JP2726244B2 - Molding material, method for producing the same, and molded article using the molding material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molding material suitably used for producing molded articles having various patterns such as granite pattern, marble pattern and spotted pattern on the surface thereof, and a method for producing the same. And a molded article using a molding material.

[0002]

2. Description of the Related Art As a method for producing a marble or artificial stone (molded article) having an agate-like appearance, a synthetic resin serving as a fabric is mixed with a patterning material that forms a so-called streak or cloud pattern. The present inventors have previously proposed the following method. That is, a semi-cured gel-like polymer having a specific viscosity (viscosity that deforms when an external force is applied) obtained by subjecting a curable resin to three-dimensional cross-linking using a curing agent such as an organic peroxide is used as the above-mentioned polymer. This artificial stone is manufactured by crushing this semi-cured gel polymer to a predetermined size, mixing with a synthetic resin as a material, and curing and molding the material (Japanese Unexamined Patent Publication No. 157146). That is, the conventional artificial stone is designed to exhibit a pattern on the surface of the artificial stone by the semi-cured gel polymer.

[0003]

However, since the above semi-cured gel polymer is obtained by polymerizing a curable resin by a radical polymerization reaction, it is difficult to control the viscosity, hardness and the like to suitable values. . For this reason, when the semi-cured gel polymer is mixed with the synthetic resin serving as the dough, and both are kneaded using a kneader or the like, when the viscosity or hardness is not adjusted to a value within a predetermined range, The surface of the semi-cured gel polymer melts. That is, a part of the semi-cured gel polymer is dissolved in the synthetic resin, and the boundary (pattern) between the semi-cured gel polymer and the synthetic resin is blurred. For this reason, the shape of the crushed surface of the semi-cured gel polymer cannot be maintained, and an artificial stone having a desired pattern cannot be obtained.

When producing artificial stones having an appearance resembling natural stones such as granite and granite, several types of resin particles colored in different colors to express these patterns in a synthetic resin as a fabric are used. Is generally dispersed and cured. The above resin particles are roughly pulverized using a hammer or the like to a lump of a cured synthetic resin to be the resin particles, and then finely pulverized using a pulverizer such as a jaw crusher, a roll pulverizer, or a hammer mill, Furthermore, it is manufactured by classifying the pulverized product and adjusting it to a predetermined particle size.

[0005] However, in the above method, pulverization is time-consuming and a large amount of resin particles finely pulverized smaller than a desired particle diameter is generated. The yield (the so-called pulverization yield) at the time of obtaining resin particles that can be used for the above is low. Also, when the resin particles are dispersed and cured in the synthetic resin serving as the cloth, the adhesive strength at the interface between the synthetic resin and the resin particles that have already been cured is reduced,
Physical properties such as mechanical strength of the obtained artificial stone are inferior.
Furthermore, usually, the above resin particles are porous, and when mixed with a synthetic resin serving as a fabric, the synthetic resin absorbs the synthetic resin, so that the viscosity of the synthetic resin increases and the dispersibility of the resin particles decreases, Resin particles are biased. In other words, the conventional method has a problem that it is difficult to produce an artificial stone having good physical properties such as mechanical strength and a desired pattern.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned conventional problems, and has as its object to be able to crush easily and with good yield, and to be used even when mixed with synthetic resin as a dough. Another object of the present invention is to provide a molding material capable of maintaining a shape of a crushed surface and exhibiting a desired pattern, and a method of manufacturing the same. Another object of the present invention is to provide a molded article such as an artificial stone, which has good physical properties such as mechanical strength and has a desired pattern.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies on a molding material and a method for producing the same in order to achieve the above object. As a result, the compound A having a plurality of reactive substituents and the compound A Compound B, which reacts with A, is bonded by a reaction other than a radical reaction, and a molding material comprising a reaction compound swollen by a liquid monomer polymerized by a radical polymerization reaction is appropriately soft. It can be easily crushed to the size of, and, for example, even when mixed with synthetic resin as a dough, it has been found that the shape of the crushed surface can be maintained and a desired pattern can be expressed, and the present invention has been developed. It was completed.

That is, the molding material according to the first aspect of the present invention.
In order to solve the above problem,Compound A has a hydroxyl group
And multiple reactive substituents selected from carboxyl groups
Compound B is a polyfunctional polyisocyanate
Compounds, organoaluminum compounds and alkaline earth
A compound that is at least one of a class of metal oxides,
At least one of compound A and compound B is trifunctional or more
Comprising the above compound,Compound A and compound
B,Compound B with the reactive substituentBy the reaction3D
CrosslinkingReaction compound formed by bondingButFor radical polymerization reaction
More polymerizable liquid monomer XComposition swollen by
Is crushed to a predetermined size.
You.

