JPH09188555A - Molding product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the three-dimensional feeling and mechanical strength by forming a spotted pattern having a streaky or a cloudy pattern formed therein on the surface of a molding product. SOLUTION: This molding product is obtained by combining a compound A with a compound B in the presence of a monomer A according to a reaction other than a free radical reaction, providing a primary reactional, product mixture swelled with the monomer A, mixing the primary reactional product mixture with a compound C, a compound D and a monomer C, crushing the primary reactional product mixture, combining the compound C with the compound D according to a reaction other than the free radical reaction, affording a secondary reactional product mixture swelled with the monomers A and C, mixing the resultant secondary reactional product mixture with a monomer B copolymerizable with the monomers A and C, crushing the secondary reactional product mixture and then curing the secondary reactional product mixture. The resultant molding product has the secondary reactional product mixture, comprising the primary reactional product dispersed therein and dispersed in a substrate 3 composed of a cured product of the monomer B and further a spotted pattern formed of a streaky or a cloudy pattern of the secondary reactional product mixture on the surface thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a molded article having various patterns such as a granite pattern, a marble pattern, and a speckled pattern on its surface.

[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 the purpose of having good physical properties such as mechanical strength and the like, such as a granite pattern or a marble pattern on its surface.
It is intended to provide a molded product in which various patterns such as a speckled pattern are developed.

[0007]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a molded article in order to achieve the above-mentioned object. As a result, for example, a spotted pattern having a streak-shaped or cloud-shaped pattern is formed on the surface. A molded article having, for example, a cured product formed by a radical polymerization reaction, a primary reaction product mixture formed by a reaction other than the radical reaction is dispersed and mixed, and the primary reaction product mixture Molding in which a secondary reaction product mixture formed by a reaction other than the radical reaction is present, and the primary reaction product mixture and the secondary reaction product mixture are present on a part of the surface of the cured product. It was found that the product has good physical properties such as mechanical strength and that a desired pattern can be developed on the surface, and the present invention has been completed.

That is, in order to solve the above-mentioned problems, the molded article according to the first aspect of the present invention has a speckled pattern having a streak-like or cloud-like pattern formed on its surface. I am trying.

In order to solve the above problems, the molded article according to the second aspect of the present invention comprises a reaction product mixture formed by a reaction other than the radical reaction on the surface of a cured product formed by the radical polymerization reaction. A speckled pattern is formed, and a streak-shaped or cloud-shaped pattern is formed in the speckled pattern.

In order to solve the above problems, the molded article according to the third aspect of the present invention is a cured product formed by a radical polymerization reaction, which is formed by a reaction other than the radical reaction and has a streak or cloud shape. A reaction product mixture obtained by mixing the colorants so that the colorants are not completely mixed so as to form a pattern is dispersed and mixed, and the reaction product mixture is present on a part of the surface of the cured product. It is characterized by

In order to solve the above-mentioned problems, in the molded article of the invention described in claim 4, a primary reaction product mixture formed by a reaction other than a radical reaction is dispersed in a cured product formed by a radical polymerization reaction. And a secondary reaction product mixture formed by a reaction other than a radical reaction exists around the primary reaction product mixture, and the primary reaction product is formed on a part of the surface of the cured product. It is characterized by the presence of a mixture and a secondary reaction product mixture.

In order to solve the above-mentioned problems, the molded product of the invention as defined in claim 5 is the molded product according to claim 4, wherein
Around the secondary reaction product mixture, there is another reaction product mixture formed by a reaction other than the radical reaction,
In addition, the reaction product mixture other than the above is present on a part of the surface of the cured product.

According to the above method, a molding material having good physical properties such as mechanical strength and capable of expressing a desired spotted pattern having a so-called sharp edge surface formed on the surface thereof. Can be manufactured easily and easily. Then, since various patterns such as so-called streaks and clouds are formed in the molding material, by molding the molding material obtained by the above-described method, a molded product rich in three-dimensional appearance, for example, granite It is possible to easily and easily manufacture artificial stones and the like having an appearance resembling natural stones such as stone, granite and marble.

