JP4379073B2 - Resin composition for artificial marble and artificial marble obtained by heat-curing the composition - Google Patents

Description

  The present invention relates to an artificial marble used as a furniture member or building material. More specifically, the present invention relates to a material used for a part requiring heat resistance and impact resistance, such as a wash counter or a kitchen counter. The present invention relates to a suitable artificial marble and a composition for artificial marble used for obtaining the artificial marble.

  As raw materials for artificial marble, polyester resins, acrylic resins, vinyl ester resins and the like have been conventionally used. Among these resins, the vinyl ester resin has an unsaturated group only at the terminal, and a cured product obtained after heat curing is likely to have a uniform performance. Moreover, repetition of the ether group in the skeleton contributes to improvement of the toughness of the cured product, and the hydroxyl group contributes to wet adhesion with the filler. Furthermore, since the ester group is also present only at the terminal, the content of the ester group in the cured product is low, so that it is difficult to be hydrolyzed and has good water resistance and chemical resistance. Yes. However, artificial marble made of vinyl ester resin has a heat distortion temperature (HDT) of about 120 ° C. or less and has poor heat resistance, such as a material for parts requiring heat resistance such as a wash counter or kitchen counter. Was unsuitable. Thus, it has been studied to increase the heat distortion temperature and improve the heat resistance by controlling the cross-linked state and molecular weight of the cured product using a vinyl ester resin as a thermosetting type. When the deformation temperature is raised by such a device, the heat resistance is improved, but on the other hand, the impact resistance of the cured product is lowered, and there is a problem as a material used for a part such as a wash counter or a kitchen counter.

Therefore, the present inventors previously proposed the technique of Patent Document 1 in order to provide an artificial marble excellent in both heat resistance and impact resistance. In this technology, by using a bisphenol vinyl ester resin and a novolac vinyl ester resin in combination as a vinyl ester resin, the heat resistance and impact resistance of the artificial marble can be improved in a balanced manner. The effect was obtained. However, further improvement in heat resistance and impact resistance has been demanded.
Japanese Patent Laid-Open No. 13-64064 (see [Claims])

  This invention is made | formed in view of such a condition, The objective is to provide the artificial marble excellent in heat resistance and impact resistance. Moreover, the other object of this invention is to provide the composition for artificial marble used when manufacturing the said artificial marble.

The resin composition for artificial marble according to the present invention that has solved the above problems is a resin composition for artificial marble containing a vinyl ester resin, a cross-linking agent component, and a filler, and the cross-linking agent component includes two types. It is composed of more crosslinking agent, of which Ri crosslinker der represented by one the following general formula (1), the occupied cross-linking agent component, and a crosslinking agent represented by the following general formula (1), the following Ratio with the total of crosslinking agents other than the crosslinking agent represented by the general formula (1) [crosslinking agent represented by the following general formula (1) / total crosslinking agents other than the crosslinking agent represented by the following general formula (1)] but on a mass basis, with the gist in that Ru der 0.6 to 1,300. However, in the following formula (1), R ¹ is a lower alkyl group.

As the crosslinking agent component, as a crosslinking agent other than the crosslinking agent represented by the general formula (1), styrene, (meth) acrylic acid ester, a crosslinking agent represented by the following general formula (2), and the following general formula (3 It is preferable to include one or more of the crosslinking agents represented by However, in formula (2) below, R ² is hydrogen or a lower alkyl group, and in formula (3), R ³ is an alicyclic group which may have a double bond.

In the resin composition for artificial marble of the present invention, the blending ratio of the crosslinking agent component to the vinyl ester resin is preferably 30 to 65 parts by mass with respect to the former 100 parts by mass .

  The present invention also includes an artificial marble obtained by heat-curing the resin composition for artificial marble.

  ADVANTAGE OF THE INVENTION According to this invention, the artificial marble which is excellent in heat resistance and also excellent in impact resistance can be provided. Moreover, according to this invention, the resin composition for artificial marble suitable as a material used when manufacturing such artificial marble can be provided.

  The inventors have made various studies in order to improve the heat resistance and impact resistance of artificial marble obtained by heat-curing the resin composition. As a result, a vinyl ester resin is selected as the base resin constituting the artificial marble, and when this resin is crosslinked, two or more kinds of crosslinking agents are used as a crosslinking agent component, and one of them has a specific basic skeleton. The present inventors have found that the above problems can be solved brilliantly by using a crosslinking agent having the present invention. Hereinafter, the function and effect of the present invention will be described in detail.

  First, the resin composition for artificial marble that can be suitably used when manufacturing the artificial marble according to the present invention will be described.

  The resin composition for artificial marble of the present invention includes a vinyl ester resin, a cross-linking agent component, and a filler, and the cross-linking agent component is composed of two or more types of cross-linking agents. It is a crosslinking agent shown by Formula (1).

  That is, when the vinyl ester resin is heat-cured, by using two or more kinds of crosslinking agent components containing the crosslinking agent represented by the general formula (1) as an essential component, the vinyl ester resin, the general formula (1) ) And a crosslinking agent other than the crosslinking agent represented by the general formula (1) are entangled with each other to form a dense three-dimensional network structure. It was denser than the three-dimensional structure formed when only the crosslinking agent represented by the general formula (1) was used as the agent. And by increasing the crosslink density, an artificial marble excellent in both heat resistance and impact resistance could be realized.

  Here, as a vinyl ester resin used as the base of the resin composition for artificial marble, a bisphenol-type vinyl ester resin and a novolac-type vinyl ester resin can be used alone, or both can be mixed at an arbitrary ratio.

