JP3150915B2 - Molding - Google Patents

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 spot pattern on the surface thereof.

[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.
An object of the present invention is to provide a molded article in which various patterns such as a spot-like pattern are expressed.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a molded product in order to achieve the above-mentioned object. As a result, for example, a spot-like pattern having a streak-like or cloud-like pattern formed on a surface thereof is obtained. A molded article having, for example, in 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 Around, a secondary reaction product mixture formed by a reaction other than a radical reaction exists, and the molding in which the primary reaction product mixture and the secondary reaction product mixture exist on a part of the surface of the cured product It has been found that the product has good physical properties such as mechanical strength and that a desired pattern can be expressed on the surface thereof, thereby completing the present invention.

That is, in the molded article according to the first aspect of the present invention, in order to solve the above-mentioned problems, compound A contains hydroxyl groups and
Has multiple reactive substituents selected from ruboxyl groups
Compound B, compound B is a polyfunctional polyisocyanate
Compounds, organoaluminum compounds and alkaline earth metals
A compound that is at least one of oxides,
In the presence of a liquid monomer A polymerized by the polymerization reaction,
Compound A and Compound B are combined with the reactive substituent and Compound B
And swollen by monomer A
Forming a reactive compound with a three-dimensional crosslinked structure,
Monomer that polymerizes with the monomer A by a radical polymerization reaction
B, after adding the swollen reaction compound,
The reaction compound is crushed to a predetermined size to obtain a molding material,
The monomer A and the monomer B are subjected to a radical polymerization reaction.
The molding material is obtained by copolymerizing
It is characterized in that.

According to a second aspect of the present invention, there is provided a molded article comprising a compound A having a hydroxyl group and a carboxy group.
Compound having a plurality of reactive substituents selected from sil groups
Wherein compound B is a polyfunctional polyisocyanate compound,
Organoaluminum compounds and alkaline earth metal oxides
Wherein the compound C is hydroxyl
Reactive substitutions selected from carboxyl and carboxyl groups
A compound having a group, and the compound D is a polyfunctional polyisocy
Anate compounds, organoaluminum compounds and alka
The compound is at least one of the earth metal oxides.
Liquid monomer A polymerized by a radical polymerization reaction
Compound A and Compound B are reacted with the reactive substituent in the presence of
And the compound B to form a bond.
Product mixture P having a three-dimensional cross-linked structure swollen by
After performing the forming step, the swollen reaction product mixture P
And the compound C, the compound D, and the monomer A.
Swelling reaction after mixing with liquid monomer C
The resulting mixture P is crushed to a predetermined size,
Compounds C and D are reacted with the reactive substituent of Compound C and Compound D
Containing the crushed reaction product mixture P
First, another reaction product mixture Q swollen by the monomer C
The step of forming is repeated at least once, and then the monomer
A, C and monomer B polymerized by radical polymerization reaction
After adding the swollen reaction product mixture Q, the swollen reaction product mixture Q was added.
The reaction product mixture Q is crushed to a predetermined size to form a molding material.
To obtain the monomer A, the monomer B and the monomer C
The copolymerization is carried out by a dical polymerization reaction.
It is characterized by being obtained by molding a molding material .

[0010]

[0011]

[0012]

According to the above-mentioned method, a molding material having good physical properties such as mechanical strength and exhibiting a spot-like desired pattern having a so-called sharp edge surface formed on its surface. Can be easily and easily manufactured. 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 the sake of convenience, when it is necessary to distinguish reaction product mixtures, a reaction product mixture P obtained by combining compounds A and B by a reaction other than a 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 compounds C and D by a reaction other than a radical reaction (another reaction product mixture).
Q ) 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 that binds to the compound B by a reaction other than a radical reaction. 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 a monomer having two or more hydroxyl groups and carboxyl groups as reactive substituents in one molecule, and a polymer thereof (that is, a thermoplastic resin). For example, as a monomer, polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylolpropane, bisphenol A; malonic acid,
Examples include polycarboxylic acids such as adipic acid, isophthalic acid, and terephthalic acid. Examples of the polymer include vinyl ester; unsaturated polyester; saturated polyester;
Polymers of acrylic acid compounds such as hydroxyethyl methacrylate; copolymers of acrylic acid compounds with aromatic vinyl compounds such as styrene and α-methylstyrene;

