JPH02147622A - Curable resin composition, artificial marble produced by molding and curing the same composition and production thereof - Google Patents

Abstract

PURPOSE:To get rid of cracks during curing and to improve moldability by compounding a radical-polymerizable monomer, an epoxy resin, a polyfunctional carboxylic acid (anhydride), a thermoplastic resin and an inorg. filler. CONSTITUTION:100 pts.wt. (hereinbelow merely pts.) radical-polymerizable monomer (A) which is a mixture of 100 pts. monofunctional radical-polymerizable monomer which is liq. at ordinary temp. and 0-400 pts. polyfunctional (meth) acrylate, 10-100 pts. epoxy resin (B) having an epoxy equivalent of 70-250, an average MW of 140-1,000 and two or more epoxy groups in the molecule, 0.5-4.0 equivalents (provided that an acid anhydride group is deemed to be bifunctional) polyfunctional carboxylic acid (anhydride) (C) based on one equivalent of the component B, 5-75 pts. thermoplastic resin (C) soluble or dispersible in the component A, having a functional group reactive with the component B or C and a wt.-average MW of 3,000-400,000 and 100-1,000 pts. inorg. filler (E) which is pref. a metal oxide hydrate [e.g. Al(OH)3] are compounded together.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention provides a cured product with an astronomical appearance that is suitable for use in household appliances such as washstands and bathtubs, decorative items, etc., and has excellent moldability. The present invention relates to a resin composition having the following.

(Prior art) Articles with a marble-like appearance have traditionally been manufactured by mixing various fillers with radically polymerizable resins such as unsaturated polyester resins and acrylic silica resin, and molding and curing the mixture. (USP 4.544.5
84, JP-A-50-107045, JP-A-52-129
722).

However, the volume of these radically polymerizable resin compositions containing fillers decreases during curing, resulting in cracks and cracks in the molded product when molded into three-dimensional structures with complex shapes other than flat plates. Easy to occur and mold release! ! It had some problems such as 1 difficulty.

On the other hand, as a method to reduce shrinkage during curing, a method is used in which a resin composition in which a thermoplastic resin is mixed in advance with a radically polymerizable resin is used, and the thermoplastic resin is phase-separated or foamed during curing to reduce shrinkage (tJsP3 .701.748) is already known. However, when using this method (when the synthetic resin is made to have low shrinkage), the appearance of the obtained cured product becomes opaque and cloudy, and the transparent astronomical stone-like texture is lost.
It also had the problem of poor horse dyeing resistance.

(Problem to be solved by the invention) The present invention solves these problems.

Therefore, it is an object of the present invention to provide a cured product that provides an article with a transparent appearance and an astronomical stone appearance, and that has excellent moldability without cracking or breaking during curing even when molding a three-dimensional structure with a complicated shape. An object of the present invention is to provide a synthetic resin composition.

Another object of the present invention is to provide a beautiful, transparent artificial marble that can be used for three-dimensional structures such as washbasins and bathtubs, and a method for producing the same.

(Means and effects for solving the problem) As a result of various studies to solve these problems, the present inventors have discovered that, in a specific composition, curing by radical polymerization and curing by ring opening of epoxy groups can be combined. It was discovered that the intended purpose could be achieved by using them together, leading to the present invention.

That is, the present invention comprises a radically polymerizable monomer (A), a thermoplastic resin (8), an epoxy resin (C), a polyfunctional carboxylic acid and/or anhydride thereof (D), and an inorganic filler (E). The thermoplastic resin (B) is dissolved or dispersed in the radically polymerizable monomer (A), and the epoxy resin (
C) or a functional group that reacts with the polyfunctional carboxylic acid and/or its anhydride (D), and the blending ratio of these components is based on 100 parts of the radically polymerizable monomer (A). Thermoplastic resin (B) 5 to 75 parts by weight, epoxy resin (C) 10 to 100 parts by weight, and inorganic filler (E) 100 to 1,000 parts by weight, and 1 equivalent of epoxy resin (C). In contrast, a curable resin composition having a polyfunctional carboxylic acid and/or its anhydride (D) in the range of 0.5 to 4.0 equivalent M (however, the acid anhydride group is considered to be difunctional) and the curable This invention relates to artificial marble obtained by molding and curing a resin composition.

Furthermore, when manufacturing artificial marble by molding and curing the curable resin composition, the curable resin composition is mixed with a radical polymerization initiator, and then this mixture is poured into a mold at room temperature or The mixture in the mold was cured at least to the extent that it could be removed from the mold by allowing a radical synthesis reaction to proceed under heating, and then the semi-hardened mixture was removed from the mold and a holder was attached as necessary to retain the shape. The present invention relates to a method for producing artificial marble, which is characterized in that the mixture is then heated to advance the curing reaction of the epoxy resin in the mixture to completely cure the mixture.

