JPH08127629A - Resin composition for artificial marble - Google Patents

Abstract

PURPOSE: To obtain a resin composition for a artificial marble composed of a specific acid anhydride-modified vinylester resin, a vinylic compound and an inorganic filler, capable of keeping transparency even if exposed to hot water or high temperature for a long time and not causing the change in appearance such as discoloration or whitening. CONSTITUTION: This composition consists essentially of (A) an acid anhydride- modified vinyl ester resin obtained by reacting a hydroxyl group in an epoxy vinyl ester resin with a polybasic acid anhydride having a long-chain alkyl or long-chain alkenyl (preferably an alkyl-substituted aliphatic dibasic acid anhydride such as hexylsuccinic anhydride), (B) a vinylic compound (preferably an aromatic monovinyl compound such as styrene) and (C) inorganic filler (preferably aluminum hydride). Furthermore, the epoxy vinyl ester resin constituting the component A is normally obtained by reaction by an epoxy resin with an unsaturated monobasic acid such as (meth)acrylic acid and a bisphenol-type epoxy resin is preferably used as the epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for artificial marble which is useful for bathtubs, vanities, countertops and the like having excellent hot water resistance and transparency.

[0002]

2. Description of the Related Art As resins for artificial marble, acrylic resin systems using acrylic syrup, unsaturated polyester resins, etc. are mainly used. However, since artificial marble using these cannot give a deep and transparent feeling, so-called vinyl ester resin, which is obtained by modifying epoxy resin with (meth) acrylic acid in recent years, has excellent transparency and excellent texture. Widely studied from the point of having, as a specific group, bisphenol type epoxy resin modified with acrylic acid to give an epoxy vinyl ester resin, an acid anhydride obtained by reacting the hydroxyl group present in this resin with phthalic acid. A technique using a substance-modified vinyl ester resin is known.

[0003]

However, an artificial marble molded article obtained by using a conventional acid anhydride-modified vinyl ester resin has an interfacial peeling at the interface between the filler and the resin due to boiling for several tens of hours. It becomes white and loses its transparency.
Further, there is a problem that defects such as discoloration occur.

The problem to be solved by the present invention is to provide a hot water-resistant material which does not lose the transparency and does not change its appearance such as discoloration even when the cured product is exposed to hot water for a long time. It is to provide an excellent resin composition for artificial marble.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that by adding a specific acid anhydride to a vinyl ester resin, the hot water or high temperature for a long time can be maintained. It was found that a resin composition for artificial marble excellent in hot water resistance, which loses transparency and does not change in appearance such as whitening or discoloration, can be obtained even when exposed, and completed the present invention. .

That is, the present invention provides an acid anhydride-modified vinyl ester having a structure obtained by reacting a hydroxyl group in an epoxy vinyl ester resin with a polybasic acid anhydride having a long chain alkyl group or a long chain alkenyl group in the molecular structure. The present invention relates to a resin composition for artificial marble, which comprises a resin (A), a vinyl compound (B), and an inorganic filler (C) as essential components.

The epoxy vinyl ester resin constituting the acid anhydride vinyl ester resin (A) used in the present invention has a structure obtained by the reaction between the epoxy resin and the unsaturated monobasic acid. Has a secondary hydroxyl group formed by the reaction between the glycidyl group in the epoxy resin and the carboxylic acid in the unsaturated monobasic acid.

First, as the epoxy resin used here, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, tetrabromobisphenol A type epoxy resin or other bisphenol type epoxy resin; phenol novolac type epoxy resin, phenol novolac type Glycidyl ethers of polyhydric alcohols such as epoxy resins, cresol novolac type epoxy resins and other novolac type epoxy resins; dipropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, diglycidyl ether of alkylene oxide adduct of bisphenol A, etc. 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate,
Alicyclic epoxy resins such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and 1-epoxyethyl-3,4-epoxycyclohexane; phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, diglycidyl Glycidyl esters such as p-oxybenzoic acid and dimer acid glycidyl ester; tetraglycidyl diaminodiphenylmethane, tetraglycidyl m-xylylenediamine,
Glycidyl amines such as triglycidyl P-aminophenol and N, N-diglycidyl aniline; heterocyclic epoxy resins such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate;
2 ', 4,4'-tetraglycidoxy biphenyl, dimethyl bisphenol C diglycidyl ether, bis beta trifluoromethyl diglycidyl bisphenol A
And the like. These resins may be used alone or in combination of two or more.