Further, according to the method for producing a molding material of the invention described in claim 5, the compound A is used for solving the above-mentioned problems.
Multiple reactivity selected from hydroxyl group and carboxyl group
A compound having a substituent, wherein the compound B is a polyfunctional polyimide.
Socyanate compounds, organoaluminum compounds and
A compound that is at least one of the alkaline earth metal oxides
Wherein at least one of the compound A and the compound B is
A compound containing a compound having three or more functional groups ,
Compound B is mixed with a liquid monomer X which is polymerized by a radical polymerization reaction, and the compound A and the compound B are reacted with each other.
Be coupled by reaction with sexual substituents as compound B, to form a reaction compound having a three-dimensional crosslinked structure which is swollen by the monomer X, the crushing reaction compound moistened bulging into a predetermined size Features.

According to a sixth aspect of the present invention, there is provided a method for producing a molding material, wherein the compound A has a hydroxyl group.
Reactive substituents selected from carboxylic and carboxyl groups
Wherein the compound B is a polyfunctional polyisocyanate
Nate compounds, organoaluminum compounds and alkalis
A compound that is at least one of an earth metal oxide,
At least one of the compound A and the compound B is trifunctional
A compound containing the above compound, a compound A, a compound B, and a liquid monomer X that is polymerized by a radical polymerization reaction are mixed, and the compound A and the compound B are subjected to the reactive substitution.
By reacting the group with the compound B to form a reaction compound having a three-dimensional cross-linked structure swollen by the monomer X, and crushing the swollen reaction compound to a predetermined size. after forming the is characterized by mixing the crushed material in a monomer Y which is polymerized by the monomer X and the radical polymerization reaction.

Further, the molded article of the invention according to claim 7 is:
In order to solve the above problems, any one of claims 1 to 4
Molded using the molding material described in any one of the above.
It is characterized in that that.

Hereinafter, the present invention will be described in detail. The molding material according to the present invention is a liquid comprising a compound A having a plurality of reactive substituents and a compound B reacting with the compound A, which are bonded by a reaction other than a radical reaction, and are polymerized by a radical polymerization reaction. The reaction compound (composition) swollen by the monomer X in the form of particles is crushed to a predetermined size.

The compound A as a raw material of the molding material according to the present invention is not particularly limited as long as it has a plurality of reactive substituents . Examples of the compound A include a compound having two or more hydroxyl groups or carboxyl groups as reactive substituents in one molecule, and a polymer (that is, a thermoplastic resin). Specifically, for example, Examples of the compound include ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylolpropane, bisphenol A
And polycarboxylic acids such as malonic acid, adipic acid, isophthalic acid and terephthalic acid. Examples of the polymer include vinyl esters; unsaturated polyesters; saturated polyesters; polymers of acrylic compounds such as 2-hydroxyethyl methacrylate; and aromatic vinyl compounds such as styrene and α-methylstyrene and acrylic compounds. And the like.

Compound B, which is a raw material of the molding material according to the present invention, reacts with the reactive substituent to contain a liquid.
To form a three-dimensional cross-linked structure that swells with the compound A
The compound is not particularly limited as long as it is a compound for thickening. As the above compound B, specifically,
Examples thereof include polyfunctional polyisocyanate compounds such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, methylene diisocyanate, and hexamethylene diisocyanate; organic aluminum compounds such as aluminum isopropoxide; alkaline earth metal oxides such as magnesium oxide. .

The monomer X as a raw material of the molding material according to the present invention is not particularly limited as long as it is a liquid monomer which is polymerized by a radical polymerization reaction. Incidentally, the monomer X will be described later.

The reaction compound is obtained by reacting compounds A and B by a well-known method. These compounds A and B may be used in an appropriate combination depending on, for example, the use of a molded article obtained by molding a molding material, physical properties required for the molded article, physical properties required at the time of molding, and the like. That is, the compounds A and B in the molding material
Is not particularly limited. The reaction conditions for reacting the compounds A and B are not particularly limited. Therefore, as the compounds A and B, any compounds that bind by a reaction other than a radical reaction can be used. Compounds A and B
May have a functional group that undergoes a radical reaction, such as a double bond.

When the compound A and the compound B are combined by reaction (so-called thickening), a thickening catalyst can be used. Examples of the above-mentioned thickening catalyst include compounds such as dibutyltin dilaurate, but are not particularly limited. The amount of the thickening catalyst used is not particularly limited. By combining compound A and compound B, a reaction compound having a three-dimensional crosslinked structure is obtained.

