JPH05155993A - Resin for artificial marble - Google Patents

Abstract

PURPOSE:To obtain the subject resin which is useful for producing a highly transparent artificial marble by selecting such a specific oligomer as exhibits a given refractive index upon curing. CONSTITUTION:Selected is an oligomer having an allyl ester group at its terminal and comprising repeating units of formula I (wherein A is an organic residue derived from a 6-20C dibasic organic acid; and B is a divalent organic residue derived from a 2-30C diol) and formula II (wherein (x) is 2-10; and (z) is an organic residue derived from a polyol having OH groups numbering in (X+1)) in proportions of 90-100wt.% and 10-0wt.%, respectively. In the oligomer, 10-100mol% of the component A comprises an organic residue derived from naphthalenedicarboxylic acid, and 20-100mol% of the component B compresses and organic residue derived from an alkylene oxide adduct of bisphenol A. Upon curing, the oligomer has a refractive index of 1.57-1.59 to give the objective resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin for artificial marble, and also relates to a resin for artificial marble and a compound which use aluminum hydroxide as an inorganic filler and have excellent transparency, gloss and boiling resistance. ..

[0002]

2. Description of the Related Art Conventionally, artificial marble is used for vanities, bathtubs,
Widely used for sanitary ware such as kitchen counters, interior and exterior materials for construction, etc. When the artificial marble is obtained as a resin molded article, a resin as a matrix constituting the artificial marble is mixed with, for example, an inorganic filler or a fibrous reinforcing material and kneaded, and the composition is filled in a molding die and cured. The molding method is adopted. In addition, inorganic fillers and other extenders are blended with the resin, impregnated into glass fibers, etc., and both sides are wrapped with a film to form a sheet-like SMC (sheet molding compound) or similarly BMC (bulk-like). It is carried out by a molding method in which compression molding is performed using a molding compound).

The resin as the matrix is generally a methacrylic resin, an unsaturated polyester resin, an epoxy resin or the like, and has been improved as a resin for artificial marble. However, as a resin for the compression molding method, no system has been completed, and a compounding system excellent in transparency and gloss has not yet been obtained. Although it is said that the method of obtaining artificial marble by applying a gel coat and molding by cast molding is widely practiced industrially and it is almost completed, conversely, if importance is attached to transparency and luster, the particle size becomes large. There is a problem that an inorganic filler must be used, the amount used should be suppressed to 200 parts by weight or less with respect to 100 parts by weight of the resin, and the gel coat layer should be thickened and then polished to finish.

If an inorganic filler having a fine particle size is used,
Although gloss is obtained without applying a gel coat, in this case, there is a problem in that the resin system does not give a transparent feeling.
First, we filed a patent for a system using the following allyl ester oligomer as a matrix resin. -(COACOOBO) -Structure-1-(COACOO) _X -ZO-COACOO-Structure-2 where A is an organic residue derived from a divalent organic acid having 6 to 20 carbon atoms, and B is Divalent organic residue derived from diol having 2 to 30 carbon atoms, X is 2 or more 1
It is an integer of 0 or less, and Z represents an organic residue derived from a polyol having X + 1 hydroxyl groups.

This system is characterized in that it is hard to be cracked even when subjected to compression molding, has excellent boiling resistance, and has a low shrinkage ratio, so that it gives an artificial marble molded article having excellent luster. .. Regarding the transparency, although it is superior to the resin system, when a large amount of the inorganic filler is used to reduce the cost, there is a drawback that the transparency is deteriorated, especially for avoiding polishing finish. When an inorganic filler having a small particle size was used, the transparency was completely lost.

[0006]

[Problems to be Solved by the Invention]
We develop a resin for artificial marble and a compound for artificial marble that does not need to be polished and does not lose transparency even if an inorganic filler with a small particle size is used, and that has excellent boiling resistance and compression moldability.

[0007]

[Means for Solving the Problems] Focusing on the boiling resistance and moldability of allyl ester oligomers, the results of studies aimed at improving transparency in this system revealed that
The inventors have found that the above-mentioned problems can be achieved by using a specific allyl ester resin and an inorganic filler, and have completed the present invention.