Among them, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol type epoxy resins such as tetrabromobisphenol A type epoxy resins, and phenol novolac type epoxy resins are excellent in boiling resistance. Resin, novolac type epoxy resin such as cresol novolac type epoxy resin is preferable,
Particularly, a bisphenol type epoxy resin is preferable because it has excellent fluidity and good adhesion with the inorganic filler (C).

Next, the unsaturated monobasic acid to be reacted with the epoxy resin is not particularly limited,
Examples thereof include acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, acrylic acid dimer, monomethylmalate, monopropylmalate, monobutylmalate, mono (2-ethylhexyl) malate, and sorbic acid. These acids may be used alone or in combination of two or more kinds.

The mixing ratio of the epoxy resin and the unsaturated monobasic acid is not particularly limited, but is usually 1.0 equivalent of the epoxy group of the resin to the carboxyl group in the unsaturated monobasic acid. Of 0.8 to 1.2 equivalents, and above all, a range of 0.90 to 1.05 equivalents is preferable from the viewpoint of obtaining a resin having excellent curability and storage stability.

In the reaction between the epoxy resin and the unsaturated monobasic acid, it is preferable to use an esterification catalyst in order to efficiently proceed the esterification reaction and suppress other side reactions.

Examples of the esterification catalyst include triethylamine, benzyldimethylamine, α-methylbenzyldimethylamine, dimethylaminomethylphenol,
Tertiary amines such as tridimethylaminomethylphenol; quaternary ammonium salts such as trimethylammonium chloride, trimethylammonium bromide, triethylbenzylammonium chloride; imidazole compounds such as 2-methylimidazole and 2-ethyl-4-methylimidazole An organic phosphine compound such as triphenylphosphine and the like.

When such an esterification catalyst is used, the amount used is usually in the range of 0.01 to 5.0% with respect to the total weight of the epoxy resin and the unsaturated monobasic acid, preferably 0.05. A range of up to 2.0% is suitable.

In the esterification reaction, a polymerization inhibitor is used to prevent gelation during the production of the vinyl ester resin and to prevent gelation of the finished vinyl ester resin during storage. It is preferable to do.

Examples of such a polymerization inhibitor include hydroquinone, pt-butylcatechol, and 2,5-di-t.
-Hydroquinones such as butyl hydroquinone and mono-t-butyl hydroquinone; p-benzoquinone, naphthoquinone, phenanthraquinone, 2,5-diphenyl-
Quinones such as p-benzoquinone; hydroquinone monomethyl ether, di-t-butyl-p-cresol,
Examples thereof include phenols such as 2,5 di-t-butyl 4-methylphenol; copper salts such as copper naphthenate.

The reaction temperature is not particularly limited, but usually it can be carried out in the range of 90 to 120 ° C.

As described above, the epoxy vinyl ester resin thus obtained has a hydroxyl group formed by the reaction of a glycidyl group and a carboxyl group. In the present invention, the hydroxyl group is a long-chain alkyl group. Alternatively, the desired acid anhydride vinyl ester resin (A) can be obtained by reacting a polybasic acid anhydride having a long-chain alkenyl group.

When the epoxy resin used is a bisphenol type epoxy resin, the epoxy resin also has a hydroxyl group, and this hydroxyl group has a long-chain alkyl group or a long-chain alkenyl in the molecular structure. It may be modified with a polybasic acid anhydride having a group.