The radically polymerizable monomer (A) used in the present invention is:
A monofunctional radical-neutralizable IJi chain or a monofunctional radical-polymerizable monomer and a polyfunctional (meth)acrylate that are liquid at room temperature.
It is a mixture of 1 to 1.

Examples of monofunctional radically polymerizable monomers include (meth)
Acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate,
Examples include (meth)acrylic acid esters such as 2-ethylhexyl (meth)acrylate and hydroxyethyl (meth)acrylate; aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene; and the like.

In addition, polyfunctional (meth)acrylate means - 2 in the molecule.
1 [1! Refers to compounds having the above (meth)acryloyl groups, such as ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate,
Examples include neobentyl glycol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane i.s(meth)acrylate, dipentaerythritol hekiza(meth)acrylate, bisphenol A di(meth)acrylate, etc. can.

The mixing ratio t of the monofunctional radically polymerizable monomer and the polyfunctional (meth)acrylate in the radically polymerizable monomer (A) is the polyfunctional (meth)acrylate for 100 parts by weight of the monofunctional radically polymerizable hanging body. The amount of acrylate is preferably in the range of 80 to 400 parts by weight.

If the amount of polyfunctional (meth)acrylate exceeds 400 parts by weight, the resulting resin composition tends to shrink more during curing, which is undesirable because the cured product is more likely to crack or break. Among them, radically polymerizable monomers (A
), if a mixture of 100 parts by weight of a monofunctional radically polymerizable monomer, preferably an aromatic vinyl compound, and a polyfunctional (meth)acrylate at a ratio of 5 to 80 parts by weight is used, This is desirable because the hardness of the obtained resin composition during curing due to the radical Φ combination reaction is high, and the time required for demolding can be shortened.

The thermoplastic resin (Bl) used in the present invention is dissolved or dispersed in the radically polymerizable hollow body (A) and reacts with the epoxy resin (C) or the polyfunctional carboxylic acid and/or the anhydride (D). For example, a thermal compound having one or more functional groups selected from the group consisting of a boxy group, a thioepoxy group, an aziridine group, an oxazoline group, and an N-hydroxyalkylamide group in its molecule. Examples include plastic resins, the weight average molecular weight of which is from 3,000 to 400,000, preferably e.
,ooo~200.000.

Such a thermoplastic resin (B) requires a polymerizable monomer having a reactive group such as an epoxy group, a thioepoxy group, an aziridine group, an oxytamine group, or an N-hydroxyalkylamide group in the molecule. (2) A method of polymerizing with other polymerizable monomers by reacting a compound having the above-mentioned reactive group in the molecule with a polymer having a group capable of reacting with the compound, and adding the reactive group to the polymer. Method of introduction: (1) A polymer having a functional group that is not reactive with the epoxy resin (C) or the polyfunctional carboxylic acid and/or its anhydride (D) is added to the molecule by a known method to introduce the reactive group into the molecule. A method of converting into a polymer, such as a thermoplastic resin (which can be synthesized by
When B) is used, the obtained resin composition does not become cloudy when cured, and it is possible to obtain an astronomical stone-like cured product with an excellent appearance.

The thermoplastic resin (B) must be used in a range that does not cause foaming or layer separation during curing, resulting in an opaque and cloudy appearance. (A) is determined in consideration of compatibility with
5 to 100 parts by weight of radically polymerizable monomer (A)
It is used in a range of 75 parts, more preferably 10 to 40 parts. If the amount of the thermoplastic resin (8) used is as small as less than 5 parts by weight, the resulting 1fi4 resin composition tends to shrink more during curing, which is undesirable because the cured product is more likely to crack or break. On the other hand, if the number of openings exceeds 75, the appearance of the cured product becomes opaque and cloudy, making it impossible to obtain an article with a stone-like appearance, and the heat resistance of the cured product tends to decrease, which is undesirable.

The epoxy resin (C) used in the present invention has 2
A compound having a molecular weight of 1140 or more and having epoxy groups of 1,140 or more, such as bisphenol A epoxy resin, bisphenol F epoxy resin, novolak epoxy resin, cycloaliphatic epoxy resin, etc. The resins can be neutralized or two or more can be used in combination. Such epoxy resin (C
), the average molecular ff with an epoxy equivalent of 70 to 250
It is preferable to use a compound having a molecular weight of 1,140 to 1,000 because it can be completely cured without clouding the appearance of the cured product and also provides a cured product with excellent heat resistance and water resistance.

It is also possible to use such an epoxy resin (C) in combination with a reactive diluent such as n-butyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, vinyl cyclohexene monoepoxide.

The amount of the epoxy resin (C) used is in the range of 10 to 100 parts by weight, more preferably 30 to 70 parts by weight per 100 parts of the radically polymerizable monomer (A). If the amount of epoxy resin (C) used is as small as less than 1041 parts, the shrinkage of the resulting resin composition during curing tends to be large, which is undesirable. On the other hand, if the amount exceeds 100,
This is not desirable because the hardness increases slowly when the resin composition is cured, and it tends to take a long time to demold the cured product.

