JP2006199544A - Resin composition for artificial marble, and artificial marble - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition for a non-gel coat artificial marble which is excellent in surface gloss even when it is cured and formed at ordinary temperature, and to provide the artificial marble. <P>SOLUTION: The resin composition for the artificial marble contains an unsaturated polyester resin or a vinylester resin and 20-80 wt.% vinyltoluene and further contains an inorganic filler as occasion demands. The artificial marble is obtained by forming the resin composition for the artificial marble and has at least 90% in a 60°specular glossiness stipulated by JISK 7105. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a resin composition for artificial marble having excellent surface gloss and an artificial marble.

Artificial marble using unsaturated polyester resin and vinyl ester resin has excellent design properties such as luxury, weight, texture, transparency, luxury, etc., and is often used in wash counters, kitchen counters, bathtubs, etc. ing.
Further, in the conventional artificial marble, a gel coat layer is formed on the surface of the molded product in order to give a high-class feeling.
However, in order to construct a gel coat layer, a gel coat coating process is required, and productivity is poor, which is a problem in the work environment. Moreover, when it is used for a long time, problems such as discoloration and blistering due to the gel coat layer occur.

On the other hand, for the purpose of improving productivity and working environment in the gel coat application process, and improving the occurrence of discoloration, swelling and the like due to long-term use, non-gel coat artificial marble has been studied in which the gel coat application process is omitted.
However, since non-gel-coated artificial marble does not have a gel coat layer, its surface gloss is inferior to gel-coated artificial marble.
As a measure to improve the surface gloss of this non-gel coated artificial marble, medium temperature molding (70
˜90 ° C.) and glossing is performed by a buffing process (see, for example, Patent Document 1). However, it is difficult to improve the surface gloss of molded products molded at room temperature even if glazing is performed by a buff process.
International Publication No. 98/35816 Pamphlet

  An object of the present invention is to provide a resin composition for non-gel-coated artificial marble, which is excellent in surface gloss even at room temperature molding, and artificial marble.

As a result of intensive studies on these problems, the present inventors have found that the above problems can be solved by using vinyltoluene as a matting agent for artificial marble. It has come.
That is, the present invention provides a resin composition for artificial marble comprising vinyl toluene and an unsaturated polyester resin or vinyl ester resin. Furthermore, the present invention provides an artificial marble obtained by molding a resin composition for artificial marble and having a 60 ° specular glossiness of 90% or more as defined by JISK7105.

  Even when the resin composition for artificial marble of the present invention is cured and molded at room temperature, a non-gel-coated artificial marble having excellent surface gloss can be obtained.

The present invention is described in further detail below.
The resin composition for artificial marble of the present invention contains the vinyl toluene and an unsaturated polyester or vinyl ester resin.

The vinyltoluene used in the present invention is a mixture of a vinyl group with respect to a methyl group in the aromatic ring having a meta position and a para position.
The content of the vinyl toluene is preferably 20 to 80% by weight in the composition of the present invention.
The unsaturated polyester used in the present invention is obtained by a condensation reaction between an α, β-unsaturated dibasic acid and a polyhydric alcohol. The molecular weight of the unsaturated polyester is preferably in the range of 500 to 5000 in terms of number average molecular weight.
Examples of the α, β-unsaturated dibasic acid used for preparing the unsaturated polyester include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like. If necessary, a saturated dibasic acid can be used in combination. Saturated dibasic acids include phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic anhydride, hexahydroterephthalic acid, Hexahydroisophthalic acid, succinic acid, malonic acid, glutaric acid, adipic acid, sebacic acid, 1,
12-dodecanedioic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4,4′-biphenyldicarboxylic acid, and These dialkyl esters can be mentioned. Furthermore, acetoacetyl acid or an acid chloride of the compound may be used in combination with the unsaturated dibasic acid or saturated dibasic acid.

Examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, and 2-methyl. 1,3-propanediol, 2-methyl-1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, neopentyl glycol Hydrogenated bisphenol A, 1,4-butanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3 -Propanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclo Xanglycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol, 2,7-decalin glycol, etc. Can be mentioned.
In the unsaturated polyester used in the present invention, a dicyclopentadiene compound can be used as a raw material as long as the performance is not impaired. The dicyclopentadiene compound can be introduced by various known methods and is not particularly limited. For example, an addition product (sidedecanol monomaleate) of dicyclopentadiene and maleic acid is a single base. Examples thereof include a method of introducing it into a polyester skeleton using it as an acid.

  Examples of the vinyl ester resin used in the present invention include di (meth) acrylate of a bisphenol type epoxy resin, di (meth) acrylate of an epoxy resin in which a bisphenol type epoxy resin and a novolac type epoxy resin are used in combination. Can be mentioned. Such a vinyl ester resin is obtained by reacting an epoxy resin having an average epoxy equivalent of preferably 150 to 450 with an unsaturated monobasic acid in the presence of an esterification catalyst. It is.

Examples of the bisphenol type epoxy resin include di (meth) acrylate of bisphenol A type epoxy resin, di (meth) acrylate of hydrogenated bisphenol A type epoxy resin, di (meth) acrylate of bisphenol A ethylene oxide addition type epoxy resin, Di (meth) acrylate of bisphenol A propylene oxide addition type epoxy resin, di (meth) acrylate of bisphenol F type epoxy resin, di (meth) of 1,6-naphthalene type epoxy resin
An acrylate etc. can be mentioned.

Examples of the novolak type epoxy resin include an epoxy resin obtained by a reaction of phenol novolak or cresol novolak with epichlorohydrin or methyl epichlorohydrin.

Furthermore, examples of the unsaturated monobasic acid described above include acrylic acid, methacrylic acid, cinnamic acid, crotonic acid, sorbic acid,
Examples thereof include monomethyl malate, monopropyl malate, monobutyl malate, and mono (2-ethylhexyl) malate. Acetoacetyl acid can be used in combination with these unsaturated monobasic acids.

  These unsaturated monobasic acids may be used alone or in combination of two or more. The reaction between the epoxy resin and the unsaturated monobasic acid is preferably performed using an esterification catalyst at a temperature in the range of 60 to 140 ° C., particularly preferably in the range of 80 to 120 ° C.

As the esterification catalyst, known and commonly used compounds can be used as they are. Examples thereof include various tertiary amines such as triethylamine, N, N-dimethylbenzylamine, N, N-dimethylaniline or diazabicyclooctane; or diethylamine hydrochloride.

The vinyl ester resin has a number average molecular weight of preferably 450 to 2,500, particularly preferably 500 to 2,
A range of 200 is appropriate. If the number average molecular weight is in the range of 450 to 2,500, the resulting cured product will not be sticky, the strength properties will not decrease, the curing time will be short, and the productivity can be improved.

It is preferable that the resin composition for artificial marble of the present invention further contains an inorganic filler.
Examples of such inorganic fillers include aluminum hydroxide, calcium carbonate, magnesium hydroxide, magnesium oxide, glass frit, silica, mica, and glass beads. These inorganic fillers may be used alone or in combination of two or more, or two or more inorganic fillers having different particle diameters may be combined. Among these, it is preferable to use aluminum hydroxide which is excellent in transparency. The amount of the inorganic filler added is preferably 50 to 300 parts by weight, more preferably 100 to 250 parts by weight with respect to 100 parts by weight of the resin composition.

In the resin composition for artificial marble of the present invention, a curing agent, that is, a radical polymerization initiator, and a curing accelerator, that is, a radical polymerization accelerator are usually used.
Examples of such a curing agent include organic peroxides. Specific examples include known compounds such as diacyl peroxides, peroxyesters, hydroperoxides, dialkyl peroxides, ketone peroxides, peroxyketals, alkyl peresters, and carbonates. The addition amount of the curing agent is not particularly limited as long as the object of the present invention can be achieved, but preferably it is 100 parts by weight with respect to the total amount of the polymerizable resin and the polymerizable monomer. In addition, it is 0.01 to 5 parts by weight, and by using it in such a range, an excellent resin composition such as curing time and cured resin properties can be obtained. You may use the said hardening | curing agent in combination of 2 or more types.