Hereinafter, the present invention will be described in detail. In the following description, for convenience, when it is necessary to distinguish the reaction product mixture, the reaction product mixture obtained by combining the compounds A and B by a reaction other than the radical reaction is referred to as a primary reaction product mixture, A reaction product mixture containing the primary reaction product mixture and obtained by combining the compounds C and D by a reaction other than a radical reaction (another reaction product mixture)
Will be referred to as the secondary reaction product mixture.

The compound A used as a raw material in the method for producing a molding material according to the present invention is not particularly limited as long as it is a compound which binds to the compound B by a reaction other than a radical reaction. Further, the compound C used as a raw material in the method for producing a molding material according to the present invention is not particularly limited as long as it is a compound that binds to the compound D by a reaction other than a radical reaction. Examples of the compounds A and C include monomers having two or more hydroxyl groups or carboxyl groups as reactive substituents in one molecule, and polymers thereof (that is, thermoplastic resins). Examples of the monomer include polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylolpropane and bisphenol A; malonic acid,
Examples thereof include polycarboxylic acids such as adipic acid, isophthalic acid and terephthalic acid. As the polymer, vinyl ester; unsaturated polyester; saturated polyester; 2-
Examples thereof include polymers of acrylic acid compounds such as hydroxyethyl methacrylate; copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene, and acrylic acid compounds.

The compound A and the compound C may be the same as or different from each other. Further, when the step of forming another secondary reaction product mixture from the secondary reaction product mixture is repeated a plurality of times, the compounds C used in each step may be the same as each other,
Also, they may be different from each other.

The compound B used as a raw material in the method for producing a molding material according to the present invention is a so-called thickening compound, and is not particularly limited as long as it is a compound that binds to the above compound A by a reaction other than a radical reaction. It is not something that will be done. In addition, the compound D used as a raw material in the method for producing a molding material according to the present invention is a so-called thickening compound, and is not particularly limited as long as it is a compound that binds to the compound C by a reaction other than a radical reaction. Not something. Specific examples of the compounds B and D include polyfunctional polyisocyanate compounds such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, methylene diisocyanate and hexamethylene diisocyanate; organoaluminum compounds such as aluminum isopropoxide; Examples thereof include alkaline earth metal oxides such as magnesium oxide.

The compounds B and D may be the same as or different from each other. Further, when the step of forming another secondary reaction product mixture from the secondary reaction product mixture is repeated a plurality of times, the compound D used in each step may be the same as each other,
Also, they may be different from each other.

The monomer A used as a raw material in the method for producing a 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. The monomer C used as a raw material in the method for producing a molding material according to the present invention is the monomer A.
It is not particularly limited as long as it is a liquid monomer that copolymerizes with. Further, the monomer B used as a raw material in the method for producing a molding material according to the present invention is a monomer which is copolymerized with the monomer A or the monomer C, that is, a monomer which is polymerized by a radical polymerization reaction. The body is not particularly limited.

Examples of the above-mentioned monomers A, B and C include various conventionally used monomers and polymers thereof. Specific examples thereof include styrene and α-methylstyrene. Aromatic vinyl compounds and polymers thereof; unsaturated polyesters; acrylic acid compounds such as (meth) acrylic acid, methyl methacrylate, isobutyl methacrylate, ethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and their weights. Combined; a copolymer of an aromatic vinyl compound and an acrylic acid compound, and the like can be mentioned. 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.

Monomer A, monomer B and monomer C
May be the same as or different from each other. Further, when the step of forming another secondary reaction product mixture from the secondary reaction product mixture is repeated a plurality of times, the monomers C used in each step may be the same as each other, or It may be different.

In addition to the monomers A to C, a thermoplastic resin such as polyvinyl acetate or polybutadiene may be used as a raw material for the molding material. By blending the thermoplastic resin with the monomers A to C, the shrinkage of the molding material at the time of molding and curing becomes small, and the surface of the obtained molded product becomes smooth, and cracks can be prevented. . still,
When a thermoplastic resin is used, monomer A and monomer B
Alternatively, the thermoplastic resin may be added within the range of 5 to 50 parts by weight with respect to 100 parts by weight of the monomer C. If the thermoplastic resin is added in an amount of more than 50 parts by weight, the transparency, heat resistance, and water resistance of the resulting molded article may be undesirably reduced.