The polyfunctional carboxylic acid and/or its anhydride (D) (hereinafter simply referred to as carboxylic acid compound (D)) used in the present invention refers to - a compound having two or more carboxylic acids in the molecule and/or Its anhydride, 1 boxy resin (
It acts as a curing agent for C). Examples of such carboxylic acid compounds (D) include acids such as maleic acid, phthalic acid, 1-limellitic acid, pyromellitic acid, tetrahydrophthalic acid, and adipic acid, and their anhydrides; Carboxyl group-containing polymers such as meth)acrylic acid can also be employed.

Among such carboxylic acid compounds (D), when dicarboxylic anhydrides such as maleic anhydride and phthalic anhydride are used, the curing reaction of the epoxy resin hardly proceeds at temperatures below 120°C, and at temperatures of 130 to 200°C. Since the process proceeds quickly, the production of artificial marble from semi-curing and demolding of the resin composition to complete curing can be carried out smoothly.

Use 1 of carboxylic acid compound (D) is epoxy resin (C
) 0.5 to 4.0 hits per 1 hit, preferably 0.
8 to 3.0 equivalents (However, the acid anhydride group is considered to be difunctional.)
is within the range of

If the amount of the carboxylic acid compound (D) used is a small amount, less than 0.5 equivalent, cracks and cracks are likely to occur in the final cured product, and physical properties such as heat resistance are likely to be impaired. , undesirable. On the other hand, if the amount exceeds 4.0 equivalents, the water resistance and weather resistance of the cured product will deteriorate, which is not desirable.

Note that the thermoplastic resin (B) used is an epoxy resin (C
), it is necessary to add up the five groups of these carbo-4-syl group-containing thermoplastic resins as the five groups of the carboxylic acid compound (D). be.

In addition, in order to promote the reaction between the epoxy resin (C) and the carboxylic acid compound (D), it is also possible to add promoters such as tertiary amines, boric acid, and Lewis acid metal compounds. It is.

The inorganic filler (E) used in the present invention is an inorganic powder that has been conventionally used in the art as a filler, such as carbonate, talc, clay, silica, alumina, quartz, Examples include calcium silicate and hydrates of metal oxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide.

Among these inorganic fillers (E), when hydrates of metal oxides, particularly preferably aluminum hydroxide, are used, it is easy to obtain flame-retardant, transparent and beautiful Dalian stone-like cured products. desirable.

The amount of the inorganic filler (E) to be used is 100 to 1000 parts by weight per 100 parts of the radical-carrying monobase (A);
Preferably it is in the range of 200 to 700 parts. When the amount of inorganic filler (E) used is less than 100 parts by weight,
The heat resistance of the cured product decreases, and the heavy texture of astronomical stone cannot be obtained. On the other hand, if the amount exceeds 1M parts, the resin composition becomes highly viscous, which causes problems in workability during molding and curing, which is not desirable.

When obtaining the resin composition of the present invention, the mixing order of these components is not particularly limited, and for example, the radically polymerizable monomer (A
), a thermoplastic resin (8), an epoxy resin (C), and a carboxylic acid compound (D) are added to the resulting mixture, and an inorganic filler (E) is added and dispersed under strong stirring. be.

It is preferable to use a coupling agent when dispersing the inorganic filler (E), since this improves the water resistance of the cured product obtained by molding and curing. Examples of such coupling agents include γ-methacrylic[oxyglobiltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, vinyltriethoxysilane, vinyltriacetoxysilane,
Examples include isopropyl triisostearoyl titanate and isopropyl tri(dodecylbenzenesulfonyl) titanate.

By molding and curing the curable resin composition of the present invention, an artificial large buried stone having a transparent feel can be obtained.

In order to obtain an artificial large burial stone using the resin composition of the present invention, a radical polymerization initiator is dt-coupled with the resin composition and then heated to initiate radical polymerization reaction J3 and harden the epoxy resin in the resin composition. All you have to do is let the reaction proceed.

The method of the present invention for making an artificial implant using the resin composition described above will be specifically described below.

First, if necessary, the mold surface is subjected to mold release treatment. The molds used can be those used for casting ordinary unsaturated polyester resins, radically polymerizable syrups, etc., and FRP! ! l! Resin molds, wooden molds, aluminum molds, etc. can be used without any particular restrictions. Among these, a mold with a structure that allows the temperature of the mold to be controlled is desirable in terms of controlling the progress of the curing reaction and increasing productivity.