A filler such as mica, calcium carbonate, aluminum hydroxide or the like; a coloring agent; an internal mold release agent such as a metal soap, a phosphate compound or a wax; a length of about 1 mm to 6 mm; Glass fiber, various synthetic fibers such as polyester and aramid, reinforcing agents such as carbon fiber;
Various additives such as a metal oxide such as magnesium oxide, a thickener such as a diisocyanate compound, or a synthetic resin such as polyethylene terephthalate (PET) can be added. For example, by adding a colorant to the reaction compound, the color tone and the transparency of the obtained molding material can be appropriately changed. Further, for example, by adding a filler to the reaction compound, it is possible to impart transparency and flame retardancy to the obtained molding material, and shrinkage during molding and curing of the molding material is reduced, and The surface hardness of the obtained molded article is improved and cracks can be prevented. As described above, a molding material having predetermined physical properties and exhibiting a desired pattern can be obtained by adding the above various additives to the reaction compound.

The above-mentioned coloring agent is not particularly limited, and the above-mentioned compounds A and B, that is, organic and inorganic pigments generally used for the reaction compound can be used. Excellent in various properties such as weather resistance, and
A colorant that does not adversely affect the reaction of the compounds A and B is preferable. Further, the color of the colorant is not particularly limited, and may be appropriately adjusted according to the color of the desired pattern. By appropriately adjusting the colorant according to a desired pattern, various patterns such as a granite pattern, a marble pattern, and a spot-like pattern can be formed. Furthermore, when a more complicated and subtle pattern is developed, several types of colorants having different color tones may be used in combination. When the colorant is added to the reaction compound, the colorant may be uniformly mixed with the reaction compound, and so as to form a so-called streak or cloud pattern. The colorant may be mixed heterogeneously with the reaction compound. That is, when adding the colorant to the reaction compound, the colorant may be stirred so as to be completely mixed with the reaction compound, or the colorant may be stirred so as not to be completely mixed with the reaction compound. Is also good.

The molding material according to the present invention is obtained by mixing the compound A, the compound B and the monomer X, and then mixing the two compounds A ,
B is bonded by a reaction other than a radical reaction to form a reaction compound swollen with the monomer X , and then obtained by crushing the reaction compound to a predetermined size. The amount of the monomer X to be used with respect to the reaction compound is not particularly limited as long as the reaction compound can swell sufficiently. Compound A and compound B
The method of mixing the monomer X with the monomer X is not particularly limited. Furthermore, the crushing method is not particularly limited, and can be easily performed by a predetermined method, for example, by cutting the swollen reaction compound, that is, the composition, with a so-called cutter or the like. Since the molding material is appropriately soft, when crushed, the shape of the crushed surface becomes a so-called acute angle.

In the following description, for convenience, the molding material thus obtained is referred to as molding particles, and the molding particles are mixed with a monomer Y copolymerized with the monomer X. Distinguish from the molding material obtained. The particle diameter of the molding particles is not particularly limited, and the range may be appropriately set according to a desired pattern. Further, the molding particles may be formed by being crushed before being mixed with the monomer Y , or may be formed by swelling a reaction compound (that is, a composition) in a container equipped with a so-called rotary cutter, and After the addition of the monomer Y , the reaction compound may be formed by crushing the reaction compound by stirring the two.

The molding particles can be easily crushed to a predetermined size, and can maintain the shape of the crushed surface (for example, when an external force is applied) even when mixed with the monomer Y , for example. Suffices if it has a viscosity or hardness that does not cause deformation. The above viscosity depends on the composition of the monomer X , for example, but the value measured using a helipath viscometer is
As long as it is 10,000 poise or more, the above hardness is
The value measured with a type D durometer is H
It should be DD 100 or less. Since the molding particles are moderately soft, they can be easily crushed with relatively small force. In addition, since the molding particles have an appropriate viscosity, particles that are finely crushed smaller than a desired particle size are hardly generated, and therefore, the yield when obtaining the particles (so-called crushing yield) Can be higher.

The monomer Y as a raw material of the molding material according to the present invention is not particularly limited as long as it is a monomer copolymerized with the monomer X, that is, a monomer polymerized by a radical polymerization reaction. Not something. Examples of the above-mentioned monomers X and Y include various monomers conventionally used, and polymers thereof. Specifically, for example, aromatic vinyl compounds such as styrene and α-methylstyrene and Unsaturated polyester; Acrylic compounds such as (meth) acrylic acid, methyl methacrylate, isobutyl methacrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and polymers thereof; aromatic vinyl Copolymers of a compound and an acrylic acid compound, and the like can be given. Among these exemplified compounds, polyfunctional (meth) acrylates such as ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate are preferable because of their particularly excellent reactivity.

In addition to the monomers X and Y , a thermoplastic resin such as polyvinyl acetate or polybutadiene may be used as a raw material for molding particles or a molding material. Monomers X, Y
By blending a thermoplastic resin, shrinkage during molding and curing of the molding particles and molding material is reduced,
In addition, the surface of the obtained molded article becomes smooth and cracks can be prevented. When a thermoplastic resin is used, the thermoplastic resin may be blended within a range of 5 to 30 parts by weight based on 100 parts by weight of the monomer X or the monomer Y. If the amount of the thermoplastic resin is more than 30 parts by weight, the transparency, heat resistance and water resistance of the obtained molded article may be reduced, which is not preferable.

