JP3565589B2 - Fixing agent - Google Patents

Description

[0001]
[Industrial applications]
The present invention relates to a fixing agent for perforating a base material such as concrete or rock and fixing a fixing member such as an anchor bolt in the perforation.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, there are a capsule type and an injection type in which a fixing member such as an anchor bolt is fixed to a base material using a fixing agent in a hole.
In the former capsule type, a capsule containing a fixing agent is inserted into the perforation, and the capsule is crushed while hitting and rotating an anchor bolt or the like, and the fixing member is fixed by mixing the main agent of the fixing agent and the curing agent. How to As capsules used in this method, Japanese Patent Publication No. Sho 62-37076, "Fixing material for anchor bolt anchoring with excellent corrosion resistance", Japanese Patent Laid-Open Publication No. Sho 61-243876, "Adhesive mainly composed of acrylic compound", Japanese Patent Application Laid-Open No. 61-254681 discloses a "fixing agent composition and a fixing agent composition for anchor bolts using the same".
[0003]
Next, the latter injection molds include an on-site preparation type and a cartridge type. In the case of the on-site preparation type, the base material and the curing agent contained in each container are mixed, injected into the perforations, and the fixing member is fixed. In the case of the cartridge type, the main agent and the curing agent in the cartridge are discharged in appropriate amounts by a hand gun, hydraulic pressure, or the like, and the fixing agent mixed by a mixer such as a static mixer is injected into the perforations and fixed. Secure the member. Japanese Patent Application Laid-Open No. Sho 59-24714, "Two-component mortar material" is known as one used in this method.
[0004]
For the fixing agent used in these methods, a two-component radical curable resin is preferably used because of its good curability, and N, N-dimethylaniline, N, N-dimethyl-p-toluidine, Aromatic anilines in which the nitrogen substituent is an alkyl group such as N, N-diethylaniline, cobalt octoate, cobalt naphthenate, and a cobalt / amine mixing accelerator are generally used.
[0005]
[Problems to be solved by the invention]
Epoxy acrylate resin or unsaturated polyester resin is generally used for the two-component radical curable resin used as an adhesive, but the adhesive has excellent properties such as concrete alkali resistance and vibration resistance. Epoxy acrylate resins are most suitable. However, epoxy acrylate resins have poor storage stability and cause the resin to thicken and deteriorate during storage, resulting in a short shelf life, resulting in a short shelf life and losing its excellent performance before use. Problem.
In view of the above, an object of the present invention is to solve these problems and to provide a resin composition for fixing a fixing member, which hardly increases the viscosity of the resin during storage and does not deteriorate.
[0006]
[Means for Solving the Problems]
In order to solve the above-mentioned problems, the present invention provides a fixing agent comprising a main agent and a curing agent, wherein the main agent is an acrylic epoxy acrylate resin obtained by adding only acrylic acid to a bisphenol A epoxy resin. It is characterized by containing N, N-dihydroxypropyl-p-toluidine as an agent.
The accelerator that can be used in the present invention is N, N-dihydroxypropyl-p-toluidine, which may be placed anywhere as long as it does not come into direct contact with the curing agent, but promotes the curing of the resin uniformly. For this reason, it is preferable to mix them in the main agent in advance. The content may be about 0.1 to 5 wt%, but preferably 0.5 to 1.5 wt%.
[0007]
This accelerator can be used alone or in combination with an accelerator generally used conventionally, such as N, N-dimethylaniline.
The essential acrylic epoxy acrylate resin that can be used in the present invention is a terminal acrylic acid addition reaction product obtained by adding only acrylic acid to a bisphenol A epoxy resin , and it is preferable to add two or more acrylic acid.
[0008]
Other resins such as an unsaturated polyester resin and / or an epoxy resin may be added to such an extent that the effect is not lost. Generally, the resin is used after being diluted with a polymerizable monomer.
The epoxy resin used here is bisphenol A type, bisphenol AD type, bisphenol S type, bisphenol F type, novolak type, biphenyl type, naphthalene type, phthalic acid type, hexahydrophthalic acid type, benzoic acid type diglycidyl ether, And glycol-type diglycidyl ether, and bisphenol A type is generally used.
[0009]
Polymerizable monomers that can be used in the present invention include vinyl monomers, acrylic monomers, acrylates, and the like.
