JP2002212513A - Fixing agent for fixing bolt - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fixing agent which is used for fixing bolts, has excellent fast curability and low temperature curability, has excellent basic performances such as alkali resistance, corrosion resistance, and weather resistance, and especially has an excellent fixing force. SOLUTION: This fixing agent for fixing bolts, comprising (A) a (meth)acrylic monomer having a (meth)acryloyl group and a carbon-carbon double bond except the carbon-carbon double bond originated from the (meth)acryloyl group in the molecule, and (B) a (meth)acrylic polymer is characterized in that the weight ratio of (A) the (meth)acrylic monomer to (B) the (meth)acrylic polymer is 5/95 to 90/10.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fixing agent for fixing bolts.

[0002]

2. Description of the Related Art The fixing agent for fixing bolts is concrete,
It is used to fix anchor bolts etc. to the foundation of bedrock etc. In recent years, those that have sufficient adhesion (adhesive strength) for construction, repair and reinforcement of various concrete structures such as buildings and expressways Has become indispensable. As a method of fixing an anchor bolt or the like with a fixing agent for bolt fixing, for example, a hole is drilled in a base, a container containing the fixing agent is loaded in the hole, and then the anchor bolt or the like joined to a hammer drill or the like is rotated. A method has been put to practical use in which the container is crushed by inserting the container while applying an impact to crush the container and the fixing agent is cured. It can also be carried out by in-situ blending or by injecting a fixing agent into the holes using a cartridge.

[0003] As such a fixing agent for fixing a bolt,
A glass container filled with a resin containing a liquid unsaturated polyester resin as a main component, and a curing agent containing an organic peroxide such as benzoyl peroxide as a main component sealed in a glass tube. A contained fixing agent is known. When this fixing agent is used, good handleability and fixing power will be exhibited, but at low temperatures such as in winter, it may take a long time to cure. There was room for research to be able to respond to various construction conditions.

Japanese Patent Publication No. Sho 62-37076 discloses a fixing agent for bolts having good corrosion resistance and comprising an epoxy acrylate resin whose main component contains or does not contain a reactive monomer. However, this fixing agent for fixing bolts has insufficient curability, so there is room for contriving both excellent corrosion resistance, quick curing property, and low-temperature curing property. Due to the fact that the main component is an epoxy acrylate resin, there has been a problem that alkali resistance, weather resistance and the like are not sufficient.

Japanese Unexamined Patent Publication (Kokai) No. 61-2779 discloses an anchor obtained by adding an aggregate and a curing agent to a mixture of a polymer and a monomer component such as a methacrylate or a tertiary amine. An adhesive for bolts is disclosed. However, although the anchoring agent for anchor bolts has good low-temperature curability, by improving the adhesive force, the performance as an adhesive agent can be sufficiently exhibited to adapt to various concrete structures and the like. There was room.

JP-A-8-295864 discloses an epoxy (meth) acrylate diluted with a reactive monomer which is a polyfunctional ester of a carboxylic acid and an alcohol as a main component, and an organic peroxide as a curing agent. And a tertiary aromatic amine are disclosed. However, in this adhesive for building structures, since the main agent is epoxy (meth) acrylate diluted with a reactive monomer, the performance as an adhesive is improved by improving alkali resistance and weather resistance. There is room for contrivance to improve the durability of concrete structures and the like by sustaining them.

[0007]

DISCLOSURE OF THE INVENTION The present invention provides a quick-curing,
It is an object of the present invention to provide a fixing agent for bolts which is excellent in low-temperature curability, is excellent in basic performance such as alkali resistance, corrosion resistance and weather resistance, and is particularly excellent in fixing force.

[0008]

The present invention has a (meth) acryloyl group and a carbon-carbon double bond other than the carbon-carbon double bond derived from the (meth) acryloyl group in one molecule. (Meth) acrylic monomer (A)
And a (meth) acrylic polymer (B), comprising: the (meth) acrylic monomer (A) and the (meth) acrylic polymer (B). Is a fixing agent for fixing bolts having a weight ratio of 5/95 to 90/10.

The present inventors have studied various fixing agents for fixing bolts. Among them, radical polymerization for curing the fixing agent in one molecule as a main component in a resin composition constituting the fixing agent for bolt fixing is described. A carbon other than a carbon-carbon double bond derived from a (meth) acryloyl group as an unsaturated double bond having a possible (meth) acryloyl group and having poor radical polymerizability and not considered to be involved in curing of the fixing agent. -When a specific (meth) acrylic monomer also having a carbon double bond and a (meth) acrylic polymer are essentially contained in a specific weight ratio, the (meth) acrylic monomer and (meth) ) The resin is composed of an acrylic polymer, and has excellent fast-curing properties and low-temperature curability,
Basic performance such as alkali resistance, corrosion resistance, weather resistance, etc. is improved, and furthermore, the adhesion strength is considered to be caused by the unsaturated double bond of a specific (meth) acrylic monomer having poor radical polymerizability. By focusing on the fact that the above problem can be solved brilliantly, the use of a (meth) acryl-based polymer having a plurality of polymerizable double bonds in the molecule is more effective. Attention has been paid to the present invention. Hereinafter, the present invention will be described in detail.

The fixing agent for fixing bolts of the present invention has a (meth) acryloyl group in one molecule and a carbon-carbon bond other than a carbon-carbon double bond derived from the (meth) acryloyl group.
It comprises a (meth) acrylic monomer (A) also having a carbon double bond, and a (meth) acrylic polymer (B).

