JPH08134426A - Adhesive - Google Patents

Abstract

PURPOSE: To provide an epoch-making adhesive which does not undergo thickening nor degradation during storage, is excellent in tensile strength, a property important for an adhesive for bonding a stationary member, and exhibits the increase in tensile strength after embedding. CONSTITUTION: A two-component free-radical-curable adhesive is provided which comprises the main component and a curative, the main component being an acrylic type epoxy acrylate resin and contg. N,N-dihydroxypropyl-p-toluidine as an accelerator.

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 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, a fixing member such as an anchor bolt is fixed to a base material by using a fixing agent in a hole.
There are capsule type and injection type. The former capsule type inserts a capsule containing a fixing agent into the perforation, crushes the capsule while hitting and rotating the anchor bolt etc., and fixes the fixing member by mixing the main agent of the fixing agent and the curing agent. Is the way to do it. As a capsule used in this method, Japanese Patent Publication No. 62-37076, “Fixing material for fixing anchor bolts, which is excellent in corrosion resistance”, JP-A-61-161
Japanese Patent No. 243876 "Acrylic compound-based adhesive" and Japanese Patent Laid-Open No. 61-254681 "Adhesive composition and adhesive composition for anchor bolts using the same" are known.

The latter injection type is classified into a field type and a cartridge type. On-site formula
The main agent and 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 members. As a material used in this method, there is known Japanese Unexamined Patent Publication No. 59-24714, "two-component mortar material".

A two-component radical curable resin is preferably used for the fixing agent used in these methods because of its good curability, and N, N-dimethylaniline, N, N-dimethyl-p is used as an accelerator thereof. Aromatic anilines whose nitrogen substituents are alkyl groups such as -toluidine, N, N-diethylaniline, cobalt octanoate, cobalt naphthenate, and cobalt / amine mixing accelerators are generally used.

[0005]

As the two-component radical curable resin used as an adhesive, an epoxy acrylate resin or an unsaturated polyester resin is generally used. Epoxy acrylate resin, which is excellent in various properties such as vibration, is most suitable. However, the epoxy acrylate resin has poor storage stability and causes thickening and deterioration of the resin during storage, resulting in a short shelf life, resulting in a short period of use and loss of its excellent performance before use. There was a problem that it would end up.

In view of the above points, it is an object of the present invention to solve these problems and to provide a resin composition for fixing a fixing member, in which the resin does not increase in viscosity during storage and does not deteriorate.

[0007]

In order to solve the above problems, the present invention is a fixing agent comprising a main agent and a curing agent, the main agent being an acrylic epoxy acrylate resin, and N as an accelerator. , N-dihydroxypropyl-p
Characterized in that it contains toluidine. The accelerator that can be used in the present invention is N, N-dihydroxypropyl-p-toluidine, which may be arranged anywhere as long as it avoids direct contact with the curing agent, but uniformly promotes curing of the resin. Therefore, it is preferable to mix them in the main ingredient in advance. The content may be about 0.1 to 5 wt%, but preferably 0.5 to 1.5 wt%.

This accelerator can be used alone or in a mixture with a conventionally used accelerator such as N, N-dimethylaniline. The acrylic epoxy acrylate resin that can be used in the present invention is an epoxy resin and a terminal acrylic acid addition reaction product of acrylic acid, acrylic acid-maleic anhydride or the like, and it is preferable to add two or more.

Other epoxy acrylate resins, unsaturated polyester resins and / or epoxy resins may be added to the extent that their effects are not lost. In addition, the resin is generally diluted with a polymerizable monomer before use. The epoxy resin used here is bisphenol A type, bisphenol AD type, bisphenol S type, bisphenol F type.
Type, novolac type, biphenyl type, naphthalene type, phthalic acid type, hexahydrophthalic acid type, benzoic acid type diglycidyl ether, glycol type diglycidyl ether and the like, and bisphenol A type is generally used.

Polymerizable monomers that can be used in the present invention include vinyl monomers, acrylic monomers, and acrylic acid esters. For example, styrene, vinyltoluene, 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. However, styrene is generally used. Further, the mixing ratio of the polymerizable monomer is a viscosity depending on the type of resin and monomer,
It is not particularly limited because the number of functional groups and the polymerizability are different, but the curable resin composition is 10 to 70 wt% and the resin viscosity is 0.1.
It is advisable to mix the mixture with about 200 poise (E-type viscometer, 25 ° C.) as a guide.