  A bisphenol-type vinyl ester resin is an addition reaction product of a bisphenol-type epoxy resin and an unsaturated acid, and has a reactive unsaturated group only at both ends. As the bisphenol type epoxy resin, for example, bisphenol A type, bisphenol AD type, bisphenol S type, bisphenol F type and the like can be used alone or in admixture of two or more selected arbitrarily.

  On the other hand, the novolak-type vinyl ester resin is an addition reaction product of a novolak-type epoxy resin and an unsaturated acid, and has a reactive unsaturated group not only at both ends but also in the side chain portion.

  As an unsaturated acid to be added to a bisphenol type epoxy resin or a novolak type epoxy resin, an unsaturated monobasic acid having radical polymerizability can be usually used. For example, acrylic acid, methacrylic acid, crotonic acid, cinnamic acid Further, hydroxyethyl methacrylate / malate, hydroxyethyl acrylate / malate, hydroxypropyl methacrylate / malate, hydroxypropyl acrylate / malate, dicyclopentadiene / malate, and the like can be used.

As the bisphenol-type vinyl ester resin as described above, specifically, for example, those represented by the following general formula (4) can be used. On the other hand, as the novolac type vinyl ester resin, those represented by the following formula (5) can be used. In the formulas (4) and (5), n represents a positive integer, and R represents H or CH ₃ .

  Among these vinyl ester resins, in order to particularly improve the impact resistance of the artificial marble, it is preferable to use a vinyl ester resin obtained from a bisphenol A type epoxy resin.

  The crosslinking agent component is composed of two or more types of crosslinking agents, and one of these crosslinking agents is a crosslinking agent represented by the above general formula (1). By using the cross-linking agent represented by the above general formula (1) as a cross-linking agent, the unsaturated group at the end of the vinyl ester resin and the above general in the presence of a curing agent (that is, radical polymerization initiator) at the time of heat curing. Since the polymerization cross-linking reaction with the cross-linking agent represented by the formula (1) proceeds and a strong and extremely stable three-dimensional network structure is formed, the artificial marble obtained after heat-curing has heat resistance and impact resistance. It will be excellent.

In the crosslinking agent represented by the general formula (1), R ¹ is a lower alkyl group. Lower alkyl is a hydrocarbon group having 1 to 6 carbon atoms. Among these, vinyl toluene in which R ¹ is a hydrocarbon group having 1 carbon atom (methyl group) is easily available and can be suitably used.

  And the resin composition for artificial marble of this invention needs to contain at least 1 sort (s) of crosslinking agents other than the crosslinking agent shown by the said General formula (1). That is, a mixture of a vinyl ester resin, a crosslinking agent represented by the general formula (1) and a crosslinking agent other than the crosslinking agent represented by the general formula (1) is used as a curing agent (that is, a radical polymerization initiator). This is because these components form a dense three-dimensional network structure by carrying out a polymerization crosslinking reaction in the presence. As described above, the idea of improving the characteristics of the artificial marble finally obtained by specifying a basic structure of one kind of crosslinking agent in combination with a plurality of kinds of crosslinking agents is unique to the present invention. Yes, I think that it was not in the past.

Examples of the crosslinking agent other than the crosslinking agent represented by the general formula (1) include styrene, (meth) acrylic acid ester, the crosslinking agent represented by the following general formula (2), and the following general formula (3). One or more of the crosslinking agents can be used. However, in formula (2) below, R ² is hydrogen or a lower alkyl group, and in formula (3), R ³ is an alicyclic group which may have a double bond.

  These compounds cause a polymerization crosslinking reaction in the presence of a curing agent (that is, a radical polymerization initiator) at the time of heat curing, and the three-dimensional network structure formed by this polymerization crosslinking reaction is further densified and becomes stronger. To improve the heat resistance and impact resistance of artificial marble obtained after heat curing.

  As the (meth) acrylic acid ester, for example, methyl (meth) acrylate can be used.

The crosslinking agent represented by the general formula (2) is divinylbenzene having two vinyl groups in the aromatic ring, and the aromatic ring may further have a lower alkyl group. That is, divinylbenzene in which R ² in the above formula (2) is hydrogen or a divinylbenzene derivative having a lower alkyl group having 1 to 6 carbon atoms as R ² can be suitably used.

The crosslinking agent represented by the general formula (3) is a vinyl compound having an alicyclic group as R ³ . An alicyclic group is a group in which carbon atoms are bonded in a cyclic manner, and is a group that does not belong to an aromatic ring. The carbon number of the alicyclic group is not particularly limited, but vinyl compounds having a 5-membered ring having 5 carbon atoms or a 6-membered ring having 6 carbon atoms are easily available and can be suitably used. Of course, it may be a vinyl compound having a 3-membered ring having 3 carbon atoms or a 4-membered ring having 4 carbon atoms. Further, the alicyclic group may be any of cycloparaffin having a saturated carbocyclic ring and cycloolefin having a double bond in the ring. As the crosslinking agent represented by the general formula (3), for example, vinylcyclohexene can be suitably used.

  As the cross-linking agent other than the cross-linking agent represented by the general formula (1), in consideration of availability, one containing at least one of styrene, methyl (meth) acrylate, divinylbenzene, and vinylcyclohexene is preferable. .

  In addition, when using two or more crosslinking agents other than the crosslinking agent shown by the said General formula (1), what is necessary is just to use it combining arbitrarily, so that the characteristic requested | required of the artificial marble product finally obtained may be used.