The molding material according to the present invention is obtained by mixing the compound A, the compound B and the monomer X, and then mixing the two compounds A ,
B is bonded by a reaction other than a radical reaction to form a reaction compound swollen with the monomer X , and then the reaction compound is crushed to a predetermined size to form molding particles (crushed material). After the formation, it is obtained by mixing the molding particles with the monomer Y. The method of mixing the molding particles with the monomer Y is not particularly limited.

When the above-mentioned monomers X and Y are copolymerized, that is, when a molding material is molded to obtain a molded product, a curing agent (that is, a polymerization initiator) is used. be able to. Examples of the above curing agent include benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, t-butyl peroxy octoate, t-butyl peroxy pivalate, bis (4-t- (Butylcyclohexyl) peroxydicarbonate, diisopropylperoxydicarbonate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 2,4,4-trimethylpentylperoxyneodecanate, etc. , But are not particularly limited. The curing agent may be used in an amount of 0.5 to 2.0 parts by weight based on 100 parts by weight of the total amount of the monomer X and the monomer Y. By copolymerizing the monomer X and the monomer Y , a molded article having a three-dimensional crosslinked structure can be obtained. The method of adding the curing agent is not particularly limited. For example, the curing agent may be added in advance to the monomer X , that is, the molding particles, or may be added to the monomer Y. .

[0027] Then, mica or calcium carbonate monomer Y, filler such as aluminum hydroxide; coloring agents; metallic soap or phosphoric acid ester compound, an internal mold release agent such as waxes; about 1mm~6mm length of Various reinforcing fibers such as glass fibers, various synthetic fibers such as polyester and aramid, and carbon fibers; thickening agents such as metal oxides such as magnesium oxide and diisocyanate compounds; polymerization regulators such as octyl β-mercaptopropionate; An additive or a synthetic resin such as polyethylene terephthalate (PET) can be added. For example, by adding a colorant to the monomer Y , the color tone and transparency of the obtained molded article can be appropriately changed. Further, for example, by adding a filler to the monomer Y , shrinkage during molding and curing of the molding material is reduced, and the surface hardness of the obtained molded product is improved, and transparency and flame retardancy are also reduced. And cracks can be prevented. As described above, by adding the various additives described above to the monomer Y , it is possible to obtain a molded article having predetermined physical properties and exhibiting a desired pattern. The colorant is not particularly limited, and the above-mentioned colorants can be used.

The mixing ratio between the molding particles monomers Y is not particularly limited, for example, depending on the desired pattern or the like, may be appropriately determined, with respect to the monomer Y 100 parts by weight Thus, the molding particles may be used within a range of about 5 to 30 parts by weight. When a more complicated and beautiful pattern is developed, several types of molding particles having different color tones may be used in combination. Further, the method of mixing the molding particles and the monomer Y is not particularly limited, and for example, the mixing may be performed using a kneader such as a middle / low speed stirrer or a kneader. Since the molding particles are sufficiently swollen, never absorb the monomer Y be mixed monomer Y. Therefore,
The viscosity of the monomer Y , that is, the viscosity of the molding material is maintained at a predetermined value, the workability of mixing and the like is improved, the dispersibility of the molding particles is improved, and the pattern is not biased.

The molded article according to the present invention is obtained by molding particles for molding. The molded article is formed by molding a molding material. That is, the above-mentioned molding particles and molding material can be easily formed into a molded article by heating and pressing into a desired shape by a known molding method such as compression molding or injection molding. Then, for example, when the molding material is cured and molded, the monomer X in the molding particles,
Since the monomer Y and the monomer Y undergo a copolymerization reaction, the adhesive strength at the interface between the molding particles and the monomer Y increases. Also, for example, when the molding particles are cured and molded, the monomer in the molding particles
Since X undergoes a polymerization reaction, the adhesive strength at the interface between the molding particles increases. For this reason, the physical properties such as the mechanical strength of the obtained molded product are improved. The molding method and molding conditions of the molding particles and the molding material are not particularly limited. Further, the shape and the like of the molded product are not particularly limited.

Further, when the desired pattern is more complicated, the above-mentioned molding material can be made into molding particles again by crushing the above-mentioned molding material by a predetermined method. That is, the molding material can be mixed again with another monomer Y as molding particles. Molding particles (secondary particles) obtained by crushing molding material
Has a predetermined pattern in its particles,
When a molded product, for example, an artificial stone is manufactured using the molding particles, the artificial stone has a more complicated and beautiful pattern.

As described above, the molding particles according to the present embodiment are obtained by combining the compound A and the compound B by a reaction other than the radical reaction, and the reaction compound swollen by the monomer X is reduced to a predetermined size. It is configured to be crushed.
Since the molding particles are moderately soft, they can be easily crushed with relatively small force. In addition, since the molding particles have an appropriate viscosity, particles that are finely crushed smaller than a desired particle diameter are hardly generated, and therefore, the so-called crushing yield can be increased.