Examples of the polybasic acid anhydride having an alkyl group or an alkenyl group in the molecular structure (hereinafter simply referred to as "polybasic acid anhydride") used herein include, for example, hexyl succinic anhydride and octyl succinic anhydride. Acid, nonyl succinic anhydride, decyl succinic anhydride, undecyl succinic anhydride, dodecyl succinic anhydride, tridecyl succinic anhydride, tetradecyl succinic anhydride, pentadecyl succinic anhydride, hexadecyl succinic anhydride, octadecyl succinic anhydride, pentyl glutaric anhydride Acids, dodecyl glutaric anhydride, alkyl-substituted aliphatic dibasic acid anhydrides such as octadecyl glutaric anhydride, pentenyl succinic anhydride, hexenyl succinic anhydride, octenyl succinic anhydride, decenyl succinic anhydride, undecenyl succinic anhydride, dodecenyl anhydride Succinic acid, toride Alkenyl-substituted aliphatic dibasic anhydrides such as succinic anhydride, tetradecenyl succinic anhydride, pentadecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, pentenyl glutaric anhydride, dodecenyl glutaric anhydride, octadecenyl glutaric anhydride, etc. Alkyl-substituted aromatic dibasic anhydrides such as pentyl phthalic anhydride, dodecyl phthalic anhydride and octadecyl phthalic anhydride, alkenyl-substituted aromatic dibasic anhydrides such as pentenyl phthalic anhydride, dodecenyl phthalic anhydride and octadecenyl phthalic anhydride Acid anhydrides, pentyltetrahydrophthalic anhydride, dodecyltetrahydrophthalic anhydride, octadecyltetrahydrophthalic anhydride, pentylhexahydrophthalic anhydride, dodecylhexahydrophthalic anhydride, octadecylhexyl Alkyl-substituted alicyclic dibasic acid anhydrides such as hydrophthalic anhydride, pentenyltetrahydrophthalic anhydride, dodecenyltetrahydrophthalic anhydride, octadecenyltetrahydrophthalic anhydride, pentenylhexahydrophthalic anhydride, Examples thereof include alkenyl-substituted alicyclic dibasic acid anhydrides such as decenyl hexahydrophthalic anhydride and octadecenyl hexahydrophthalic anhydride.

Among these, from the viewpoint that the flexibility of the present invention is particularly high and the effect of the present invention is remarkable, an alkyl-substituted aliphatic dibasic acid anhydride, an alkenyl-substituted aliphatic dibasic acid anhydride, an alkyl-substituted alicyclic dibase Acid anhydrides, alkenyl-substituted alicyclic dibasic acid anhydrides and the like are preferable.

The long-chain alkyl group or the long-chain alkenyl group of these polybasic acid anhydrides has 5 to 5 carbon atoms.
It is preferable that the number is 0, especially 6 to 20, because the transparency is not deteriorated due to discoloration or whitening.

The reaction ratio between the polybasic acid anhydride and the vinyl ester resin is usually 0.03 to 0.03 of the acid anhydride group of the polybasic acid anhydride with respect to 1.00 equivalent of the hydroxyl group of the vinyl ester resin. Within the range of 0.50 equivalents, the range of 0.05 to 0.40 equivalents is suitable since the deterioration of transparency due to discoloration or whitening is small. The reaction temperature is not particularly limited, but is preferably in the range of 60 to 100 ° C.

The acid anhydride vinyl ester resin (A) thus obtained is not particularly specified in its specific structure, and its number average molecular weight is usually 1,000 to 2,
It is preferably 000, and for example, a bisphenol type epoxy resin reacted with (meth) acrylic acid and a polybasic acid anhydride reacted therewith include those represented by the following structural formulas. To be

[0025]

Embedded image

(Wherein R'represents a hydrogen atom or a methyl group, X represents a linear alkylene group, alicyclic alkylene group, or arylene group, and Y represents a long-chain alkyl group or a long-chain alkenyl group. , N represents the average degree of polymerization,
It is an integer of 0-4. )