Then, the primary reaction product mixture is the compound A
-It can be obtained by reacting B by a known method. The secondary reaction product mixture can be obtained by reacting the compounds C and D by a known method. These compounds A, B, C and D are used, for example, for the purpose of a molded article obtained by molding a molding material, physical properties required for the molded article,
It may be used in an appropriate combination depending on the physical properties required at the time of molding. That is, the compounding composition of the above-mentioned compounds A and B to be the primary reaction product mixture in the molding material, the usage amounts of both, and the compounding of the above-mentioned compound C and D to be the secondary reaction product mixture in the molding material. The composition, the amount used of both, and the like are not particularly limited. Also,
The reaction conditions and the like when reacting the compounds A and B, and the reaction conditions and the like when reacting the compounds C and D are not particularly limited. Therefore, the compounds A, B, C and D are
Any compound that binds by a reaction other than a radical reaction can be used. Compounds A, B, C, D
May have a functional group that undergoes a radical reaction, such as a double bond.

When the above-mentioned compound A and compound B are combined by reaction (so-called thickening) and when the above-mentioned compound C and compound D are combined by reaction,
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 primary reaction product mixture having a three-dimensional crosslinked structure is obtained. Also,
By combining the compound C and the compound D, a secondary reaction product mixture having a three-dimensional crosslinked structure is obtained.

The above-mentioned primary reaction product mixture and /
Alternatively, a filler such as mica, colored mica, calcium carbonate, aluminum hydroxide, etc., in the secondary reaction product mixture; colorant; internal release agent such as metal soap, phosphate ester compound, wax, etc .; length of about 1 mm to 6 mm Glass fibers, various synthetic fibers such as polyester and aramid, reinforcing agents such as carbon fibers; metal oxides such as magnesium oxide, thickeners such as diisocyanate compounds; various additives such as polyethylene terephthalate (PET) The synthetic resin, colored PET film pieces, and the like can be added. For example, by adding a colorant to the reaction product mixture,
The color tone and transparency of the obtained molding material can be appropriately changed. Further, for example, by adding a filler to the reaction product mixture, it is possible to impart transparency and flame retardancy to the obtained molding material, and reduce shrinkage during molding and curing of the molding material, and The surface hardness of the obtained molded product is improved and cracks can be prevented. As described above, by adding the above-mentioned various additives to the reaction product mixture, a molding material having predetermined physical properties and exhibiting a desired pattern can be produced. The method of adding the additives and the like is not particularly limited.

The colorant is not particularly limited, and the compounds A, B, C and D, that is, the organic and inorganic pigments generally used for the reaction product mixture are used. However, a colorant that is excellent in various properties such as weather resistance and does not adversely affect the reaction of the compounds A to D 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 the desired pattern, for example, a granite pattern or a marble pattern,
Various patterns such as a speckled pattern can be formed. Furthermore, when expressing an even more complicated and subtle pattern,
What is necessary is just to use several kinds of coloring agents from which a color tone differs. When the colorant is added to the reaction product mixture, the colorant may be uniformly mixed with the reaction product mixture, and a so-called streak or cloud pattern can be formed. Alternatively, the colorant may be non-uniformly mixed with the reaction product mixture. That is, when the colorant is added to the reaction product mixture, the colorant may be stirred so as to be completely mixed with the reaction product mixture, and the colorant may not be completely mixed with the reaction product mixture. You may stir.

Since the secondary reaction product mixture has a predetermined pattern derived from the primary reaction product mixture,
When a molded article, for example, an artificial stone is manufactured using the molding material obtained using the secondary reaction product mixture,
A more complicated and beautiful pattern will be provided.