  The blending ratio of the crosslinking agent component to the vinyl ester resin is not particularly limited, but it is preferable to mix 30 to 65 parts by mass of the crosslinking agent component with respect to 100 parts by mass of the vinyl ester resin. If the content is less than 30 parts by mass, the crosslinking density is insufficient and the hardness and heat resistance of the artificial marble cannot be sufficiently increased. On the other hand, when it exceeds 65 parts by mass, the hardness tends to be too high and becomes brittle. Moreover, when the compounding quantity of a crosslinking component increases too much, an unreacted crosslinking agent component will remain as a monomer in hardened | cured material (namely, molded article), and will cause a product characteristic to fall. A more preferable lower limit of the above-mentioned blending ratio is 35, and a more preferable upper limit is 55.

  Ratio of the crosslinking agent represented by the above general formula (1) to the total of the crosslinking agents other than the crosslinking agent represented by the above general formula (1) in the crosslinking agent component [shown by the above general formula (1) The crosslinking agent / the total of crosslinking agents other than the crosslinking agent represented by the general formula (1)] is not particularly limited, but is preferably 0.6 to 1300 on a mass basis. That is, when the crosslinking agent other than the crosslinking agent represented by the general formula (1) is excessively increased and the ratio is less than 0.6, the crosslinking structure forming the three-dimensional network structure is a crosslinking agent other than the general formula (1). Because it is composed of the main body, it has a tendency to improve the denseness and heat resistance compared to the case where the cross-linking agent of the above general formula (1) is the main body, but it becomes a very brittle form and impact resistance is reduced. It tends to go. On the other hand, if the cross-linking agent represented by the general formula (1) is excessive and the ratio exceeds 1300, the resulting three-dimensional network structure becomes denser and becomes stronger, heat resistance and impact resistance. It tends to be difficult to obtain the object of the present invention to improve the property. A more preferable lower limit of the ratio is 1.0, and a more preferable upper limit is 130.

  The artificial marble resin composition of the present invention contains a filler as an essential component. The filler increases the strength of the artificial marble and improves the impact resistance, and also increases the heat capacity and contributes to the improvement of heat resistance.

  As the filler, for example, aluminum hydroxide, silica, glass powder, clay and the like can be used alone or in admixture of two or more selected arbitrarily.

  In particular, since aluminum hydroxide has a refractive index close to that of bisphenol-type vinyl ester resin or novolac-type vinyl ester resin, transparency as an artificial marble can be improved and appearance can be improved. Moreover, since aluminum hydroxide has a large heat capacity, the heat capacity of artificial marble is improved and the heat resistance is remarkably improved.

  The amount of the filler in the artificial marble resin composition is preferably 10 to 300 parts by mass with respect to 100 parts by mass of the vinyl ester resin. Even if the amount of the filler is less than 10 parts by mass, the finally obtained artificial marble has good impact strength, but may not be satisfactory in terms of heat resistance. On the other hand, when the mixing exceeds 300 parts by mass, the heat resistance of the artificial marble is improved, but the impact strength tends to decrease. More preferably, the amount is 30 to 280 parts by mass with respect to 100 parts by mass of the vinyl ester resin.

  The size of the filler is not particularly limited, but it is preferable to use a filler having an average particle size in the range of 2 to 100 μm. The smaller the filler used, the better the impact strength of artificial marble. However, when the average particle size is less than 2 μm, the viscosity of the resin composition for artificial marble tends to increase rapidly, making it difficult to manufacture. is there. On the other hand, when the filler becomes large, the viscosity of the resin composition for artificial marble decreases and it becomes easy to produce, but when the average particle size exceeds 100 μm, the impact strength of the artificial marble tends to decrease. is there. A more preferable lower limit of the average particle diameter is 5 μm, and a more preferable upper limit is 50 μm.

  The filler may be used as it is (untreated). For example, if the surface of the filler is subjected to a silane coupling treatment in advance, the adhesion between the filler and the vinyl ester resin can be improved. The impact strength of the artificial marble finally obtained can be increased.

  In the resin composition for artificial marble of the present invention, for example, an ultraviolet absorber, a chain transfer agent, a viscosity reducing agent, a release agent, glass fiber, a colorant and the like can be blended as components other than those described above.

  In order to improve the light resistance of the artificial marble resin composition and the artificial marble formed from this composition and to stabilize the quality against light deterioration, for example, a cyanoacrylate UV absorber is blended as the UV absorber. It is preferable to do. Since the cyanoacrylate ultraviolet absorber is a white powder or a transparent liquid, the color tone can be controlled even in a light color system, and a light color artificial marble can be obtained. In addition, an artificial marble having a very high light resistance can be obtained.

  The cyanoacrylate-based ultraviolet absorber that can be used in the present invention is not particularly limited, but it is preferable to use one having a melting point (or boiling point) of 80 ° C. or higher. If the melting point (or boiling point) of the cyanoacrylate-based ultraviolet absorber is less than 80 ° C., the resulting artificial marble may have reduced thermal shock performance (high and low temperature thermal shock properties; heat shock performance). For example, heat shock resistance performance is particularly good in areas where there is a possibility of heat and temperature differences, such as where the kitchen counter is near a gas stove, where hot water is applied to the wash counter, or where there is sunlight and where it does not. If it is required and the thermal shock resistance is not high, it may not be used for the above-mentioned purposes. In addition, since it is so preferable that melting | fusing point (or boiling point) of a cyanoacrylate type ultraviolet absorber is high, an upper limit is not set.