For example, styrene, vinyl toluene, methyl methacrylate, diallyl phthalate, diallyl isophthalate, triallyl isocyanurate, phenoxyethyl (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate , 2-hydroxyethyl (meth) acrylate, vinylpyrrolidone, phenylmaleimide, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, 2,5-dimethylstyrene, p-chlorostyrene, dimethyl maleate And styrene is generally used. The mixing ratio of the polymerizable monomer is not particularly limited because the viscosity, the number of functional groups, and the polymerizability vary depending on the type of the resin and the monomer, but the mixing ratio is 10 to 70 wt% of the curable resin composition and the resin viscosity is 0.1 to 200 poise ( It is advisable to mix using an E-type viscometer at 25 ° C.)
[0010]
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 the main component as needed and mixed.
If necessary, an aggregate, a filler, a thixotropic agent, a diluent, a plasticizer, and the like can be added to and mixed with the curing agent component.
[0011]
The polymerization inhibitor used in the present invention includes quinones, hydroquinones, phenols and the like. Necessary amounts of t-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. However, quinones may change in color and the like with amines, and it is preferable to add hydroquinones and phenols.
[0012]
The colorant, pigment, and ultraviolet absorber that can be used in the present invention are added as necessary as a light-resistant stabilizer that prevents gelation of the resin due to sunlight or the like. These additives include lake pigments, azo pigments, phthalocyanine pigments, higher organic pigments and inorganic pigments, alone or in mixtures thereof.
For example, “Toner Yellow”, “Toner Brown”, “Toner Green” (manufactured by Takeda Pharmaceutical Co., Ltd.), “Color Tex Brown”, “Color Tex Orange”, “Color Tex Maron” (manufactured by Sanyo Pigment Co., Ltd.) And "Oplus Yellow" (manufactured by Orient Chemical Co., Ltd.) can be added. However, the amount of addition cannot be univocally determined because the type of resin in the main component, the type of monomer, and the effect of the additive are different.
[0013]
Surfactants that can be used in the present invention include anionic, cationic, nonionic and amphoteric surfactants, but anionic surfactants that are effective for stabilizing tensile strength in water are preferred. Anionic surfactants include carboxylate salts such as alkyl ether carboxylate salts ("Bureite EAC" manufactured by Sanyo Chemical Co., Ltd.), and sulfonates include dialkyl sulfosuccinates ("Sansepara 100" manufactured by Sanyo Chemical Co., Ltd.). )), Alkyl allyl sulfosuccinates, alkyl sulfo acetates, α-olefin sulfonates, etc., and sulfates such as alkyl allyl sulfates, alkyl ether sulfates, and phosphate esters such as alkyl ether phosphates. Can be
[0014]
Particularly preferably, when a surfactant is added to a resin, it is desirable to use a dialkyl sulfosuccinate or an alkyl allyl sulfosuccinate which does not promote gelation of the resin. These anionic surfactants are preferably monovalent and divalent metal salts or ammonium salts, and more preferably sodium salts.
These surfactants may be placed anywhere, but are preferably mixed in the resin. Although the amount of use is not particularly limited, it is preferable to suppress the amount to 30% by weight or less in terms of strength. Further, the surfactant may be used after being dissolved in a reactive monomer or a solvent.
[0015]
Curing agents that can be used in the present invention include organic peroxides such as diacyl peroxides, ketone peroxides, hydroperoxides, dialkyl peroxides, peroxyketals, alkyl peresters, and peroxycarbonates. For example, there are benzoyl peroxide, methyl ethyl ketone peroxide, lauryl peroxide, dicumyl peroxide, cumene hydroperoxide and the like. Most commonly, benzoyl peroxide is used. This curing agent is generally used after being diluted with a diluent.
[0016]
Diluents for the curing agent that can be used in the present invention include inorganic substances such as calcium sulfate and calcium carbonate, dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, aliphatic hydrocarbons, aromatic hydrocarbons, silicone oil, and liquid paraffin. There are polymerizable monomers, water and the like.
Examples of the aggregate 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.
[0017]
Fillers that can be used in the present invention include quartz sand, silica sand, silica powder, calcium carbonate, gypsum, glass flake, mica, volcanic ash, shirasu, shirasu micro balloon, concrete powder, foamed concrete powder, glass micro balloon, and hollow filler. Glass, fly ash, carbon black, alumina, iron, aluminum, silica, and the like.