The (meth) acrylic monomer (A) includes, for example, one (meth) acryloyl group in one molecule.
And monofunctional (meth) acrylic monomers having only one, and polyfunctional (meth) acrylic monomers having two or more (meth) acryloyl groups in one molecule. The number of carbon-carbon double bonds other than the carbon-carbon double bond derived from the (meth) acryloyl group in the monomer in one molecule is not particularly limited. Incidentally, a carbon-carbon double bond other than a carbon-carbon double bond derived from a (meth) acryloyl group means a conjugation represented by a so-called α, β-unsaturated carbonyl group such as a (meth) acryloyl group. It does not mean an unsaturated hydrocarbon bond having an unsaturated hydrocarbon bond having a poor copolymerizability with a conjugated unsaturated hydrocarbon bond represented by the above α, β-unsaturated carbonyl group. It means a hydrogen bond, more specifically, an unsaturated hydrocarbon bond derived from an allyl group, a butenyl group, a cyclic ene, or the like. It is preferably an unsaturated hydrocarbon bond having no conjugation. More preferably, it is an unsaturated hydrocarbon bond derived from a cycloalkenyl group.

In the above (meth) acrylic monomer (A), by adjusting the use ratio of a monofunctional (meth) acrylic monomer or a polyfunctional (meth) acrylic monomer, it is possible to fix bolts. The curability and fixing power of the fixing agent can be adjusted. For example, by using a small amount of a polyfunctional (meth) acrylic monomer, the fixing power can be improved. As the monofunctional (meth) acrylic monomer, for example, since the fixing force of a fixing agent for bolt fixing is improved, the following general formula (1);

[0013]

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(In the formula, R ₁ is a hydrogen atom or a methyl group. R ₂ is the same or different and is a lower alkylene group having 2 to 5 carbon atoms, specifically, preferably ethylene. (N is an integer of 0 to 5), and a (meth) acrylate having a dicyclopentenyl group is preferable, and other (meth) acrylates having an allyl group such as allyl (meth) acrylate Is mentioned. These may be used alone or in combination of two or more. Specific chemical names of the (meth) acrylate having a dicyclopentenyl group include, for example, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and the like.

As the polyfunctional (meth) acrylic monomer, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, etc.
Acrylic-modified butadiene-based oligomers and the like can be mentioned. Among these, it is preferable to use a butadiene-based oligomer having both ends modified with (meth) acryl.

The butadiene oligomer having both ends modified with (meth) acryl is a copolymer or homopolymer of butadiene having (meth) acryloyl groups at both ends, and has a weight average molecular weight of 1,000 to 10,000. Is preferred. For example, both ends methacryl-modified liquid polybutadiene (trade name “TE-2000”, manufactured by Nippon Soda Co., Ltd.), both ends acryl-modified liquid polyacrylonitrile butadiene (trade name “HycarVTBNX”, manufactured by Ube Industries, Ltd.), both ends methacryl-modified liquid portion Examples include hydrogenated polybutadiene (trade name “TEAI-1000”, manufactured by Nippon Soda Co., Ltd.), and a polybutadiene modified at both ends with acrylic (trade name “BAC-45”, manufactured by Osaka Organic Co., Ltd.).

The (meth) acrylic polymer (B) in the present invention is preferably soluble in the (meth) acrylic monomer (A). It is preferable to have two or more in the molecule. This allows
When the (meth) acrylic syrup cures, the (meth) acrylic polymer (B) is crosslinked, and the fixing force of the fixing agent for bolt fixing is improved. In the present specification, a mixture of a (meth) acrylic monomer (A) and a (meth) acrylic polymer (B) having a plurality of polymerizable double bonds in a molecule is crosslinked (meth). ) Acrylic syrup. The crosslinkable (meth) acrylic syrup may contain a (meth) acrylic polymer (B) having no polymerizable double bond. The amount of the (meth) acrylic polymer (B) having a plurality of polymerizable double bonds in the molecule is as follows: (meth) acrylic polymer (B)
Is 100% by weight, the content is preferably in the range of 50 to 100% by weight. It is more preferably in the range of 60 to 100% by weight, and still more preferably in the range of 80 to 100% by weight.

The polymerizable double bond equivalent of the (meth) acrylic polymer (B) is not particularly limited.
It is preferably from 00 to 20,000. If it is less than 500, cracks may occur in the cured product, and 2
If it exceeds 0000, the basic performance such as heat resistance and solvent resistance of the cured product may be reduced. More preferably, 30
00 to 15000, more preferably 4000 to 10000.
10,000. The polymerizable double bond equivalent can be determined by (weight average molecular weight of polymer) / (average number of polymerizable double bonds in one molecule of polymer).

The molecular weight of the (meth) acrylic polymer (B) is not particularly limited. For example, the weight average molecular weight in terms of polystyrene by gel permeation chromatography is preferably from 3,000 to 1,000,000. If it is less than 3000, the basic performance of the cured product may be reduced, and if it exceeds 1,000,000,
The viscosity of the (meth) acrylic syrup may increase, and the mixing with the aggregate and the curing agent may become non-uniform, or the cured product may become too hard and the fixing force may decrease. More preferably, it is 5,000 to 100,000, still more preferably, 10,000 to 60,000, particularly preferably,
10,000 to 40,000, most preferably 10
000 to 30,000. The weight average molecular weight in terms of polystyrene by gel permeation chromatography was determined using an SC-8020 system (trade name, manufactured by Tosoh Corporation) using TSKgelGMH (trade name, manufactured by Tosoh Corporation) as a column and tetrahydrofuran as a developing solvent. Can be measured at a solvent flow rate of 1 ml / min.

The method for producing the (meth) acrylic polymer (B) is not particularly limited. For example, as the first step reaction, a (meth) acrylic polymer is converted from a (meth) acrylic monomer or the like. In the synthesis, a (meth) acrylic polymer having a functional group in the molecule is synthesized by copolymerizing a polymerizable monomer having a functional group, and the (meth) acrylic polymer is used as a second-stage reaction. The (meth) acrylic polymer (B) having a polymerizable double bond can be obtained by reacting a polymerizable monomer having a functional group reactive with the functional group of the united polymer with each other. In addition, the first-stage reaction and the second-stage reaction may be performed stepwise or may be performed simultaneously.