Next, as the vinyl compound (B),
Although not particularly limited, for example, aromatic monovinyl compounds such as styrene, vinyltoluene, p-methylstyrene, α-methylstyrene, t-butylstyrene, halogenated styrene; vinyl pivalate, vinyl 2-ethylhexanoate. Carboxylic acid monovinyl esters such as vinyl laurate and vinyl benzoate; 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate Esters of (meth) acrylic acid, such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate; hydroxyethyl (meth) acrylate, hydroxypropyl Pill hydroxyalkyl (meth) acrylates such as (meth) acrylate; methoxyethyl (meth) acrylate, ethoxyethyl (meth)
Alkoxyalkylene glycol mono (meth) acrylates such as acrylates; N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, t- Aminoalkyl (meth) acrylates such as butylaminoethyl (meth) acrylate; (meth) acrylamide, N-methyl (meth) acrylamide, N, N-dimethylacrylamide, N, N-dimethyl (meth) acrylamide, (meth) (Meth) acrylamides such as acryloylmorpholine; vinylpyrrolidone, trimethylolpropane tri (meth) acrylate, glyceryl tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythrium Alkylene polyols poly (meth) acrylates such as litol tetra (meth) acrylate, dipentaerythritol-penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate; polyethoxylated trimethylolpropane tri (meth) acrylate, poly Polyoxyalkylene glycol poly (meth) acrylates such as propoxylated trimethylolpropane tri (meth) acrylate; hydroxyalkyl poly (meth) acrylates such as pentaerythritol tri (meth) acrylate; tris [(meth) acryloxyethyl] Examples include isocyanurate-type poly (meth) acrylates such as isocyanurate; allyl monomers such as triallyl isocyanurate; and tri (meth) acrylate phosphate.

These monomers having an ethylenically unsaturated double bond can be used alone or in combination of two or more. Of these, aromatic monovinyl compounds are particularly preferable.

The amount of the vinyl compound (B) used is 100% of the acid anhydride-modified vinyl ester resin (A).
20 to 300 parts by weight, especially 30 to 2 parts by weight
The range of 100 parts by weight is preferable because workability and performance of the cured product are excellent.

Typical examples of the inorganic filler (C) used in the present invention are aluminum hydroxide, aluminum oxide, calcium carbonate, barium sulfate, calcium silicate,
Examples thereof include talc, kaolin, mica powder, clay, silica, alumina, asbestos, quartz powder, ceramic powder, glass powder, and silica sand. Among them, aluminum hydroxide having a refractive index close to that of the vinyl ester cured product of the present invention, glass. A powder, particularly aluminum hydroxide, is more preferable because an artificial marble having excellent transparency can be obtained.

The surface treatment of these inorganic fillers with a silane coupling agent, a titanium coupling agent, an alkylcarboxylic acid salt, an alcohol or the like can be similarly used. The inorganic filler (C) is used in an amount of 20 to 300 parts by weight, especially 50 to 150 parts by weight, based on 100 parts by weight of the acid anhydride-modified vinyl ester resin (A) and the vinyl compound (B). A range of parts by weight is preferable. When the amount of the filler is less than the above range, the appearance and texture of the artificial marble molded product cannot be obtained, and the molding shrinkage ratio becomes large. When the amount of the filler is more than the above range, it becomes difficult to uniformly mix the filler,
Mechanical strength and wear resistance decrease.

By the way, the composition of the present invention can be sufficiently cured by simply heating it without using a curing catalyst, but it is needless to say that an organic peroxide is used, and photopolymerization is initiated. By using an agent, it is also possible to cure with active energy rays such as ultraviolet rays and electron rays.