In the method for producing molding particles according to the present embodiment, the compound A, the compound B and the monomer X are mixed and then the compounds A and B are combined by a reaction other than a radical reaction. A swollen reaction compound is formed by the monomer X , and then the swollen reaction compound is crushed to a predetermined size. Further, the method for producing a molding material according to the present example is a method in which the above-mentioned molding particles are mixed with the monomer Y. Since the molding particles are sufficiently swollen, never absorb the monomer Y be mixed monomer Y. Accordingly, the viscosity of the monomer Y 2 , that is, the viscosity of the molding material is maintained at a predetermined value, the workability of mixing and the like is improved, the dispersibility of the molding particles is improved, and the pattern is not biased. The molding particles have a viscosity and hardness that can maintain the shape of the crushed surface even when mixed with the monomer Y , for example, so that a desired pattern can be exhibited.

In the molding material having the above structure, a so-called streak or cloud pattern is formed in the molding particles. That is, since the molding particles having a pattern are used, the molding material having the above configuration can exhibit various patterns. Therefore, by molding the above-mentioned molding material, it is possible to easily and easily produce a molded article rich in three-dimensional appearance, for example, an artificial stone having an appearance resembling natural stone such as granite, granite, marble and the like. The above-mentioned molding material is applicable to various fields, and is particularly suitable for mass production of the above-mentioned artificial stone or the like in which a desired pattern is expressed.

The molded article according to the present embodiment has a configuration in which molding particles are molded. When the molding particles are cured and molded, the monomer X in the molding particles undergoes a polymerization reaction, so that the bonding strength at the interface between the molding particles increases.
For this reason, the physical properties such as the mechanical strength of the obtained molded product are improved.

[0035]

According to the above construction, since the molding material is appropriately soft, it can be easily crushed with a relatively small force. Further, since the molding material has an appropriate viscosity, particles which are finely crushed smaller than a desired particle size are hardly generated, and therefore, a so-called crushing yield can be increased.

Further, according to the above-mentioned method, it is possible to produce a molding material capable of exhibiting a desired pattern such as a so-called streak or cloud. And since various patterns such as so-called streaks and clouds are formed in the molding material,
It is possible to easily and easily manufacture a molded product having a high three-dimensional effect, for example, an artificial stone having an appearance resembling natural stone such as granite, granite, and marble.

Further, according to the above configuration, it is possible to easily obtain a molded article such as an artificial stone having good physical properties such as mechanical strength and exhibiting a desired pattern.

[0038]

The present invention will be described in more detail with reference to the following Examples and Comparative Examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" indicates "parts by weight".

Example 1 A styrene-2-hydroxyethyl methacrylate copolymer as a compound A (trade name: LM, manufactured by Sekisui Chemical Co., Ltd.) was added to 70.9 parts of methyl methacrylate as a monomer X.
SH200) was mixed to form a syrup. 4.1 parts of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX) as compound B, 0.01 part of dibutyltin dilaurate as a thickening catalyst, and 1,1 as a curing agent were added to this syrup. -Screw
(t-butylperoxy) -3,3,5-trimethylcyclohexane (trade name: Perhexa 3M, manufactured by NOF Corporation)
0.5 part and aluminum hydroxide as filler (manufactured by Sumitomo Chemical Co., Ltd .: trade name CW-325B)
160 parts were added and stirred and mixed using a mixer to obtain a mixture.

Next, the above mixture was divided into three equal parts, and a different coloring agent (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to each divided mixture. That is, 1.0 part of a white toner (AT-3) as a colorant is added to the first divided mixture.
By stirring, the split mixture was colored white.
Similarly, 1.8 parts of a black toner (trade name AT-256) as a colorant is added to the second divided mixture to color black, and a brown toner (trade name as a colorant) is added to the third divided mixture. (AT-96) 0.8 parts was added and colored brown. The bubbles contained in these divided mixtures were decompressed and defoamed by a predetermined method.

Next, the above-mentioned divided mixture was mixed to such an extent that the colors did not completely mix, then poured into a mold having a predetermined shape, and heated at 60 ° C. for 30 minutes. This allows
A reaction compound obtained by thickening a styrene-2-hydroxyethyl methacrylate copolymer with a hexamethylene diisocyanate trimer and expressing a desired pattern by the three colors;
That is, a rubbery reaction compound (composition) swollen with methyl methacrylate was obtained. The hardness of the above reaction compound measured with a type A durometer was HDA 25.

Then, the above reaction compound is cut with a so-called cutter and classified to obtain a particle diameter of 4%.
Molding particles of mm to 0.15 mm were obtained. In the obtained molding particles, a so-called streak-like or cloud-like pattern was formed.