Further, if necessary, 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. 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 inhibitor used in the present invention includes 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 in coloration with amines.

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 or the like. 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 Dye Co., Ltd.) and "Oplus Yellow" (Orient Chemistry) Co., Ltd.) can be added. However, the amount to be added cannot be uniquely determined because the type of resin, the type of monomer and the effect of the additive in the main agent are different.

The surfactant which can be used in the present invention includes anionic type, cationic type, nonionic type and amphoteric type, but 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
Valent and divalent metal salts or ammonium salts are preferred,
Particularly, sodium salt is more preferable. These surfactants may be arranged anywhere, but are preferably mixed in the resin. The amount used is not particularly limited, but it is 3 in terms of strength.
It is preferable to suppress it to 0 wt% or less. The surfactant may be used by dissolving it in a reactive monomer or a solvent.

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. 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 agents that can be used in the present invention include 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 mogs, 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.

[0021]

According to the present invention, the thickening of the resin during storage is small,
It has no deterioration and is excellent in tensile strength, which is important for fixing a fixing member, and the tensile strength is improved after embedding.

[0022]

EXAMPLES The present invention will be described below with reference to examples.

[0023]

Example 1 Acrylic epoxy acrylate resin 6 obtained by adding acrylic acid to bisphenol A epoxy resin 6
5 wt%, styrene monomer 34 wt%, N, N-dihydroxypropyl-p-toluidine 1 wt as an accelerator
% Of resin was filled in an outer glass container having an outer diameter of 17 mm, a wall thickness of 1.0 mm and a length of 120 mm, and benzoyl peroxide diluted with calcium carbonate to a 40% concentration as a curing agent component. 1.2g is 6m outside diameter
m, wall thickness 0.5 mm, length 90 mm enclosed in a glass inner container and placed in an outer container. Next, 24 g of magnesia clinker having a particle size of 1.5 to 3.0 mm was filled in the outer container as an aggregate, and then the outer container was sealed to produce a capsule.

The capsules manufactured here were heated in a constant temperature bath 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. The tensile load was measured as follows. Size 500 × 500 × 100
A hole having a drilling diameter of 19 mm and a drilling length of 130 mm was drilled in a concrete block of 0 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. Insert the above capsule into the perforation and insert the tip into
Full-screw bolt M16 with an outer diameter of 16 mm cut to 5 degrees
(Material SNB7) was attached to an electric hammer drill, and while being rotated and hit, it was embedded up to the bottom of the hole and the fixing strength was measured after a curing time of 1 day. As a measuring instrument, an anchor bolt tensile tester ANSER-5-III (manufactured by Asahi Kasei Corporation) was used. In addition, if it exceeds 15 ton due to the limit of the tensile strength of the bolt used, 15 t
The measurement was stopped when it was on.

The results are shown in Table 1.

[0026]

Example 2 Acrylic epoxy acrylate resin 6 obtained by adding acrylic acid to bisphenol A epoxy resin 6
5 wt%, styrene monomer 34 wt%, N, N-dihydroxypropyl-p-toluidine 1 wt as an accelerator
% Of resin blended in a proportion of 40%, particle size 74-210μ
20 g of silica sand and 1.2 g of erogel were mixed to prepare the main agent. Then, with 20 g of benzoyl peroxide diluted to 40% concentration with dibutyl phthalate, a particle size of 74
A hardening agent was prepared by mixing 20 g of ˜210 μm silica sand and 1.2 g of erogel.

Next, the tensile load was measured. First, a hole having a diameter of 16 mm and a length of 60 mm was drilled 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 curing agent prepared previously were mixed at a ratio of 8: 1 and poured into the hole, the tip-cut D13 deformed steel bar was inserted to the hole bottom, and the tensile load was measured 1 day after curing.

The results are shown in Table 3.

[0029]

Example 3 Acrylic epoxy acrylate resin 6 obtained by adding acrylic acid to bisphenol A epoxy resin 6
5 wt%, styrene monomer 34 wt%, N, N-dihydroxypropyl-p-toluidine 1 wt as an accelerator
% Of resin mixed with 2.2 g of outer diameter 10.5 mm,
Filling an outer glass container having a wall thickness of 0.6 mm and a length of 90 mm, and as a curing agent component, 0.3 g of benzoyl peroxide diluted to 40% concentration with calcium carbonate has an outer diameter of 4 m.
It is enclosed in a glass inner container of m, wall thickness of 0.5 mm, and length of 67 mm, and placed in an outer container. Next, 5.8 g of magnesia clinker having a particle size of 1.5 to 3.0 mm was filled in the outer container as an aggregate, and then the outer container was sealed to produce a capsule.