Typical organic peroxides are ketone peroxides such as methyl ethyl ketone peroxide, methyl isobutyl ketone peroxide, and cyclohexanone peroxide; diacyl peroxides such as benzoyl peroxide and isobutyl peroxide; cumene. Hydroperoxides such as hydroperoxide and t-butyl hydroperoxide; Dialkyl peroxides such as dicumyl peroxide and di-t-butyl peroxide; 1,1-di-t-butylperoxy-3, 3,5-
Peroxyketals such as trimethylcyclohexanone, 2,2-di- (t-butylperoxy) -butane; t
-Butyl perbenzoate, t-butyl peroxy-2
-Alkyl peresters such as ethylhexanoate;
Examples thereof include percarbonates such as bis (4-t-butylcyclohexyl) peroxydicarbonate and t-butylperoxyisobutylcarbonate, which can be heat-cured using these organic peroxides. These can be used singly or as a mixture of two or more kinds, and are cured by a combination of metal salts such as cobalt naphthenate and cobalt octenoate and ketone peroxides such as methyl ethyl ketone peroxide and methyl isobutyl ketone peroxide. System: It is possible to cure at room temperature by using a redox catalyst system such as a combination of aromatic tertiary amines such as N, N-dimethylaniline and acyl peroxides such as benzoylperoxide. The amount used is 0.1 to 10 parts by weight, preferably 0. 5-5
It is the ratio of parts by weight.

Typical examples of the photopolymerization initiator include benzoin and its alkyl ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl methyl ketal; acetophenone,
2,2-dimethoxy-2-phenylacetophenone, 2
-Hydroxy-2-methyl-1-phenylpropane-1
-One, diethoxyacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -Acetophenones such as propan-1-one; methylanthraquinone, 2-ethylanthraquinone, 2-tacharybutylanthraquinone, 1
Anthraquinones such as -chloroanthraquinone and 2-amylanthraquinone; thioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4
Thioxanthones such as dichlorothioxanthone, 2-methylthioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenones such as benzophenone and 4,4-bismethylaminobenzophenone and azo There are compounds, etc. These can be used alone or as a mixture of two or more kinds, and further, a tertiary ethanol such as triethanolamine or methyldiethanolamine can be used.
A secondary amine; it can be used in combination with a photoinitiator aid such as a benzoic acid derivative such as 2-dimethylaminoethylbenzoic acid or ethyl 4-dimethylaminobenzoate. The amount used is 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the vinyl ester resin composition.

Furthermore, in the resin composition of the present invention, if necessary, an inorganic thixotropic agent such as silica powder, an organic thixotropic agent such as hydrogenated castor oil, a coloring agent, a leveling agent, an antifoaming agent, Fillers, mold release agents, polymerization inhibitors, inorganic fibers, organic fibers and the like can be used in combination.

As a method for producing an artificial marble from the composition of the present invention, for example, the above-mentioned components (excluding the curing agent) are mixed with a stirring mixer, and then the above-mentioned organic peroxide is added if necessary. A method in which the fluid compound is degassed if necessary, then filled in a casting mold and cured at room temperature or by heating.

When mixing the above-mentioned components,
As described above, a stirring mixer is usually used, but when the resin viscosity is extremely high, it may be carried out by melt mixing with an extruder.

The molding method is not limited to the above-mentioned method, either.
You may manufacture the so-called bulk molding compound by stirring and mixing each said component, and press-mold this. In the case of producing a sheet-shaped molded product, after impregnating the sheet-like inorganic filler (C) with the acid neglected substance-modified vinyl ester resin (A), the vinyl compound (B) and the photopolymerization initiator Alternatively, it may be cured by irradiation with ultraviolet rays to obtain a molded product.

The composition of the present invention is not only used for artificial marble products such as countertops and bathtubs, but also for hand lay-up molding, cast molding, civil engineering adhesion, electrical insulation,
It can also be used for applications such as composite materials and UV curable paints.

[0040]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, all parts and% are based on weight unless otherwise specified.