Next, a radical polymerization initiator and, if necessary, a polymerization accelerator are added and mixed to the resin composition. The type and type of radical polymerization initiator and polymerization accelerator to be used are determined by taking into account the pot life from the time they are added until the completion of casting and the curing time from casting to IB2 type. . As the polymerization initiator and polymerization accelerator used, those used for curing ordinary unsaturated polyester resins, radically polymerizable syrups, etc. can be used.

As such a radical polymerization initiator, peroxides such as benzoyl peroxide, cyclohexylinone peroxide, and methyl ethyl ketone peroxide can be suitably used.

Moreover, organic metal salts, organic amines, etc. can be used as the polymerization accelerator.

The polymerization initiator used preferably has a 10-hour half-life temperature of 50° C. or higher in order to obtain a sufficient pot life. If the 10-hour half-life temperature is less than 50"C, the pot life will be short and workability will be poor. However, when casting while continuously mixing the radical polymerization initiator using a line mixer, etc., it will take 10 hours. It is also possible to use hand initiators with a half-life temperature below 50°C.

Examples of the radical polymerization initiator having a 10-hour half-life temperature of 50°C or higher include methyl ethyl ketone peroxide,
Methyl isobutyl ketone peroxide, lauroyl peroxide, benzoyl peroxide, t-butyl peroxybivalate, t-butyl peroxy-2-ethylhexanoate, t-butyl peroxy-isobutylene-1, etc. Can be done.

The amount of radical polymerization initiator used is based on radical polymerization ttx
m body (A) and thermoplastic resin (8) total 9 to 100
When expressed as parts by weight, the range is from 0.1 to io,0 parts by weight, more preferably from 0.2 to 5.0 parts by weight.

If the amount of the polymerization initiator is less than 0.1 ω parts, the radical polymerization reaction will proceed slowly and it will take a long time to demold, which is not desirable. On the other hand, if the amount exceeds 10.01 stone parts, radical polymerization will proceed rapidly and thick portions will tend to crack or become yellow, which is undesirable.

In addition, when the radical polymerization reaction is carried out using only the polymerization 6n initiator without using a polymerization accelerator, the resulting artificial marble molded product has less coloring and has excellent weather resistance and heat discoloration resistance. It is desirable because it can be obtained.

Next, a mixture obtained by mixing the radical polymerization initiator 1m into the resin composition is poured into the mold and heated at room temperature or under heating, preferably at the 10-hour half-life temperature of the used radical polymerization initiator. Taking this into consideration, the mold is heated to a humidity of 40°C or higher to allow the radical polymerization reaction to proceed. The mold may be heated by placing the mold in a heating furnace, or a mold configured to allow circulation of a heat medium may be used.

The mixture inside the mold is cured by a radical polymerization reaction,
The mixture is held in the mold until it hardens and reaches a hardness that allows it to be demolded.

Until the semi-cured molded product is demolded, give priority to the radical polymerization reaction and prevent the reaction between the epoxy resin (C) and the carboxylic acid compound (D) from proceeding as much as possible, and the uncured epoxy resin ( C) exerts a plasticizer-like effect to alleviate the internal stress caused by curing shrinkage caused by the progress of the radical polymerization reaction, and can prevent cracks and cracks that are likely to occur during curing in the mold.

Therefore, epoxy resin (C) and carboxylic acid compound (D)
It is best to heat the mold to a temperature of 120°C or lower to allow the radical polymerization reaction to proceed in order to prevent the reaction from proceeding with the polymerization initiator. It is desirable that the time half-life temperature is 110°C or less.

Next, the mold is demolded at a stage where the radical polymerization reaction has sufficiently progressed and the mold has been cured to the extent that it can be demolded at least. in general,
It is extremely difficult to control the radical polymerization reaction and demold the material in a semi-cured state.

This is because the radical polymerization rate is fast and the reaction progresses at an accelerated rate due to the reaction heat.
According to the present invention, since the semi-cured state is maintained at the time when the radical polymerization reaction is almost completely completed, it is easy to control it.

The demolded semi-cured molded product is made of low-molecular bond epoxy resin (C
) and carboxylic acid compound (D), it tends to creep under sustained stress. Therefore, if necessary, after attaching a holder to the semi-cured molded product to prevent deformation, the epoxy resin (C) and the carboxylic acid compound (D)
The semi-cured molded product is heated to a temperature sufficient to cause the reaction of It hardens completely until it becomes hard enough to be used as marble.

The artificial marble thus obtained is subjected to processing such as cutting and polishing as necessary, and then put into practical use.

(Effects of the Invention) The curable resin composition of the present invention can eliminate the problems of cracks and cracks caused by shrinkage during curing, so even complex three-dimensional structures can be easily molded. Also,
Since no foaming or layer separation occurs during curing, it is possible to obtain a cured product that has a transparent astronomical stone-like appearance and has excellent stain resistance.

Therefore, according to the resin composition of the present invention, three-dimensional structures that require aesthetic appearance, such as washstands and bathtubs, can be efficiently manufactured.

