing accelerator, and 0.06 of 2,6-di-t-butyl-p-cresol as a polymerization inhibitor.
Add 5 g. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 11 40 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin, and a dicyclopentadiene compound (formula (1): R as a reactive monomer).
₁ = methyl, R ₂ = ethyl, n = 1) 60w monomer A
t% resin 100 g, N, N-dihydroxypropyl-p-toluidine 1 g as a curing accelerator, and 2,6-di-t-butyl-p-cresol 0.0 as a polymerization inhibitor.
Add 5 g. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 12 40 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin, and a dicyclopentadiene compound (formula (1): R as a reactive monomer).
₁ = methyl, R ₂ = ethyl, n = 1) 60w monomer A
To 100 g of t% resin, 1 g of N, N-dihydroxypropyl-p-toluidine as a curing accelerator and 0.05 g of hydroquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 13 40 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin, and a dicyclopentadiene compound (Formula (1): R as a reactive monomer.
₁ = methyl, R ₂ = ethyl, n = 1) 60w monomer A
To 100 g of t% resin, 1 g of N, N-dihydroxypropyl-p-toluidine as a curing accelerator and 0.05 g of p-benzoquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 14 100 g of a resin containing 40 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin and 70 wt% of trimethylolpropane trimethacrylate as a reactive monomer, and N, N as a curing accelerator.
1 g of dihydroxypropyl-p-toluidine and 0.05 g of 2,6-di-t-butyl-p-cresol as a polymerization inhibitor are added. Using the resin prepared here 60
A ℃ heating test was performed. The results are shown in Table 2.

Example 15 100 g of a resin containing 40 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin and 70 wt% of trimethylolpropane trimethacrylate as a reactive monomer, and N, N as a curing accelerator.
1 g of dihydroxypropyl-p-toluidine and 0.05 g of hydroquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 16 100 g of a resin containing 40 wt% of an epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin and 70 wt% of trimethylolpropane trimethacrylate as a reactive monomer, and N, N as a curing accelerator.
1 g of dihydroxypropyl-p-toluidine and 0.05 g of p-benzoquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 17 Resin 1 containing 40 wt% of epoxy acrylate resin obtained by adding acrylic acid to bisphenol A type epoxy resin and 60 wt% of triallyl trimetate as a reactive monomer.
To 00 g, 1 g of N, N-dihydroxypropyl-p-toluidine as a curing accelerator and 2,6- as a polymerization inhibitor
0.05 g of di-t-butyl-p-cresol is added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 18 Resin 1 containing 40 wt% of epoxy acrylate resin obtained by adding acrylic acid to bisphenol A type epoxy resin and 60 wt% of triallyl trimellitate as a reactive monomer.
To 00 g, 1 g of N, N-dihydroxypropyl-p-toluidine as a curing accelerator and 0.05 g of hydroquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Example 19 Resin 1 containing 40 wt% of epoxy acrylate resin obtained by adding acrylic acid to bisphenol A type epoxy resin and 60 wt% of triallyl trimetate as a reactive monomer.
To 00 g, 1 g of N, N-dihydroxypropyl-p-toluidine as a curing accelerator and 0.05 g of p-benzoquinone as a polymerization inhibitor are added. A 60 ° C. heating test was performed using the resin prepared here. The results are shown in Table 2.

Comparative Example 1 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
To 500 g of 5 wt% resin, N, N-dimethylaniline having no hydroxyl group in the nitrogen substituent as a curing accelerator is added.
g, 0.25 g of p-benzoquinone as a polymerization inhibitor, and 5 g of surfactant sodium dioctylsulfosuccinate were mixed. Using the resin prepared here, the curing characteristics, 60 ° C. heating test and tensile load were measured in the same manner as in Example 1. Table 1 shows the results.

Comparative Example 2 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
N, N-dimethylaniline 5 having no hydroxyl group in the nitrogen substituent as a curing accelerator was added to 500 g of 5 wt% resin.
g, 0.25 g of hydroquinone as a polymerization inhibitor, and 5 g of surfactant sodium dioctylsulfosuccinate were mixed. Using the resin prepared here, the curing characteristics and the 60 ° C. heating test were measured in the same manner as in Example 1. Table 1 shows the results.

The tensile load was measured by the curing characteristics such that the minimum curing time (C.T.) was too fast, and the maximum exothermic temperature (T.
Since (max) was too low, the work could not be performed at a high temperature, and it could not be cured at a low temperature.