  Moreover, the benzotriazole type and benzophenone type conventionally used can also be used. However, since benzotriazole-based and benzophenone-based UV absorbers are yellow powder, when added to the resin composition for artificial marble, the resin composition is colored yellow. Therefore, it is necessary to pay attention because the color tone cannot be controlled especially when aiming at a light color tone.

  As a thickener, for example, product number “W996” manufactured by BKY, as a mold release agent, for example, “Separ (trade name)” manufactured by Chukyo Yushi Co., Ltd., as a glass fiber, for example, product number manufactured by Nippon Sheet Glass Co., Ltd. "RES03X-BM" etc. can be mix | blended and used.

  Moreover, it is preferable to mix a pattern material in order to give the artificial marble a high-class feeling. As the pattern material, it is possible to use various thermosetting resins that have been heat-cured and molded in advance, but the same kind as the vinyl ester resin that is the base of the resin composition for artificial marble according to the present invention. It is preferable to use one that has been heat-cured and molded in advance, because the pattern material itself has high hardness and heat resistance, and the integrity with the matrix material also increases.

  Next, a method for producing the artificial marble according to the present invention will be described.

  The artificial marble according to the present invention is obtained by injecting a resin composition for artificial marble containing a vinyl ester resin, a cross-linking agent component and a filler into a casting mold and then curing the resin composition.

  That is, after blending a vinyl ester resin with a crosslinking agent component, filler, curing agent, etc., vacuum defoaming treatment is performed by stirring for about 30 to 60 minutes under a reduced pressure of about 2.66 to 6.66 kPa (20 to 50 Torr). To obtain a resin composition for artificial marble, then release from the reduced pressure state, and pour the resin composition into a casting mold provided with a heating pipe. After injecting the resin composition, the mold is heated through a heating medium in the heating pipe, and the resin composition is heated at about 40 to 120 ° C. for about 60 to 300 minutes. The artificial marble resin composition is heated to react with the reactive unsaturated group in the vinyl ester resin, the crosslinking agent represented by the general formula (1), and the crosslinking agent represented by the general formula (1). A copolymerization reaction proceeds with the reactive unsaturated group contained in the cross-linking agent to form a three-dimensional structure, and a cured vinyl ester resin (artificial marble) is obtained.

  Further, in addition to the crosslinking agent component, filler, curing agent and the like, the vinyl ester resin is further mixed with a colorant, and then stirred for about 30 to 60 minutes under a reduced pressure of about 2.66 to 6.66 kPa (20 to 50 Torr). Thus, a vacuum defoaming treatment is performed to obtain a resin composition, and a pattern material can be obtained by heat curing under the same conditions as described above. And if this pattern material is mixed with the said resin composition for artificial marble obtained without mix | blending a coloring agent, and it heat-hardens on the conditions similar to the above, the artificial marble containing a pattern material can be obtained.

  Examples of the curing agent (radical polymerization initiator) include 1,1,3,3-tetramethylbutylperoxy-2-ethylhexaate, t-hexylperoxy-2-ethylhexanoate, and bis (4 -Tbutyl-cyclohexyl) peroxydicarbonate or the like can be used. 1,1,3,3-tetramethylbutyl peroxy-2-ethylhexanoate is “Percure WO (trade name)” manufactured by NOF Corporation, t-hexylperoxy-2-ethylhexanoate For example, “Percure HO (trade name)” manufactured by Nippon Oil & Fats Co., Ltd., and “Perkadox 16 (trade name)” manufactured by Kayaku Akzo Corporation as bis (4-t-butylcyclohexyl) peroxydicarbonate. Is available.

  The cured product (artificial marble) thus obtained has high hardness and excellent heat resistance. Therefore, it is possible to relax the use restriction of the product utilizing the artificial marble (molded product), and it is possible to obtain the artificial marble which is not easily damaged and is resistant to heat. Therefore, the artificial marble obtained by heat-curing the composition for artificial marble of the present invention is, for example, at a site where heat resistance and impact resistance are required, such as a wash counter, kitchen counter, bathtub, wash bowl, etc. It can use suitably as a material of the goods used. Of course, the artificial marble of the present invention can also be used as a material used for parts such as floor materials and furniture surface materials.

  Hereinafter, the present invention will be described in more detail with reference to experimental examples, but the following experimental examples are not intended to limit the present invention, and may be implemented with appropriate modifications within a range that can meet the purpose described above and below. These are all possible and are within the scope of the present invention.

Experimental example 1
A vinyl ester resin (made by Mitsui Takeda Chemical Co., Ltd., “Prominate P-310 (trade name)”) containing a styrene monomer as a crosslinking agent is set in a vacuum distillation separator rotary evaporator and gradually removed by an oil bath under reduced pressure. To remove the styrene monomer.

  Vinyl toluene as a crosslinking agent was mixed with the vinyl ester resin from which the styrene monomer was separated and removed to obtain a vinyl toluene-containing vinyl ester resin containing 38% by mass of vinyl toluene.

  The resulting vinyltoluene-containing vinyl ester resin has 10.5 parts by mass of methyl methacrylate as a crosslinking agent and 100% by mass of aluminum hydroxide (Showa Showa) as a cross-linking agent with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. 150 parts by mass of “H-320 (trade name)”, average particle diameter: 10 μm) manufactured by Denko Co., Ltd. was added to obtain a resin composition A.

