JP2002363394A - Unsaturated polyester resin resin concrete composition and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an unsaturated polyester resin resin concrete composition which solves the problem of workability and griming of a die in a resin concrete composition and excels in mechanical properties. SOLUTION: The unsaturated polyester resin resin concrete composition comprises a powdered shrinkage reducing agent, an unsaturated polyester resin, an aggregate, and a filler, and is manufactured by directly introducing the powdered shrinkage reducing agent without being dissolved in a styrene monomer together with the aggregate and the filler into the unsaturated polyester resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an unsaturated polyester resin resin concrete composition capable of obtaining a molded article having a small shrinkage upon curing and excellent in dimensional accuracy, and a method for producing the same.

[0002]

BACKGROUND OF THE INVENTION Unsaturated polyester resins, low shrinkage agents,
Resin concrete composition consisting of aggregate and filler,
Water and sewage-related products such as manholes, pipes, sewage masles,
It is used for repair of cracks in cement concrete and landscape formations such as lanterns. Conventionally, the unsaturated polyester resin resin concrete composition is formed by mixing an unsaturated polyester resin and a low-shrinkage agent dissolved in a styrene monomer, and using the mixture, aggregate and filler. Examples of the low-shrinkage agent include a mixture of polystyrene, polyethylene, a styrene-vinyl acetate block copolymer or the like dissolved in a styrene monomer, and a liquid mixture of a saturated polyester, an acrylic resin, or a vinyl acetate resin. It is used.

As described above, in the conventional method for producing a resin concrete composition, it is necessary to previously mix the two kinds of low-shrinkage agents as described above, resulting in inferior workability and low liquidity. Since the shrinking agent is used, there is a problem that stringing occurs at the time of demolding, and the mold is stained.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an unsaturated polyester resin resin concrete composition having excellent mechanical properties by solving the above-mentioned problems of workability and mold stain in the resin concrete composition. To provide.

[0005]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems in the resin concrete composition, the present inventors have found that by adding a powdery low-shrinking agent directly to an unsaturated polyester resin and mixing it, A molded article having excellent mechanical properties equivalent to that of the unsaturated polyester resin resin concrete composition is obtained, and smoothness is improved, mold stains are reduced, and the workability is excellent. The present invention has been completed.

That is, the present invention provides an unsaturated polyester resin,
An unsaturated polyester resin resin concrete composition comprising a low-shrinkage agent, an aggregate and a filler, wherein the low-shrinkage agent is in powder form, and a powdery low-shrinkage agent,
A method for producing an unsaturated polyester resin resin concrete composition, which comprises directly charging an unsaturated polyester resin together with an aggregate and a filler without dissolving in a styrene monomer.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The unsaturated polyester resin used in the resin concrete composition of the present invention is obtained by polycondensing a polyhydric alcohol with an unsaturated polybasic acid and a saturated polybasic acid. The type of the resin is not particularly limited, and those usually used as resin for resin concrete can be used. Further, a blend of a vinyl ester resin and a diallyl phthalate resin as a part of the unsaturated polyester resin may be used.

Examples of polyhydric alcohols forming unsaturated esters include ethylene glycol, triethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, 1,2-butanediol, Diols such as 3-butanediol, 1,4-butanediol, 1,6-hexanediol, cyclohexanedimethanol, 2-methyl, 1,3-propanediol, hydrogenated bisphenol A, bisphenol A
And glycols to which ethylene oxide, propylene oxide, etc. are added, and triols such as trimethylolpropane.

The unsaturated dibasic acid forming an unsaturated ester includes, for example, maleic acid, fumaric acid, mesaconic acid, tetraconic acid and itaconic acid (including their respective anhydrides). As the saturated dibasic acid, for example, orthophthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, halogenated phthalic anhydride, hetic acid, adipic acid, succinic acid, sebacic acid and the like,
Two or more of these unsaturated dibasic acids and saturated dibasic acids may be used in combination.

The crosslinking agent for forming the unsaturated polyester resin includes styrene derivatives such as styrene, vinyltoluene, α-methylstyrene, t-butylstyrene and chlorostyrene; alkyl esters of acrylic acid or methacrylic acid; Vinyl and the like are mentioned, and styrene is particularly preferable. The mixing ratio of the unsaturated polyester and the cross-linking agent is 50-75.
Parts by weight / 50 to 25 parts by weight.

When an unsaturated polyester resin is produced, a polymerization inhibitor is used for the purpose of preventing gelation. For example, hydroquinone, tertiary butyl catechol, tertiary butyl hydroquinone, methyl hydroquinone, parabenzoquinone and the like are used, and two or more kinds may be used in combination.

Polystyrene, polyethylene, styrene-vinyl acetate block copolymer, styrene-diene block copolymer and the like are appropriately used as a low shrinkage agent in the unsaturated polyester resin resin concrete composition of the present invention. In particular, when a styrene-vinyl acetate block copolymer or a styrene-diene block copolymer is used, stringing at the time of demolding is eliminated, dirt on a mold is reduced, smoothness is improved, and leveling is improved. Becomes easier.

The styrene-diene block copolymer is a SBS or SIS thermoplastic elastomer using polystyrene as a hard segment and polybutadiene or polyisoprene as a soft segment, or water obtained by hydrogenating the above SBS or SIS system. It is an appendage. As the SEBS-based thermoplastic elastomer or a modified product, any of reactive saturated thermoplastic elastomers obtained by imparting reactivity with maleic anhydride or the like can be used. The bonding mode of the styrene-diene block copolymer is roughly classified into a type in which a polystyrene portion and a diene polymer portion take a linear bonding mode, and a radial type in which diene polymer portions are coupled to each other. Combination types can also be used. As for the ratio of a styrene part and a diene part, styrene is preferably 10 to 50% or more of the whole.