The combination of the functional groups which react in the second stage reaction is not particularly limited as long as the functional groups have reactivity, and examples thereof include a carboxyl group and a glycidyl group, a hydroxyl group, an amino group, an oxazoline group. , An aziridine group, etc .; a combination of a hydroxyl group with an acid anhydride, an isocyanate group, etc .; a combination of these, and the like. It is preferred that

In the combination of the above functional groups, there is no particular limitation on how the types and amounts of the functional groups of the polymerizable monomer having a functional group used in the first-stage reaction and the second-stage reaction are combined. Absent. Various functional groups can be introduced into the (meth) acrylic polymer (B) thus obtained together with a polymerizable double bond. When a carboxyl group is introduced together with a polymerizable double bond, The first-stage reaction may be performed using a polymerizable monomer having a carboxyl group. In this case, in the first-stage reaction, when the reactivity between the carboxyl group of the polymerizable monomer having a carboxyl group and the functional group of the polymerizable monomer having a functional group is high, the Crosslinking may be formed and gelation may occur. Therefore, as a first step reaction, a polymerizable monomer having a functional group having low reactivity with a carboxyl group is converted to a (meth) acrylic monomer, a polymerizable monomer having a carboxyl group, and other (Meth) By copolymerizing with an unsaturated monomer other than the acrylic monomer, a (meth) acrylic polymer having a carboxyl group and other functional groups is synthesized, and as a second step reaction,
A polymerizable monomer having a functional group highly reactive with the functional group of the (meth) acrylic polymer is reacted between the functional groups to form a carboxyl group and a polymerizable double bond in the (meth) acrylic polymer. Is preferably used. In addition, as a first step reaction, a (meth) acrylic polymer having a carboxyl group is synthesized, and as a second step reaction, a polymerizable monomer having a functional group having high reactivity with a carboxyl group is synthesized between functional groups. It is also possible to use a method in which the carboxyl groups of the (meth) acrylic polymer are allowed to react and the carboxyl groups of the (meth) acrylic polymer are in excess of the functional groups of the polymerizable monomer.

In the production of the (meth) acrylic polymer (B) by the first-stage reaction and the second-stage reaction, from the simplicity and convenience of the reaction, the first-stage reaction has a carboxyl group ( It is possible to use a method of synthesizing a (meth) acrylic polymer and subjecting part or all of the carboxyl group to an esterification reaction with a polymerizable monomer having a glycidyl group such as an unsaturated epoxy compound as a second step reaction. preferable. In addition, a (meth) acrylic monomer, a polymerizable monomer having a hydroxyl group, and, if necessary, a polymerizable monomer having a carboxyl group are copolymerized to form a (meth) acrylic polymer. After the synthesis, a method of reacting a polymerizable monomer having an isocyanate group with a hydroxyl group in a (meth) acrylic polymer using a urethanizing catalyst such as an organotin compound, a method of (meth) acrylic monomer, And a method in which a polymerizable monomer having a hydroxyl group is copolymerized to synthesize a (meth) acrylic polymer, and then a method of reacting an unsaturated acid anhydride with a hydroxyl group in the (meth) acrylic polymer is used. However, the present invention is not limited thereto. As a preferable combination of a polymerizable monomer having a functional group used for the first-stage reaction and a polymerizable monomer used for the second-stage reaction which is reactive with the functional group, (meth) acrylic acid and ( Glycidyl (meth) acrylate or vice versa, 2-hydroxyethyl (meth) acrylate and (meth) acrylic acid 2
-Isocyanate ethyl or vice versa, and a combination of 2-hydroxyethyl (meth) acrylate and maleic anhydride are preferred.

The (meth) acrylic monomer that can be used in the production of the (meth) acrylic polymer (B) is not particularly limited, and examples thereof include the following (1) to (7). And the like. These may be used alone or in combination of two or more.

(1) (meth) acrylic acid. (2) (meth) acrylates: methyl (meth)
Acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl ( (Meth) acrylate, glycidyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethylene glycol (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxydiethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate.

Methoxy polyethylene glycol (meth)
Acrylate, ethoxy polyethylene glycol (meth) acrylate, allyl (meth) acrylate, (meth) acrylate of oligoethylene oxide adduct of allyl alcohol, (meth) acrylate of polypropylene oxide adduct of allyl alcohol, and the like.

(3) Basic (meth) acrylates: dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and the like. (4) (meth) acrylamides: (meth) acrylamide and the like. (5) (meth) acrylates having an ultraviolet absorbing group: ethyl-2-cyano-3,5-diphenylacrylate and the like. (6) (meth) acrylates having a hydroxyl group: 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, methyl 2- (hydroxymethyl) acrylate, ethyl 2 -(Hydroxymethyl) acrylate; mono (meth) acrylates of polyhydric alcohols having two hydroxyl groups such as polyethylene glycol mono (meth) acrylate and polypropylene glycol mono (meth) acrylate; tris (hydroxyethyl)
Part (meth) acrylates of polyhydric alcohol having three or more hydroxyl groups, such as di (meth) acrylate of isocyanuric acid and pentaerythritol tri (meth) acrylate.

(7) Other (meth) acrylic monomers: (meth) acrylonitrile, (meth) acrolein and the like. Among these (meth) acrylic acid-based monomers, since the fixing force of the fixing agent for bolt fixing is improved, (meth) is included in the molecule of 2-hydroxyethyl (meth) acrylate or the like.
A polymerizable monomer having an acryloyl group and a hydroxyl group,
It is preferable to use a polymerizable monomer having a polymerizable double bond copolymerizable with a (meth) acryloyl group and a hydroxyl group.

The amount of the (meth) acrylic monomer that can be used in the production of the (meth) acrylic polymer (B) is not particularly limited. Therefore, when the total weight of the monomers constituting the (meth) acrylic polymer (B) is 100% by weight, the amount of the (meth) acrylic acid ester is preferably at least 50% by weight. preferable. More preferably, 70
% By weight or more.

