JPH0712965B2 - Composition for resin concrete - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for resin concrete.

(Prior Art) Conventionally, a resin concrete composition using 10-30 parts by weight of styrene and an unsaturated polyester resin of 90-70 parts by weight of silica sand is known, and due to its excellent properties, floor lining ， It is used in the same way as ordinary cement concrete and asphalt for road paving, repair, bridge repair, dike work, etc.

However, when styrene is used as a polymerizable monomer when curing silica sand using the above thermosetting resin composition, a considerable amount of styrene is vaporized by the time curing of the resin is completed. There is a drawback that. For this reason, the processor is troubled by the odor of these polymerizable monomers, and their emission concentrations are regulated from the viewpoint of labor hygiene and environmental safety.

In particular, when resin concrete is used for the floor lining, the surface area becomes large, so that the styrene dissipates badly, and the amount of vapor in the air may fall within the explosion limit while giving off odors when working indoors. It is not preferable from the point of view of law.

These odors can be removed by activated carbon adsorption equipment, local exhaust equipment, etc., but this method requires a large amount of equipment investment, and is a fundamental solution in view of environmental pollution. I can't say. Therefore, under the present circumstances, there is a strong demand for the appearance of an unsaturated polyester resin having a small volatilization amount of a polymerizable monomer.

Several methods have been proposed to meet these demands. The first is a method of adding a shielding agent such as paraffin wax to the unsaturated polyester resin in order to suppress the volatilization of the polymerizable monomer, but this method has a limited effect and the secondary adhesion If you have a problem. The second method is a method of lowering the molecular weight of the unsaturated polyester and reducing the amount of styrene used as a crosslinking agent, that is, a high solidification method. According to this method, various problems such as a decrease in mechanical strength due to a decrease in the molecular weight of the unsaturated polyester occur, and it is not a fundamental solution. Further, a method of using a polymerizable monomer having low evaporation property without using styrene as a crosslinking agent can be considered. In this method, the polymerizable monomer used in place of styrene is required to be inexpensive and highly reactive.

In addition, a styrene unsaturated polyester resin has a poor adhesion to silica sand, and a composition for a resin lining for a floor lining that is cracked with the passage of time and is free of cracks is required.

(Problems to be Solved by the Invention) The object of the present invention is to eliminate the above-mentioned drawbacks of the prior art, to maintain the various properties of the conventional unsaturated polyester resin, and to prevent the polymerization of the polymerizable monomer during curing. It is intended to provide a resin concrete composition suitable for floor linings and the like using an unsaturated polyester resin having a small amount of escape.

(Means for Solving Problems) The present invention comprises 40 to 70 parts by weight of an unsaturated polyester and the general formula (I) (Wherein R means a hydrogen atom or a methyl group) 10 to 30 parts by weight of a curable resin composition containing 60 to 30 parts by weight of a polymerizable monomer represented by: and silica sand having a particle size of 0.01 to 10 mm.
The present invention relates to a resin concrete composition containing 90 to 70 parts by weight.

The unsaturated polyester used in the present invention is obtained by subjecting a polybasic acid and a polyhydric alcohol to an esterification reaction by a conventional method. The reaction temperature of the esterification reaction is 150 to 2
20 ℃ is preferable, and the acid value of the reaction product is 5-50.
And the molecular weight is preferably 500 to 2,000. The reaction ratio between the polybasic acid and the polyhydric alcohol is not particularly limited, but 1.0 to 1.1 mol of the -OH group of the polyhydric alcohol is preferable to 1.0 mol of the -COOH group of the polybasic acid.

As the polybasic acid, an unsaturated polybasic acid is used and, if necessary, a saturated polybasic acid is used together. For example, phthalic anhydride, succinic acid, phthalic acid, isophthalic acid, terephthalic acid, sebacic acid, tetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, saturated polybasic acids such as hymic acid, maleic acid, fumaric acid, itaconic acid, Unsaturated polybasic acids such as maleic anhydride and trimellitic anhydride are preferably used.

Examples of the polyhydric alcohol include ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butadiene glycol, 1,6-hexanediol, neopentyl glycol and other glycols, polyethylene glycol, polypropylene glycol and other oligomeric glycols, glycerin, trimethylolpropane and other 3 A polyhydric alcohol or the like is preferably used.

The polymerizable monomer used in the present invention has the general formula (I) (Wherein R represents a hydrogen atom or a methyl group). That R is tricyclo [5,2,1,0 ^2.6] dec -8-yl methacrylate when the methyl group, when R is a hydrogen atom, in tricyclo [5,2,1,0 ^2.6] dec -8-yl acrylate is there. These compounds are known compounds obtained by subjecting hydrogenated sidedecanol obtained by hydrogenating hydroxylated dicyclopentadiene to esterification reaction of methacrylic acid or acrylic acid in the presence of an acid catalyst.

Unsaturated polyester and tricyclo [5,2,1,0 ^2.6 ]
Deca-8yl methacrylate or tricyclo [5,2,1,
Blending ratio of the 0 ^2.6] dec -8-yl acrylate, taking into account the characteristics of workability and the cured product, using 40 to 70 parts by weight of the former and the latter as a 60 to 30 parts by weight, the total amount as 100 parts by weight To be If the unsaturated polyester is less than 40 parts by weight, the physical properties of the cured product will be poor, and if it exceeds 70 parts by weight, the viscosity will be high and the workability will be poor. Tricyclo 〔5,2,1,
0 ^2.6] dec -8-yl methacrylate or tricyclo [5,2,1,0 ^2.6] dec -8-yl acrylate, may be mixed even singly.

To the resin composition of the present invention, acrylic monomers such as methyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate and 1,6-hexanediol diacrylate, styrene and the like are added. It can also be blended.

