JP2743282B2 - Composition for resin concrete - Google Patents

Description

The present invention relates to a resin concrete composition comprising at least one methacrylate monomer, a polybutadiene derivative, a resin solution comprising a thermoplastic resin and a plasticizer, and an aggregate. In particular, the present invention relates to a composition which can be formed into a resin concrete having low shrinkage and excellent toughness.

[Conventional technology]

As concrete using a two-component reaction-curable resin, epoxy resin, polyester resin, (meth) acrylic resin, polyurethane resin, and the like are currently known.

These resin concretes are faster setting than portland cement concrete, and have excellent strength, abrasion resistance, chemical resistance, etc., and are used as indoor floor coatings, road pavement materials, or various molded products. .

In particular, (meth) acrylic resin-based concrete compositions have recently been used in various applications because of their low viscosity, low-temperature curability, and rapid curability.

However, the conventionally developed (meth) acrylic resin-based concrete composition is mainly composed of methyl methacrylate, and the cured product can be a cured product having high strength, but its impact resistance is weak, There is a problem such as a large curing shrinkage, and when these are used for road pavement materials, problems such as cracks occurring in the resin concrete and peeling from the ground are likely to occur.

The present invention provides a low-shrinkage and tough resin concrete in which these disadvantages are improved.

[Problems to be solved by the invention]

An object of the present invention is to provide a composition capable of forming a resin concrete having low shrinkage and toughness.

[Means for solving the problem]

The gist of the present invention is to obtain a resin concrete composition having low shrinkage and toughness by mixing a resin composed of the following [I] and an aggregate at a compounding ratio of [II].

[I] Resin composition (1) At least one selected from alkyl methacrylates having 1 to 12 carbon atoms in the alkyl group.
To 84% by weight (2) 1,2-polybutadiene derivative 6 to 30% by weight (3) Thermoplastic polymer soluble or swellable in (1) alkyl methacrylate 10 to 35% by weight (4) Plasticizer 0 -15% by weight The alkyl methacrylate (1) used in the present invention must be contained in the resin composition [I] in a proportion of 20-84% by weight, preferably 30-50% by weight. A composition having a content of less than 20% by weight has poor workability, while a resin composition containing the compound in an amount of 84% by weight or more is not preferred in terms of its curability.

Specific examples of the alkyl methacrylate include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, and t-methacrylate.
-Butyl, 2-ethylhexyl methacrylate, lauryl methacrylate, and the like, and used alone or in a mixture thereof.

In the present invention, if necessary, vinyl monomers other than the above-mentioned methacrylic acid alkyl ester, for example, aromatic monomers such as styrene and vinyl toluene, vinyl cyanide monomers such as acrylonitrile, and acrylics such as 2-ethylhexyl acrylate. Acid esters and the like can be added in a range that does not deteriorate the properties of the composition of the present invention.

In order to reduce the curing shrinkage and improve the toughness of the resin concrete made from the composition of the present invention, the resin composition [I] contains a 1,2-polybutadiene derivative having a double bond at a terminal in an amount of 6 to 30% by weight. %, And concrete made from a composition using a resin composition having an addition amount of 6% by weight or less has insufficient toughness and large hardening shrinkage. In addition, a composition for resin concrete made from a resin composition in which the amount of the 1,2-polybutadiene derivative added is 30% by weight or more is preferable because viscosity increases, workability deteriorates, and curability decreases. Absent.

Specific examples of 1,2-polybutadiene derivatives having a double bond at the terminal include those in which an acryl group or a methacryl group is introduced at the terminal of 1,2-polybutadiene (for example, TEA-1000, TE-2000, etc., manufactured by Nippon Soda). ), Maleic acid added, or those obtained by hydrogenating a part of unsaturated double bonds of 1,2-polybutadiene in these molecules, etc., and used alone or as a mixture. Also, if necessary, improve the low-temperature properties and give rubber elasticity.
-Polybutadiene derivatives can also be added.

The resin composition [I] used in the present invention contains a thermoplastic polymer that dissolves or swells in the alkyl methacrylate for the purpose of reducing curing shrinkage of resin concrete, improving curability, improving physical properties, and the like.

As the thermoplastic polymer, a vinyl monomer homopolymer or a copolymer thereof is mainly used. Further, other thermoplastic resins can be used if necessary. Specific examples of the vinyl monomer include (meth) acrylic acid alkyl ester, aromatic vinyl, vinyl cyanide, vinyl acetate and the like.

In addition, as a method of compounding these thermoplastic polymers when preparing a resin concrete, a thermoplastic polymer is dissolved in an alkyl methacrylate to form a resin composition [I] and then kneaded with an aggregate. After uniformly or partially mixing all or a part of the polymer with the aggregate to be mixed in advance, kneading with the resin solution [I] containing no thermoplastic polymer can be used.

If the latter is used when the viscosity of the resin composition [I] becomes too high and the coating workability deteriorates, or when there is a problem in the compatibility of the resin solution [I], these disadvantages can be solved.