Synthesis Example 1 "Epiclone 1050" (Dais Nippon Ink and Chemicals Co., Ltd. bisphenol A type epoxy) was placed in a four-necked flask equipped with a stirrer, a cooler, a thermometer, a gas introduction tube, and a heating device. Resin, epoxy equivalent 470) 470 parts (1 equivalent) and methacrylic acid 86 parts (1 equivalent) were charged. To the total weight thereof, 0.28 parts of hydroquinone and 1.7 parts of triphenylphosphine were added, and 110 ° C When the acid value reached 10 after reaction for 4 hours, dodecenyl succinic anhydride was added to 10
5 parts (number of hydroxyl groups: number of acid anhydride groups = 1.0: 0.2)
Was charged and reacted at 90 ° C. for 2 hours, and when the acid value reached 50, the reaction was terminated to obtain vinyl ester resin A.

Synthesis Example 2 In the same manner as Synthesis Example 1, "Epiclone 1050" 470 was used.
(1 equivalent) and 86 parts (1 equivalent) of methacrylic acid were charged, and 0.28 of hydroquinone was added to the total weight.
Part, 1.7 parts of triphenylphosphine are added, and the temperature is 110 ° C.
When the acid value reaches 10 after reacting for 4 hours, 53 parts of dodecenyl succinic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1.0: 0.1) are charged and reacted at 90 ° C. for 2 hours. Then, when the acid value reached 30, the reaction was terminated to obtain vinyl ester resin B.

Synthesis Example 3 In the same manner as in Synthesis Example 1, "Epiclone 1050" 470 was used.
(1 equivalent) and 86 parts (1 equivalent) of methacrylic acid were charged, and 0.28 of hydroquinone was added to the total weight.
Part, 1.7 parts of triphenylphosphine are added, and the temperature is 110 ° C.
After 4 hours of reaction, when the acid value reached 10, 83 parts of octenyl succinic anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1.0: 0.2) was charged and reacted at 90 ° C. for 2 hours. The reaction was terminated when the acid value reached 50, and vinyl ester resin C was obtained.

Synthesis Example 4 In the same manner as in Synthesis Example 1, "Epiclone 1050" 470 was used.
(1 equivalent) and 86 parts (1 equivalent) of methacrylic acid were charged, and 0.28 of hydroquinone was added to the total weight.
Part, 1.7 parts of triphenylphosphine are added, and the temperature is 110 ° C.
After 4 hours of reaction, when the acid value reached 10, 84 parts of octyl succinic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1.0: 0.2) was charged and reacted at 90 ° C. for 2 hours. The reaction was terminated when the acid value reached 50, and vinyl ester resin D was obtained.

Synthesis Example 5 In the same manner as in Synthesis Example 1, "Epiclone 1050" 470 was used.
(1 equivalent) and 86 parts (1 equivalent) of methacrylic acid were charged, and 0.28 of hydroquinone was added to the total weight.
Part, 1.7 parts of triphenylphosphine are added, and the temperature is 110 ° C.
When the acid value reaches 10, the reaction mixture is charged with 111 parts of dodecenyl glutaric anhydride (the number of hydroxyl groups: the number of acid anhydride groups = 1.0: 0.2) and reacted at 90 ° C. for 2 hours. The reaction was terminated when the acid value reached 50, and vinyl ester resin E was obtained.

Synthesis Example 6 In the same manner as in Synthesis Example 1, "Epiclone 1050" 470 was used.
(1 equivalent) and 86 parts (1 equivalent) of methacrylic acid were charged, and 0.28 of hydroquinone was added to the total weight.
Part, 1.7 parts of triphenylphosphine are added, and the temperature is 110 ° C.
When the acid value reached 10 after reaction for 4 hours, 40 parts of succinic anhydride (number of hydroxyl groups: number of acid anhydride groups = 1.
0: 0.2) was charged and reacted at 90 ° C. for 2 hours to terminate the reaction when the acid value reached 50 to obtain vinyl ester resin F.

