JPH03227389A - Binder for fixing bolt - Google Patents

Abstract

PURPOSE:To obtain the subject binder for fixing an anchor bolt to a concrete, a rock wall, etc., having an improved initial adhesion and an improved alkaline resistance by blending a resin composition having a specified composition, a crosslinkable monomer and a curing agent. CONSTITUTION:An objective binder containing (A) a resin component obtained by blending 100 pts.wt. unsaturated polyester resin (preferably 2000-3500 molecular weight) containing a bisphenol A-alkylene oxide adduct as its polyvalent alcohol component with 5-80 pts.wt., preferably 20-80 pts.wt. epoxyacrylate resin (preferably 500-800 molecular weight), (B) a crosslinkable monomer (e.g. styrene or vinyl acetate) and (C) a curing agent (e.g. methyl ethyl ketone peroxide).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a bolt fixing agent for fixing anchor bolts to concrete, rock, etc.

[Prior art] Conventionally, an anchor bolt is fixed by drilling a hole in a base material such as concrete, filling the hole with a fixing agent contained in a container, and applying a rotational impact to the anchor bolt connected with a hammer drill etc. A known method is to insert an anchor bolt, crush the container, harden the adhesive contained in the container, and fix the anchor bolt.

The fixing agent used in this method is to fill a glass container with a resin whose main component is liquid unsaturated polyester resin, and then fill the container with a hardening agent whose main component is an organic peroxide such as benzoyl peroxide. A fixing agent is known in which a sealing agent is housed in a glass tube.

[Problem to be solved by the invention] Unsaturated polyester resin has a moderate viscosity and is excellent in handling, and exhibits considerable adhesion strength. It has been put into practical use because specific performance can be obtained by selecting it, but it is not possible to simultaneously satisfy initial adhesion strength and alkali resistance, and there is room for improvement.

Insufficient alkali resistance means that the cured resin at the anchor bolt fixation part is eroded by the alkaline components contained in the concrete, and the fixation strength gradually decreases over time after the anchor bolt is installed. Insufficient initial fixing force is a drawback in that it takes a long time to obtain sufficient bolt fixing force, resulting in poor workability.

Unsuitable Means to Solve Problem U] As a result of extensive research in order to solve the above problems, the present inventors found that ``(1) bisphenol A, as a polyhydric alcohol component;
A bolt comprising a resin component containing 5 to 80 parts by weight of an epoxy acrylate resin to 100 parts by weight of an unsaturated polyester resin having an alkylene oxide adduct, (2) a crosslinking monomer, and (3) a curing agent. The inventors discovered that a "fixing agent" could achieve the purpose and completed the present invention.

Hereinafter, the fixing agent of the present invention will be specifically explained.

The resin component (1) in the present invention is a mixture of a specific unsaturated polyester resin and an epoxy acrylate resin.

The unsaturated polyester resin is produced by condensing a polybasic acid component, a polyhydric alcohol component, and if necessary, a polyhydric alcohol allyl ether component when imparting air-drying properties, or in order to obtain the effects of the present invention, The point is that a bisphenol A/alkylene oxide adduct is used as the polyhydric alcohol component. The alkylene oxide is ethylene oxide or propylene oxide, and the bisphenol A/ethylene oxide adduct is a compound represented by the following general formula.

(Here, n and m are both integers of 1 or more.) The upper limits of n and m are not particularly limited, but practically, 1≦n.

Adducts with m≦3 are preferably used.

In the present invention, the above adduct may be all of the polyhydric alcohol component, but in order to obtain the effects of the present invention, the proportion of the adduct in the total amount of the polyhydric alcohol component is 10 to 8.
It is necessary that the amount is 0 mol%, preferably 30 to 60 mol%.

In addition to the adduct, polyhydric alcohol components include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1.3-butylene glycol, 2.3-butylene glycol, 1.6-hexanediol, 2- ethyl-1,
3 hexanediol, 2,2,4-trimethyl-1,3
-bentanediol, neopentyl glycol, trimethylolethane, trimethylolpropane, glycerin, pentaerythritol and the like.

Next, as the polybasic acid component in the present invention, unsaturated polybasic acids such as maleic anhydride, maleic acid, itaconic anhydride, itaconic acid, and fumaric acid are used.

Along with these unsaturated polybasic acids, phthalic anhydride, phthalic acid, terephthalic acid, -isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, het acid, citraconic acid, adipic acid, sebacic acid It is also possible to use a saturated polybasic acid such as saturated polybasic acid.