The invention according to claim 1 of the present invention is an oligomer having an allyl ester group at a terminal and having a repeating unit of the following structure:-(COACOOBO) -Structure-1 90-100 wt%-(COACOO) _X -ZO-COACOO-Structure-2 10 to 0 wt% (where A is an organic residue derived from a divalent organic acid having 6 to 20 carbon atoms, and B is from 2 to 30 carbon atoms) A divalent organic residue derived from diol, x is 2 to 10
And Z represents an organic residue derived from a polyol having x + 1 hydroxyl groups), and 10 to 100 mol% of the organic residue derived from naphthalene dicarboxylic acid is used as the A component in the A component, or Is an organic residue derived from an alkylene oxide adduct of bisphenol A as the component B in an amount of 20 to 100 mol% in the component B.
It is a resin for artificial marble in which the cured product of the above oligomer has a refractive index of 1.57 to 1.59. If the content of the structure-2 exceeds 10 wt%, the resin gels and becomes unsuitable as a resin for artificial marble.

As a method for producing the above-mentioned oligomer, (a) naphthalene dicarboxylic acid is used as the divalent organic acid for inducing the A component, or an alkylene oxide adduct of bisphenol A is used as a diol for inducing the B component. The oligomer produced using the above is prepared by using an organic acid having 6 to 20 carbon atoms as the divalent organic acid for inducing the A component, and using a diol having 2 to 30 carbon atoms as the diol inducing the B component. A method of blending with an oligomer produced using a polyol having x + 1 hydroxyl groups as the polyol for deriving the Z component,
(B) An oligomer produced by using naphthalene dicarboxylic acid as the divalent organic acid for inducing the component A and an alkylene oxide adduct of bisphenol A as the diol for inducing the component B is used to derive the component A. An organic acid having 6 to 20 carbon atoms is used as the divalent organic acid, a diol having 2 to 30 carbon atoms is used as the diol for inducing the B component, and x + 1 polyols for inducing the Z component are used. A method of blending with an oligomer produced using a polyol having a hydroxyl group, and (c) whether a divalent organic acid having 6 to 20 carbon atoms and naphthalene dicarboxylic acid are used as the divalent organic acid for inducing the component A. Or a diol having 2 to 30 carbon atoms as the diol for deriving the B component, and deriving the Z component Method for producing a time using the alkylene oxide adducts of polyols and bisphenol A having x + 1 hydroxyl groups as triol, (d)
The divalent organic acid for inducing the component A has 6 to 6 carbon atoms.
A divalent organic acid consisting of 20 and naphthalene dicarboxylic acid are used, and a diol having 2 to 30 carbon atoms as the diol for inducing the B component, a polyol having x + 1 hydroxyl groups and a bisphenol as the polyol for inducing the Z component. Examples thereof include a method of producing the alkylene oxide adduct of A at once, but are not limited thereto. The above-mentioned oligomer usually contains a residual monomer which is an unreacted raw material, but an oligomer containing this residual monomer can also be used in the present invention as the above-mentioned oligomer.

The invention of claim 2 of the present invention comprises 30 to 100 wt% of the oligomer of claim 1, 0 to 50 wt% of an unsaturated alkyd or vinyl ester, and 0 to 40 wt% of a reactive monomer. The cured product has a refractive index of 1.57
It is a resin for artificial marble which is adjusted to be ~ 1.59.

According to a third aspect of the present invention, 100 parts by weight of the oligomer of the first aspect or 100 parts by weight of the resin of the second aspect is 100 to 100 parts of aluminum hydroxide having an average particle diameter of 0.5 to 30 μm.
It is a compound for artificial marble containing 500 parts by weight and 0 to 80 parts by weight of glass fiber.

As the filler used in the present invention, it is necessary to select aluminum hydroxide having a particle size of 0.5 to 30 μm. This is important for producing transparency and luster, and only when the resin for artificial marble of the present invention and aluminum hydroxide are combined, it is possible to obtain artificial marble excellent in transparency and luster. When glass is used instead of, the transparency is significantly impaired. Further, it is not preferable to use particles having a particle size of 30 μm or more because not only the gloss is impaired but also the transparency is rather deteriorated.