In the production of the (meth) acrylic polymer (B), an unsaturated monomer copolymerizable therewith can be used in addition to the above-mentioned monomers. For example,
Styrenes such as styrene, α-methylstyrene, vinyltoluene and chlorostyrene; vinyl esters such as vinyl acetate; vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; allyl alcohol, allyl glycidyl ether, ethylene glycol monoallyl ether And allyl compounds such as propylene glycol monoallyl ether; and N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide and N-isopropylmaleimide.

The amount of the unsaturated monomer used is not particularly limited. For example, if the total weight of the monomers constituting the (meth) acrylic polymer (B) is 100% by weight, It is preferable that the amount is less than the weight%.
More preferably, it is less than 30% by weight, even more preferably less than 20% by weight.

In the first stage reaction in the production of the (meth) acrylic polymer (B), polymerization is usually carried out using a polymerization initiator. Such a polymerization initiator is not particularly limited, for example, benzoyl peroxide, lauroyl peroxide, methyl ethyl ketone peroxide, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy octoate,
tert-butyl peroxybenzoate, cumene hydroperoxide, cyclohexanone peroxide,
Organic peroxides such as dicumyl peroxide and bis (4-tert-butylcyclohexyl) peroxydicarbonate; 2,2'-azobisisobutyronitrile;
Azo compounds such as phenylazo-2,4-dimethyl-4-methoxyvaleronitrile; These may be used alone or in combination of two or more. The amount and method of addition of the polymerization initiator may be appropriately set and are not particularly limited.

In the first-stage reaction, it is preferable to add a chain transfer agent in order to adjust the average molecular weight and the like of the polymer. As the chain transfer agent, a thiol compound is particularly preferably used because the polymerization reaction of the polymerizable monomer can be extremely easily controlled, but is not particularly limited, and includes, for example, α-methylstyrene dimer. And carbon tetrachloride can also be used. These may be used alone or in combination of two or more.

The thiol compound is not particularly restricted but includes, for example, alkyl mercaptans such as tert-butyl mercaptan, n-octyl mercaptan and n-dodecyl mercaptan; aromatic mercaptans such as thiophenol and thionaphthol; thioglycolic acid; Alkyl esters of thioglycolic acid such as octyl glycolate, ethylene glycol dithioglycolate, trimethylolpropane tris- (thioglycolate) and pentaerythritol tetrakis- (thioglycolate); β-
Mercaptopropionic acid; octyl β-mercaptopropionate, 1,4-butanediol di (β-thiopropionate), trimethylolpropane tris- (β-thiopropionate), pentaerythritol tetrakis- (β-thiopropionate) Β-mercaptopropionic acid alkyl esters such as pionate). The amount of the chain transfer agent used is not particularly limited as long as it is appropriately selected according to the type thereof, the combination with the (meth) acrylic monomer and the like, and is not particularly limited. It is preferable to use 0.1 to 15% by weight based on 100% by weight of the total amount.

When the carboxyl group and the glycidyl group are esterified in the second-stage reaction, an esterification catalyst can be used to accelerate the reaction. The esterification catalyst is not particularly limited,
For example, common esterification catalysts such as amines such as triethylamine; quaternary ammonium salts such as tetraethylammonium chloride; phosphorus compounds such as triphenylphosphine can be used.
It is preferable to use a metal compound having at least one element selected from the group consisting of r and / or a quaternary phosphonium salt. These may be used alone or in combination of two or more.

The quaternary phosphonium salt is not particularly restricted but includes, for example, tetraphenylphosphonium bromide, tetraphenylphosphonium chloride, tetrabutylphosphonium bromide and butyltriphenylphosphonium bromide. preferable.

The amount of the esterification catalyst to be used may be appropriately set according to the kind thereof, the combination of the (meth) acrylic polymer and the polymerizable monomer in the second stage reaction, and is not particularly limited. For example, when the second stage reaction is a reaction between a (meth) acrylic polymer having a carboxyl group and a polymerizable monomer having a glycidyl group, 100 parts by weight of the (meth) acrylic polymer having a carboxyl group Is preferably 0.005 to 5 parts by weight.
More preferably, it is 0.05 to 3 parts by weight.

In carrying out the esterification reaction, a polymerization inhibitor may be used together, and a solvent such as water and / or an organic solvent may be used. The polymerization inhibitor is not particularly limited and includes, for example, amines such as alkylated diphenylamine; tert-butylphenol, 2,2′-methylenebis (4-methyl-6-tert-butylphenol), and 2,6-ditert-butylphenol. Phenols such as butyl-4-methylphenol, alkylated bisphenol A, styrenated phenol and methoxyphenol; hydroquinones such as hydroquinone, methylhydroquinone, methoxyhydroquinone and tert-butylhydroquinone; triphenylphosphite, tris (monononylphenyl) ) Phosphites such as alkylated phenyl phosphites such as phosphite and trialkyl phosphites such as tridecyl phosphite; dilauryl-
Examples thereof include thioethers of propionate such as 3,3 ′ thiodipropionate and thioethers such as esterified bisphenol S. These may be used alone or in combination of two or more. Among these, it is preferable to use an amine alone or two or more of an amine and another system. From the viewpoint of coloring (meth) acryl syrup, phenols such as hydroquinone and tert-butylphenol are preferred. It is preferable to use 2,2'-methylenebis (4-methyl-6-ter
It is more preferable to use (t-butylphenol).

In the above-mentioned esterification reaction, when a (meth) acrylic polymer having a carboxyl group, a polymerizable monomer having a glycidyl group such as an unsaturated epoxy compound, and a metal compound are mixed, the mixture of these is used. The order and method are not particularly limited as long as the metal compound is present during the reaction between the (meth) acrylic polymer having a carboxyl group and the polymerizable monomer having a glycidyl group.

The polymerization method in the first-stage reaction is not particularly limited, and is preferably, for example, a method in which the polymerization of the polymerizable monomer is stopped halfway, that is, a partial polymerization.