Further, a plasticizer of 0 to 15% by weight, preferably 5 to 10% by weight is added to the resin composition [I] for the purpose of preventing cracks during curing of the composition for resin concrete of the present invention and relaxing cure shrinkage. Is good. If the amount exceeds 15% by weight, the cured product of the resin concrete composition is not preferred because the strength, the leaching of the plasticizer, the curability and the like are liable to occur.

Specific examples of the plasticizer include dibutyl phthalate, di2
Phthalic acid esters such as -ethylhexyl phthalate and diisodecyl phthalate; adipic acid esters such as di-2-ethylhexyl adipate and octyl adipate;
Dibasic acid esters such as dibutyl sebacate, di-ethylhexyl sebacate, etc., dibasic fatty acid esters such as azelaic acid esters such as di-2-ethylhexyl azelate, octyl azelate, paraffin wax, chlorinated paraffin, etc. Glycols such as paraffin wax, polyethylene glycol and polypropylene glycol, epoxidized soybean oil, epoxidized polymer plasticizers such as epoxidized linseed oil, trioctyl phosphate, phosphate esters such as triphenyl phosphate,
Examples thereof include phosphites such as trioctyl phosphite and triphenyl phosphite, and polyesters such as 1,3-butylene glycol adipate and the like, and used alone or as a mixture.

In addition, the resin composition [I] has curability of resin concrete,
A crosslinking agent having at least two unsaturated bonds in one molecule can be added for improving solvent resistance and physical properties.

Specific examples of the crosslinking agent include alkanediol di (meth) acrylates such as ethylene glycol di (meth) acrylate and 1,3-butylene di (meth) acrylate, diethylene glycol di (meth) acrylate, and dipropylene glycol di (meth) acrylate. Polyoxyalkylene glycol di (meth) acrylate, diallyl phthalate, triallyl cyanurate, trimethylolpropane tri (meth) acrylate, partial ester of polyhydric alcohol (meth) acrylic acid, epoxy (meth) acrylate, urethane ( (Meth) acrylates and unsaturated polyesters.

Further, an ultraviolet absorber such as a 2-hydroxybenzophenol derivative and a benzotriazole derivative can be added to the resin composition [I].

Further, a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane can be added for the purpose of improving the strength of the resin concrete.

The resin composition [I] is used in a range of 5 to 30% by weight,
The amount of the aggregate to be used is preferably adjusted according to the type, particle size, composition and construction thickness of the aggregate to be used, and it is usually used at 8 to 20% by weight. The aggregate to be combined with the resin composition [I] is not particularly limited, and can be arbitrarily selected according to the purpose.

Specific examples include powder or powder such as gravel, silica sand, quartz powder, calcium bicarbonate, talc, mica, alumina powder, glass beads, ceramic powder, ore, metal, and slag.

Aggregate in the resin concrete composition is used in the range of 95 to 70% by weight, and varies depending on the type, particle size, composition or construction thickness of the aggregate used, but is usually used in the range of 80 to 92% by weight. .

In the present invention, according to the purpose, glass fiber, carbon fiber, nylon fiber, polyester fiber, acrylic fiber,
A fibrous material such as a metal fiber can also be added.

In the present invention, additives such as a thixotropic agent such as aerosil and a coloring agent such as a dye and a pigment may be added according to the purpose.

Known radical polymerization catalysts are used to cure the resin concrete composition of the present invention. The amount of the radical polymerization catalyst is usually 0.5 to 5.0% by weight based on 100% by weight of the resin composition [I].

Specific examples of the catalyst include, for example, a pyrolytic radical polymerization catalyst represented by benzoyl peroxide, azobisisobutylnitrile and the like, and a redox represented by benzoyl peroxide and tertiary amine, methyl ethyl ketone peroxide and cobalt naphthenate, and the like. Catalysts.

When the resin concrete is cured in the air, a wax or a higher fatty acid such as stearic acid can be added to the resin composition [I] of the present invention for the purpose of improving the surface curability.

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples.

Example 1 To 38 parts by weight of methyl methacrylate, 12 parts by weight of TEA-1000 (a polybutadiene derivative manufactured by Nippon Soda) and Toyoparax
15 parts by weight of A50 (chlorinated paraffin manufactured by Tosoh) and 1 part by weight of dimethyl paratoluidine were added and mixed and dissolved at room temperature. Then, 1 part by weight of paraffin 115 (paraffin wax made by wax made in Japan) and isobutyl methacrylate were added with stirring. 35 parts by weight of a polymer (manufactured by Mitsubishi Rayon, number average molecular weight: 55,000) was added and dissolved at 40 ° C. for 2 hours to obtain a composition (1-A).

To 100 parts by weight of the composition (1-A), 2% of B-CH50 (manufactured by Kayaku Nouri, 50% benzoyl peroxide) was added and dissolved, defoamed, and cured at room temperature in a 3 m / m thick glass cell. JI
Physical properties were measured at 20 ° C according to S K6301.
A cured product having 0 kg / cm ² and an elongation of 1% was obtained.