Example 2 30 parts of polymethyl methacrylate were mixed with 70 parts of methyl methacrylate as monomer Y and 3.0 parts of ethylene glycol dimethacrylate (trade name: Light Ester EG, manufactured by Kyoeisha Yushi Kagaku Kogyo KK). Thus, a syrup was formed. Β- as a polymerization regulator was added to this syrup.
Octyl mercaptopropionate (Yodo Chemical Co., Ltd .:
0.5 part of trade name β-MPA-2EH), 130 parts of aluminum hydroxide as a filler (trade name: CW-325LV, manufactured by Sumitomo Chemical Co., Ltd.), and the molding particles 100 obtained in Example 1 above. The mixture was stirred and mixed to obtain a mixture.

Next, 2,2 as a curing agent was added to the above mixture.
4,4-trimethylpentyl peroxyneodecanate (trade name: Trigonox 151, manufactured by Kayaku Akzo Co., Ltd.)
After further adding 0.3 part and stirring and mixing, the bubbles contained in the mixture were depressurized and defoamed by a predetermined method. Thus, a molding material having a granite pattern was obtained.

Then, the above molding material is poured into a mold having a predetermined shape and cured at 60 ° C. for 2 hours.
Cured for 1 hour at 20 ° C. As a result, a molded product having a thickness of 13 mm and exhibiting a granite pattern was obtained. Next, when the surface of the molded article was polished with a paper file having a predetermined roughness, an artificial stone having an appearance similar to granite and having a high design property was obtained.

Example 3 The same stirring and mixing operations as in Example 1 were performed to obtain a mixture. Next, the above mixture was divided into two equal parts, and a different colorant (manufactured by Dainichi Seika Kogyo Co., Ltd.) was added to each divided mixture. That is, 1.0 part of a white toner (AT-3) as a colorant was added to one of the divided mixtures, and the mixture was colored white. Similarly, to the other divided mixture, 0.6 part of a black toner (trade name: AT-256) as a colorant was added, and the mixture was colored black. The bubbles contained in these divided mixtures were decompressed and defoamed by a predetermined method.

Next, each of the divided mixtures was separately poured into a mold having a predetermined shape and heated at 60 ° C. for 30 minutes. Thereby, white and black rubbery reaction compounds (compositions) were obtained. The hardness of the above reaction compounds measured using a type A durometer was both HDA 35
Met. Then, each of the above reaction compounds is cut using a so-called cutter, and classified to obtain a particle diameter of 4%.
Molding particles of mm to 0.15 mm were obtained respectively.

Example 4 The same operations as in Example 2 were carried out except that the molding particles 1 of Example 1 were used.
Instead of using 00 parts, 100 parts of the white and black molding particles obtained in Example 3 were used in total to obtain a molded article having a thickness of 13 mm in which a granite pattern was developed. And
When the surface of the molded product was polished with a paper file having a predetermined roughness, an artificial stone having a high design property having an appearance similar to granite was obtained.

Example 5 100 parts of methacrylic acid-methyl methacrylate partial copolymer as compound A, 1.0 part of magnesium oxide as compound B, and 1,1-bis (t-butylperoxy) as a curing agent 0.5 parts of -3,3,5-trimethylcyclohexane and 160 parts of aluminum hydroxide as a filler (manufactured by Sumitomo Chemical Co., Ltd .: trade name CW-325LV) are added, and stirred and mixed using a mixer. A mixture was obtained.

Next, the above mixture was divided into two equal parts, and one of the divided mixtures was added to a white toner (AT®) as a colorant.
-3) Add 1.0 part to add white color to the other divided mixture, and add a black toner as a colorant (trade name A)
T-256) 0.6 part was added, and the mixture was colored black. The bubbles contained in these divided mixtures were decompressed and defoamed by a predetermined method. The viscosity of the split mixture is 45
poise.

Next, each of the divided mixtures was separately poured into a mold having a predetermined shape, and allowed to stand at 23 ° C. for 17 hours to increase the viscosity. Thereby, white and black rubbery reaction compounds (compositions) were obtained. The viscosity of each of the above reaction compounds was 740,000 poise, and the surface was not sticky. In addition, these reaction compounds were swollen by the methacrylic acid-methyl methacrylate partial copolymer (monomer X ) which was not thickened.

Example 6 A syrup was formed by mixing 30 parts of polymethyl methacrylate, 70 parts of methyl methacrylate as monomer Y and 3.0 parts of ethylene glycol dimethacrylate. Next, in a container equipped with a so-called rotary cutter,
The above syrup, 0.5 parts of octyl β-mercaptopropionate as a polymerization regulator, and aluminum hydroxide as a filler (manufactured by Sumitomo Chemical Co., Ltd .: trade name CW
-325LV) and 130 parts, and a total of 50 parts of the white and black reaction compounds obtained in Example 5 above. Thereafter, the mixture was stirred, and the reaction compound was crushed with a rotary cutter to obtain molding particles.