The amount of the monomer A used with respect to the primary reaction product mixture is not particularly limited as long as it can sufficiently swell the primary reaction product mixture.
Further, the amount of the monomer C used with respect to the secondary reaction product mixture is not particularly limited as long as the secondary reaction product mixture can sufficiently swell. Furthermore, the method of mixing (adding) the compound A, the compound B, and the monomer A, the method of mixing (adding) the primary reaction product mixture, the compound C, the compound D, and the monomer C, and the like are not particularly limited. It is not something that will be done.

The primary reaction product mixture is put together with the monomer B or the monomer C in a container equipped with a kneader such as a medium / low speed stirrer, a kneader, or a so-called rotary cutter, and then stirred. By doing so, it is crushed to a predetermined size. Also, the secondary reaction product mixture, for example,
After being charged with the monomer B or the monomer C in the above container, the mixture is stirred to be crushed to a predetermined size. Since the reaction product mixture is moderately soft, when it is crushed, the shape of the crushed surface becomes so-called sharp. The particle size of the crushed reaction product mixture is not particularly limited, and the range may be appropriately set according to the desired pattern. Further, the addition method of adding the reaction product mixture to the monomer B or the monomer C is not particularly limited.

The reaction product mixture can be easily crushed to a predetermined size, and the monomer B or the monomer C can be crushed.
It is sufficient that the crushed surface has such a viscosity and hardness that it can maintain the shape of the crushed surface (not to be deformed even when an external force is applied). The above viscosity depends on, for example, the composition of the monomers A and C, but the value measured using a helipass viscometer may be 10,000 poise or more.
The hardness described above may be a value less than HDD 100 measured using a type D durometer hardness meter. Since the reaction product mixture is moderately soft, it can be easily crushed with a relatively small force. Further, since the reaction product mixture has an appropriate viscosity, particles crushed finer than the desired particle size are hardly produced.

Further, since the reaction product mixture is sufficiently swollen, the addition of the monomer B or the monomer C does not absorb the monomer B / C. Therefore, the viscosities of the monomers B and C are maintained at a predetermined value, workability such as addition and mixing is good, and the dispersibility of the reaction product mixture is good, and the pattern is not biased.

When the above-mentioned monomers A and B are copolymerized, or when the monomers A, B and C are copolymerized, that is, a molding material is used. A hardener (that is, a polymerization initiator) can be used when molding to obtain a molded product. 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-
Organic peroxides such as trimethylpentylperoxyneodecanate may be mentioned, but are not particularly limited. The above curing agent is the total amount of the monomer A and the monomer B.
It may be used in an amount of 0.5 parts by weight to 2.0 parts by weight with respect to 100 parts by weight, or 100 parts by weight of the total amount of the monomers A, B and C. By copolymerizing the monomers A to C, a molded article having a three-dimensional crosslinked structure can be obtained. The method of adding the curing agent is not particularly limited, and may be added in advance to the monomer A or the monomer C, that is, the reaction product mixture, or to the monomer B, for example. You may add.

Then, a filler such as mica, colored mica, calcium carbonate, aluminum hydroxide, etc. is added to the monomer B; a coloring agent;
Internal release agents such as metal soaps, phosphate compounds and waxes; glass fibers having a length of about 1 mm to 6 mm; various synthetic fibers such as polyester and aramid; reinforcing agents such as carbon fibers; metal oxides such as magnesium oxide , A thickening agent such as a diisocyanate compound; a polymerization regulator such as octyl β-mercaptopropionate;
It is possible to add a synthetic resin such as, or a colored PET film piece. For example, by adding a colorant to the monomer B, the color tone and transparency of the obtained molded product can be appropriately changed. Further, for example, by adding a filler to the monomer B, the shrinkage of the molding material at the time of molding and curing is reduced, and the surface hardness of the obtained molded product is improved, and the transparency and flame retardancy are improved. Can be imparted and cracks can be prevented. Thus, by adding the above-mentioned various additives and the like to the monomer B, it is possible to produce a molding material having predetermined physical properties and exhibiting a desired pattern. The method of adding the additives and the like is not particularly limited. The colorant is not particularly limited, and the above-mentioned colorants can be used.