Synthesis Example 7 In the same manner as in Synthesis Example 1, "Epiclone 1050" 470 was used.
(1 equivalent) and 86 parts (1 equivalent) of methacrylic acid were charged, and 0.28 of hydroquinone was added to the total weight.
Part, 1.7 parts of triphenylphosphine are added, and the temperature is 110 ° C.
When the acid value reached 10, the reaction was terminated and vinyl ester resin G was obtained.

Example 1 To 100 parts of a vinyl ester resin composition obtained by heating and dissolving 60 parts of the vinyl ester resin A obtained in the above Synthesis Example 1 and 40 parts of styrene monomer, "HYGILITE H
-320-ST "(Showa Denko KK aluminum hydroxide) 100 parts was added and mixed, and then" perbutyl O "
After adding 1 part (t-butyl peroxy 2-ethylhexanoate manufactured by NOF CORPORATION) and thoroughly mixing and defoaming under reduced pressure,
Poured into a 5 mm thick mold made of glass plate, pre-cured at 80 ° C., and after-cured at 110 ° C. for 1 hour.
A mm-thick casting plate was prepared. A boiling test was carried out using the obtained casting plate, and the degree of discoloration was measured by color difference, and the change in transparency was measured by light transmittance. The results are shown in Table-1.

The test methods and criteria for each performance in Table 1 are as follows. [Boiling test] 95 cm square and 5 mm thick casting plate
It was immersed in hot water held at ˜98 ° C., taken out after 300 hours, and the color difference and light transmittance of the casting plate were measured.
The methods for measuring physical properties in Examples and Comparative Examples were carried out according to the following methods. (Measurement method) (1) Color difference JISK 7105 According to paragraph 5-4.

Measuring instrument DOUBLE-BEAM COLOR ANALYZAR
C-5200 (manufactured by Tokyo Denshoku Co., Ltd.)

(2) Light transmittance According to JIS K 7105 Section 5-5. Measuring machine Direct reading head computer (manufactured by Ska Testing Machine Co., Ltd.) Examples 2-5, Comparative Examples 1-2 Using the vinyl ester resins A to G obtained in Synthesis Examples 1 to 7, the results are shown in Table 1. Aluminum hydroxide "H-320-S"
A predetermined amount of “T” and a curing agent “perbutyl O” was added to obtain a resin composition, and the same test as in Example 1 was performed.

[0052]

[Table 1] From Table 1, it was confirmed that the resin compositions of the present invention of Examples 1 to 5 had significantly less light transmittance reduction and discoloration than the conventional compositions even when boiled for a long time.

[0053]

According to the present invention, even when the cured product is exposed to hot water for a long period of time, it loses its transparency and does not whiten or has a change in appearance such as discoloration. An object is to provide a resin composition for artificial marble.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C04B 14:36)

Claims (6)

[Claims] 1. An acid anhydride-modified vinyl ester resin (A) having a structure in which a hydroxyl group in an epoxy vinyl ester resin is reacted with a polybasic acid anhydride having a long-chain alkyl group or a long-chain alkenyl group in the molecular structure. ), A vinyl-based compound (B), and an inorganic filler (C) as essential components, a resin composition for artificial marble. 2. The composition according to claim 1, wherein the long-chain alkyl group or the long-chain alkenyl group is an alkyl group or alkenyl group having 5 to 50 carbon atoms. 3. The composition according to claim 1 or 2, wherein the epoxy vinyl ester resin has a structure in which a glycidyl group in the epoxy resin is reacted with an unsaturated monobasic acid. 4. The epoxy vinyl ester resin is a (meth) terminal glycidyl group of a bisphenol type epoxy resin.
The composition according to claim 3, which has a structure obtained by reacting acrylic acid. 5. An acid anhydride-modified vinyl ester resin (A)
Is a hydroxyl group of epoxy vinyl ester resin 1.0
With respect to 0 equivalent, the anhydride group in the polybasic acid anhydride is 0.
The composition according to any one of claims 1 to 4, which has been reacted at a ratio of 03 to 0.5 equivalent. 6. The composition according to claim 1, wherein the inorganic filler (C) is aluminum hydroxide.