The silica sand having a particle size of 0.01 to 10 mm used in the present invention contains 30% by weight or more of silicon oxide, and includes river sand, sea sand, mountain sand, crushed stone, and the like. The reason for limiting the grain size to 0.01 mm to 10 mm is 0.0
If it is less than 1 mm, the viscosity of the resin concrete is too high, resulting in poor workability, and if it exceeds 10 mm, it cannot be made into resin concrete.

Regarding the ratio of the curable resin composition and silica sand in the present invention, the curable resin composition is 10 to 30 parts by weight and the silica sand having a particle size of 0.01 to 10 mm is 90 to 70 parts by weight, and the total amount is 100 parts by weight. This is because when the silica sand exceeds 90 parts by weight, the viscosity becomes high and the workability is poor, and when the silica sand is less than 70 parts by weight, the strength becomes low.

Upon curing the curable resin composition of the present invention, a polymerization initiator such as methylol ethyl ketone peroxide and benzoyl peroxide, and a polymerization accelerator such as cobalt octenoate, cobalt naphthenate and dimethylaniline are used as necessary. To be done. When the curable resin composition of the present invention is used as a molding material, a reinforcing material, a lubricant, a coloring agent and the like can be added as required.

(Examples) Hereinafter, the present invention will be described with reference to Examples. Parts in the following examples mean parts by weight.

Example 1 490 parts of maleic anhydride, 740 parts of phthalic anhydride, 532 parts of propylene glycol, 536 parts of dipropylene glycol and 0.2 part of hydroquinone were condensed at 210 ° C. under a nitrogen stream,
An unsaturated polyester having an acid value of 20 was obtained. This polyester
60 parts tricyclo [5,2,1,0 ^2.6] by compatible with dec -8-yl methacrylate 40 parts, to obtain a transparent liquid resin composition of viscosity 4 poise uniform. To 100 parts of this liquid resin composition,
Cobalt octenoate (cobalt content 6%) 0.5 parts and methyl ethyl ketone peroxide (active oxygen content 10
%) 1.0 part was added to cure in about 15 minutes to obtain a transparent cured resin.

Regarding the liquid resin composition, JIS-K6901-1968
When the room temperature curing property (25 ° C) was examined by (Liquid unsaturated polyester resin test method), the gelation time was 14 minutes, the minimum curing time was 23 minutes, and the maximum exothermic temperature was 115 ° C.

On the other hand, a composition for resin concrete containing 6 g of the liquid resin composition and 24 g of silica sand having a particle diameter of 1 mm was placed in a shearer having an inner diameter of 5 cm and a depth of 1 cm to prepare a polymerizable monomer in a thermostatic chamber (40 ° C). The amount of escape (weight reduction rate of the composition) was measured. The result is shown in 1 of FIG. It is shown from 1 in FIG. 1 that the composition for resin concrete of the present invention has almost no escape amount.

When the mechanical properties of the cured product obtained by post-curing the above cured resin for 15 hours at 50 ° C were examined, the bending strength of the cast product
9 kg / mm ² , the above-mentioned composition for resin concrete was added with the above-mentioned amounts of cobalt octenoate and methyl ethyl ketone peroxide and cured for about 15 minutes, and then after-cured at 50 ° C for 15 hours (resin with a particle size of 1 mm The bending strength was 3.5 kg / mm ^{2 (} % by weight), which was higher than that of resin concrete using liquid unsaturated polyester resin.

Example 2 60 parts of the unsaturated polyester obtained in Example 1 was mixed with 20 parts of tricyclo [5,2,1,0 ^2.6 ] dec-8yl acrylate and 20 parts of styrene to obtain a liquid resin composition. Obtained.
Using this liquid resin composition, a composition for resin concrete was prepared in the same manner as in Example 1, the amount of escape at 40 ° C. was measured, and the result is shown in FIG. 2 in FIG.
From these results, it is shown that the resin concrete composition of the present invention has a relatively small amount of escape.

Comparative Example 1 A liquid resin composition was obtained by compatibilizing 60 parts of unsaturated polyester obtained in Example with 40 parts of styrene. Using this liquid resin composition, a composition for resin concrete was prepared in the same manner as in Example 1 and the amount of escape at 40 ° C. was measured. The results are shown in FIG. From 3 in FIG. 1, it is shown that the resin concrete composition of Comparative Example has an extremely large amount of escape and is inferior.

A cured product was obtained using this liquid resin composition in the same manner as in Example 1, and its mechanical properties were examined.
8 kg / mm ² , a resin concrete obtained by curing the composition for resin concrete in the same manner as in Example 1 (80% by weight of silica sand having a particle diameter of 1 mm) had a bending strength of 2.5 kg / mm ² .

(Effect of the Invention) According to the present invention, by using a specific polymerizable monomer having a low vapor pressure, while maintaining the workability and various characteristics of the conventional unsaturated polyester resin, By reducing the amount of the polymerizable monomer that escapes during curing, the working environment during curing can be significantly improved, and resin concrete with high strength can be obtained.

[Brief description of drawings]

FIG. 1 is a diagram showing the results of measuring the amount of polymerizable monomer escaped from the resin compositions for resin concrete of Examples and Comparative Examples.

Claims (1)

[Claims] 1. Unsaturated polyester 40 to 70 parts by weight and general formula (I) (Wherein R means a hydrogen atom or a methyl group) 10 to 30 parts by weight of a curable resin composition containing 60 to 30 parts by weight of a polymerizable monomer represented by: and silica sand having a particle size of 0.01 to 10 mm.
A resin concrete composition comprising 90 to 70 parts by weight.