JPH0270715A - High-strength and corrosion-resistant securing material for fixing bolt - Google Patents

Abstract

PURPOSE:To obtain the title securing material excellent in initial securing power and less deteriorated with the lapse of time by holding, in a crushable vessel, a resin which comprises a specific modified bisphenol unsaturated polyester resin as a main component and is liquid at room temperature and a curing agent isolated from the resin. CONSTITUTION:In a securing material for fixing a bolt comprising a crushable vessel, a resin which is contained in the vessel and is liquid at room temperature and a curing agent which is contained in the vessel but is isolated from the resin, the main component of the resin is a bisphenol unsaturated polyester resin modified with the glycidyl ester of an alpha, beta-unsaturated acid. This securing material is excellent both in initial securing power to a matrix and a alkali resistance, and since a resin having a securing power less deteriorated with the lapse of time is used, the reliability of an anchor bolt can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a fixing material used for fixing an anchor bolt in a hole in a concrete base, rock mass, etc. (hereinafter referred to as base material).

[Prior art and its problems] Conventionally, the method for fixing an anchor bolt in a hole in a base material is to drill a hole in the base material, load a fixing material into the hole, and then insert the anchor bolt using a hammer drill or the like. The anchor bolt is inserted into the anchor bolt while applying a rotational blow, and the anchor bolt is thereby crushed, the liquid resin inside the anchor material container and the hardening agent are mixed, the resin component is hardened, and the anchor bolt is fixed to the base material. There are known ways to do this.

The fixing material used in this method is to fill a glass container with a mixture of a liquid resin mainly composed of unsaturated polyester resin and aggregate, and to fill the container with an organic peroxide such as benzoyl peroxide. A hardening agent whose main component is stored in a thin glass tube so as not to come into contact with the liquid resin.
A closed bottle (Japanese Patent Publication No. 38-12863) is known.

In conventional technology, when a phthalic acid-based unsaturated polyester resin is used, the cured resin is gradually attacked by the alkaline components contained in concrete due to poor alkali resistance, resulting in a decrease in bonding strength over time. There was a downside to this. On the other hand, when bisphenol-based unsaturated polyester resin is used to improve alkali resistance, the alkali resistance is improved due to the low concentration of ester groups in the resin, and the above-mentioned deterioration of bonding strength over time is largely avoided. However, it has the disadvantage that the initial adhesion force with the base material is not sufficient.

[Object of the invention] The present invention has been made in view of the above problems, and
The purpose is to solve the problems of conventional unsaturated polyester resins, to find a resin that has excellent initial fixing strength and less deterioration of fixing force over time, and to provide a high-strength, corrosion-resistant fixing material for bolt fixing.

[Configuration and Effects of the Invention] The present invention provides a bolt fixing system comprising a crushable container, a resin that is liquid at room temperature stored in the container, and a hardening agent stored in the container separately from the resin. This is a fixing material for use in adhesives, in which a resin obtained by modifying a bisphenol-based unsaturated polyester resin with a glycidyl ester of an α,β-unsaturated acid is used instead of a conventional unsaturated polyester resin as the main component of the fixing resin. This is a fastening material for bolt fixing that is characterized by excellent initial fastening strength and little deterioration of fastening strength over time.

The structure of the adhesive material in the present invention is a “container” that can be crushed.
That is, one that does not shatter during transportation or storage but is easily shattered into small pieces when inserting the anchor bolt, the liquid "resin" contained in the container, and the resin contained in the container. For example, a liquid resin and, if necessary, aggregate are stored in a container made of glass, ceramics, or synthetic resin, and further, in this container (outer container), Examples include those in which a thin container (inner container) made of glass or ceramics is sealed with a hardening agent, and the container is closed. In addition, in particular, a mixture of liquid resin and aggregate and a curing agent are separately sealed in a cylindrical drug package (inner container) made of a thin synthetic resin film that can be crushed and whose interior is divided into two chambers with a partition wall. Furthermore, the fixing material in which the medicine package is housed in an easily shatterable container (outer container) made of glass, ceramics, etc. can be efficiently produced in accordance with various usage conditions, and This is a preferred example because it has excellent workability and handling.

The resin of the present invention is a bisphenol-based unsaturated polyester resin modified with glycidyl ester of α, β-unsaturated acid, and is modified with glycidyl ester of α, β-unsaturated acid such as maleic anhydride and fumaric acid. , or a portion thereof, if necessary, phthalic anhydride.

Those substituted with saturated polybasic acids such as isophthalic acid, terephthalic acid, adipic acid, and het acid, and if necessary, some of them are substituted with ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, etc. α is a bisphenol-based unsaturated polyester resin obtained by polycondensation reaction of bisphenol A substituted with a polyhydric alcohol and an ethylene oxide or propylene oxide adduct.