In the present invention, the (meth) acrylic monomer (A) and the (meth) acrylic polymer (B)
Is 5/95 to 90/10. When the mixing ratio of the (meth) acrylic monomer (A) is less than the above weight ratio, the viscosity of the (meth) acrylic syrup increases, and the mixing with the aggregate and the curing agent becomes uneven, There is a possibility that the cured product becomes too hard and the fixation force is reduced. If the weight ratio exceeds the above range, the mixing with the aggregate becomes uneven and the fixation force may be reduced. More preferably, it is 5/95 to 80/20, and still more preferably 1
0/90 to 70/30. Such a (meth) acrylic syrup usually has a viscosity of 0.01 to 10 Pa at around room temperature.
Having a viscosity of s and can be prepared at a desired viscosity by appropriately setting the weight ratio of the (meth) acrylic monomer (A) and the (meth) acrylic polymer (B). it can.

The amount of the (meth) acrylic monomer (A) may be 0.5 to 90% by weight, when the resin composition for the fixing agent for bolts is 100% by weight. preferable. More preferably, it is 10 to 90% by weight, still more preferably 10 to 80% by weight, and most preferably 10 to 60% by weight. The amount of the (meth) acrylic polymer (B) is 0.5%, assuming that the resin composition for a fixing agent for bolts is 100% by weight.
It is preferable that the content be about 90% by weight. More preferably, it is 10 to 90% by weight, still more preferably,
20-80% by weight, most preferably 20-70% by weight.
% By weight. The amount of the (meth) acrylic polymer (B) having a plurality of polymerizable double bonds in the molecule is 0.3 to 0.3% when the resin composition for a fixing agent for fixing bolts is 100% by weight. It is preferred to be in the range of 90% by weight. It is more preferably in the range of 6 to 90% by weight, still more preferably in the range of 15 to 80% by weight, and most preferably in the range of 15 to 70% by weight.

In the above resin composition for fixing a fixing agent for bolts, a method for confirming that a hydroxyl group or a double bond has been introduced into a polymer can be carried out, for example, as described below. The polymer is separated by dissolving the resin composition for fixing agent for fixing bolts in the same amount of acetone and then dropping it into 20 times the amount of methanol, followed by filtration, drying and fractionation. The separated polymer is transferred to a nuclear magnetic resonance apparatus UNITY-
Proton nuclear magnetic resonance analysis was performed using plus (manufactured by Varian Japan) under the conditions of a resonance frequency of 400 MHz, a solvent of chloroform-d, a reference substance of tetramethylsilane, and an accumulation count of 10 times, and hydroxyl groups and double bonds were introduced into the polymer. You can be sure that.

As a method for measuring the above hydroxyl group concentration,
For example, it can be performed as described below.
First, a sample is diluted with water and acetone, and the acid concentration of the sample is determined by titration of a methanol solution of potassium hydroxide. Further, the sample is diluted with ethyl acetate, and an acetylating reagent consisting of p-toluenesulfonic acid / acetic anhydride / ethyl acetate is added to acetylate all hydroxyl groups. All excess acetic acid is hydrolyzed to acetic acid with a hydrolysis reagent composed of pyridine / water, and the acid concentration after acetylation is determined by titration of a potassium hydroxide methanol solution. At the same time, a blank test is performed to determine the acid concentration of the blank. Here, (hydroxyl concentration) = (acid concentration of sample) + (acid concentration of blank) − (acid concentration after acetylation), and a unit of eg. /
Expressed in kg.

The resin composition for a fixing agent for bolt fixing according to the present invention may be any one of the above-mentioned (meth) as long as the effects of the present invention are not impaired.
In addition to the acrylic syrup, it may contain additives such as paraffin and / or wax, a thixotropy-imparting agent (thixotropic agent, thixotropic agent), a low-shrinking agent, a plasticizer, a coupling agent, and an antifoaming agent. Good. Further, for example, it may contain a polymerizable resin and / or an oligomer such as an epoxy acrylate resin, a urethane acrylate resin, an unsaturated polyester resin, and a saturated polyester resin. These may be used alone or in combination of two or more. As the content of the other polymerizable resin, for example,
The content is preferably 0 to 50% by weight with respect to 100% by weight of the resin composition for the fixing agent for bolt fixing. It is more preferably 0 to 40% by weight, and still more preferably 0 to 30% by weight.
It is.

The thixotropic agent is not particularly restricted but includes, for example, colloidal silica, fumed silica, silica aerogel, organically modified clay, clay, silica powder, cellulose acetate, sepiolite, Aerosil (trade name, Nippon Aerosil Co., Ltd.) ), Thixogel (trade name, manufactured by Yokohama Kasei Co., Ltd.), disparone (trade name, manufactured by Kusumoto Kasei Co., Ltd.), Leolo Seal (trade name, manufactured by Tokuyama Soda Co., Ltd.), and uriya urethane resin. The amount of the thixotropic agent to be used is preferably 0.1 to 5 parts by weight based on 100 parts by weight of the fixing resin composition for fixing bolts. More preferably, it is 0.5 to 3 parts by weight, and still more preferably, 1 to 2 parts by weight.

As the above-mentioned low-shrinking agent, thermoplastic resins other than the above-mentioned (meth) acrylic polymer (B) can be used, and are not particularly limited. Examples thereof include polyethylene, polypropylene, polystyrene and polyvinyl acetate. , SBS
And the like. The plasticizer is not particularly limited, and examples thereof include dibutyl phthalate, diheptyl phthalate, di-n-octyl phthalate, and chlorinated paraffin.

The amount of use of the above-mentioned low shrinkage agent and plasticizer is preferably 30 parts by weight or less based on 100 parts by weight of the resin composition for fixing agent for bolt fixing. If the amount of the plasticizer exceeds 30 parts by weight, the fixing strength of the cured product may be poor. More preferably, it is 15 parts by weight or less.