Examples of the diol having 2 to 20 carbon atoms for inducing B include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, 1,5-Pentanediol, hexamethylene glycol, heptamethylene glycol, octamethylene glycol, nonamethylene glycol, decamethylene glycol, undecamethylene glycol, dodecamethylene glycol, tridecamethylene glycol, eicosamethylene glycol, hydrogenated bisphenol- A, 1, 4
-Cyclohexanedimethanol, 2-ethyl-2,5-
Saturated glycol composed of only carbon such as pentanediol, 2-ethyl-1,3-hexanediol and styrene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, ethylene oxide adduct of bisphenol-A, bisphenol- A divalent saturated alcohol containing an ether group such as a propylene oxide adduct of A and a glycol containing bromine such as dibromoneopentyl glycol are also included. Among these, propylene glycol and 1,
When a glycol such as 3-butanediol or dipropylene glycol is used, the compatibility with other copolymerizable monomers is good and the transparency of the cured product is excellent.

As the polyol having X + 1 hydroxyl groups for inducing Z, aliphatic trihydric alcohols such as glycerin and trimethylolpropane, pentaerythritol,
Examples include aliphatic tetrahydric or higher alcohols such as sorbitol. The use of these is preferable from the viewpoint of heat resistance, but since the viscosity of the produced allyl ester oligomer is remarkably increased, it is preferable to use only a small amount.

As the divalent saturated carboxylic acid which gives A, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, β-methyladipic acid, pimelic acid,
Corkic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid,
Dodecanedicarboxylic acid, 1,2- or 1,3- or 1,4-cyclohexanedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid, diphenyl-p, p'-dicarboxylic acid, diphenyl-m, m'-dicarboxylic acid , 1,
4- or 1,5- or 2,6- or 2,7-naphthalene dicarboxylic acid, diphenylmethane-p, p'-dicarboxylic acid, diphenylmethane-m, m'-dicarboxylic acid, benzophenone-4,4'-dicarboxylic acid , P-phenylenediacetic acid, p-carboxyphenylacetic acid, methylterephthalic acid, tetrachlorophthalic acid and the like. Of these, divalent saturated carboxylic acids containing a benzene ring, such as terephthalic acid and isophthalic acid, are particularly preferable for improving heat resistance and boiling resistance.

As the component A used in the present invention, an organic residue derived from naphthalene dicarboxylic acid is added to the component 1 in the component A.
0-100 mol% is used. The naphthalene dicarboxylic acid used in the present invention includes 1,2-, 1,3-, 1,4
-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3
Mention may be made of-, 2,6-, 2,7-naphthalene dicarboxylic acid. Among these, 2,6-naphthalene dicarboxylic acid is more preferable.

Among these raw materials, at least one of a naphthalene dicarboxylic acid derivative as a divalent organic acid for inducing the component A and an alkylene oxide adduct of bisphenol A as a diol for inducing the component B may be used. 2, as a divalent organic acid that induces component A
It is also possible to use a 6-naphthalene dicarboxylic acid derivative and further use an alkylene oxide adduct of bisphenol A as a diol that induces the B component.

In order to set the refractive index after curing of the artificial marble resin of the present invention in the range of 1.57 to 1.59, bisphenol-A as a diol having 2 to 20 carbon atoms for inducing B is used. 1,4 as a divalent saturated carboxylic acid such as ethylene oxide adduct, propylene oxide adduct of bisphenol-A, and / or A
-Or 1,5- or 2,6- or 2,7-naphthalene dicarboxylic acid by using a part of the raw material,
It can be included within the range of the refractive index.

However, since the refractive index changes depending on the combination of the raw materials used, and the additive rule does not hold depending on the combination of the raw materials, there is a problem that it is difficult to unconditionally specify. Next, specific examples for setting the refractive index after curing to the range of 1.57 to 1.59 will be described. Induce the A component 2
When only benzenedicarboxylic acid such as isophthalic acid or terephthalic acid is used as the valent organic acid, 20 mol% or more of the diol for inducing the B component is bisphenol-A.
The alkylene oxide adduct of is used. When the diol that induces the B component is only a saturated aliphatic hydrocarbon such as propylene glycol or neopentyl glycol,
As the divalent organic acid for inducing the component A, naphthalene dicarboxylic acid is used in the range of 30 to 70 mol%, and the rest is benzene dicarboxylic acid. When adipic acid is used as the divalent organic acid that induces the component A, it is necessary to use 50 to 90 mol% of naphthalene dicarboxylic acid.