Furthermore, in the present invention, when it is necessary to impart air drying properties to the resulting unsaturated polyester resin, a polyhydric alcohol allyl ether component is used. Polyhydric alcohol allyl ether components include pentaerythritol triallyl ether, pentaerythritol diallyl ether, trimethylolpropane diallyl ether, trimethylolpropane monoallyl ether, trimethylolethane diallyl ether, trimethylolethane monoallyl ether, glycerin diallyl ether, Glycerin monoallyl ether, tetramethylol cyclohexanol diallyl monocrotyl ether, hexamethylol melamine diallyl diallyl dicrotyl ether, hexanetriol diallyl ether, pentaerythritol diallyl crotyl ether, tetramethylol soclohexanol triallyl ether, tetramethylol cyclohexanone diallyl Examples include allyl ethers having at least one hydroxyl group in the molecule, such as ether and hexamethylolmelamine tetraallyl ether. Dicyclopentadiene can also be used for the same purpose if necessary.

The polyhydric alcohol allyl ether component is desirably used in an allyl group of 0.05 mole or more, particularly 02 mole or more, per mole of the polybasic acid component; if it is less than 0.05 mole, air drying properties are insufficient. The upper limit is possible up to the reaction limit.

The desired unsaturated polyester resin can be obtained by reacting each of the above components at a temperature of about 150 to 250° C. in an inert gas atmosphere according to a conventional method. In the present invention, molecules j11500 to 4000, preferably 20
00-3500 unsaturated polyester resins are preferably used.

Next, the epoxy acrylate resin used in the present invention is a resin obtained by reacting the epoxy group of hisphenol A epoxy resin with acrylic acid or methacrylic acid, and has the general formula (however, R
is hydrogen or a methyl group, n is an integer of 1 to 3).

Those having a molecular weight of 1000 or less, preferably 500 to 800 are preferably used.

(1) The mixing ratio of air-drying unsaturated polyester resin and epoxy acrylate resin in the component should be 5 to 80 parts by weight, preferably 20 to 80 parts by weight, per 100 parts by weight of the former.Epoxy acrylate resin should be 5 parts by weight.
If the amount is less than 80 parts by weight, no effect of improving initial fixation, low-temperature curability or alkali resistance will be observed, while if the amount is 80 parts by weight or more, the initial fixation will be poor.

(2) Examples of crosslinking monomers include styrene, vinyltoluene, monochlorostyrene, α-methylstyrene, noacyl phthalate, triallyl annulate, and acrylic acid! Ester, methacrylic acid ester, glycine methacrylate ÷ persyl methacrylate, 2-hydroxy〉1 dacrylate glycine ether, hinyl acetate, vinyl chloride, methylenebisacrylamide, divinylbenzene, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, diethylene glycol diacrylate , dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, 1,6-hexanediol diacrylate, vinylcyclohexane monooxide, tung oil, linseed oil, soybean oil, cottonseed oil, safflower oil, palm Examples include known crosslinking monomers for unsaturated polyesters such as oil.

(3) As the curing agent, methyl ethyl ketone peroxide, nclohexanone peroxide, cumene hydroperoxide, benzoyl peroxide, dicumyl peroxide, t-butyl perbenzoate, etc. are used.

Moreover, aggregate or filler can be mixed into the fixing agent of the present invention, if necessary.

The aggregate is not particularly limited, but natural crushed stone or artificial stone such as magnene alinker can be used.

Fillers include, but are not limited to, calcium carbonate,
Calcium sulfate, silicic anhydride, clay, etc. can be used.

Further, a curing accelerator can be used to accelerate curing of the resin. However, in this case, the curing accelerator must be separated from the curing agent. Examples of hardening accelerators include amines such as dimethylaniline, noethylaniline, and dimethylparatoluidine, metal soaps such as cobalt naphthenate, cobalt octoate, manganese naphthenate, and calcium naphthenate, vanadyl acetylacetonate, and iron acetylacetonate. It is a chelate compound such as nate.

Furthermore, a polymerization inhibitor such as hydroquinone or naphthoquinone may be added to maintain the stability of the resin.

In addition, pigments (titanium white, cyanine blue, cream yellow, watching red, hengara,
Carbon black, aniline black, manganese blue, iron black, ultramarine blue, Hansa red, chrome yellow, chrome green, etc.), abrasives (zinc stearate, fine talc, etc.), leveling agents (silicone, quinoa, methanol, ethanol, butanol,
acetone, methyl isobutyl ketone, methyl ethyl ketone, cellosolves, noacetone alcohol, etc.), thermoplastic resins such as trocellulose, vinyl chloride-vinyl acetate copolymer, vinyl acetate resin, acrylic resin, butylated melamine, butylated urea, etc.) , can also be blended.