The coupling agent is not particularly limited as long as it has an effect of stabilizing the fixing force of the fixing agent for fixing bolts. For example, γ-methacryloxypropyltrimethoxysilane, γ-glycidic Xypropyltrimethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. The amount of the coupling agent to be used is preferably 10 parts by weight or less based on 100 parts by weight of the resin composition for fixing agent for bolts. More preferably, it is 5 parts by weight or less.

The defoaming agent is not particularly restricted but includes, for example, surfactants such as anionic surfactants, cationic surfactants, nonionic surfactants and amphoteric surfactants. Among these, an anionic type is preferable. For example, as a carboxylate, an alkyl ether carboxylate (trade name “Buelite E, manufactured by Sanyo Chemical Co., Ltd.)
AC "), dialkyl sulfosuccinates (manufactured by Sanyo Chemical Industries, trade name" Sansepara 10
0 "), 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. No. The amount of the defoaming agent to be used is preferably 30 parts by weight or less based on 100 parts by weight of the resin composition for a fixing agent for bolts from the viewpoint of strength.

The fixing agent for bolt fixing of the present invention may contain a filler, an aggregate and the like in addition to the resin composition for fixing agent for bolt fixing. The filler is not particularly limited, for example, quartz sand, silica sand, silica powder, calcium carbonate, gypsum, glass flakes, mica, volcanic ash, shirasu, shirasu micro balloon, concrete powder, foamed concrete powder, glass micro balloon, hollow Glass pigments, fly ash, alumina, iron, aluminum, silica, etc., which have a filling action, as well as coloring pigments and dyes can be used. The color pigment or dye is not particularly limited, and examples thereof include titanium oxide, barium sulfate, carbon black, chrome vermillion, red iron oxide, ultramarine, cobalt blue, phthalocyanine blue, and phthalocyanine green.

The above-mentioned aggregate is not particularly restricted but includes, for example, artificial aggregates such as magnesia clinker, glass beads, ceramics and hard plastics; 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 also be used. The amount of the filler or the aggregate is preferably 1,000 parts by weight or less based on 100 parts by weight of the resin composition for the fixing agent for bolt fixing.

In the resin composition for a fixing agent for bolt fixing of the present invention, the resin composition for a fixing agent for bolt fixing is cured by the action of a curing agent. Such a curing agent is not particularly limited, and for example, a radical polymerization initiator can be used. Examples of the radical polymerization initiator include organic peroxides described in (1) to (8) below. And azo compounds described in (9) to (13), and it is preferable to use an organic peroxide from the viewpoint of curability. These may be used alone or in combination of two or more.

(1) Ketone peroxides: methyl ethyl ketone peroxide, cyclohexanone peroxide and the like. (2) Peroxyketals: 1,1-bis (tert
-Butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxy) cyclohexane and the like.

(3) Hydroperoxides: ter
t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramenthane hydroperoxide and the like. (4) Dialkyl peroxides: di-tert-butyl peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, α, α′-bis (te
rt-butylperoxy-meta-isopropyl) benzene and the like.

(5) Diacyl peroxides: acetyl peroxide, isobutyl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, 3,3,5-trimethylhexanoyl peroxide, succinic acid peroxide Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, meta-toluoyl peroxide and the like.

(6) Peroxydicarbonates: diisopropylperoxydicarbonate, di-2-ethylhexylperoxydicarbonate, dinormal propylperoxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, Jee
2-ethoxyethyl peroxydicarbonate and the like.

(7) Peroxyesters: tert-
Butylperoxyacetate, tert-butylperoxyisobutyrate, tert-butylperoxyoctoate, tert-butylperoxypivalate, t
tert-butyl peroxy neodecanoate, cumyl peroxy neodecanoate, tert-butyl peroxy-2-ethylhexanoate, tert-butyl peroxy-3,3,5-trimethylhexanoate, te
rt-butyl peroxy laurate, tert-butyl peroxy benzoate and the like. (8) Other organic peroxides: acetylcyclohexylsulfonyl peroxide, tert-butylperoxyallyl carbonate, and the like.

(9) Azonitrile compounds: azobisisobutyronitrile and the like. (10) Azoamidine compounds: 2,2'-azobis (2-methylpropionamidine) dihydrochloride and the like. (11) Cyclic azoamidine compounds: 2,2 ′
-Azobis [2- (2-imidazolin-2-yl) propane] and the like. (12) Azoamide compound: 2,2'-azobis @ 2-
Methyl-normal- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide} and the like. (13) Alkyl azo compounds: 2,2'-azobis (2,4,4-trimethylpentane) and the like.

In the present invention, an accelerator can be used to accelerate the curing of the fixing resin composition for fixing bolts. However, in this case, it is necessary to separate the accelerator and the curing agent. Such an accelerator is not particularly limited, and examples thereof include compounds described in the following (1) to (6). These may be used alone or in combination of two or more.

(1) Thiourea derivatives: diethylthiourea, dibutylthiourea, ethylenethiourea, tetramethylthiourea and the like. (2) amines: N, N-dimethyl-p-toluidine,
N, N-diethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, N, N-diisopropanol-p-toluidine, N, N-di (2-hydroxypropyl) -p-toluidine, triethylamine, Tripropylamine, ethyldiethanolamine, N, N-dimethylaniline, ethylenediamine, triethanolamine and the like.

(3) Organic acid metal salts: cobalt naphthenate, copper naphthenate, zinc naphthenate, cobalt octylate, copper octylate, zinc octylate and the like. (4) Organic metal chelate compounds: copper acetylacetonate, titanium acetylacetonate, manganese acetylacetonate, chromium acetylacetonate, iron acetylacetonate, vanadinyl acetylacetonate, cobalt acetylacetonate and the like. (5) Other decomposition accelerators: condensation products of aldehydes and amines. (6) Metal salts of organic acids: cobalt salts such as cobalt naphthenate, cobalt octylate and acetylacetone cobalt.