It is modified with glycidyl ester of β-unsaturated acid. Here, the glycidyl ester of an α,β-unsaturated acid is a compound represented by the general formula (in the formula, R is a hydrogen atom or a lower alkyl group), and specifically, glycidyl acrylate, glycidyl methacrylate, , glycidyl acrylate, etc., and glycidyl methacrylate is preferably used.

Since the resin in the present invention is mainly composed of bisphenol-based unsaturated polyester resin, it has a low ester group concentration and is less susceptible to hydrolysis reactions than conventional phthalic acid-based resins. Resin has excellent corrosion resistance, especially alkali resistance, which is important when anchor bolts are fixed to concrete base material. However, conventional bisphenol-based resins lack visibility, and although they have excellent alkali resistance, they do not have sufficient initial adhesion to the base material. It was discovered that by modifying polyester resin with glycidyl ester of α,β-unsaturated acid, the initial adhesion strength increased by a factor of 11, and the high corrosion resistance characteristic of bisphenol resins was hardly impaired. .

At this time, the main component bisphenol resin is
α is a mixture of an adduct of bisphenol A with ethylene oxide or propylene oxide and a polyhydric alcohol such as propylene glycol.

It is preferable to use a resin obtained by reacting with a β-unsaturated dibasic acid, and the amount of glycidyl ester of an α,β-unsaturated acid to be added is based on 100 parts by weight of the above-mentioned main component bisphenol resin. In contrast, a range of 1 to 50 parts by weight is appropriate, and a range of 6 to 25 parts by weight is particularly preferred.

The resin in the present invention is a resin that is liquid at room temperature, and the modified unsaturated polyester resin is styrene.

The viscosity is adjusted to any desired value by adding reactive monomers such as chlorostyrene, divinylbenzene, diallyl phthalate, acrylic acid derivatives, and methacrylic acid derivatives.
If necessary, thixotropy may be imparted by adding an additive such as amorphous fine powder silica.

The curing agent used in the present invention is an organic peroxide, and examples thereof include benzoyl peroxide, cyclohexanone peroxide, dicumyl peroxide, lauroyl peroxide, and methyl ethyl ketone peroxide.

If necessary, a suitable curing accelerator may be added to the resin of the present invention, depending on the type of curing agent selected from among tertiary amines such as dimethylaniline and diethylaniline, and cobalt naphthenate. can be used.

Furthermore, the fixing material of the present invention includes the above liquid resin.

In addition to curing agents and curing accelerators, aggregate or/
and fillers can be added, these are on the resin side,
It may be added to either side of the curing agent.

Examples of the aggregate include, but are not limited to, natural crushed stone, magnesia clinker, and glass peas.

Artificial aggregates such as ceramic balls can be used, but it is preferable to use spherical artificial aggregates such as glass beads and ceramic balls because they improve productivity and reduce resistance when driving anchor bolts. .

Fillers that can be additionally added to the present invention include, but are not limited to, calcium carbonate, aluminum hydroxide,
One or more types of talc, fine glass peas, etc. can be used.

The composition of the high-strength, corrosion-resistant bolt fixing material of the present invention can be selected from a wide range depending on the purpose and application. 1 to 20 parts by weight of a curing agent and 0.01 to 0.01 parts by weight of a curing accelerator to 100 parts by weight of bisphenol unsaturated polyester resin modified with glycidyl ester of an α,β-unsaturated acid.
5 parts by weight, O to 600 parts by weight of aggregate and/or filler.

[Example] The present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 (Preparation of Resin A) Bisphenol resin 100 consisting of 55 mol% propylene oxide 2 mol adduct of bisphenol A, 50 mol% propylene glycol, and 100 mol% fumaric acid.
@Styrene 35v, a modified bisphenol resin with 13 parts by weight of glycidyl methacrylate added to the end of the weight part
A t% resin solution was prepared.

Further, the following additives were mixed with 100 parts by weight of the above 35 wt% styrene resin solution to prepare resin A.

1) Inorganic thixotropy 2.0 parts by weight 2) Thixotropy aid
0.2 NoI3) Accelerator (amine type)
2.0 ll4) Stabilizer 0.19 7
1 Comparative Example 1 <Preparation of Resin B) Resin B was prepared in the same manner as in Example 1 except that modification with glycidyl methacrylate was not performed.

Comparative Example 2 (Preparation of Resin C) Propylene glycol 106 mol%, phthalic anhydride 30
A 35 wt % styrene resin solution of an ortho resin consisting of mol % and maleic anhydride 70 mol % was prepared.