  Examples of the curing accelerator include metal soaps, metal chelate compounds, and amines. Examples of the metal soaps include cobalt naphthenate, cobalt octylate, vanadyl octylate, copper naphthenate, barium naphthenate, calcium naphthenate, and potassium hexoate. Examples of the metal chelate compound include vanadyl acetyl acetate, cobalt acetyl acetate, and iron acetylacetonate. Examples of amines include N, N-dimethylamino-p-benzaldehyde, N, N-dimethylaniline, N, N-diethylaniline, N, N-dimethyl-p-toluidine, N-ethyl-m-toluidine, tri Examples include ethanolamine, m-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, diethanolaniline and the like. Of these curing accelerators, amines and metal soaps are preferred. These curing accelerators may be used alone or in combination of two or more. These curing accelerators may be added to the resin in advance, or may be added at the time of compound preparation. The addition amount of the curing accelerator is not particularly limited as long as the object of the present invention can be achieved, but it is preferably 0.1% with respect to 100 parts by weight of the total amount of the resin used in the present invention. 1 to 5 parts by weight.

In order to further adjust the curing time, a polymerization inhibitor is preferably used for this resin composition. Examples of such polymerization inhibitors include trihydrobenzene, toluhydroquinone, 1,4-naphthoquinone, parabenzoquinone, toluhydroquinone, hydroquinone, benzoquinone, hydroquinone monomethyl ether, p-tert-butylcatechol, 2,
Examples include 6-di-tert-butyl-4-methylphenol. Such a polymerization inhibitor is added to the resin composition at 10 to 10%.
00 ppm is preferably added, and 50 to 200 ppm is more preferably added. By using in such a range, a resin composition excellent in resin storage stability, cast molding curing time, and cured product strength expression can be obtained.
In the resin composition for artificial marble of the present invention, various other additives as necessary, for example, colorants, pigments, ultraviolet absorbers, thickeners, inorganic and organic fiber base materials, antifoaming agents, Coupling agent, internal mold release agent, low shrinkage agent such as thermoplastic resin, when low shrinkage agent is incompatible with radical polymerizable resin, compatibilizer, anti-aging agent, plasticizer, aggregate, flame retardant, Additional components such as stabilizers may be added.

The resin composition for artificial marble of the present invention preferably uses an apparatus such as a stirrer, a kneader, a roll mill, a screw extrusion kneader, etc., in order to uniformly mix the respective components. Care should be taken during mixing so that the admixture does not gel due to frictional heat. From the viewpoint of curability, transparency, and hot water resistance, it is preferable that the resin composition sufficiently degass the air entrained during mixing by decompression or the like before curing.
Various artificial marbles can be obtained by molding the resin composition for artificial marble of the present invention. Examples of the molding method include a press molding method and a cast molding method.

In order to perform press molding, a mold capable of reducing the pressure inside the mold and a press molding machine for pressurization are required. Manufacture of artificial marble with good water resistance by placing molding material between molds, reducing the pressure inside the mold before venting the mold, venting the air inside the mold, and pressurizing and curing the mold Can do.
Depending on the mold shape of the molded article and the physical properties of the artificial marble resin composition used, the molding temperature is 100 to 150 ° C.
Of these, 110 to 130 ° C. is particularly preferable, and the molding pressure is preferably 60 to 400 mmHg.
150 to 360 mmHg is particularly preferable.