Among the above curing agents and accelerators, diacyl peroxides are preferred as the curing agent, and amines are preferred as the accelerator, from the viewpoint of quick curing and low temperature curing. More preferably, the curing agent is benzoyl peroxide and the accelerator is toluidines. These benzoyl peroxides and the like are preferably used in the form of a paste or powder diluted with an inert liquid or solid to a concentration of about 50% by weight in order to avoid danger in handling. Examples of the diluent used for diluting the curing agent include inorganic substances such as calcium sulfate and calcium carbonate; dimethyl phthalate, dibutyl phthalate, dicyclohexyl phthalate, dioctyl phthalate, aliphatic hydrocarbon, aromatic hydrocarbon, silicone oil, and liquid paraffin. Organic compounds such as polymerizable monomers; water and the like.

The amount of the curing agent or accelerator used is 100 parts by weight of the resin composition for fixing agent for bolt fixing.
0.1 to 10 parts by weight of curing agent, 0.01 to 10 parts of accelerator
It is preferred to be parts by weight. If the amount is less than the above amount, the curability may decrease. If the amount exceeds the above amount, the curing speed or the like may not be improved, and the fixing force may be rather decreased. More preferably, the curing agent is 0.2 to
5 parts by weight, 0.1 to 4 parts by weight of accelerator.

In order to stabilize the curing together with the above-mentioned curing agents and accelerators, tributyl phosphite, tri (2
Phosphites such as-(ethylhexyl) phosphite, tridecyl phosphite, tristearyl phosphite, tris (nonylphenyl) phosphite, and triphenyl phosphite can be used as necessary. These may be used alone or in combination of two or more.

In the present invention, a polymerization inhibitor may be used in order to maintain the stability of the resin composition for the fixing agent for fixing bolts. Such a polymerization inhibitor is not particularly limited, and includes, for example, the above-mentioned hydroquinones, phenols, quinones, and the like, and one or more kinds may be used. Of these, hydroquinones and phenols are preferably used since quinones may cause changes such as coloring with amines. Most preferred are cresols. Further, the amounts of these polymerization inhibitors used are not particularly limited.

The form of the fixing agent for bolt fixing according to the present invention includes a resin composition and a curing agent for fixing agent for bolt fixing composed of (meth) acrylic syrup and additives, and a filler and an aggregate if necessary. Is contained in a container, and the resin composition for fixing the fixing agent for bolts and the curing agent are preferably separated from each other, for example, by including a crushable inner container in a crushable outer container. (1) an inner container in which a curing agent is sealed, the resin composition for a fixing agent for fixing bolts, and, if necessary, a filler and an aggregate, which are housed and sealed in an outer container; and (2) An inner container in which the resin composition for the fixing agent for fixing bolts is sealed, a curing agent, and a filler and an aggregate, if necessary, are contained in an outer container and sealed.
In such a form, the filler and the aggregate may be mixed in either the resin composition for the fixing agent for bolt fixing or the curing agent. Further, a form in which the resin composition for a fixing agent for fixing bolts, a filler and an aggregate as needed, are contained in a container, and a curing agent is applied to the outer wall of the container may also be mentioned.

The above-mentioned container is not particularly limited as long as it is a container which is not broken during transportation or storage and is easily broken when inserting an anchor bolt and becomes a small piece. For example, glass, porcelain, synthetic resin, paper, metal, etc. The container formed of a synthetic resin may be a hard one or a soft one prepared from a film or the like. Examples of the form include capsules, cartridges, cans, packs, and the like.

The viscosity of the resin composition for fixing a bolt for fixing composed of the above (meth) acrylic syrup, additives and the like is not particularly limited, and is preferably, for example, 5.0 Pa · s or less. When it exceeds 5.0 Pa · s,
The fixing force may be reduced. More preferably, 0.
5 to 2.0 Pa · s.

The fixing agent for fixing bolts of the present invention is used for fixing anchor bolts or the like to a base such as concrete or bedrock, and is excellent in quick-setting properties and low-temperature setting properties, as well as in alkali resistance, corrosion resistance, weather resistance, etc. Because of its excellent basic performance, especially its excellent adhesive strength, it can be suitably applied to construction, repair and reinforcement of various concrete structures and the like such as buildings and expressways.

[0071]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. “Parts” are “parts by weight” unless otherwise specified.
Means “%” Means “% by weight”.

Synthesis Example 1 Synthesis of methacrylic syrup (1) 100 parts of methyl methacrylate was charged into a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer, and the inside of the reactor was replaced with nitrogen gas. Next, the mixture was heated to 80 ° C. with stirring, and 0.1 part of azobisisobutyronitrile and 1.4 parts of n-dodecylmercaptan were added.
After a time-copolymerization reaction (hereinafter, referred to as a copolymerization reaction time), air was blown into the system, and simultaneously, 0.01 part of hydroquinone (hereinafter, referred to as HQ) was added to terminate the polymerization. The obtained methacrylic wrap was designated as methacrylic wrap (1). The solid concentration is 48%, the weight average molecular weight in terms of polystyrene by gel permeation chromatography is 26,000, and the viscosity is 6.0 Pa ·
s.

Synthesis Example 2 Synthesis of methacrylic syrup (2) In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer, 96.5 parts of methyl methacrylate and 3.
5 parts were charged, and the inside of the reactor was replaced with nitrogen gas. Next, the mixture was heated to 80 ° C. while stirring, and 0.1 part of azobisisobutyronitrile and 1.4 parts of mercaptopropionic acid were added to carry out a copolymerization reaction for 4.5 hours. Thereafter, at the same time as air was blown into the system, 0.01 part of HQ was added to terminate the polymerization.