Since the allyl ester oligomer of the artificial marble resin of the present invention has poor curability, it is possible to improve the curability by adding an unsaturated polyester resin or vinyl ester resin. If the amount of these compounds used is too large, the good boiling resistance of the allyl ester is impaired in addition to the decrease in the refractive index. In the case of the unsaturated alkyd, about 30 wt% is the limit of the amount that can be used, and generally it should be limited to 50 wt% or less, more preferably 30 wt% or less in the organic component.

Further, other reactive monomer may be added for the purpose of improving the polymerizability and surface hardness. Examples of such reactive monomers include unsaturated fatty acid esters, aromatic vinyl compounds, unsaturated fatty acids and their derivatives, unsaturated dibasic acids and their derivatives, saturated aliphatic or aromatic carboxylic acid vinyl esters and their derivatives. Examples thereof include derivatives and vinyl cyanide compounds such as (meth) acrylonitrile.

As the unsaturated fatty acid ester, methyl (meth) acrylate, ethyl (meth) acrylate,
Alkyl (meth) acrylates such as butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 1
-Naphthyl (meth) acrylate, chlorophenyl (meth) acrylate, bromophenyl (meth) acrylate, tribromophenyl (meth) acrylate, methoxyphenyl (meth) acrylate, biphenyl (meth)
There are (meth) acrylic acid aromatic esters such as acrylate and bromobenzyl (meth) acrylate, and (meth) acrylic acid esters such as glycidyl (meth) acrylate.

As the aromatic vinyl compound, styrene or α-methylstyrene, α-ethylstyrene, α-
Α-Substituted styrene such as chlorostyrene, nuclear substituted styrene such as fluorostyrene, chlorostyrene, bromostyrene, chloromethylstyrene and methoxystyrene.

The unsaturated fatty acid and its derivative include
There are (meth) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and (meth) acrylic acid.

Examples of the unsaturated dibasic acid and its derivative include N-methylmaleimide, N-ethylmaleimide and N-methylmaleimide.
-Butyl maleimide, N-cyclohexyl maleimide,
There are N-substituted maleimides such as N-phenylmaleimide, N-methylphenylmaleimide, N-chlorophenylmaleimide and N-carboxyphenylmaleimide, maleic acid, maleic anhydride, fumaric acid and the like.

Vinyl esters of saturated aliphatic or aromatic carboxylic acids and derivatives thereof include vinyl acetate, vinyl propionate, vinyl benzoate, n-vinyl butyrate and the like.

A crosslinkable polyfunctional monomer can also be used,
As such, for example, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth)
Acrylate, tetraethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentadiol Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Hydroxypivalic acid neopentyl glycol ester di (meth) acrylate, oligoester di (meth) acrylate, polybutadiene di (meth) acrylate,
2,2-bis (4- (meth) acryloyloxyphenyl) propane, 2,2-bis (4- (ω- (meth) acryloyloxypolyethoxy) phenyl) propane,
2,2-bis (4- (ω- (meth) acryloyloxypolyethoxy) dibromophenyl) propane, 2,2-
Di (meth) acrylates such as bis (4- (ω- (meth) acryloyloxypolypropoxy) phenyl) propane and bis (4- (ω- (meth) acryloyloxypolyethoxy) phenyl) methane, diallyl phthalate, diallyl Isophthalate, diallyl terephthalate, 2,6-naphthalenedicarboxylic acid diallyl ester, diallyl carbonate, diethylene glycol diallyl carbonate, divinylbenzene, N, N'-m-
Bifunctional crosslinkable monomers such as phenylene bismaleimide, trimethylolethane tri (meth) acrylate,
Trifunctional cross-linking of trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tri (meth) allyl isocyanurate, tri (meth) allyl cyanurate, triallyl trimellitate, diallyl chlorendate, etc. And a tetrafunctional crosslinking monomer such as pentaerythritol tetra (meth) acrylate.