Other compounding agents used in the resin concrete composition of the present invention include a curing agent, an aggregate, a filler, a curing accelerator and the like. As the curing agent, a peroxide can be used as appropriate. For example, diacyl peroxide, peroxyester, diallyl peroxide, ketone peroxide, peroxyketal,
Alkyl perester type, percarbonate type and the like are used, and two or more types may be used in combination.

As the aggregate, for example, crushed stone, sand, cold water stone, marble, limestone, river sand and the like are used. The average particle size of the aggregate used depends on the size and thickness of the molded product, but is 0.05 to 50 mm, preferably 0.1 to 20 mm.
It is.

As the filler, for example, calcium carbonate, fly ash, glass powder, aluminum hydroxide,
Marble waste and the like. The average particle size of the filler is 0.5μ
m to about 20 μm.

As the curing accelerator, for example, cobalt naphthenate, cobalt octenoate, copper naphthenate, vanadyl acetyl acetate, iron acetyl acetate, N, N
-Dimethylaniline and the like.

A feature of the unsaturated polyester resin resin concrete composition of the present invention is that, in the above-mentioned components, a low-shrinking agent is particularly contained in a powder form. As long as the low-shrinking agent is contained in the form of a powder, the resin concrete composition of the present invention is not particularly limited to the method for producing the resin concrete composition. Instead, the resin concrete composition of the present invention can be suitably obtained by directly charging the unsaturated polyester resin together with the aggregate and the filler.

The molded articles obtained from the resin concrete composition of the present invention include manholes, water collecting lids, CC boxes, artificial marble, car stops and the like. Examples of the molding method include an injection molding method of pouring into a mold, centrifugal molding of pouring while rotating a cylindrical mold, and compression molding by a press machine.

[0020]

Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples.

Examples 1 to 5, Comparative Examples 1 to 3 [Production of unsaturated polyester resin (UP)] 532 g of propylene glycol, 186 g of ethylene glycol, 134 g of dipropylene glycol, 392 of maleic anhydride
g, phthalic anhydride 888 g, and polymerization inhibitor hydroquine 0.34 g were all charged in a four-necked flask at a time.
C. to 215.degree. C. in an inert gas atmosphere, and the process was terminated when the acid value became 40 or less. When the temperature in the flask became 140.degree.
2 g were charged. Thereafter, when the temperature became 40 ° C. or lower, 19.0 g of cobalt octenoate was added. The unsaturated polyester resin thus obtained is referred to as UP.

In order to confirm the difference between the powdery low-shrinking agent and the low-shrinking agent dissolved in the styrene monomer, the obtained U was obtained.
The resin concrete composition kneaded with the compounding ratio shown in Table 1 using P is 60 mm long × 60 mm wide × 240 m long.
m and filled with a vibrator to remove air bubbles. After curing at room temperature and standing for 14 days, measurement of strength, measurement of linear shrinkage, stain on mold, workability,
The appearance of the molded product was confirmed. In addition, 55% methyl ethyl peroxide is a trade name of Permec N (manufactured by NOF Corporation).
It was used.

Table 1 shows the amounts (parts by weight) and the results of measurement and evaluation in each of the examples and comparative examples. The bending test in the strength measurement was performed according to JIS A 1184 “Method of testing bending strength of polyester resin concrete”, and the compression test was performed according to JIS A 1182 “Test method of compressive strength of polyester concrete”. As for the linear shrinkage, a change in the dimensions of the mold frame and the dimensions of the resin cone was read using a reading microscope. The stain on the mold was checked visually and by finger touch. The workability was visually evaluated based on the kneading state of the resin con, the fluidity of the resin con, and the like. The appearance of the molded product was visually evaluated.

[0024]

[Table 1]

In Examples 1, 2, 3, 4 and 5 using the powdery low-shrinkage agent, there was no mold stain, and the workability and the appearance of the molded product were good. there were. On the other hand, in Comparative Examples 1, 2 and 3 using the liquid low-shrinkage agent, mold staining was observed, workability was poor, and whitening was confirmed in the molded product.

[0026]

The resin concrete composition of the present invention comprises:
It shows the same mechanical performance as the resin concrete composition using the conventional liquid low-shrinkage agent, gives molded products without cracks, improves smoothness, and improves workability due to reduction of mold stains. It will be an improvement. Further, in the method for producing the resin concrete composition of the present invention, since the step of dissolving the low-shrinkage agent can be reduced by using the low-shrinkage agent of the powder without dissolving, the workability is further improved. INDUSTRIAL APPLICABILITY The resin concrete composition of the present invention and the method for producing the same can be applied to all conventional resin concrete molded articles, and can efficiently produce molded articles having little shrinkage upon curing and excellent dimensional accuracy.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Satomi Nonaka 3501-5 Shichihongi, Kamisato-cho, Kodama-gun, Saitama (72) Inventor Akihiko Kanai 874-104 Katashima, Ibogawa-cho, Ibo-gun, Hyogo F-term (reference) 4J002 BP01X BP03X CF21W CF22W DE146 DE236 DL006 DM006 FD016 FD20X GL00

Claims (3)

[Claims] 1. An unsaturated polyester resin, a low-shrinking agent,
An unsaturated polyester resin resin concrete composition comprising an aggregate and a filler, wherein the low-shrinking agent is in a powder form. 2. The unsaturated polyester resin resin concrete composition according to claim 1, wherein the powdery low-shrinking agent is a styrene-vinyl acetate block copolymer and / or a styrene-diene block copolymer. 3. An unsaturated polyester resin resin concrete composition characterized in that a powdery low-shrinking agent is directly introduced into an unsaturated polyester resin together with an aggregate and a filler without being dissolved in a styrene monomer. Manufacturing method.