[0018]
The thixotropic agent which can be used in the present invention includes finely divided silica (trade name: Egille), powder-free alumina, talc, asbestos and colloidal hydrous aluminum silicate / organic composite (trade name: Orben), bentonite, castor oil derivatives and the like There is. However, when the above diluents, aggregates, fillers, thixotropic agents and the like 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.
[0019]
Containers that can be used in the present invention are not damaged during transportation or storage, and may be any as long as they can be sealed without leakage of adhesive, and may be made of glass, ceramics, synthetic resin, paper, metal, etc. , Capsules, cartridges, cans, packs and the like. In this case, the shape and material of the container may be appropriately selected according to the use of the capsule type and the injection type. Further, it is desirable to select a curing agent container in consideration of safety according to the characteristics of the curing agent.
[0020]
[Action]
ADVANTAGE OF THE INVENTION According to this invention, the thickening of the resin at the time of storage is small, there is no deterioration, and also the tensile strength which is important for fixing a fixing member is excellent, and the tensile strength is improved after embedding.
[0021]
【Example】
Hereinafter, the present invention will be described with reference to examples.
[0022]
Embodiment 1
8.7 g of a resin prepared by mixing 65 wt% of an acrylic epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin, 34 wt% of a styrene monomer, and 1 wt% of N, N-dihydroxypropyl-p-toluidine as an accelerator. A glass outer container having a diameter of 17 mm, a wall thickness of 1.0 mm, and a length of 120 mm was filled, and 1.2 g of benzoyl peroxide diluted with calcium carbonate to a concentration of 40% was used as a curing agent component. It is sealed in a glass inner container having a length of 5 mm and a length of 90 mm and put into an outer container. Next, 24 g of magnesia clinker having a particle size of 1.5 to 3.0 mm as an aggregate was filled in the outer container, and the outer container was sealed to produce a capsule.
The capsule produced here was heated in a thermostat at 60 ° C., and the viscosity and tensile load after 35 days were measured.
The viscosity was measured at 25 ° C. using an E-type viscometer.
[0023]
The measurement of the tensile load was performed in the following manner. A hole having a diameter of 19 mm and a length of 130 mm was formed in a concrete block having a size of 500 × 500 × 1000 mm and a compressive strength of 210 kg / cm 2, and the inside of the hole was cleaned using a blower and a nylon brush. The above capsule was inserted into the hole, and a 16 mm-diameter full screw bolt M16 (material SNB7) whose tip was cut at 45 degrees was mounted on an electric hammer drill, and buried to the bottom of the hole while rotating and hitting. After a curing time of one day, the fixing strength was measured. The measurement was performed using an anchor bolt tensile tester ANSER-5-III (manufactured by Asahi Kasei Corporation). In addition, when exceeding 15 ton because of the limit of the tensile strength of the used bolt, the measurement was stopped at 15 ton.
Table 1 shows the results.
[0024]
Embodiment 2
Particle size of 74 g of a resin blended with 65 wt% of an acrylic epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin, 34 wt% of a styrene monomer, and 1 wt% of N, N-dihydroxypropyl-p-toluidine as an accelerator. A main agent was prepared by mixing 20 g of silica sand of up to 210 μm and 1.2 g of Ezrol. Then, 20 g of benzoyl peroxide diluted to a concentration of 40% with dibutyl phthalate, 20 g of silica sand having a particle size of 74 to 210 μm, and 1.2 g of Ezrol were mixed to prepare a curing agent.
[0025]
Next, the tensile load was measured. First, a hole having a hole diameter of 16 mm and a hole length of 60 mm was formed in the same concrete block as in Example 1, and the inside of the hole was cleaned using a blower and a nylon brush. Then, the main agent and the hardening agent prepared above were mixed at a ratio of 8: 1 and poured into the hole, and a D13 deformed steel bar with a tip cut to the bottom of the hole was inserted. One day after curing, the tensile load was measured.
Table 3 shows the results.