Unsaturated polyester resins and vinyl ester resins can be used as well as these copolymerizable monomers.

Of these, considering the copolymerizability with the allyl group in the polymerizable oligomer of the artificial marble resin of the present invention, aromatic allyl esters such as diallyl phthalate, diallyl isophthalate and diallyl terephthalate, and (meth) acrylic acid. Esters and vinyl acetate are preferred. Further, there is 2,6-naphthalene dicarboxylic acid diallyl ester as a monomer for increasing the refractive index, and it is particularly preferable to add a crosslinkable polyfunctional monomer in order to increase the surface hardness.

If the amount of the reactive monomer used is too large, the refractive index will be lowered depending on the monomer, and the shrinkage ratio will be large, resulting in loss of the moldability of the allyl ester. Therefore, generally, 40% by weight or less, and more preferably 20% by weight or less in the organic component is suitable. However, the amount of reactive monomer compounded is
Depending on the monomers used, the limit is about 5 wt% for methyl methacrylate monomers, but up to about 60 wt% can be used for monomers with a high refractive index such as phenyl methacrylate.

As described above, in order to enhance the transparency, the cured product of the resin for artificial marble of the present invention has a refractive index of 1.57 to.
It should be within the range of 1.59, more preferably 1.575 to 1.585. When the above-mentioned aluminum hydroxide having a small particle size is used together with the resin for artificial marble of the present invention to form the compound for artificial marble of the present invention, the most transparent feeling is obtained when the resin having the refractive index of about 1.58 is used. .. When a resin having a refractive index of 1.575 or less, or 1.585 or more is used, the transparency is drastically reduced.

The ratio of the resin for artificial marble to aluminum hydroxide in the compound for artificial marble of the present invention is as follows:
If the artificial marble resin is too small, there is a problem that it is difficult to knead. On the other hand, if the ratio is too large, the shrinkage ratio becomes large and the transparency is not so improved. Therefore, it is desirable to use 100 to 500 parts by weight of aluminum hydroxide, more preferably 150 to 450 parts by weight, based on 100 parts by weight of the resin for artificial marble.

Further, glass fibers can be used to improve the strength of the cured product, but if too much is used, the surface gloss will be poor, so 120 parts by weight or less, more preferably 100 parts by weight of the artificial marble resin, is more preferable. Is preferably controlled to 80 parts by weight or less.

The compound for artificial marble of the present invention can be molded as artificial marble by polymerizing and hardening. The curing agent used here is heat,
Any radical polymerization initiator can be used as long as it can generate radicals by microwaves, infrared rays, or ultraviolet rays, and can be appropriately selected depending on the use, purpose, blending ratio of components, curing method and the like.

Examples of the radical polymerization initiator which can be used in the polymerization by heat, microwave and infrared rays include 2,
Azo compounds such as 2'-azobisisobutyronitrile and 2,2'-azobisisovaleronitrile, ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, cyclohexanone peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide lauroyl peroxide, p
-Diacyl peroxides such as chlorobenzoyl peroxide, hydroperoxides such as 2,4,4-trimethylpentyl-2-hydroperoxide, cumene hydroperoxide and t-butyl peroxide, dicumyl peroxide, t -Butyl cumyl peroxide, di-t-butyl peroxide, dialkyl peroxides such as tris (t-butylperoxy) triazine, 1,1-di-
t-butylperoxycyclohexane, 2,2-di (t
-Butylperoxy) butane, etc., peroxyketals, t-butylperoxypivalate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, di-t-butylperoxy Hexahydroterephthalate, di-t-butylperoxyazelate, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxyacetate,
Alkyl peresters such as t-butyl peroxybenzoate, di-t-butyl peroxytrimethyl adipate, diisopropyl peroxydicarbonate, di-
Percarbonates such as sec-butyl peroxydicarbonate and t-butyl peroxyisopropyl carbonate can be mentioned.