The compound A and the compound C may be the same as each other, or may be 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,
Further, 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 compound A by a reaction other than a radical reaction. It is not something to be done. 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 above compounds BD include polyfunctional polyisocyanate compounds such as tolylene diisocyanate, hydrogenated tolylene diisocyanate, methylene diisocyanate, and hexamethylene diisocyanate; organic aluminum compounds such as aluminum isopropoxide; Examples thereof include alkaline earth metal oxides such as magnesium oxide.

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

Examples of the above-mentioned monomers A, B and C include conventionally used various monomers and polymers thereof. Specifically, for example, styrene, α-methylstyrene, etc. 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, and trimethylolpropane tri (meth) acrylate; Coalescing; a copolymer of an aromatic vinyl compound and an acrylic acid compound, and the like. 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.

Incidentally, monomer A, monomer B and monomer C
May be the same 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, 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 of the molding material. By blending the thermoplastic resin with the monomers A to C, shrinkage during molding and curing of the molding material is reduced, and the surface of the obtained molded product is smooth and cracks can be prevented. . still,
When a thermoplastic resin is used, monomer A, monomer B
Alternatively, the thermoplastic resin may be blended within a range of 5 to 50 parts by weight based on 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.

The primary reaction product mixture is the compound A
It is obtained by reacting B by a known method. The secondary reaction product mixture can be obtained by reacting compounds C and D by a known method. These compounds A, B, C, and D are used, for example, for the purpose of molded articles obtained by molding molding materials, physical properties required for the molded articles,
Any combination may be used as appropriate according to the physical properties required at the time of molding. That is, the composition of the above-mentioned compounds A and B to be a primary reaction product mixture in the molding material, the amounts of the two used, etc., and the compounding of the above-mentioned compounds C and D to be a secondary reaction product mixture in the molding material The composition, the amounts 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. Thus, the compounds A, B, C, D
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 compound A and compound B are combined by reaction (so-called thickening), and when 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 compound C and compound D, a secondary reaction product mixture having a three-dimensional crosslinked structure is obtained.

Further, the primary reaction product mixture and / or
Or a filler such as mica, colored mica, calcium carbonate, aluminum hydroxide or the like in the secondary reaction product mixture; a colorant; an internal mold release agent such as a metal soap, a phosphate ester compound, or a wax; a length of about 1 mm to 6 mm Various additives such as glass fibers, various synthetic fibers such as polyester and aramid, and carbon fibers; thickeners such as metal oxides such as magnesium oxide and diisocyanate compounds; and polyethylene terephthalate (PET) Or a colored PET film piece 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 shrinkage during molding and curing of the molding material is reduced, and In addition, the surface hardness of the obtained molded product is improved, and cracks can be prevented. As described above, by adding the above-described various additives to the reaction product mixture, a molding material having predetermined physical properties and exhibiting a desired pattern can be manufactured. 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, 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 and the like 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, granite pattern or marble pattern,
Various patterns such as a spot-like 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-like or cloud-like pattern may be formed. Alternatively, the colorant may be mixed heterogeneously with the reaction product mixture. That is, when adding the colorant to the reaction product mixture, the colorant may be stirred so as to be completely mixed with the reaction product mixture, and to the extent that the colorant is not 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 in the primary reaction product mixture is not particularly limited as long as the primary reaction product mixture can swell sufficiently.
The amount of the monomer C to be used with respect to the secondary reaction product mixture is not particularly limited as long as the secondary reaction product mixture can swell sufficiently. Furthermore, the method of mixing (adding) the compound A, the compound B and the monomer A, and the method of mixing (adding) the primary reaction product mixture, the compound C, the compound D, and the monomer C are particularly limited. It is not something to be done.