Next, 2,2 as a curing agent was added to the above mixture.
4,4-trimethylpentyl peroxyneodecanate 0.3
Then, after stirring and mixing, the bubbles contained in the mixture were depressurized and defoamed by a predetermined method. This allows
A molding material having a granite pattern was obtained.

Then, the above molding material was poured into a mold having a predetermined shape and cured at 60 ° C. for 2 hours.
Cured for 1 hour at 20 ° C. As a result, a molded product having a thickness of 13 mm and exhibiting a granite pattern was obtained. Next, when the surface of the molded article was polished with a paper file having a predetermined roughness, an artificial stone having an appearance similar to granite and having a high design property was obtained.

Example 7 The same stirring and mixing operations as in Example 1 were performed to obtain a mixture. Next, the above mixture is divided into three equal parts, and the first divided mixture is added to a white toner (AT-3) as a colorant.
1.0 part was added to color white. Also, a yellow toner (trade name: AT-5) as a colorant is added to the second divided mixture.
09) Add 1.0 part to add yellow color, and add a black toner (trade name A) as a colorant to the third divided mixture.
T-256) 1.8 parts were added and the mixture was colored black. The bubbles contained in these divided mixtures were decompressed and defoamed by a predetermined method.

Next, the above-mentioned divided mixture was mixed to such an extent that the colors did not completely mix with each other, poured into a mold having a predetermined shape, and heated at 60 ° C. for 30 minutes. This allows
A rubber-like reaction compound (composition) having a desired pattern expressed by the three colors was obtained. The hardness of the above reaction compound measured using a type A durometer is as follows.
Met.

Then, 250 g of the above reaction compound was added to the blade length.
Cutting was performed by rotating the blade at 1,000 rpm for 8 seconds using a 25 mm rotary cutter (trade name: TM-800, manufactured by Tescom Electric Co., Ltd.). Then, by classifying the cut reaction compound, the particle diameter is 4 mm to 0.15 mm
Was obtained. In the obtained molding particles, a so-called streak-like or cloud-like pattern was formed.

Example 8 The same operations as in Example 2 were carried out except that the molding particles 1 of Example 1 were used.
Instead of using 00 parts, 50 parts of the molding particles obtained in Example 7 were used, and the thickness in which a granite pattern was developed
A molded product of 13 mm was obtained.

[0059] Results of various physical properties of the resulting molded article was measured by a predetermined method, bending strength 7.3kgf / mm ^2, the flexural modulus 820 kgf / mm ^2, Izod impact strength 3.8 kgf · cm
/ cm, Barcol 934-1 Hardness was 65. Then, when the surface of the molded product was polished with a paper file having a predetermined roughness, an artificial stone having an appearance similar to granite and having a high design property was obtained.

Example 9 The particles for molding obtained in Example 7 were subjected to heat and pressure molding. That is, 500 g of the above-mentioned molding particles were filled in a mold having a predetermined shape, and the upper mold temperature was 120 ° C., the lower mold temperature was 125 ° C., and the pressure was 37 ton.
Press molding under the conditions described above for 10 minutes. This allows the vertical 2
A molded product having a size of 20 mm x 24 mm x 7 mm was obtained. This molded article had no cracks or warpage, and exhibited a beautiful pattern on its surface that could not be seen with natural stone.

Comparative Example 1 3.0 parts of ethylene glycol dimethacrylate, 100 parts of methyl methacrylate partial polymer, and aluminum hydroxide
After adding 160 parts and 0.3 part of 2,4,4-trimethylpentylperoxyneodecanate, stirring and mixing, the bubbles contained in the mixture are depressurized and defoamed by a predetermined method to thereby obtain the mixture. I got

Next, the above mixture was poured into a mold having a predetermined shape and cured at 60 ° C. for 2 hours.
For 1 hour to obtain a cured product having a thickness of 13 mm. The Barcol 934-1 hardness of the cured product was 64. The cured product was roughly ground using a jaw crusher, and then finely ground using a roll mill. Then, the pulverized cured product was classified to obtain comparative molding particles of 20 mesh to 80 mesh. The pulverization yield of the comparative molding particles was as low as 66%, and a large amount of resin particles finer than 80 mesh were produced.

Next, 30 parts of polymethyl methacrylate, 70 parts of methyl methacrylate, and 3.0 parts of ethylene glycol dimethacrylate were mixed to form a syrup.
Then, to this syrup, 0.5 parts of octyl β-mercaptopropionate, 130 parts of aluminum hydroxide, 0.3 part of 2,4,4-trimethylpentylperoxyneodecanate, and 40 parts of the molding particles for comparison described above were added. In addition, after stirring and mixing, the foam contained in the mixture was depressurized and defoamed by a predetermined method to obtain a molding material for comparison.