In the casting molding method, a molding material is obtained by pouring and filling a molding material into a mold and heating to polymerize and cure the molding material.
In the curing step, in order to avoid mold release of the molded product due to curing shrinkage, pressure is applied to follow the curing shrinkage,
It is preferable to provide a temperature difference as appropriate between the upper mold and the lower mold. Moreover, you may devise, such as shaping | molding an artificial marble resin composition by putting a reinforcing material in order to give intensity | strength to a molded article, or putting a material in a type | mold for patterning.
It is preferable to grind the surface of the artificial marble obtained above. By performing surface grinding, the surface gloss can be further increased to enhance the transparency and further enhance the design.
The glossiness of the artificial marble of the present invention is not particularly limited, but the 60 ° specular glossiness measured by the method defined in JISK7105 is preferably 90% or more.

The artificial marble obtained by the present invention can be used for, for example, an indoor member, a bathtub, a kitchen counter, a wash counter, and a vanity. Other pipes and pipes, manholes, drainage masses, building material blocks, paving blocks, lids, repair materials, etc., molded articles for civil engineering and construction, molded articles for landscapes, chairs, benches, C.I. C. It can also be used for boxes (wire joint grooves), information-related molded products, power-related molded products, and the like. Also, for molded products that require particularly aesthetic and chemical contamination resistance such as bathtubs,
A gel coat or top coat may be applied.

Furthermore, resin concrete can be produced using the resin composition for artificial marble of the present invention as a resin concrete composition.
In this case, for example, crushed stone, sandstone, cold water stone, marble, quartz, granite, limestone, quartzite, quartz sand, river sand and the like are preferably used as the aggregate. Light weight aggregates such as sintered shale, perlite, shirasu balloon, glass balloon, etc. can be used for weight reduction.
The average particle diameter of the aggregate used varies depending on the size and thickness of the molded product, but is preferably 0.05 to 50 mm, more preferably
0.1 to 20 mm. The addition amount is preferably 12.5 to 92.5% by weight in the resin concrete composition. In addition, No. 1 silica sand (average particle size of 5-2.5 mm), No. 2 silica sand (particle size of 2.5-1.2 mm), No. 3 silica sand (particle size of 1.2-0.
6 mm), No. 4 silica sand (particle size 0.6-0.3 mm), No. 5 silica sand (particle size 0.3-0.15 mm), No. 6 silica sand (particle size 0.15)
˜0.074 mm), No. 7 silica sand (particle size 0.074 mm or less) can also be used. Cast molding resin composition compound can be cured by heating as it is, and can be made into a cast molded product, but it is necessary to use organic peroxide as a curing catalyst at an appropriate temperature and in a short time. It is preferable to obtain a sufficient degree of curing.

EXAMPLES Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these Examples. In addition, “parts” in the text indicates parts by weight.

[Synthesis Example 1] Synthesis of unsaturated polyester Propylene glycol 13 was added to a 5-liter four-necked flask equipped with a thermometer, a stirrer, a gas inlet, and a reflux condenser.
95.5 parts, 1568.8 parts of phthalic anhydride, and 675.2 parts of maleic anhydride are added, 0.1 part of phosphoric acid is added, the temperature is raised to 210 ° C. in a nitrogen atmosphere, and the reaction is performed for 12 hours. When the temperature reached 0.4, 0.19 part of toluhydroquinone was added and cooled to 100 ° C. To this was added 1397 parts of vinyl toluene to obtain a homogeneous solution, and unsaturated polyester resin 4
655 parts were obtained.

[Synthesis Example 2] Synthesis of unsaturated polyester Propylene glycol 13 was added to a 5-liter four-necked flask equipped with a thermometer, stirrer, gas inlet, and reflux condenser.
95.5 parts, 1568.8 parts of phthalic anhydride, and 675.2 parts of maleic anhydride are added, 0.1 part of phosphoric acid is added, the temperature is raised to 210 ° C. in a nitrogen atmosphere, and the reaction is performed for 12 hours. When it became .4, 0.19 part of toluhydroquinone was added and cooled to 100 ° C. To this was added 1397 parts of styrene monomer to make a uniform solution, and unsaturated polyester resin 4
655 parts were obtained.