(Examples) Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that the parts in the examples are heavy items.

Example 1 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved was charged into a flask equipped with a stirrer, an inert gas introduction tube, a reflux cold IJ tube, and a thermometer.

A mixture of 16 parts of benzoyl peroxide dissolved in a previously prepared polymerizable monomer consisting of 2,112,196 parts and 4 parts of isopropenyl oxaprine was added thereto, and stirred at high speed to form a uniform suspension. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension.

This polymer suspension was filtered through F>5, washed, and dried to form a polymer having oxazoline as a reactive group (
1) was obtained. When the number average molecular weight and ff1ffi average molecular m of this polymer (1) were determined by GPC measurement, Mn = 5,800 and MW = 12.000.
Met.

After dissolving 25 parts of polymer (1) in a mixed solution of 40 parts of styrene J3 and 10 parts of trimethylolbu[] pantriacrylate, 1 part of bisphenol A-based epoxy resin (manufactured by Ciba Geigy, Araldite GY250, 1 part of epoxy) was dissolved.
1185) and 4 parts of maleic anhydride are added and mixed uniformly, and then 200 parts of aluminum hydroxide 1 cum (manufactured by Showa Denko ■, Hisilite H-320) is added and mixed to obtain the resin composition of the present invention. (1) was obtained.

This resin composition (1) was added with a radical polymerization initiator (manufactured by Herbal Medicine Nouri Co., Ltd., Kaya Ester 0110 hours 50% luJ temperature 7
4°C) was added and mixed.

On the other hand, after undergoing mold release treatment, the lower part is 50Hn, and the depth is 550M.
, FR used to mold a washbasin with a depth of 130m
P-type was previously heated to 60°C.

A mixture obtained by mixing the resin composition (1) described above with a radical polymerization initiator was poured into this mold, and the mold was kept in an air bath whose temperature was controlled to 65°C for 60 minutes to initiate a radical polymerization reaction. When the progress was completed, it was cured to the extent that it could be removed from the mold.

At this point, the molded washbowl was removed from the mold, the periphery of the molded product was supported with a holder, and then placed in an air bath at 160°C for 4 hours to cause the epoxy resin to harden. A washbowl molded product having an astronomical stone appearance was obtained, and no cracks or cracks occurred.

The linear shrinkage rate for mold dimensions of the molded product is 0.4%.
And 6#Ill! Total light transmittance at thickness is 25
%Met. In addition, the heat distortion temperature of the molded product was determined by ASTMD-
When measured according to the method of No. 648, the temperature was 98°C.

Example 2 The same flask used in Example 1 was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved. A mixture of 16 parts of penzoyl bicarbonate Y side dissolved in a pre-prepared polymerizable omega compound consisting of 194.9 parts of styrene and 5.1 parts of glycidyl methacrylate was added, and the mixture was stirred at high speed to obtain a uniform suspension. It was made into a cloudy liquid. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension. This polymer suspension was filtered, washed, and then dried to obtain a polymer (referred to as polymer (2)) having on average one evo4nidium group in each molecule as a reactive group. The intermolecular content of this polymer (2) was determined by GPC measurement.
n=5.500 and Mw=11.000.

Polymer (2110 parts dissolved in a mixture of 40 parts of styrene and 10 parts of trimethylolpropane triacrylate)
! After removing the liquid, add bisphenol A-based epoxy resin (manufactured by Ciba Geigy, Araldite GY250,
15 parts of maleic anhydride were added and mixed uniformly, and then aluminum hydroxide (Showa Denko Kuma, Hisilite 1-(-341>2
50 parts were added and mixed to obtain a resin composition (2) of the present invention.

When this resin composition (2) was molded and cured in the same manner as in Example 1, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.3%, and the total light transmittance at a thickness of 6 m was 24%. Moreover, the heat distortion temperature of the molded article was 160°C.

Example 3 The same flask used in Example 1 was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved. Methyl methacrylate 10 prepared in advance
A mixture of 16 parts of benzoyl peroxide dissolved in a polymerizable body consisting of 0 parts, butyl acrylate, 94.3 parts, and 2.3-evithiopropyl methacrylate, and 16 parts of benzoyl peroxide, was stirred at a speed of A suspension was obtained. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension. This polymer suspension was filtered, washed, and dried to give an average of 1 buoeboxy group as a reactive group.
A polymer having one polymer in the molecule (referred to as polymer (3)) was obtained. The molecular weight of this polymer (3) was determined by GPC measurement.
=5.800 and Mw=12.000.

After dissolving 10 parts of polymer (3) in a mixed solution of 45 parts of styrene and 10 parts of trimethylolpropane triacrylate, a bisphenol A-based epoxy resin (manufactured by Diba Geigy, Araldite GY250, epoxy resin
185) and 12 parts of maleic anhydride were added and mixed uniformly, and then 250 parts of aluminum hydroxide (Hisilite H-320, manufactured by Showa Den J■) was added and mixed to obtain the resin composition of the present invention ( 3) was obtained.