Comparative Example 3 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
N, N-dimethylaniline 5 having no hydroxyl group in the nitrogen substituent as a curing accelerator was added to 500 g of 5 wt% resin.
g, surfactant dioctyl sodium sulfosuccinate 5
g, 2,6-di- which is a cresol as a polymerization inhibitor
0.5 g of t-butyl-p-cresol was mixed. Using the resin prepared here, the curing characteristics and the 60 ° C. heating test were measured in the same manner as in Example 1. Table 1 shows the results.

The minimum curing time (C.T.) in the curing characteristics.
Was too fast, and the maximum exothermic temperature (Tmax) was too low. Therefore, the tensile load could not be measured because the work was poor at a high temperature and uncured at a low temperature.

Comparative Example 4 55 wt% of an epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, and 4 of diethylene glycol dimethacrylate as a reactive monomer.
To 500 g of 5 wt% resin, 3 g of N, N-dimethyl-p-toluidine having no hydroxyl group in the nitrogen substituent as a curing accelerator, and p-benzoquinone 0.5 as a polymerization inhibitor.
g, surfactant dioctyl sodium sulfosuccinate 5
g were mixed. Using the resin prepared here, the curing characteristics and the 60 ° C. heating test were measured in the same manner as in Example 1. Table 1 shows the results.

In the measurement of the tensile load, the minimum curing time (C.T.) was too fast in the curing characteristics, and the maximum exothermic temperature (T.
Since (max) was too low, the work could not be performed at a high temperature, and it could not be cured at a low temperature.

[0069]

[Table 1]

[0070]

[Table 2]

Note 1 Cone failure: Concrete block failure Note 2 Adhesive failure: Cured resin-concrete block interface failure From the results in Table 1, as shown in Comparative Examples 2 to 4, there was a hydroxyl group in the nitrogen substituent. It was not possible to adjust the curability by using a tertiary amine that does not exist, and furthermore it was not possible by using a polymerization inhibitor such as a cresol-based polymerization inhibitor. Therefore, the curing time is fast, and it hardens at the time of mixing and injecting the fixing agent at a high temperature such as in summer, and it becomes impossible to embed the bolt and the like.

Further, as shown in Comparative Examples 1 to 4, the maximum exothermic temperature (Tmax) during curing is low, the curability at low temperatures such as in winter is poor, and tensile strength is not exhibited. On the other hand, it is clear from the 60 ° C. heating test that the fixing agent according to the present invention has a resin composition having excellent resin stability. Furthermore, from the results of Table 2, since all of Examples 4 to 19 have a gelation period of 28 days or longer in the 60 ° C. heating test, the resin composition has excellent stability and has a long shelf life. I understand.

[0073]

According to the present invention, the main component is an epoxy acrylate resin diluted with a reactive monomer, the reactive monomer is an ester of carboxylic acid and alcohol, and at least one of them is a reactive double bond. Since the ester is composed of those having the following, the curing agent is an organic peroxide, and the curing accelerator is a tertiary aromatic amine having a hydroxyl group in the nitrogen substituent, a higher temperature can be obtained without using a styrene monomer. It can be used in a wide range of environments such as low temperature and low temperature, and is excellent in stability.

Claims (6)

[Claims] 1. A fixing agent for a building structure comprising a main agent and a curing agent, the main agent being an addition reaction product of an epoxy resin diluted with a reactive monomer and an unsaturated monobasic acid, The reactive monomer is an ester of a carboxylic acid and an alcohol, and at least one is a polyfunctional ester consisting of those having a reactive double bond, the curing agent is an organic peroxide, the curing A fixing agent for building structures, wherein the accelerator is a tertiary aromatic amine having a hydroxyl group in the nitrogen substituent. 2. The fixing agent for a building structure according to claim 1, wherein the addition reaction product of the epoxy resin and the unsaturated monobasic acid is a methacrylic epoxy acrylate resin. 3. The fixing agent for building structures according to claim 1, wherein the accelerator is N, N-dihydroxypropyl-p-toluidine. 4. The reactive monomer is an ester composed of methacrylic acid and / or acrylic acid and a divalent and / or trivalent alcohol.
An adhesive for building structures according to any one of 1. 5. The reactive monomer is an ester composed of allyl alcohol and / or methacrylic alcohol and a divalent and / or trivalent carboxylic acid, according to any one of claims 1 to 3. Adhesives for building structures as described. 6. The reactive monomer is 30 wt% or more and 70 wt% with respect to the addition reaction product of the epoxy resin and the unsaturated monobasic acid.
% Or less, The fixing agent for building structures according to any one of claims 1 to 5.