[Synthesis Example 3] Synthesis of vinyl ester resin 100 parts of bisphenol A type epoxy resin having an epoxy equivalent of 240 and 305 parts of bisphenol A type epoxy resin having an epoxy equivalent of 481 were charged and heated to 100 to 105 ° C. When the epoxy equivalent reached 380 ± 10, 1.7 parts of 2,6-di-Tert-til-4-methylphenol and 86 parts of methyl methacrylate were charged. Next, 1.0 part of Daito Clark HD-ACC-43 (trimethylbenzylammonium chloride, manufactured by Daito Sangyo Co., Ltd.) was charged and reacted at 90 to 93 ° C., and reacted with an acid value of 9 to 11. When hydroquinone monomethyl ether was 0.60. To this was added 56.6 parts of vinyltoluene to obtain a homogeneous solution to obtain 549.9 parts of vinyl ester resin.

[Synthesis Example 4] Synthesis of vinyl ester resin 100 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 240 and 305 parts of a bisphenol A type epoxy resin having an epoxy equivalent of 481 were charged and heated to 100 to 105 ° C. When the epoxy equivalent reached 380 ± 10, 1.7 parts of 2,6-di-Tert-butyl-4-methylphenol and 86 parts of methyl methacrylate were charged. Next, 1.0 part of Daito Clark HD-ACC-43 was charged and reacted at 90 to 93 ° C., and after reacting until the acid value was 9 to 11, 0.60 part of hydroquinone monomethyl ether was added to this, and styrene monomer 56.6 was added. Part was added to obtain a homogeneous solution to obtain 549.9 parts of vinyl ester resin.

[Example 1]
To 100 parts of the unsaturated polyester resin obtained in Synthesis Example 1, 200 parts of high white aluminum hydroxide 326S (manufactured by Sumitomo Chemical Co., Ltd.), Co-NAPHTHENATE 6% (6% cobalt naphthenate, manufactured by Dainippon Ink & Chemicals, Inc.) 0.5 parts and 1 part of Kayamek Kaya M (55% methyl ethyl ketone peroxide, manufactured by Kayaku Akzo) were added and mixed well to obtain a casting compound.
This casting compound was applied to a counter with a wash ball of 60 cm × 90 cm and a thickness of 13 mm coated with a release agent.
After pouring into the RP type and the compound gelled, it was left in a furnace at 60 ° C. for 1 hour, cooled and demolded to prepare a counter with a wash bowl. As a glazing process for the created wash counter, Sunjet P-555 (white rubbing compound,
Sansai Kako Co., Ltd.) was applied to a wash counter and polished using a polisher, wool buff or the like.

[Example 2]
A wash counter was prepared in the same manner as in Example 1 except that the unsaturated polyester resin in Example 1 was replaced with the vinyl ester resin obtained in Synthesis Example 3.
[Comparative Example 1]
A wash counter was prepared in the same manner as in Example 1 using the unsaturated polyester resin obtained in Synthesis Example 2.
[Comparative Example 2]
A wash counter was prepared in the same manner as in Example 1 using the vinyl ester resin obtained in Synthesis Example 4.

[Measurement test method]
From the flat part of the wash counter obtained in [Example 1], [Example 2], [Comparative Example 1] and [Comparative Example 2], test pieces of 60 mm × 60 mm × original thickness were respectively obtained based on JISK7105. The surface was measured for 60-degree specular gloss “Gs (60 °)” using a table-type gloss meter (GM-26D manufactured by Murakami Color Research Laboratory).

Claims (4)

A resin composition for artificial marble, comprising vinyl toluene and unsaturated polyester or vinyl ester resin. The resin composition for artificial marble according to claim 1, wherein the content of vinyl toluene is 20 to 80% by weight. Furthermore, the resin composition for artificial marble of Claim 1 or 2 containing an inorganic filler. An artificial marble obtained by molding the resin composition for artificial marble according to any one of claims 1 to 3, and having a 60-degree specular gloss of 90% or more measured by a method defined in JISK7105.