Then, glycidyl methacrylate 4.0
Part, tetraphenylphosphonium bromide (hereinafter, T
100 ° C. after adding 0.1 part to the contents
And reacted under an air atmosphere for 2.0 hours (hereinafter referred to as esterification reaction time) to obtain methacryl syrup. This was designated as methacryl syrup (2). Solids concentration 55%, weight average molecular weight 17000, viscosity 1
It was 2.0 Pa · s. After dissolving the resin composition for fixing agent for bolt fixing in the same amount of acetone,
Separation was carried out by dropping to 0 times the volume of methanol, followed by filtration, drying and fractionation. The separated polymer was subjected to a resonance frequency of 400 MHz, a solvent of chloroform-d, a reference substance of tetramethylsilane, and a cumulative number of 10 using a nuclear magnetic resonance apparatus UNITY-plus (trade name, manufactured by Varian Japan).
Proton nuclear magnetic resonance analysis was performed under the same measurement conditions, and it was confirmed that a double bond or a hydroxyl group had been introduced into the polymer.
Hereinafter, polymers of other examples were similarly confirmed.

Synthesis Example 3 Synthesis of methacrylic syrup (3) 96.5 parts of t-butyl methacrylate and 3.5 parts of methacrylic acid were charged into a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe and a stirrer. The reaction was carried out in the same manner as in Synthesis Example 2.
The obtained methacryl syrup was designated as methacryl syrup (3). The solid concentration was 57%, the weight average molecular weight was 15,000, and the viscosity was 20.0 Pa · s.

Examples 1 to 7 and Comparative Examples 1 and 2 The components shown in Table 1 were blended in various amounts to obtain a resin composition for fixing a fixing agent for bolts containing an aggregate and a hardener. This was applied to the dried and cleaned concrete under a temperature condition of -5 ° C and cured. The Kenken-type adhesive strength was measured, and the adhesive strength was measured. In all of Examples 1 to 7, it was found that good workability and physical properties were obtained as a resin composition for a fixing agent for bolts in which an aggregate, a curing agent, and the like were blended, and that the resin composition could be used well.

Further, as Examples 1 to 7, the outer diameter was 5 mm,
30mm calcium sulfate in a 70mm long glass inner container
2 parts by weight of a curing agent diluted to a concentration of 0.1% by weight are sealed and stored in a glass container having an outer diameter of 13 mm and a length of 85 mm.
Further, 80 parts by weight of a natural silica sand having a diameter of 2 mm and 20 parts by weight of the resin composition for a fixing agent for bolts of Examples 1 to 7 were filled.
The adhesive was adjusted by sealing with a nylon cap, and the inside diameter was 14.5 mm in concrete having a compressive strength of 21 N / m ² .
After making a hole of 100 mm in length and inserting each of the above-mentioned adhesives into the hole, a M12 full screw SC with a 45 degree cut at the tip is made.
An M435 bolt was attached to the electric drill, and inserted into the hole bottom while applying a rotational impact. After curing at 25 ° C. for 30 minutes, all the fixing agents for fixing bolts were in a good fixed state. Table 1 shows the results of the physical properties of the fixing agent for bolt fixing. In addition, various test methods of the fixing agent for bolt fixing in the following Examples and Comparative Examples are as follows.

[Viscosity] Among the components shown in Table 1, the viscosities of all the compounds except for the aggregate were measured at 25 ° C. using a B-type viscometer.

[Curing time at −5 ° C.] The fixing agent resin composition for fixing bolts is mixed with a curing agent under application conditions of −5 ° C., filled into a test tube having a diameter of 18 mm to a height of 100 mm, and the curing agent is added. The time from mixing to loss of fluidity was measured.

[Adhesive Strength] A Kenken-type adhesive strength was measured for the fixing agent for bolt fixing (four days after the application), which was applied under the above-mentioned application condition of −5 ° C.

Example 8 To the composition of Example 5, 1 part by weight of a silane coupling agent γ-methacryloxypropyltrimethoxysilane was added to obtain a resin composition for a fixing agent for fixing bolts. As a result of testing the physical properties in the same manner as in Examples 1 to 7, it was found that they could be used well as in Examples 1 to 7. Various test results were a viscosity of 1500 mPa · s, a curing time at −5 ° C. for 14 minutes, and an adhesive strength of 250 N / cm ² .

[0082]

[Table 1]

Table 1 is described below. SUMIPEX LG-6A (trade name, manufactured by Sumitomo Chemical Co., Ltd.): polymethyl methacrylate, average weight molecular weight 60000 HEMA: 2-hydroxyethyl methacrylate MHMA: methyl 2- (hydroxymethyl) acrylate EGDMA: ethylene glycol dimethacrylate 4EGDMA: tetraethylene Glycol dimethacrylate 1,9 NDDMA: 1,9-nonanediol dimethacrylate Aggregate: Mixed silica sand (3/5/5/8 / silica powder = 30 /
30/30/10 parts by weight) The silica sand and silica powder are manufactured by Sanei Kosan Co., Ltd. DM-PT: N, N-dimethyl-p-toluidine Niper FF (trade name, manufactured by NOF Corporation): 50% benzoyl peroxide

[0084]

The fixing agent for fixing bolts according to the present invention has the above-mentioned constitution, so that it has excellent fast-curing properties and low-temperature curing properties, as well as excellent basic properties such as alkali resistance, corrosion resistance and weather resistance. Because of its excellent fixing force, it can be suitably applied to construction, repair, and reinforcement of various concrete structures such as buildings and expressways.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Tomohiro Mizutani 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd. F-term (reference) 2E125 AA76 AF01 AG10 AG13 BA13 BB08 BD01 BE07 BE08 BF01 CA86 EA00 4J040 FA081 FA082 FA151 FA152 FA231 FA232 JB02 KA16 KA17 KA42 LA01 LA05 LA06 LA07 MA02 NA12

Claims (2)

[Claims] 1. A (meth) acrylic monomer having a (meth) acryloyl group in one molecule and also having a carbon-carbon double bond other than a carbon-carbon double bond derived from the (meth) acryloyl group. A fixing agent for bolts comprising (A) and a (meth) acrylic polymer (B), wherein the (meth) acrylic monomer (A) and the (meth) acrylic polymer The weight ratio with (B) is 5/95 to 90
The fixing agent for fixing bolts, which is / 10. 2. The (meth) acrylic polymer (B)
Is a (meth) acrylic polymer having a plurality of polymerizable double bonds in a molecule thereof.