The composition of the adhesive for bolt fixing of the present invention varies widely depending on the application, but it is usually 30 to 50 parts by weight of the crosslinking monomer (2), preferably 35 parts by weight, based on 100 parts by weight of the resin (1). 45 parts by weight, (3) 0.5 to 1 parts by weight of the curing agent, preferably 1 to Y parts by weight, and 0 to 500 parts by weight of the aggregate or filler.

The shape of the fixing agent of the present invention includes a container, (1) a resin housed in the container, (2) a crosslinkable monomer, and the (1) and (2)
and (3) a curing agent, which is isolated from and housed in the container.

The configuration of the fixing agent can be designed over a wide range and is not particularly limited, but for example, it may consist of a crushable outer container and a crushable inner container, and (3) an inner container sealed with a hardening agent; 1) A resin and (2) a crosslinkable monomer and, if necessary, aggregates housed in an outer container and sealed, or an inner container in which (1) a resin and (2) a crosslinkable monomer are sealed, and (3)
) Examples include those in which a curing agent and, if necessary, aggregate are housed in an outer container and sealed.

However, the aggregate may be mixed with either the resin or the curing agent. Furthermore, as another configuration, a container may contain (+) a resin, (2) a crosslinking monomer, and, if necessary, aggregate, and be sealed, and (3) a curing agent may be applied to the outer wall of the container.

Containers that can be used in the present invention are containers that do not break during transportation or storage, are easily broken into pieces when an anchor bolt is inserted, and are made of glass, ceramics, synthetic resin, or synthetic resin film.

[Function] In the present invention, by combining a specific unsaturated polyester resin containing an alkylene oxide adduct in bisphael A as a condensation component and an epoxy acrylate resin, a bolt fixing fastener with significantly improved initial fixing properties and alkali resistance is produced. agent is obtained.

[Example] Next, the present invention will be explained in more detail by giving examples.

Production of unsaturated polyester resin [Resin I] Maleic anhydride 1 in a flask equipped with a stirrer and reflux condenser
mol, 0.55 mol of ethylene glycol and bisphenol A/propylene oxide adduct (n=1 ml
) 0.55 mol and acid value 20 m9K at 2oo℃
The reaction was continued until OH/9.

Then, styrene monomer was added while cooling to obtain a resin having a resin composition molar ratio of maleic anhydride/ethylene glycol/adduct = Ilo of 5110.51. The molecular weight was 2490.

Similarly, the following unsaturated polyester resin was obtained.

[Resin ■]

The composition molar ratio is maleic anhydride/propylene glycol/
Bisphenol A/propylene oxide adduct (n-
1, m=1) -1,010,710,45, an unsaturated polyester resin with a molecular weight of 24oo0 [Resin ■
] The composition molar ratio is maleic anhydride/ethylene glycol/bisphenol A/propylene oxide (n-1, m2
) Adduct - Unsaturated polyester resin consisting of 1,010,5510,,70 with a molecular weight of 25500 [Resin IV]
(Comparative Example) An epoxy acrylate resin having a composition molar ratio of anhydrous maleic to 1 propylene glycator resin and a molecular weight of 2100° or less was prepared.

[Resin A]

Bisphenol A diglycidyl ether diacrylate (n = 1. molecular weight 520) [Resin B] Bisphenol A diglycidyl ether dimethanorelay (n = 1. molecular weight 560) [Resin C] Bisphenol A diglycidyl ether diacrylate (n = 2 .molecular weight: 800) Examples 1 to 7, Comparative Examples 1 to 4 Comparisons were made between Examples comprising the formulations of the present invention and their comparative examples using the resins produced above.

Initial fixation strength and maximum fixation strength A hardening agent diluted with calcium sulfate to a concentration of 30% was sealed in a glass inner container with an outer diameter of 5 mm and a length of 70 mm, and the hardening agent was placed in a glass container with an outer diameter of 13 mm and a length of 851 mm. Further, natural silica sand with a diameter of 2 mm, an unsaturated polyester resin, an epoxy acrylate resin, or a mixture thereof, a crosslinking monomer, and dimethylaniline were filled, and the mixture was sealed with a nylon cap to prepare a fixing agent. In Examples 1 to 7, the unsaturated polyester resin and epoxy acrylate resin were blended within the scope of the present invention, and in Control Examples 1 to 4, the blends were blended outside the range.

Next, a hole with an inner diameter of 14.5 mm and a length of 100 mm was made in the concrete with a compressive strength of 210 kg/cm. After inserting the above-mentioned adhesive into the hole, an M12 full screw S 0M435 bolt with a 45 degree cut at the tip was inserted. was attached to an electric drill and inserted to the bottom of the hole without applying any rotational impact.

Next, as a test of initial adhesion strength, the pull-out load after curing for 30 minutes was measured at room temperature. In addition, as a test of the adhesion strength after sufficient curing, the pull-out load after curing for one day was measured. The results are shown in Table 1.