  In the obtained resin composition A, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition A, 0.5 parts by mass of a brown toner as a colorant and “Percure WO (trade name)” as a curing agent What added 2.0 mass parts (made by Nippon Oil & Fat Co., Ltd.) was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum degassing treatment to obtain a resin composition for a pattern material. The obtained resin composition for pattern material was injected and filled into a casting mold, and the mold temperature was set to 100 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material a. The average particle diameter of the pattern material a is 2.1 mm.

  Next, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition A, 6.5 parts by mass of the pattern material a and “Percure WO (trade name)” as a curing agent (Japan) A resin composition for artificial marble was obtained by adding 2.0 parts by mass of Ogyu Co., Ltd. and stirring and mixing under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental example 2
The vinyl toluene-containing vinyl ester resin obtained in Experimental Example 1 was further mixed with 10.5 parts by mass of vinyl toluene as a cross-linking agent with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. 150 parts by mass of aluminum hydroxide (manufactured by Showa Denko KK, “H-320 (trade name)”, average particle size: 10 μm) was added to obtain a resin composition B.

  In the obtained resin composition B, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition B, 0.5 part by mass of brown toner as a colorant and “Percure WO (trade name)” as a curing agent What added 2.0 mass parts (made by Nippon Oil & Fat Co., Ltd.) was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum degassing treatment to obtain a resin composition for a pattern material. The obtained resin composition for pattern material was injected and filled into a casting mold, and the mold temperature was set to 100 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material b. The average particle diameter of the pattern material b is 2.1 mm.

  Next, to the resin composition A obtained in Experimental Example 1, 6.5 parts by mass of the pattern material b and 100 parts by mass of “Percure WO” as a curing agent with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition A. (Product name) "(made by Nippon Oil & Fats Co., Ltd.) added with 2.0 parts by mass was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for artificial marble. Obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental example 3
A vinyl ester resin (“Lipoxy R-806 (trade name)” manufactured by Showa Polymer Co., Ltd.) containing a styrene monomer as a crosslinking agent is set in a rotary evaporator using a vacuum distillation separator and gradually removed by an oil bath under reduced pressure. To remove the styrene monomer.

  Vinyl toluene as a crosslinking agent was mixed with the vinyl ester resin from which the styrene monomer was separated and removed to obtain a vinyl toluene-containing vinyl ester resin containing 44% by mass of vinyl toluene.

  In the obtained vinyl toluene-containing vinyl ester resin, 5.5 parts by mass of divinylbenzene as a crosslinking agent and aluminum hydroxide (Nippon Light Metal) as a filler with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. 140 parts by mass of “BW-103 (trade name)” (average particle diameter: 8 μm) manufactured by Co., Ltd. was obtained to obtain a resin composition C.

  In the obtained resin composition C, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition C, 1.2 parts by mass of white toner as a colorant and “Percure WO (trade name)” (as a curing agent) ( What added 2.0 parts by mass of Nippon Oil & Fats Co., Ltd. was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum degassing to obtain a resin composition for a pattern material. The obtained resin composition for pattern material was injected and filled into a casting mold, and the mold temperature was set to 100 ° C. and cured by heating for 110 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material c. The average particle diameter of the pattern material c is 2.0 mm.

  Next, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition C, 4.5 parts by mass of the pattern material c and “Percure WO (trade name)” (Japan) A resin composition for artificial marble was obtained by adding 2.0 parts by mass of Ogyu Co., Ltd. and stirring and mixing under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 4
As a crosslinking agent, the vinyl toluene-containing vinyl ester resin obtained in Experimental Example 3 was further added with 5.5 parts by mass of vinyl toluene as a crosslinking agent with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. 140 parts by mass of aluminum hydroxide (manufactured by Nippon Light Metal Co., Ltd., “BW-103 (trade name)”, average particle diameter: 8 μm) was obtained to obtain a resin composition D.

  In the obtained resin composition D, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition D, 1.2 parts by mass of white toner as a colorant and “Percure WO (trade name)” as a curing agent ( What added 2.0 parts by mass of Nippon Oil & Fats Co., Ltd. was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum degassing to obtain a resin composition for a pattern material. The obtained resin composition for pattern material was injected and filled into a casting mold, and the mold temperature was set to 100 ° C. and cured by heating for 110 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material d. The average particle diameter of the pattern material d is 2.0 mm.

  Next, the resin composition C obtained in Experimental Example 3 was added with 4.5 parts by mass of the pattern material d and 100 parts by weight of “Percure WO” as a curing agent with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition C. (Product name) "(made by Nippon Oil & Fats Co., Ltd.) added with 2.0 parts by mass was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for artificial marble. Obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 5
A vinyl ester resin (“Neopor 8100X3” (trade name), manufactured by Nippon Yupica Co., Ltd.) containing a styrene monomer as a cross-linking agent is set in a vacuum evaporator / separator rotary evaporator and gradually heated by an oil bath under reduced pressure. Then, the styrene monomer was separated and removed.

  Vinyl toluene as a crosslinking agent was mixed with the vinyl ester resin from which the styrene monomer was separated and removed to obtain a vinyl toluene-containing vinyl ester resin containing 36% by mass of vinyl toluene.

  In the obtained vinyl toluene-containing vinyl ester resin, 6.5 parts by mass of vinylcyclohexene as a cross-linking agent and silica (Tatsumori Co., Ltd.) as a crosslinking agent with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. The resin composition E was obtained by adding 130 parts by mass of “CRYSTALIE M-3K (trade name)”, average particle size: 20 μm.