When this resin composition (3) was molded and cured in the same manner as in Example 1, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.3%, and the total light transmittance at a thickness of 6 shoes was 30%. Further, the heat distortion temperature of the molded product was 142°C.

Example 4 The same flask used in Example 1 was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved. A mixture of 16 parts of benzoyl peroxide dissolved in a polymerizable monomer consisting of 89.8 parts of styrene 'I and 10.2 parts of glycidyl methacrylate, prepared in advance, was added thereto, and the mixture was stirred at high speed to obtain a uniform suspension. It was made into a cloudy liquid. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirred at this temperature for 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer suspension. This polymer suspension is filtered, washed, and dried to give a reactive M with an average of 1 epoxy group.
A small polymer (referred to as polymer (4)) having two polymers in the molecule was obtained. The molecular weight of this one-part union (4) was determined by GPC measurement.
n = 5.500 and MW = i o, o o
It was o.

After dissolving 5 parts of the polymer (4) in a mixed solution of 50 parts of styrene and 10 parts of trimedylolbroban trimethacrylate, a bisphenol A-based epoxy resin (manufactured by Cibagai 1K Co., Ltd., Araldye I-G Y-250, epoxy 23 parts of equivalent weight 185) and 12 parts of maleic anhydride were added and mixed uniformly, and then 250 parts of aluminum hydroxide (manufactured by Showa Denko @ J, Hisilite H-341) was added and mixed for 1 time to form the resin composition of the present invention. Product (4) was obtained.

When this resin composition (4) was molded and cured in the same manner as in Example 1, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.3%, and the total light transmittance at a thickness of 6 m was 32%. Further, the heat distortion temperature of the molded product was 130°C.

Example 5 200 parts of toluene and 200 parts of methyl isobutyl ketone were charged into the same flask as used in Example 1, and heated to 80° C. while blowing nitrogen gas. A mixture of 4 parts of benzoyl peroxide dissolved in a polymerizable monomer consisting of 190 parts of styrene and 10 parts of 2-(1-aziridinyl)delmethacrylate prepared in advance was added thereto.
The polymer solution was added dropwise from the dropping funnel over a period of time and stirred for an additional 5 hours to carry out the polymerization reaction, and then cooled to form a polymer solution of 1:1.
is. 2,000 parts of methanol was added to 100 parts of this polymer solution, reprecipitated, and then dried to obtain a polymer having an aziridine group as a reactive base (referred to as polymer (5)). The molecular weight of this polymer (5) was determined by GPC measurement to be Mn = 3.0.
00 and MW=8.0OO.

After dissolving 3 parts of polymer (5) in a mixed solution of 30 parts of styrene, 20 parts of methyl methacrylate, and 1 to 5 parts of trimethylolpropane, a bisphenol A-based epoxy resin (manufactured by Cibagai F-Co., Ltd., Araldite G) was dissolved.
Y-250, 23 parts of epoxy m185) and 12 parts of phthalic anhydride were added and mixed uniformly, and the soaked aluminum hydroxide (Hisilite H-341, manufactured by Showa Denko Kuma) was added.
200 parts were added and mixed to obtain a resin composition (5) of the present invention.

When this resin composition (5) was molded and cured in the same manner as in Example 1, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.4%, and the total light transmittance at 6# thickness was 25%. Further, the heat distortion temperature of the molded product was 115°C.

Example 6 Into the same flask used in Example 1, cyclohexane 4
Add 60 parts and 2 parts of Rheodol 5P-810 (manufactured by Kao ■) and heat to 75°C while blowing nitrogen gas. , thirsty. There, 60 parts of acrylamide prepared in advance, N
- A mixture of a polymerizable monomer consisting of 15.2 parts of vinylpyrrolidone and 1.6 parts of N-hydroxyethylmethacrylamide, to which 140 parts of deionized water and 2 parts of ammonium persulfate were added was added over a period of 1.5 hours using a dropping roller. 1. Add more drops,
Stirring was continued for an additional 0.5 hour to carry out the polymerization reaction. After cooling, remove the cyclohexane and reduce the polymer to 80-100
Dry under reduced pressure at °C to obtain a polymer having N-hydroxyalkylamide groups as reactive groups (referred to as hand polymer (6)).
I got it. The molecule M of this hand coalescence (6) was determined by GPC measurement to be M n = 12. OOO and MW=34.000
Met.

Polymer (6) instead of polymer (5) in Example 5
A resin composition (6) of the present invention was obtained in the same manner as in Example 5 except that the following was used.

When this resin composition (6) was molded and cured in the same manner as in Example 1, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No cracks or cracks were observed in this molded product, the linear shrinkage rate was 0.4%, and the total light transmittance at 6#Ill thickness was 28%. In addition, the heat distortion temperature of the molded product is 115℃
Met.