The primary reaction product mixture is charged together with the monomer B or the monomer C into a container equipped with a kneader such as a medium / low speed stirrer, a kneader, or a so-called rotary cutter, and then stirred. As a result, it is crushed to a predetermined size. Also, the secondary reaction product mixture, for example,
After being charged together with the monomer B or the monomer C into the above-described container, the mixture is stirred to be crushed into a predetermined size. Since the reaction product mixture is moderately soft, when crushed, the shape of the crushed surface becomes a so-called acute angle. The particle size of the crushed reaction product mixture is not particularly limited, and the range may be appropriately set according to a desired pattern. The 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 C
In the case where it is added, it is only necessary to have a viscosity or hardness of such an extent that the shape of the crushed surface can be maintained (they do not deform 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 helipath viscometer may be 10,000 poise or more.
The above hardness may be any value as long as the value measured using a type D durometer is less than HDD100. Since the reaction mixture is moderately soft, it can be easily crushed with relatively small force. Further, since the reaction product mixture has an appropriate viscosity, particles that are finely crushed smaller than a desired particle size are hardly generated.

Further, since the reaction product mixture is sufficiently swollen, the monomer B or C will not be absorbed even when added to the monomer B or the monomer C. Accordingly, the viscosities of the monomers B and C are maintained at predetermined values, the workability of addition and mixing, etc. is improved, and the dispersibility of the reaction mixture is improved, so that the pattern is not biased.

When the above-mentioned monomer A and monomer B are copolymerized, or when the monomer A, monomer B and monomer C are copolymerized, When a molded article is obtained by molding, a curing agent (that is, a polymerization initiator) can be used. 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 monomer A and monomer B
It may be used within a range of 0.5 parts by weight to 2.0 parts by weight based on 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. For example, the curing agent may be added in advance to the monomer A or the monomer C, that is, the reaction product mixture. It may be added.

And, a filler such as mica, colored mica, calcium carbonate, aluminum hydroxide, etc .;
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;
And the like, and colored PET film pieces and the like can be added. For example, by adding a colorant to the monomer B, the color tone and the transparency of the obtained molded article can be appropriately changed. Further, for example, by adding a filler to the monomer B, 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 improved. And cracks can be prevented. Thus, by adding the above-mentioned various additives to the monomer B, a molding material having predetermined physical properties and exhibiting a desired pattern can be manufactured. 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 (addition) ratio of the reaction product mixture and the monomer B is not particularly limited, and may be appropriately set according to, for example, a desired pattern.
The reaction product mixture may be used within a range of about 5 parts by weight to 500 parts by weight based on 100 parts by weight. When a more complicated and beautiful pattern is developed, several types of reaction product mixtures having different color tones may be used in combination.

A molded article is obtained by molding the molding material produced by the production 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.
Then, when the molding material is cured and molded, 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 a molding material according to the present embodiment, the compound A and the compound B are bonded by a reaction other than a radical reaction in the presence of the monomer A, Forming a swollen primary reaction product mixture,
Next, after adding the swollen primary reaction product mixture to the monomer B copolymerized with the monomer A, the swollen primary reaction product mixture is crushed to a predetermined size. Further, the method for producing a molding material according to the present example is such that, after adding the swollen primary reaction product mixture, the compound C, the compound D and the monomer C, the swollen primary reaction product mixture is reduced to a predetermined size. And both compounds C.
The step of bonding D by a reaction other than a radical reaction to form a secondary reaction product mixture swollen by the monomers A and C is repeated at least once, and then the monomer copolymerized with the monomers A and C After adding the swollen secondary reaction product mixture to the monomer B, the swollen secondary reaction product mixture is crushed to a predetermined size. Since the reaction mixture is moderately soft, it can be easily crushed with relatively small force. Further, since the reaction product mixture has an appropriate viscosity, particles that are finely crushed smaller than a desired particle size are hardly generated.