  With respect to 100 parts by mass of the vinyl ester resin contained in the resin composition E, 0.35 parts by mass of beige toner as a colorant and “Percure WO (trade name)” as a curing agent are obtained. What added 2.5 mass parts (made by Nippon Oil & Fat Co., Ltd.) was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for a pattern material. The obtained resin composition for a pattern material was injected and filled into a casting mold, and the mold temperature was set to 90 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material e. The average particle diameter of the pattern material e is 2.5 mm.

  Next, in the resin composition E, 6.7 parts by mass of the pattern material e with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition E, and “Percure HO (trade name)” (Japan) A resin composition for artificial marble was obtained by adding 2.5 parts by mass of Yushi Co., Ltd. and stirring and mixing under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming. The resulting resin composition for artificial marble was poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and the mold temperature was set to 90 ° C. and cured by heating for 120 minutes. )

Experimental Example 6
To 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin obtained in Experimental Example 5 above, 6.5 parts by mass of vinyl toluene as a crosslinking agent, and as a filler 130 parts by mass of silica (manufactured by Tatsumori Co., Ltd., “CRYSTALIE M-3K (trade name)”, average particle size: 20 μm) was added to obtain a resin composition F.

  In the obtained resin composition F, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition F, 0.35 parts by mass of beige toner as a colorant and “Percure WO (trade name)” as a curing agent. What added 2.5 mass parts (made by Nippon Oil & Fat Co., Ltd.) was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for a pattern material. The obtained resin composition for a pattern material was injected and filled into a casting mold, and the mold temperature was set to 90 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material f. The average particle diameter of the pattern material f is 2.5 mm.

  Next, in the resin composition E obtained in Experimental Example 5, the pattern material f is 6.7 parts by mass with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition E, and “Percure HO” is used as a curing agent. (Product name) "(manufactured by Nippon Oil & Fats Co., Ltd.) with 2.5 parts by mass was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for artificial marble. Obtained. The resulting resin composition for artificial marble was poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and the mold temperature was set to 90 ° C. and cured by heating for 120 minutes. )

Experimental Example 7
A vinyl ester resin (“Neopor 8250L” (trade name), manufactured by Nippon Yupica Co., Ltd.) containing a styrene monomer as a cross-linking agent is set in a vacuum evaporator / separator rotary evaporator and gradually heated by an oil bath under reduced pressure. Then, the styrene monomer was separated and removed.

  Vinyl toluene as a crosslinking agent was mixed with the vinyl ester resin from which the styrene monomer was separated and removed to obtain a vinyl toluene-containing vinyl ester resin containing 30% by mass of vinyl toluene.

  Into the obtained vinyl toluene-containing vinyl ester resin, with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin, 3.5 parts by mass of styrene and 7.8 parts by mass of methyl methacrylate as a crosslinking agent, Aluminum hydroxide (Showa Denko Co., Ltd., “H-320 (trade name)”, average particle size: 10 μm) and glass powder (Nihon Frit Co., Ltd., “GF-2-30A (trade name)”, average 155 parts by mass of a mixed powder with a particle size of 30 μm was added to obtain a resin composition G. The mixing ratio of aluminum hydroxide and glass powder is 90:10 on a mass basis.

  In the obtained resin composition G, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition G, 0.20 parts by mass of a brown toner as a colorant and 0.25 parts by mass of a black toner are used as a curing agent. A resin composition for a pattern material obtained by adding 2.0 parts by mass of “Percure HO (trade name)” (manufactured by NOF Corporation) under a reduced pressure [2.66 kPa (20 Torr)] for 60 minutes with vacuum defoaming treatment. I got a thing. The obtained resin composition for pattern material was poured and filled into a casting mold, and the mold temperature was set to 95 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material g. The average particle diameter of the pattern material g is 2.2 mm.

  Next, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition G, the resin composition G has 5.0 parts by mass of the pattern material g and “Percure HO (trade name)” (Japan) A resin composition for artificial marble was obtained by adding 2.0 parts by mass of Ogyu Co., Ltd. and stirring and mixing under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming. The resulting resin composition for artificial marble is injected and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 95 ° C. for 120 minutes. )

Experimental Example 8
The vinyltoluene-containing vinyl ester resin obtained in Experimental Example 7 was further added with 11.3 parts by mass of vinyltoluene as a crosslinking agent and 100 parts by mass of the vinylester resin contained in the vinyltoluene-containing vinylester resin. Aluminum hydroxide (Showa Denko Co., Ltd., “H-320 (trade name)”, average particle size: 10 μm) and glass powder (Nihon Frit Co., Ltd., “GF-2-30A (trade name)”, average grain 155 parts by mass of a mixed powder with a diameter of 30 μm was added to obtain a resin composition H. The mixing ratio of aluminum hydroxide and glass powder is 90:10 on a mass basis.

  In the obtained resin composition H, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition H, 0.20 parts by mass of a brown toner as a colorant and 0.25 parts by mass of a black toner are used as a curing agent. A resin composition for a pattern material obtained by adding 2.0 parts by mass of “Percure HO (trade name)” (manufactured by NOF Corporation) under a reduced pressure [2.66 kPa (20 Torr)] for 60 minutes with vacuum defoaming treatment. I got a thing. The obtained resin composition for pattern material was poured and filled into a casting mold, and the mold temperature was set to 95 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized by a pulverizer and classified to obtain a pattern material h. The average particle diameter of the pattern material h is 2.2 mm.