Then, the comparative molding material was poured into a mold having a predetermined shape, cured at 60 ° C. for 2 hours, and further cured at 120 ° C. for 1 hour to obtain a comparative molded product having a thickness of 13 mm. I got

As a result of measuring various physical properties of the obtained comparative molded product by a predetermined method, the flexural strength was 6.0 kgf / mm ² , the flexural modulus was 820 kgf / mm ² , and the Izod impact strength was 2.5 kF
gf · cm / cm 2, Barcol 934-1 Hardness was 65. Therefore, it can be seen that the comparative molded product is inferior in physical properties such as mechanical strength as compared with the molded product of Example 8.

As is clear from the results of Examples 1 to 9 and Comparative Example 1, the reaction compound is moderately soft and can be easily crushed with a relatively small force. In addition, since the obtained molding particles have an appropriate viscosity, particles that are finely crushed smaller than a desired particle size are hardly generated, and thus the so-called crushing yield can be increased. In addition, by molding the molding material obtained by the method of the present example, the physical properties such as mechanical strength are good, and a molded article such as an artificial stone having an appearance resembling natural stone can be easily and easily obtained. It can be seen that it can be manufactured. That is, it can be seen that the molding particles and the molding material of this example can be suitably used for the production of a molded product having a desired pattern.

[0067]

According to the above construction, there is an effect that the material can be easily crushed with a relatively small force and a molding material having a high crushing yield can be obtained.

Further, according to the above-mentioned method, there is an effect that a molding material which can exhibit a desired pattern such as a so-called streak or cloud shape can be produced. And since various patterns such as so-called streaks and clouds are formed in the molding material, molded articles with a rich three-dimensional effect, for example, artificial stones having an appearance resembling natural stones such as granite, granite and marble. Can be easily and easily manufactured.

Further, according to the above configuration, it is possible to easily obtain a molded product such as an artificial stone having good physical properties such as mechanical strength and a desired pattern.

Claims (7)

(57) [Claims] (1) The compound A is a hydroxyl group or a carboxyl group.
A compound having a plurality of reactive substituents selected from
Compound B is a polyfunctional polyisocyanate compound, an organic alcohol
Low in minium compounds and alkaline earth metal oxides
The compound A and the compound
Wherein at least one of the product B contains a trifunctional or higher functional compound
A in the Compound A and Compound B, with the reactive substituents compound B
Reacting the compound made by three-dimensionally crosslinking by reaction with
Is a liquid monomer X polymerized by a radical polymerization reaction
A molding material obtained by crushing a composition swollen by the above into a predetermined size. Wherein said composition claims, characterized in that in which the shape of the crushing surfaces can be maintained when it is crushed
The molding material according to 1 . 3. The reaction between the reactive substituent and the compound B is as follows:
3. The molding material according to claim 1, wherein the reaction is a reaction between a hydroxyl group or a carboxyl group and a polyfunctional polyisocyanate compound, or a reaction between a carboxyl group and an organic aluminum compound or an alkaline earth metal oxide. 4. The molding material according to claim 1, wherein the viscosity of the composition is 10,000 poise or more as measured by a helipath viscometer. 5. The compound according to claim 1, wherein the compound A is a hydroxyl group or a carboxyl group.
A compound having a plurality of reactive substituents selected from
Compound B is a polyfunctional polyisocyanate compound, an organic alcohol
Low in minium compounds and alkaline earth metal oxides
The compound A and the compound
Wherein at least one of the product B contains a trifunctional or higher functional compound
Wherein a compound A, a compound B, and a liquid monomer X which is polymerized by a radical polymerization reaction are mixed, and the compound A and the compound B are mixed with the reactive substituent and the compound B. 3 which has been swelled by the monomer X
A method for producing a molding material, comprising: forming a reaction compound having a three-dimensional crosslinked structure; and crushing the swollen reaction compound to a predetermined size. 6. The compound according to claim 1, wherein the compound A is a hydroxyl group or a carboxyl group.
A compound having a plurality of reactive substituents selected from
Compound B is a polyfunctional polyisocyanate compound, an organic alcohol
Low in minium compounds and alkaline earth metal oxides
The compound A and the compound
Wherein at least one of the product B contains a trifunctional or higher functional compound
Wherein a compound A, a compound B, and a liquid monomer X which is polymerized by a radical polymerization reaction are mixed, and the compound A and the compound B are mixed with the reactive substituent and the compound B. 3 which has been swelled by the monomer X
To form a reaction compound having a dimension crosslinked structure, after forming the crushed material by crushing the reaction compound moistened bulging into a predetermined size, monomer is polymerized by the monomer X and the radical polymerization reaction Y A method for producing a molding material, wherein the crushed material is mixed with the mixture. 7. A molded article characterized by being molded using the molding material according to any one of claims 1 to 4.