The measurement method is as shown in Figure 1, where a tension bar (high tensile strength steel rod) is attached to the head of bolt l fixed via coupler 2.
3, attach the load cell 4, ram 5, and dial gauge 7, then increase the oil pressure of the hydraulic pump 6, and fix the ram 5.
The load cell 4 detects the pullout load on the bolt l via the tension bar 3 and displays it on the digital measuring device 8.

From the results of this test, regarding the initial adhesion strength of the adhesion agent, all the pull-out strengths after 30 minutes curing in Examples 1 to 7 were lower than that of the control example.
It is nearly twice as strong as the strength of the unsaturated polyester resin alone, and is almost equivalent to the epoxy acrylate resin of Control Example 2, which clearly shows that the blending effect of the unsaturated polyester resin and the epoxy acrylate resin is effective.

Regarding the adhesion strength after sufficient curing, the maximum pull-out strength of Examples 1 to 7 is higher than that of the unsaturated polyester resin alone in Control Example 1 and the strength of the epoxy acrylate resin alone in Control Example 2. In addition, the initial stiffness of the anchor calculated from the load and deformation during pull-out is much higher than that of the unsaturated polyester resin in Examples 1 to 7 of Control Example I. It is clear that a blend of resins in an appropriate range is far superior to using each resin alone. In addition, orthophthalic blended resin, which is said to have poor alkali resistance, as in Comparative Example 4, also showed good performance.

Example 8, Comparative Examples 5 and 6 Low-temperature fixing strength
, 2 was used to confirm the pull-out strength under the above construction specifications in an environment of -5°C. The curing time is 1 day. The results were as follows.

From this test result, the blended resin of Example 8
It can be seen that this is far superior to the unsaturated polyester resin of Control Example 5 or the epoxy acrylate resin of Control Example 6. Moreover, although this result shows a similar tendency to the result of curing for one day at room temperature, there is a larger difference.

Examples 9 to 13, Comparative Examples 7 to 10 The cured resin of the adhesive embedded in the alkali-resistant concrete was
It is expected that the physical properties will deteriorate over time due to the strong alkalinity of concrete, so Examples 3 to 7
For the resins used in Control Examples 1 to 4, 5% of the curing agent was added.
In addition, a cured molded product of 10×70×3++un was prepared and immersed in a 10% aqueous sodium hydroxide solution at 100° C. for 100 hours, and the change in gravity was measured. The results are shown in the table.

From the results of this test, the alkali resistance of the cured resin products of the blended resins of Examples 9 to I3, which are within the scope of the present invention, was comparable to that of the bisphenol-based unsaturated polyester resin of Control Example 7. It can be seen that this resin is superior to the epoxy acrylate resin of Control Example 8. In addition, the orthophthalic unsaturated polyester resin blend of Control Example 4, which exhibited relatively good performance in terms of adhesion, was significantly inferior in alkali resistance like Control Example 1O.
There are concerns about its long-term use as an anchor.

[Effects] In the present invention, by using a polyester resin containing a bisphenol A/alkylene oxide adduct as a condensation component and an epoxy acrylate resin, it is possible to produce a fixing agent with improved initial fixing strength and alkali resistance.

[Brief explanation of drawings]

FIG. 1 is an explanatory diagram of a bolt extraction load measuring device. 1...Fixed bolt, 2...Coupler 3...
...Tension bar, 4...Load cell, 5...
・Ram, 6...Hydraulic pump, 7...Dial gain, 8...Digital measuring instrument. No. 1 (!1 Procedural amendment bag Eyo March 22, 1991 2, Title of invention: Fixing agent for bolt fixation Relationship with the case Patent applicant address: 9-6 Nozaki-cho, Kita-ku, Osaka-shi (Postal code 53o)
Name (410) Representative of Nippon Gosei Chemical Industry Co., Ltd.
Masa Ohashi Amendment subject 5, content of amendment (1) "Bisphenol A/ethylene oxide adduct" on page 4, line 15 of the specification has been changed to "
Bisphenol A/propylene oxide adduct.''

Claims (1)

[Claims] 1. (1) Bisphenol A as a polyhydric alcohol component
・A resin component containing 5 to 80 parts by weight of an epoxy acrylate resin to 100 parts by weight of an unsaturated polyester resin having an alkylene oxide adduct, (2) a crosslinking monomer, and (3) a curing agent. A fixing agent for bolt fixing 2, a container, (1) a resin component housed in the container, and (2)
2. The adhesive for bolt fixing according to claim 1, comprising:) a crosslinkable monomer; and (3) a curing agent, which is separated from said (1) and (2) and contained in said container.