Radical polymerization initiators that can be used in the polymerization by ultraviolet rays include, for example, acetophenone, 2,
2-dimethoxy-2-phenylacetophenone, 2,2
-Diethoxyacetophenone, 4'-isopropyl-2
-Hydroxy-2-methylpropiophenone, 2-hydroxy-2-methylpropiophenone, 4,4'-bis (diethylamino) benzophenone, benzophenone,
Methyl (o-benzoyl) benzoate, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (o-benzoyl) oxime, benzoin , Benzoin methyl ether, benzoin ethyl ether,
Benzoin isopropyl ether, benzoin isobutyl ether, benzoin octyl ether, benzyl,
Carbonyl compounds such as benzyl dimethyl ketal, benzyl diethyl ketal and diacetyl, anthraquinones or thioxanthone derivatives such as methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone, sulfur compounds such as diphenyldisulfide and dithiocarbamate. Be done.

These are preferably used in an amount of 0.1 to 10 parts by weight, more preferably 0.5 to 3 parts by weight, based on the polymerizable oligomer of the artificial marble resin of the present invention. It goes without saying that the polymerization initiator may be used in combination with another polymerization accelerator.

If necessary, other known additives such as a plasticizer, a lubricant, a mold release agent, a colorant, a flame retardant, an ultraviolet absorber and the like may be added to the artificial marble resin and artificial marble compound of the present invention. It can be contained within a range that does not impair transparency and physical properties.

The resin for artificial marble and the compound for artificial marble of the present invention are prepared by blending the above-mentioned materials and stirring them sufficiently to obtain a homogenized composition. The composition thus obtained is poured into a mold having a desired shape, deaerated, and polymerized and cured by heating to obtain a molded body. The homogenized composition may be wrapped with a film to form a sheet-shaped SMC or a block-shaped BMC, which can be cured by pressure molding according to ordinary molding means to form a molded article.

[0040]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the invention is not limited to the examples without departing from the gist of the present invention. Method for producing allyl ester oligomer (Reference Example 1) 2.5 l of diallyl terephthalate (hereinafter abbreviated as DAT) was placed in a 10 l autoclave equipped with a distillation apparatus.
2.5 kg of 2,6-naphthalene dicarboxylic acid diallyl ester (hereinafter abbreviated as DAN), propylene glycol (hereinafter abbreviated as PG) 0.943 kg, and dibutyltin oxide (hereinafter abbreviated as DBO) 6 g were charged under a nitrogen stream. The resulting allyl alcohol was distilled off. When about 1.0 kg of allyl alcohol was distilled, the pressure inside the reaction system was reduced to 50 mmHg to accelerate the distillation rate of allyl alcohol. After the theoretical amount of allyl alcohol had been distilled off, the reaction was allowed to react for an additional hour and the reaction mass was cooled.
The reaction liquid contained 12 wt% of residual monomer,
This was used as it was as a raw material for a resin for artificial marble and a compound for artificial marble. This product has an iodine value of 5
9.3, the molecular weight by GPC is Mn = 1.45 ×
10 ² and Mw = 3.13 × 10 ³ . The iodine value was measured with the residual monomer contained.

Reference Examples 2 to 4 The raw materials of Reference Example 1 are shown in Table 1.
Reactions were performed in the same manner as in Reference Example 1 except that the composition was changed to that shown in Table 1 to obtain a resin for artificial marble and a raw material for a compound for artificial marble.

Reference Examples 5 to 7 An organic residue derived from naphthalene dicarboxylic acid as the component A used in the present invention or a bisphenol as the component B for use as a raw material of the resin for artificial marble of the present invention. An allyl ester oligomer containing no organic residue derived from the alkylene oxide adduct of A was prepared by reacting in the same manner as in Reference Example 1 using the composition shown in Table 1. The analytical values of these raw materials are also shown in Table 1.

[0043]

[Table 1]

Example 1 The polymerizable oligomer resin for artificial marble obtained in Reference Example 1 was mixed with the aliester oligomer of Reference Example 7 in a liquid-liquid state at a ratio shown in Table 2, Add 2 parts by weight of dicumyl peroxide,
A spacer is sandwiched between two cellophane-tensioned glass plates, the silicone tube is surrounded on three sides, and the mixture is cast between the glass plates. 110 ° C / 1 hr in a gear oven.
The curing reaction was performed at 160 ° C., and after-curing at 160 ° C. for 5 hours, the refractive index of the cured product was measured. The refractive index of the cured product is shown in Table 2.
Are shown together with.