The mixing (adding) ratio of the reaction product mixture and the monomer B is not particularly limited and may be appropriately set depending on, for example, a desired pattern, and the like.
The reaction product mixture may be used within the range of about 5 to 500 parts by weight with respect to 100 parts by weight. Further, in the case of expressing a more complicated and beautiful pattern, several kinds of reaction product mixtures having different color tones may be used together.

A molded product is obtained by molding the molding material manufactured by the manufacturing method according to the present invention. That is, the above-mentioned molding material can be easily formed into a molded product by heating and pressing into a desired shape by a known molding method such as compression molding or injection molding.
When the molding material is cured and molded, the monomers A to
Since C undergoes a copolymerization reaction, the adhesive strength at the interface between the reaction product mixture and the monomer B 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 material are not particularly limited. Further, the shape and the like of the molded product are not particularly limited.

As described above, in the method for producing the molding material according to this example, the compound A and the compound B are combined by a reaction other than the radical reaction in the presence of the monomer A, and the monomer A is used. Forming a swollen primary reaction product mixture,
Then, the swollen primary reaction product mixture is added to the monomer B copolymerized with the monomer A, and the swollen primary reaction product mixture is crushed to a predetermined size. In addition, in the method for producing a molding material according to this example, the swollen primary reaction product mixture, the compound C, the compound D, and the monomer C are added, and then the swollen primary reaction product mixture is added to a predetermined size. Crushing into two
A step of combining D with a reaction other than a radical reaction to form a secondary reaction product mixture swollen with the monomers A and C is repeated once or more, and then copolymerized with the monomers A and C. In this method, the swollen secondary reaction product mixture is added to the monomer B, and the swollen secondary reaction product mixture is crushed to a predetermined size. Since the reaction product mixture is moderately soft, it can be easily crushed with a relatively small force. Further, since the reaction product mixture has an appropriate viscosity, particles crushed finer than the desired particle size are hardly produced.

Since the reaction product mixture is sufficiently swollen, even if the reaction product mixture is added to the monomer B or the monomer C, the monomer B.
It does not absorb C. Therefore, the viscosities of the monomers B and C are maintained at a predetermined value, workability such as addition and mixing is good, and the dispersibility of the reaction product mixture is good, and the pattern is not biased. Then, the reaction product mixture has a viscosity and hardness that can maintain the shape of the crushed surface when added to the monomer B or the monomer C, so that a desired pattern is exhibited. You can Therefore, for example, the molding material obtained by the above method (method having a step of forming a secondary reaction product mixture) has a so-called streak-like or cloud-like pattern formed in the reaction product mixture. That is, since the primary reaction product mixture having a pattern is used, the molding material having the above-described structure can express various patterns. Therefore, by molding the molding material obtained by the above method, a molded article rich in three-dimensional effect,
For example, artificial stone having an appearance resembling natural stone such as granite, granite, or marble can be easily and easily manufactured. When the molding material is cured and molded, the monomer A
To C undergo a copolymerization reaction, the reaction product mixture and the monomer B
The adhesive strength at the interface with and becomes high. For this reason, the physical properties such as the mechanical strength of the obtained molded product are improved. The molding material obtained by the above-mentioned method is applicable to various fields, and is particularly suitable for mass production of molded articles such as the artificial stones having a desired pattern.

[0038]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. In addition, "part" described in the examples indicates "part by weight".

Example 1 70.9 parts of methyl methacrylate as the monomer A was mixed with 25 parts of styrene-2-hydroxyethyl methacrylate copolymer as the compound A (manufactured by Sekisui Chemical Co., Ltd .: trade name LMSH200). To form a syrup. In this syrup, hexamethylene diisocyanate trimer as compound B (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name Coronate HX) 4.1
Parts, dibutyltin dilaurate 0.01 as a thickening catalyst
Part, 1,1-bis (t-butylperoxy) -3, as a curing agent
3,5-trimethylcyclohexane (manufactured by NOF CORPORATION)
0.5 parts of trade name Perhexa 3M) and 160 parts of aluminum hydroxide (Sumitomo Chemical Co., Ltd .: trade name CW-325B) as a filler were added, and the mixture was 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.
The split mixture was colored white by stirring.
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. Then, 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 styrene-2-hydroxyethyl methacrylate copolymer is thickened with hexamethylene diisocyanate trimer, and swelled with a primary reaction product mixture in which a so-called streak or cloud pattern is developed by the above three colors, that is, methyl methacrylate. A rubbery primary reaction product mixture was obtained. Type A
The hardness of the above-mentioned primary reaction product mixture was measured using a durometer durometer of HDA 25.