Furthermore, Example 1 was added to the styrene 35 wt% resin liquid.
Resin C was prepared by mixing various additives in the same formulation.

Example 2 According to the method described in Japanese Patent Publication No. 56-48444, a cylindrical container with a diameter of 14 mm and whose interior was divided into two chambers by a partition wall was continuously formed using a polyethylene terephthalate strip thin film with a wall thickness of 36 μl. , and in one chamber there were 8.5 g of resin A prepared in Example 1 and silane-coated glass beads manufactured by Toshiba Ballotini@, trade name GB501.
MC (particle size: between 0.84 and 1.19) 17.0tr
and in the other chamber a paste of benzoyl peroxide diluted to a concentration of 40x with dibutyl phthalate 1.04. and fine-grained calcium carbonate 1°04 were sealed, and both ends were sealed with a fastening ring to make a cylindrical drug package with a length of 110 mm, and this drug package was further sealed with an outer diameter of 16.5 mm and an inner diameter of 14°. The samples were placed in a brown glass container measuring 9 parts and 120 parts long, and the mouth was closed with a polyethylene cap to prepare a fixing material.

Next, the compressive strength is 300! Drill a hole with an inner diameter of 19 mm and a depth of 1301 mm in the r/cd concrete, insert the fixing material described in E into the hole, and then use an electric hammer drill to install a fully threaded bolt (M 16 x 180 mm) with a 45 degree diagonal cut at the tip. Attach it to the hole and drive to the bottom of the hole while applying a rotational blow. 2 at room temperature to prevent the bolt from moving.
After curing for 0 hours, the pull-out load was measured and the results shown in Table 1 were obtained.

Example 3 Resin A, glass beads, curing agent, W! A fixing material was prepared in the same manner as in Example 2, except that the amount of one grain of calcium carbonate was reduced to 85% of the amount described in Example 2, and casting and pulling tests were performed. We obtained the results shown below.

The results shown in Table 1 were obtained.

Table 1 (Unit: Ton) Comparative Example 3 The adhesive material was prepared, placed, and placed in the same manner as in Example 2, except that the resin in Example 2 was changed from Resin A to Resin B prepared in Comparative Example 1. A pullout test was conducted and the results shown in Table 1 were obtained.

Comparative Example 4 In the same manner as in Example 2, except that the resin in Example 2 was changed from Resin A to Resin C prepared in Comparative Example 2,
Example 4: Preparation of adhesive material, casting and pulling tests were carried out. Comparative example 5,
6 (Alkali resistance test) For each of resins A, B, and C, 8.0 g of resin, 0 curing agent
．． After stirring and mixing 98g of fine calcium carbonate and 0.98f of calcium carbonate, immediately pour it into a casting plate to form a mold with a length of 75m+ and a medium size of 25+.
A test piece with a thickness of 3fi was obtained. These are JISK69
19 (Liquid unsaturated polyester resin for reinforced plastics) alkali resistance test method, 10% NaOH
It was boiled in an aqueous solution at 100±1° C. for 100 hrs, washed with water, and dried for 100±1° C. for 2 hrs, and the weight change rate 1 dimensional change rate was determined. The results are shown in Table-2.

From the results in Tables 1 and 2, the resin of the present invention has superior initial adhesion strength to the base material compared to conventional unsaturated polyester resins, and also has excellent alkali resistance due to its non-bisphenol base, which is said to have high corrosion resistance. It is clear that there is almost no difference from saturated polyester resin.

Table 2 [Effects of the Invention] As described above, the bolting fixing material of the present invention is a high-strength, corrosion-resistant bolting fixing material that has excellent initial bonding strength with the base material and zero deviation in alkali resistance. This provides the excellent effect of improving the reliability of anchor bolts for owners, contractors, etc.

Claims (1)

[Claims] 1. A fixing material for bolt fixing consisting of a container that can be crushed, a resin that is liquid at room temperature stored in the container, and a hardening agent stored in the container separated from the resin. , the main component of the resin is bisphenol-based unsaturated polyester resin.
A high-strength, corrosion-resistant fixing material for bolt fixing, characterized in that it is made of a material modified with glycidyl ester of β-unsaturated acid. 2. A resin and a curing agent are each isolated and sealed in a cylindrical drug package made of a thin synthetic resin film that can be crushed and whose interior is divided into two chambers with a partition wall, and the drug package is further placed in a container that can be crushed. The high-strength, corrosion-resistant bolt fixing material according to claim 1, wherein the fastening material is housed in a bolt. 3. The high-strength, corrosion-resistant bolt fixing material according to claim 1 or 2, wherein the hardening agent is an organic peroxide.