[0026]
Embodiment 3
An acrylic type epoxy acrylate resin obtained by adding acrylic acid to a bisphenol A type epoxy resin, 65% by weight of styrene monomer, 34% by weight of a styrene monomer, and 1% by weight of N, N-dihydroxypropyl-p-toluidine as an accelerator, 2.2 g of a resin compounded was added. A glass outer container having a diameter of 10.5 mm, a thickness of 0.6 mm and a length of 90 mm is filled, and as a hardening agent component, 0.3 g of benzoyl peroxide diluted to 40% concentration with calcium carbonate has an outer diameter of 4 mm and a thickness of 4 mm. It is sealed in a glass inner container having a length of 0.5 mm and a length of 67 mm and put into an outer container. Next, after filling 5.8 g of magnesia clinker having a particle size of 1.5 to 3.0 mm as an aggregate into the outer container, the outer container was sealed to produce a capsule.
[0027]
Next, a concrete block (compression strength 230 kg / cm 2) was pierced with a piercing diameter of 12 mm and a piercing length of 90 mm, and an M10 anchor bolt having a 45-degree cut end was mounted on an electric hammer drill, while rotating and hitting. It was embedded up to the bottom of the hole, and the tensile load was measured. Table 4 shows the results.
[0028]
[Comparative Example 1]
A methacrylic epoxy acrylate resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, 65 wt% of a styrene monomer, and a main resin blended at a ratio of 1 wt% of N, N-dimethylaniline as a promoter were used in the same manner as in Example 1. The capsules were manufactured by heating and subjected to a heating test. Table 1 shows the results.
[0029]
[Comparative Example 2]
A methacrylic vinyl ester resin obtained by adding methacrylic acid to a bisphenol A type epoxy resin, 47 wt% of an unsaturated polyester resin, 18 wt% of a styrene monomer, 24 wt% of a styrene monomer, and N, N-dimethylaniline of 1 wt% as an accelerator. A capsule was produced in the same manner as in Example 1 and a heating test was performed. Table 1 shows the results.
Further, the secular change of the tensile load after the embedding of the bolt at each curing time was observed. Table 2 shows the results.
[0030]
[Comparative Example 3]
Acrylic epoxy acrylate resin obtained by adding acrylic acid to bisphenol A type epoxy resin, 65% by weight of styrene monomer, 34% by weight of styrene monomer, and 1% by weight of N, N-dimethylaniline as a promoter are mixed in 20 g of resin, and silica sand having a particle size of 74 to 210 μm. 20 g and 1.2 g of Ezrol were mixed to prepare a main ingredient. Then, 20 g of benzoyl peroxide diluted to a concentration of 40% with dibutyl phthalate, 20 g of silica sand having a particle size of 74 to 210 μm, and 1.2 g of Ezrol were mixed to prepare a curing agent. Next, the tensile load was measured in the same manner as in Example 2.
Table 3 shows the results.
[0031]
[Table 1]
[0032]
[Table 2]
[0033]
[Table 3]
[0034]
[Table 4]
[0035]
As described above, from the results in Table 1, in some comparative examples, the resin viscosity became four times or more the initial viscosity and gelled in some cases. In addition, although the gel was not gelled, the tensile load was reduced by about 10%, whereas the resin viscosity was less than 3 times in the examples, indicating that the tensile load was not reduced at all. Further, it is understood that the initial tensile load is most excellent. Furthermore, from Table 2, it can be seen that the secular change at each curing time after embedding results in a surprisingly appropriate increase in the tensile load after one month of curing.
[0036]
【The invention's effect】
The present invention relates to a fixing agent comprising a main agent and a curing agent, wherein the main agent is an acrylic epoxy acrylate resin obtained by adding only acrylic acid to a bisphenol A epoxy resin, and N, N-dihydroxypropyl- is used as an accelerator. By including p-toluidine, the resin has a small viscosity increase upon storage, does not deteriorate, and has an excellent tensile strength which is important for fixing a fixing member. Surprisingly, the tensile strength is improved after embedding. It is intended to provide a fixing agent.

Claims (2)

A fixing agent comprising a main agent and a curing agent, wherein the main agent is an acrylic epoxy acrylate resin obtained by adding only acrylic acid to a bisphenol A epoxy resin, and N, N-dihydroxypropyl-p-toluidine is used as an accelerator. A fixing agent, comprising:   2. The fixing agent according to claim 1, comprising 0.1 to 5% by weight of an accelerator.