Next, 70.9 parts of methyl methacrylate as the monomer C was mixed with 25 parts of styrene-2-hydroxyethyl methacrylate copolymer as the compound C (manufactured by Sekisui Chemical Co., Ltd .: trade name LMSH200). A syrup was formed. Then, in a container equipped with a rotary cutter (trade name: TM-800, manufactured by Tescom Electric Co., Ltd.) having a blade length of 25 mm, the above-mentioned syrup, 50 parts of the above-mentioned primary reaction product mixture, and hexamethylene diisocyanate 3 as compound D 4.1 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd .: trade name: Coronate HX), 0.01 parts by weight of dibutyltin dilaurate as a thickening catalyst, 1,1-bis (t-
Butyl peroxy) -3,3,5-trimethylcyclohexane (trade name: Perhexa 3M, manufactured by NOF CORPORATION) 0.5
And 130 parts of aluminum hydroxide (CW-325B, manufactured by Sumitomo Chemical Co., Ltd.) as a filler. Thereafter, the mixtures were stirred, and the blade of the rotary cutter was rotated at 1,000 rpm for 10 seconds to crush the primary reaction product mixture.

Next, the bubbles contained in the above mixture are
After depressurizing and defoaming by a predetermined method, the mixture was poured into a mold having a predetermined shape and heated at 60 ° C. for 30 minutes. As a result, a rubber-like secondary reaction product mixture in which a so-called spot-like pattern was developed by the primary reaction product mixture was obtained.

Next, 30 parts of polymethylmethacrylate,
70 parts of methyl methacrylate as monomer B and 3.0 parts of ethylene glycol dimethacrylate (manufactured by Kyoeisha Oil and Fat Chemical Co., Ltd .: trade name Light Ester EG) were mixed to form a syrup. Next, in a vessel equipped with the above-mentioned rotary cutter, 100 parts of the above-mentioned syrup, the above-mentioned secondary reaction product mixture, and octyl β-mercaptopropionate (trade name: β- MPA-2EH) 0.5 part, aluminum hydroxide as filler (manufactured by Sumitomo Chemical Co., Ltd .: trade name C)
130 parts of W-325LV) and 0.3 part of 2,4,4-trimethylpentylperoxyneodecanate (trade name: Trigonox 151, manufactured by Kayaku Akzo Co., Ltd.) as a curing agent. Thereafter, these mixtures were stirred, and the blade of the rotary cutter was rotated at 1,000 rpm for 10 seconds to crush the secondary reaction product mixture.

Next, the bubbles contained in the above mixture are
The pressure was reduced 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, and then further 1
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.

In the artificial stone, as shown in FIG. 1, the crushed secondary reaction product mixture 2 ... Is dispersed in the dough 3 made of the cured product of the monomer B, and the secondary reaction product is produced. A so-called spotted pattern was developed by the mixture 2.
Further, the crushed primary reaction product mixtures 1... Were appropriately dispersed in the secondary reaction product mixtures 2..., And the primary reaction product mixtures 1.

Example 2 100 parts of a methacrylic acid-methyl methacrylate partial copolymer as the compound A, 1.0 part of magnesium oxide as the compound B, and a curing agent
0.5 parts of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and aluminum hydroxide as a filler (Sumitomo Chemical Co., Ltd .: trade name CW-3
25 LV) 160 parts was added, and the mixture was stirred and mixed using a mixer to obtain a mixture.