Example 7 10 parts of the polymer (2) obtained in Example 2 was mixed with 27 parts of styrene.
After dissolving in a mixed solution of 18 parts of methyl methacrylate and 10 parts of trimethylolpropane triacrylate, bisphenol A-based Evo4 resin (manufactured by Ciba Geigy, Araldite GY-250, Epoxy Tonagi 185)
) and 12 parts of maleic anhydride were added and mixed uniformly, and then 250 parts of aluminum hydroxide (Hisilite 1-1-320, manufactured by Showa Denko Corporation) was added and mixed.
A resin composition (1) of the present invention was obtained.

When this resin composition (7) was molded and cured in the same manner as in Example 1, a molded product of a full wash basin having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.3%, and the total light transmittance at a thickness of 6 m was 30%. Further, the heat distortion temperature of the molded product was 166°C.

Example 8 The same flask used in Example 1 was charged with 400 parts of deionized water in which 0.2 part of polyvinyl alcohol was dissolved. A mixture of 1 part of penzoyl veroxide dissolved in a polymerizable monomer consisting of 92,196 parts of sub and 4 parts of isopropenyl oxaprine was added thereto, and stirred at high speed to form a uniform suspension. did. Next, the mixture was heated to 80° C. while blowing nitrogen gas, and stirring was continued at this temperature for 5 hours to carry out a polymerization reaction, followed by cooling to obtain a polymer suspension. This polymer suspension is filtered, washed, and dried to obtain a polymer (f) having an oxazoline group as a reactive group.
! Polymer 7)) was obtained. The molecular weight of this polymer (7) was determined by GPC measurement to be M11=58,000 and Mw
=150. It was OOO.

Polymer (7) instead of polymer (1) in Example 1
A resin composition (8) of the present invention was obtained in the same manner as in Example 1 except that the following was used.

When this resin composition (8) was molded and cured in the same manner as in Example 1, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.4%, and the total light transmittance of the 6M thick countermeasure was 25%. Further, the heat distortion temperature of the molded product was 98°C.

Example 9 200 parts of toluene and 200 parts of methyl isobutyl ketone were charged into the same flask as used in Example 1, and heated to 80° C. while blowing nitrogen gas. A mixture prepared in advance by dissolving 1 part of benzoyl peroxide in a polymerizable monomer consisting of 190 parts of styrene and 10 parts of 2-(1-aziridinyl)ethyl methacrylate was added dropwise from the dropping funnel over a period of 2 hours. The mixture was stirred for an additional 5 hours to carry out a polymerization reaction, and then cooled to obtain a polymer solution. 2000 parts of methanol was added to 100 parts of this polymer solution, reprecipitation was performed, and the mixture was dried to obtain a polymer having an aziridine group as a reactive group (referred to as Polymer (8)). The molecule m of this polymer (8) is Mn according to the GPCill determination.
= 30,000 and M vt = 85,000 te.

Polymer (8) instead of polymer (5) in Example 5
A resin composition (9) of the present invention was obtained in the same manner as in Example 5 except that the following was used.

When this resin composition (9) was molded and cured in the same manner as in Example 5, a molded product of a washbowl having a translucent astronomical stone appearance was obtained.

No breaks or cracks were observed in this molded product, the linear shrinkage rate was 0.4%, and the total light transmittance at a thickness of 6M was 25%. Further, the heat distortion temperature of the molded product was 115°C.

Comparative Example 1 In Example 1, a comparative resin composition (1) was obtained in which the epoxy resin and maleic anhydride were not mixed.

Comparative resin composition obtained? 5 (1) was molded and cured in the same manner as in Example 1, many cracks and cracks were generated on the surface of the obtained hemispherical cured product.
Due to surface whitening, only an opaque white cured product was obtained.

Claims (1)