  Next, to the resin composition G obtained in Experimental Example 7, 5.0 parts by mass of the pattern material h and 100 parts by mass of “Percure HO” as a curing agent with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition G. (Product name) "(made by Nippon Oil & Fats Co., Ltd.) added with 2.0 parts by mass was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for artificial marble. Obtained. The resulting resin composition for artificial marble is injected and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 95 ° C. for 120 minutes. )

Experimental Example 9
A vinyl ester resin (“Prominate P-311 (trade name)” manufactured by Mitsui Takeda Chemical Co., Ltd.) containing a styrene monomer as a crosslinking agent is set in a vacuum distillation separator rotary evaporator and gradually removed by an oil bath under reduced pressure. To remove the styrene monomer.

  The vinyl ester resin from which the styrene monomer was separated and removed was mixed with vinyl toluene as a crosslinking agent to obtain a vinyl toluene-containing vinyl ester resin containing 30% by mass of vinyl toluene.

  In the obtained vinyl toluene-containing vinyl ester resin, 2.5 parts by mass of divinyl benzene as a crosslinking agent, 8.0 parts by mass of methyl methacrylate, and vinyl are included with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. 5.5 parts by mass of cyclohexene, aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd., “CW-316 (trade name)”, average particle size: 15 μm) and glass powder (manufactured by Nippon Frit Co., Ltd., “GF-2”) The resin composition I was obtained by adding 160 parts by mass of mixed powder of “-30A (trade name)” and average particle size: 30 μm). The mixing ratio of aluminum hydroxide and glass powder is 85:15 on a mass basis.

  In the obtained resin composition I, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition I, 0.20 parts by mass of a brown toner as a colorant and 0.10 parts by mass of a black toner as a curing agent, A resin composition for a pattern material obtained by adding 2.0 parts by mass of “Percure HO (trade name)” (manufactured by NOF Corporation) under a reduced pressure [2.66 kPa (20 Torr)] for 60 minutes with vacuum defoaming treatment. I got a thing. The obtained resin composition for pattern material was poured and filled into a casting mold, and the mold temperature was set to 95 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material i. The average particle diameter of the pattern material i is 2.0 mm.

  Next, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition I, 7.0 parts by mass of the pattern material i and “Percure HO (trade name)” (Japan) A resin composition for artificial marble was obtained by adding 2.0 parts by mass of Ogyu Co., Ltd. and stirring and mixing under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 10
As a filler, the vinyl toluene-containing vinyl ester resin obtained in Experimental Example 9 is further filled with 16.0 parts by mass of vinyl toluene as a crosslinking agent with respect to 100 parts by mass of the vinyl ester resin contained in the vinyl toluene-containing vinyl ester resin. Aluminum hydroxide (manufactured by Sumitomo Chemical Co., Ltd., “CW-316 (trade name)”, average particle size: 15 μm) and glass powder (manufactured by Nippon Frit Co., Ltd., “GF-2-30A (trade name)”, average grain 160 parts by mass of mixed powder with a diameter of 30 μm) was added to obtain a resin composition J. The mixing ratio of aluminum hydroxide and glass powder is 85:15 on a mass basis.

  In the obtained resin composition J, with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition J, 0.20 parts by mass of a brown toner as a colorant and 0.10 parts by mass of a black toner, and “ A resin composition for a pattern material obtained by adding 2.0 parts by mass of “Percure HO (trade name)” (manufactured by NOF Corporation) under a reduced pressure [2.66 kPa (20 Torr)] for 60 minutes with vacuum defoaming treatment. I got a thing. The obtained resin composition for pattern material was poured and filled into a casting mold, and the mold temperature was set to 95 ° C. and cured by heating for 120 minutes. The obtained cured product was pulverized with a pulverizer and classified to obtain a pattern material j. The average particle diameter of the pattern material j is 2.0 mm.

  Next, to the resin composition I obtained in Experimental Example 9, 7.0 parts by mass of the handle material j and 100 parts by mass of the vinyl ester resin contained in the resin composition I, and “Percure HO” as a curing agent. (Product name) "(made by Nippon Oil & Fats Co., Ltd.) added with 2.0 parts by mass was stirred and mixed under reduced pressure [2.66 kPa (20 Torr)] for 60 minutes under vacuum defoaming treatment to obtain a resin composition for artificial marble. Obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 11 (for comparison)
6.5 parts by mass of the pattern material a obtained in Example 1 above with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition B in the resin composition B obtained in Example 2 above, and a curing agent For artificial marble, add 2.0 parts by weight of “Percure WO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under vacuum [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 12 (for comparison)
6.5 parts by mass of the pattern material b obtained in Example 2 above with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition B in the resin composition B obtained in Example 2 above, and a curing agent For artificial marble, add 2.0 parts by weight of “Percure WO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under vacuum [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 13 (for comparison)
In resin composition D obtained in Experimental Example 4 above, 4.5 parts by mass of the pattern material c obtained in Experimental Example 3 above with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition D, and a curing agent For artificial marble, add 2.0 parts by weight of “Percure WO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under vacuum [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 14 (for comparison)
In resin composition D obtained in Experimental Example 4 above, 4.5 parts by mass of the pattern material d obtained in Experimental Example 4 above with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition D, and a curing agent For artificial marble, add 2.0 parts by weight of “Percure WO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under vacuum [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 15 (for comparison)
6.7 parts by mass of the pattern material e obtained in Example 5 above with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition F in the resin composition F obtained in Example 6 above, and a curing agent For artificial marble, add 2.5 parts by mass of “Percure HO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under reduced pressure [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The resulting resin composition for artificial marble was poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and the mold temperature was set to 90 ° C. and cured by heating for 120 minutes. )