Next, the above mixture was divided into two equal parts, and one divided mixture was mixed with white toner (trade name AT
-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. Then, 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, the above divided mixture was separately poured into a mold having a predetermined shape and left standing at 23 ° C. for 17 hours to increase the viscosity. Thereby, white and black rubbery primary reaction product mixtures were obtained. The viscosities of the primary reaction product mixtures were both 740,000 poise, and the surfaces were not sticky. Incidentally, these primary reaction product mixtures are
It was swollen by the methacrylic acid-methyl methacrylate partial copolymer (monomer A) which was not thickened.

Next, 30 parts of polymethylmethacrylate,
70 parts of methyl methacrylate as monomer B and 3.0 parts of ethylene glycol dimethacrylate are mixed,
A syrup was formed. Next, in a container equipped with the rotary cutter, a total of 50 parts of the syrup and the primary reaction product mixture, 0.5 part of octyl β-mercaptopropionate as a polymerization regulator, and water as a filler were used. Aluminum oxide (manufactured by Sumitomo Chemical Co., Ltd .: Trade name C)
W-325LV) 130 parts. Then, these mixtures were stirred, and the primary reaction product mixture was crushed with a rotary cutter.

Next, to the above mixture, as a curing agent, 2,
4,4-Trimethylpentyl peroxyneodecanate 0.3
After further adding and stirring and mixing, the bubbles contained in the mixture were decompressed and defoamed by a predetermined method. This allows
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, and then further 1
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.

As is clear from the results of Examples 1 and 2, the reaction product mixture is moderately soft and therefore can be easily crushed with a relatively small force. Further, it can be seen that since the obtained reaction product mixture has an appropriate viscosity, almost no particles crushed smaller than the desired particle size are generated. 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 material manufactured by the method of the present example can be suitably used for manufacturing a molded product having a desired pattern.

[0055]

EFFECTS OF THE INVENTION According to the above-mentioned method, molding having good physical properties such as mechanical strength and capable of expressing a desired spotted pattern having a so-called sharp edge surface formed on the surface thereof. The material for use can be manufactured easily and easily. Since various patterns such as so-called streaks and clouds are formed in the molding material, molding the molding material obtained by the above method can give a molded article rich in three-dimensional appearance, for example, granite. It is possible to easily and easily manufacture an artificial stone or the like having an appearance resembling a natural stone such as a granite or a marble.

[Brief description of the drawings]

FIG. 1 is a front view of a main part of an artificial stone (molded product) obtained by a manufacturing method according to an embodiment of the present invention.

[Explanation of symbols]

 1 Primary reaction product mixture (reaction product mixture) 2 Secondary reaction product mixture (reaction product mixture) 3 Dough (monomer B cured product)

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Claims (5)

[Claims] 1. A molded article having a speckled pattern on the surface of which a streak-shaped or cloud-shaped pattern is formed. 2. A speckled pattern composed of a reaction product mixture formed by a reaction other than a radical reaction is formed on the surface of a cured product formed by a radical polymerization reaction,
In addition, a molded article characterized in that a streak-shaped or cloud-shaped pattern is formed in the spot-shaped pattern. 3. A cured product formed by a radical polymerization reaction, which is formed by a reaction other than the radical reaction and is mixed to such an extent that the colorants are not completely mixed with each other so as to form a striped or cloud-like pattern. A molded article in which the reaction product mixture obtained by the above is dispersed and mixed, and the reaction product mixture is present on a part of the surface of the cured product. 4. A primary reaction product mixture formed by a reaction other than a radical reaction is dispersed and mixed in a cured product formed by a radical polymerization reaction, and a radical reaction is formed around the primary reaction product mixture. Molding characterized by the presence of a secondary reaction product mixture formed by a reaction other than, and the primary reaction product mixture and the secondary reaction product mixture being present on a part of the surface of the cured product. Goods. 5. Another reaction product mixture formed by a reaction other than a radical reaction is present around the secondary reaction product mixture, and the other reaction product mixture is present on a part of the surface of the cured product. 5. The molded article according to claim 4, wherein the molded article is present.