[Claims] 1. Radical polymerizable monomer (A), thermoplastic resin (B)
, an epoxy resin (C), a polyfunctional carboxylic acid and/or its anhydride (D), and an inorganic filler (E),
The thermoplastic resin (B) is dissolved or dispersed in the radically polymerizable monomer (A) and has a functional group that reacts with the epoxy resin (C) or the polyfunctional carboxylic acid and/or its anhydride (D). The mixing ratio of these components is 5 to 75 parts by weight of thermoplastic resin (B) and 1 part by weight of epoxy resin (G) to 100 parts by weight of radically polymerizable monomer (A).
0-100 parts by weight and inorganic filler (E) 100-1
Polyfunctional carboxylic acid and/or its anhydride (D) in a range of 000 parts by weight and per equivalent of epoxy resin (C)
A curable resin composition having an equivalent weight of 0.5 to 4.0 (however, the acid anhydride group is considered to be bifunctional). 2. Claim 1 in which the thermoplastic resin (B) has one or more functional groups selected from the group consisting of an epoxy group, a thioepoxy group, an aziridine group, an oxazoline group, and an N-hydroxyalkylamide group. The curable resin composition described. 3. The curable resin composition according to claim 1, wherein the radically polymerizable monomer (A) contains a polyfunctional (meth)acrylate and an aromatic vinyl compound as essential components. 4. The curable resin composition according to claim 1, wherein the inorganic filler (E) is a hydrate of a metal oxide. 5. The curable resin composition according to claim 4, wherein the inorganic filler (F) is aluminum hydroxide. 6. The epoxy equivalent of the epoxy resin (C) is 70 to 250
The curable resin composition according to claim 1, which is within the range of. 7. The curable resin composition according to claim 1, wherein the polyfunctional carboxylic acid and/or its anhydride (D) is a dicarboxylic anhydride. 8. Radical polymerizable monomer (A), thermoplastic resin (8)
, an epoxy resin (C), a polyfunctional carboxylic acid and/or its anhydride (D), and an inorganic filler (E),
The thermoplastic resin (B) is dissolved or dispersed in the radically polymerizable monomer (A) and has a functional group that reacts with the epoxy resin (C) or the polyfunctional carboxylic acid and/or its anhydride (D). The mixing ratio of these components is 5 to 75 parts by weight of thermoplastic resin (B) and 1 part by weight of epoxy resin (G) to 100 parts by weight of radically polymerizable monomer (A).
0-100 parts by weight and inorganic filler (E) 100-1
Polyfunctional carboxylic acid and/or its anhydride (D) in a range of 000 parts by weight and per equivalent of epoxy resin (C)
Artificial marble formed by molding and curing a curable resin composition having an equivalent weight of 0.5 to 4.0 (however, the acid anhydride group is considered to be bifunctional). 9. The thermoplastic resin (B) has one or more functional groups selected from the group consisting of an epoxy group, a thioepoxy group, an aziridine group, an oxazoline group, and an N-hydroxyalkylamide group in the molecule. Artificial marble as described. 10. The artificial marble according to claim 8, wherein the radically polymerizable monomer (A) contains a polyfunctional (meth)acrylate and an aromatic vinyl compound as essential components. 11. The artificial marble according to claim 8, wherein the inorganic filler (E) is a hydrate of a metal oxide. 12. The artificial marble according to claim 11, wherein the inorganic filler (E) is aluminum hydroxide. 13. The epoxy equivalent of the epoxy resin (C) is 70 to 25
9. The artificial marble according to claim 8, wherein the artificial marble is in the range of 0. 14. Polyfunctional carboxylic acid and/or its anhydride (D)
The artificial marble according to claim 8, wherein is a dicarboxylic acid anhydride. 15, radically polymerizable monomer (A), thermoplastic resin (B
), an epoxy resin (C), a polyfunctional carboxylic acid and/or its anhydride (D), and an inorganic filler (E), in which the thermoplastic resin (B) is dissolved or It has a functional group that is dispersed and reacts with the epoxy resin (C) or the polyfunctional carboxylic acid and/or its anhydride (D), and the blending ratio of these components is 100% of the radically polymerizable monomer (A). Thermoplastic resin (B) 5 to 75 parts by weight, epoxy resin (C)
10 to 100 parts by weight and inorganic filler (E) 100 to
Polyfunctional carboxylic acid and/or its anhydride (D
) 0.5 to 4.0 equivalents (however, the acid anhydride group is considered to be bifunctional). After mixing the radical polymerization initiator, this mixture is poured into a mold and the radical polymerization reaction is allowed to proceed at room temperature or under heating to harden the mixture in the mold at least to the extent that it can be demolded, and then the semi-hardened mixture is cured. Manufacture of artificial marble characterized by removing it from the mold, attaching a holder to hold the shape as necessary, and heating the mixture to advance the curing reaction of the epoxy resin in the mixture to completely harden the mixture. Method. 16. Using a peroxide catalyst with a 10-hour half-life temperature of 50 to 110°C as a radical polymerization initiator, the radical polymerization reaction proceeds at a temperature of 40 to 120°C, and the curing reaction of the epoxy resin is carried out at a temperature exceeding 120°C. 16. The method for producing artificial marble according to claim 15, which is carried out in the following steps. 17. The method for producing artificial marble according to claim 15, wherein the mold is for molding a three-dimensional structure having a complicated shape. 18. The method for producing artificial marble according to claim 17, wherein the three-dimensional structure is a washbowl or a bathtub. 19. The method for producing artificial marble according to claim 15, wherein the radically polymerizable monomer (A) contains a polyfunctional (meth)acrylate and an aromatic vinyl compound as essential components. 20. The method for producing artificial marble according to claim 15, wherein the inorganic filler (E) is a hydrate of a metal oxide.