100 parts by weight of the artificial marble resin mixed in the proportions shown in Table 2 and 200 parts by weight of fine-grained aluminum hydroxide (Showa Denko, trade name: Hijilite H-320ST) were stirred under heating and uniformly mixed. Dispersed. Further, 2 parts by weight of dicumyl peroxide was added thereto, and the mixture was stirred and deaerated under reduced pressure to obtain a compound for artificial marble.

The artificial marble compound thus obtained was cast into a metal mold of 40 mmφ × 40 mm, and 1
When cured by heating at 70 ° C. for 1 hour, a marble-like molded product which scatters light beautifully and which has both depth and concealing property and which is very excellent in transparency is obtained. About the obtained molded product,
The Hunter chromaticity was measured with a colorimeter and the hardness was measured with a Barcol hardness meter. These results are shown in Table 2.
Are shown together with.

(Examples 2 to 6) The same procedure as in Example 1 was carried out except that the artificial marble resin mixed in the proportions shown in Table 2 was used. When the obtained compound for artificial marble was heat-cured in the same manner as in Example 1, a marble-like molded product which scatters light beautifully and which has both depth and concealing property and which is very excellent in transparency is obtained. .. The results are also shown in Table 2.

Comparative Example 1 The same procedure as in Example 1 was repeated except that the allyl ester oligomer of Reference Example 7 and methyl methacrylate (abbreviated as MMA monomer) were mixed in the proportions shown in Table 2. It was When the obtained artificial marble compound was heat-cured in the same manner as in Example 1, a marble-like molded product was obtained, but the hardness and transparency were poor. The results are also shown in Table 2.

The lower the L value, the higher the transparency. Therefore, when an allyl ester oligomer having a refractive index in the range of 1.57 to 1.59 is used as a resin for artificial marble, the marble-like appearance is excellent. It can be seen that a molded product is obtained.

[0050]

[Table 2]

[0051]

EFFECT OF THE INVENTION By using the resin for artificial marble of the present invention having a refractive index after curing of 1.57 to 1.59 as a resin constituting a matrix of artificial marble, artificial marble having an excellent transparency. It became possible to obtain. The resin for artificial marble and the compound for artificial marble of the present invention can be used without loss of transparency and gloss even when press-molded, and therefore has a great industrial utility value.

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Claims (3)

[Claims] 1. An oligomer having an allyl ester group at a terminal and having a repeating unit of the following structure:-(COACOOBO) -Structure-1 90-100 wt%-(COACOO) _X -ZO-COACOO- Structure-2 10 to 0 wt% (where A is an organic residue derived from a divalent organic acid having 6 to 20 carbon atoms, and B is a divalent organic residue derived from a diol having 2 to 30 carbon atoms) Organic residue, x is 2 to 10
And Z represents an organic residue derived from a polyol having x + 1 hydroxyl groups), and 10 to 100 mol% of the organic residue derived from naphthalene dicarboxylic acid is used as the A component in the A component, or Uses an organic residue derived from an alkylene oxide adduct of bisphenol A as the B component in an amount of 20 to 100 mol% in the B component, whereby the cured product of the oligomer has a refractive index of 1.57 to 1.59. Resin for artificial marble made in this way. 2. The oligomer of claim 1, 30 to 100 wt%, unsaturated alkyd or vinyl ester, 0 to 50 wt%, and reactive monomer, 0 to 40 wt%, are blended, and the cured product of these blends has a refractive index of 1. 57
Resin for artificial marble designed to be ~ 1.59. 3. 100 parts by weight of the oligomer of claim 1 or 100 parts by weight of the resin of claim 2 and 100 to 500 parts by weight of aluminum hydroxide having an average particle diameter of 0.5 to 30 μm, and 0 to 80 parts by weight of glass fiber. Compound for artificial marble.