Next, a concrete block (compressive strength 230 kg / cm ² ) has a perforation diameter of 12 mm and a perforation length of 90 m.
m was drilled and the M10 anchor bolt, the tip of which was cut at 45 degrees, was attached to an electric hammer drill, embedded into the hole bottom while giving rotation and impact, and the tensile load was measured. The results are shown in Table 4.

[0031]

[Comparative Example 1] A main resin mixed with methacrylic epoxy acrylate resin 65 wt% obtained by adding methacrylic acid to bisphenol A epoxy resin, styrene monomer 34 wt% and N, N-dimethylaniline 1 wt% as a promoter is used. Capsules were produced in the same manner as in Example 1 and subjected to a heating test. Table 1 shows the results.

[0032]

Comparative Example 2 Methacrylic vinyl ester resin 47 obtained by adding methacrylic acid to bisphenol A type epoxy resin 47
A capsule was manufactured in the same manner as in Example 1 using the main resin mixed with wt%, unsaturated polyester resin 18 wt%, styrene monomer 24 wt%, and N, N-dimethylaniline 1 wt% as a promoter, and a heating test. I went.
Table 1 shows the results.

Further, the secular change of the tensile load after embedding the bolt at each curing time was observed. The results are shown in Table 2.

[0034]

[Comparative Example 3] Acrylic epoxy acrylate resin 6 obtained by adding acrylic acid to bisphenol A epoxy resin 6
5 g by weight, 34% by weight of styrene monomer, and 1 g by weight of N, N-dimethylaniline as an accelerator were mixed with 20 g of a resin, and 20 g of silica sand having a particle size of 74 to 210 μm and 1.2 g of erogel were mixed to prepare a main component. Then, 20 g of benzoyl peroxide diluted to 40% concentration with dibutyl phthalate was added to silica sand 2 having a particle size of 74 to 210 μm.
A curing agent was prepared by mixing 0 g and 1.2 g of Erosil.
Next, the tensile load was measured in the same manner as in Example 2.

The results are shown in Table 3.

[0036]

Comparative Example 4 1.35 g of a polymerizable unsaturated compound obtained by mixing and stirring 31 parts of methyl methacrylate with 68 parts of β-hydroxy ester was added to paraffin 6.7 × having a melting point of 50 to 52 ° C.
10 ^-3 g and N, N-di (2-hydroxypropyl)
-P-toluidine 1.35 × 10 ^-2 g was added and dissolved and put into a cylindrical body with an outer diameter of 10.5 mm and a length of 80 mm, and further, BPO powder 4.0 × 10 ^-2 was filled and sealed. A small glass tube thus prepared and 5.5 g of an aggregate having a particle size of 0.6 mm or less were put therein and hermetically sealed to form a capsule.

Next, a concrete block (compressive strength 230 kg / cm ² ) has a perforation diameter of 12 mm and a perforation length of 90 m.
m was drilled, an M10 anchor bolt was press-fitted with a bolt press-fitting machine, and the tensile load was measured. The results are shown in Table 4.
Shown in

[0038]

[Table 1]

[0039]

[Table 2]

[0040]

[Table 3]

[0041]

[Table 4]

From the results shown in Table 1 above, in some Comparative Examples, the resin viscosity was 4 times or more the initial viscosity, and some gelled. The tensile load was about 10% although it did not gel.
On the other hand, in the examples, the resin viscosity is less than 3 times, and it can be seen that the tensile load is not reduced at all. Also,
It can be seen that it is most excellent in the initial tensile load. Furthermore, it can be seen from Table 2 that the tensile load is surprisingly increased from one month of curing with the aging change at each curing time after implantation.

[0043]

The present invention is a fixing agent comprising a main agent and a curing agent, the main agent being an acrylic epoxy acrylate resin and containing N, N-dihydroxypropyl-p-toluidine as an accelerator. In addition, it provides an epoch-making adhesive agent in which the viscosity of the resin during storage is small, there is no deterioration, and the tensile strength, which is important for fixing fixing members, is excellent and, surprisingly, the tensile strength improves after embedding. is there.

Claims (1)

[Claims] 1. A fixing agent comprising a main agent and a curing agent, the main agent being an acrylic epoxy acrylate resin, and N, N-dihydroxypropyl-p as an accelerator.
A sticking agent characterized in that it comprises toluidine.