Experimental Example 16 (for comparison)
The resin composition F obtained in Experimental Example 6 is 6.7 parts by mass of the pattern material f obtained in Experimental Example 6 with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition F, and a curing agent. For artificial marble, add 2.5 parts by mass of “Percure HO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under reduced pressure [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The resulting resin composition for artificial marble was poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and the mold temperature was set to 90 ° C. and cured by heating for 120 minutes. )

Experimental Example 17 (for comparison)
The resin composition H obtained in Experimental Example 8 is 5.0 parts by mass of the pattern material g obtained in Experimental Example 7 with respect to 100 parts by mass of the vinyl ester resin contained in the resin composition H, and a curing agent. For artificial marble, add 2.0 parts by mass of “Percure HO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under reduced pressure [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The resulting resin composition for artificial marble is injected and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 95 ° C. for 120 minutes. )

Experimental Example 18 (for comparison)
With respect to 100 parts by mass of the vinyl ester resin contained in the resin composition H in the resin composition H obtained in the experimental example 8, 5.0 parts by mass of the pattern material h obtained in the experimental example 8 and a curing agent For artificial marble, add 2.0 parts by mass of “Percure HO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under reduced pressure [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The resulting resin composition for artificial marble is injected and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 95 ° C. for 120 minutes. )

Experimental Example 19 (for comparison)
With respect to 100 parts by mass of the vinyl ester resin contained in the resin composition J in the resin composition J obtained in the experimental example 10, 7.0 parts by mass of the pattern material i obtained in the experimental example 9 and a curing agent For artificial marble, add 2.0 parts by mass of “Percure HO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under reduced pressure [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

Experimental Example 20 (for comparison)
With respect to 100 parts by mass of the vinyl ester resin contained in the resin composition J in the resin composition J obtained in the experimental example 10, 7.0 parts by mass of the pattern material j obtained in the experimental example 10 and a curing agent For artificial marble, add 2.0 parts by mass of “Percure HO (trade name)” (manufactured by Nippon Oil & Fats Co., Ltd.) under reduced pressure [2.66 kPa (20 Torr)] while stirring and mixing for 60 minutes under vacuum defoaming. A resin composition was obtained. The obtained resin composition for artificial marble is poured and filled into a casting mold having a flat plate shape and a thickness of 15 mm, and is cured by heating at a mold temperature of 100 ° C. for 120 minutes. )

  Table 1 below shows the types of resin compositions and types of pattern materials used in Experimental Examples 1 to 20, respectively.

  Next, the glass transition point and hardness of the artificial marble (molded article) obtained in Experimental Examples 1 to 20 were measured, and the heat resistance was evaluated at the glass transition point, and the impact resistance was evaluated at the hardness.

  As for the glass transition point (Tg) of the artificial marble, the linear expansion coefficient was measured by TMA (Thermo Mechanical Analysis) analysis according to JIS standard K7197, and the place where the linear expansion coefficient greatly changed was defined as Tg. Further, the hardness of the artificial marble was measured in accordance with JIS standard K6911. The results of measuring the glass transition point and Barcol hardness are also shown in Table 1 below.

  As is apparent from Table 1, the artificial marble obtained in Experimental Examples 1 to 10 uses two or more types of crosslinking agents as the crosslinking agent component, and one of them uses vinyltoluene. Excellent impact and heat resistance.

  On the other hand, since the artificial marble obtained in Experimental Examples 11 to 20 uses only vinyl toluene as a cross-linking agent, it is inferior in both properties of impact resistance and heat resistance.

  In addition, an artificial marble obtained by blending a pattern material obtained by heat curing using two or more kinds of crosslinking agents containing vinyltoluene as a crosslinking agent component is heated and cured using only one kind of crosslinking agent. Compared with the artificial marble obtained by blending the pattern material obtained in this way, the impact resistance and heat resistance characteristics were almost the same or slightly better.

  In addition, the artificial marble obtained in the above experimental example had transparency and good design.

Claims (4)

A resin composition for artificial marble containing a vinyl ester resin, a crosslinking agent component, and a filler,
Wherein being configured crosslinking agent component in two or more crosslinking agents, Ri crosslinker der to them one is represented by the following general formula (1),
Ratio of the crosslinking agent represented by the following general formula (1) to the total of the crosslinking agents other than the crosslinking agent represented by the following general formula (1) in the crosslinking agent component [shown by the following general formula (1) crosslinking agent / the following general formula (1) total crosslinking agent other than the crosslinking agent represented by] are, by weight, artificial marble resin composition characterized from 0.6 to 1300 der Rukoto.

However, in formula (1), R ¹ is a lower alkyl group. As the crosslinking agent other than the crosslinking agent represented by the general formula (1),
styrene,
(Meth) acrylic acid ester,
A crosslinking agent represented by the following general formula (2):

A crosslinking agent represented by the following general formula (3):

The resin composition for artificial marble according to claim 1, comprising at least one of them.
However, in formula (2), R ² is hydrogen or a lower alkyl group, and in formula (3), R ³ is an alicyclic group which may have a double bond.   The resin composition for artificial marble according to claim 1 or 2, wherein the blending ratio of the crosslinking agent component to the vinyl ester resin is 30 to 65 parts by mass of the latter with respect to 100 parts by mass of the former. An artificial marble, which is obtained by heat-curing the resin composition for artificial marble according to any one of claims 1 to 3.