12 parts by weight of TEA-1000, 15 parts by weight of Toyoparax A50, 1 part by weight of dimethyl paratoluidine, and 1 part by weight of paraffin 115 were added to 38 parts by weight of methyl methacrylate, and 40 ° C.
For 2 hours to obtain a composition (1-B).

After adding and dissolving 0.26 parts by weight of B-CH50 to 8.5 parts by weight of the composition (1-B), 4.5 parts by weight of a polymer (powder) of isobutyl methacrylate, 25 parts by weight of silica sand 8, 25 parts by weight of silica sand Two
5 parts by weight, a mixture of 37 parts of silica sand No. 37 was uniformly mixed and kneaded. The mixture was poured into a mold (4 cm × 4 cm × 16 cm), cured at room temperature, and measured for compressive strength and flexural strength at 20 ° C. results were respectively 650 kg / cm ² and 210 kg / cm ^2.

The mixture blended under the same conditions was poured into a gutter (length: 2 m, depth: 3 cm) coated with a release agent, and the linear shrinkage before and after curing at 20 ° C. was measured to be 0.04%.

To 13 parts by weight of the composition (1-B), 0.4 part by weight of B-CH50 was added and dissolved, and immediately thereafter, 7 parts by weight of an isobutyl methacrylate polymer, 20 parts by weight of silica sand 8, and 20 parts by weight of silica sand 6 were added. ,
Add 40 parts by weight of silica sand No. 5 to the uniformly mixed composition, knead the mixture, put it in a mold of 10 m / m thickness and cure it.
C) was obtained.

This plate-shaped cured product (1-C) was evaluated at 20 ° C. using a DuPont impact tester. As a result, cracks and cracks did not occur at a height of 30 cm or 40 cm under a load of 1 kg.

 The above results are shown in Tables 1 and 2.

(Examples 2 to 4) Compositions for resin concrete having the compositions shown in Table 1 were prepared and implemented in the same manner as in Example 1, and the evaluation results were shown in Tables 1 and 2.

Comparative Example 1 5 parts by weight of TEA-1000 (a polybutadiene derivative manufactured by Nippon Soda), 15 parts by weight of dioctyl phthalate (DOP), and 1 part by weight of dimethyl paratoluidine were added to 65 parts by weight of methyl methacrylate and mixed at room temperature. After dissolving, add 1 paraffin 115 (paraffin wax made by Nippon Seiro) with stirring.
15 parts by weight of methyl methacrylate polymer (manufactured by Mitsubishi Rayon Co., Ltd., number average molecular weight 40,000) was added and dissolved at 40 ° C. for 2 hours to obtain a composition (1-A).

B-CH50 was added to 100 parts by weight of the composition (1-A), dissolved and deaerated, and cured at room temperature in a glass cell having a thickness of 3 m / m.
As a result of measuring the physical properties at 20 ° C according to 6301, the tensile strength was 32.
A cured product having 0 kg / cm ² and an elongation of 5% was obtained.

To 13 parts by weight of the composition (1-A) was added and dissolved 0.26 parts by weight of B-CH50, and immediately 32 parts by weight of silica sand No. 8 and 5 parts of silica sand
No. 25 parts by weight, Silica sand No. 3 30 parts by weight are added and mixed, then mixed and poured into a mold (4 cm x 4 cm x 16 cm), cured at room temperature, and measured for compressive strength and bending strength at 20 ° C. As a result, they were 990 kg / cm ² and 340 kg / cm ² , respectively.

The mixture blended under the same conditions was poured into a gutter (length: 2 m, depth: 3 cm) coated with a release agent, and the linear shrinkage before and after curing at 20 ° C. was measured to be 0.40%.

20 parts by weight of the composition (1-A) was dissolved by adding 0.4 parts by weight of B-CH50, and immediately, 20 parts by weight of silica sand No. 8 and 6 parts by weight of silica sand
No. 20 parts by weight and Silica Sand No. 5 40 parts by weight were added to a uniformly mixed composition, kneaded, and placed in a mold having a thickness of 10 m / m to cure to obtain a plate-like cured product (-B).

This plate-shaped cured product (-B) was evaluated with a 20 ° C. DuPont impact tester. As a result, no cracks or cracks occurred at a load of 1 kg and a height of 30 cm, but cracks occurred at a height of 40 cm. .

 The above results are shown in Tables 1 and 2.

(Comparative Examples 2 to 4) Further, the results of curing and evaluating the resin compositions for concrete described in Tables 1 and 2 in the same manner as in Comparative Example 1 are shown in Table 1.
1 and 2.

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Claims (1)

(57) [Claims] 1. A resin concrete composition comprising 5 to 30% by weight of the following resin composition [I] and 95 to 70% by weight of aggregate [II]. Resin composition [I] (1) At least one alkyl methacrylate having an alkyl group having 1 to 12 carbon atoms 20 to 84% by weight (2) 1,2-Polybutadiene derivative 6 to 30% by weight (3) (1) 10 to 35% by weight of a thermoplastic polymer soluble or swellable in the alkyl methacrylate (4) 0 to 15% by weight of a plasticizer