Since the reaction product mixture has sufficiently swelled, the monomer B.
It does not absorb C. Accordingly, the viscosities of the monomers B and C are maintained at predetermined values, the workability of addition and mixing, etc. is improved, and the dispersibility of the reaction mixture is improved, so that the pattern is not biased. When the reaction product mixture is added to the monomer B or the monomer C, the reaction product mixture has a viscosity and hardness that can maintain the shape of the crushed surface. Can be. Therefore, for example, in the molding material obtained by the above method (a method having a step of forming a secondary reaction product mixture), a so-called streak or cloud pattern is 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 configuration can exhibit various patterns. Therefore, by molding the molding material obtained by the above method, a molded product rich in three-dimensional appearance,
For example, artificial stones having an appearance resembling natural stones such as granite, granite, and marble can be easily and easily manufactured. When the molding material is cured and molded, the monomer A
~ C undergo a copolymerization reaction, the reaction product mixture and the monomer B
And the adhesive strength at the interface with the substrate increases. 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 25 parts of a styrene-2-hydroxyethyl methacrylate copolymer (trade name: LMSH200, manufactured by Sekisui Chemical Co., Ltd.) as compound A was mixed with 70.9 parts of methyl methacrylate as monomer A. To form a syrup. A hexamethylene diisocyanate trimer as compound B (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX) was added to this syrup.
Parts, dibutyltin dilaurate 0.01 as thickening catalyst
Part, 1,1-bis (t-butylperoxy) -3,
3,5-trimethylcyclohexane (manufactured by NOF Corporation:
0.5 parts of trade name Perhexa 3M) and 160 parts of aluminum hydroxide as a filler (manufactured by Sumitomo Chemical Co., Ltd .: trade name CW-325B) 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.
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 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, 25 parts of styrene-2-hydroxyethyl methacrylate copolymer (trade name: LMSH200, manufactured by Sekisui Chemical Co., Ltd.) as compound C was mixed with 70.9 parts of methyl methacrylate as monomer C. 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, these mixtures were stirred, and the primary reaction product mixture was crushed by rotating the blade of the rotary cutter at 1,000 rpm for 10 seconds.

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 polymethyl methacrylate,
70 parts of methyl methacrylate as the monomer B and 3.0 parts of ethylene glycol dimethacrylate (trade name: Light Ester EG, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) 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 secondary reaction product mixture was crushed by rotating the blade of the rotary cutter at 1,000 rpm for 10 seconds.

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.
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 shown in FIG. 1, in the artificial stone, a crushed secondary reaction product mixture 2 is dispersed in a dough 3 made of a cured product of monomer B. A so-called spot-like 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 1.0 part of magnesium oxide as compound B, 100 parts of methacrylic acid-methyl methacrylate partial copolymer as compound A,
0.5 parts of 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane and aluminum hydroxide as a filler (manufactured by Sumitomo Chemical Co., Ltd .: trade name CW-3)
(25LV) 160 parts, 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 of the divided mixtures was added to a white toner (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. 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 left 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 polymethyl methacrylate,
Mixing 70 parts of methyl methacrylate as monomer B and 3.0 parts of ethylene glycol dimethacrylate,
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. Thereafter, these mixtures were stirred, and the primary reaction product mixture was crushed with a rotary cutter.

Next, 2,2 as a curing agent was added to the above mixture.
4,4-trimethylpentyl peroxyneodecanate 0.3
Then, the mixture was stirred and mixed, and then 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-mentioned 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.

As is clear from the results of Examples 1 and 2, the reaction product mixture is moderately soft and can be easily crushed with relatively small force. Further, it can be seen that since the obtained reaction product mixture has an appropriate viscosity, particles finely crushed smaller than a desired particle size are hardly 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]

According to the above-mentioned method, there can be obtained a molding which has good physical properties such as mechanical strength and can exhibit a spot-like desired pattern having a so-called sharp edge surface on its surface. Material can be easily and easily manufactured. 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, marble and the like.

[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 Fabric (cured product of monomer B)

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI E04F 13/08 E04F 13/08 E 13/18 13/18 C // (C04B 26/02 16:04) 111: 54 C08L 101 References: JP-A-2-157147 (JP, A) JP-A-62-197346 (JP, A) JP-A-8-199078 (JP, A) (58) Fields investigated (Int. . ^7, DB name) C08J 5/00 C04B 16/04 C08F 2/44 C08L 101/00

Claims (2)

(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
A liquid monomer A that is polymerized by a radical polymerization reaction.
In the presence, compound A and compound B are converted to the reactive substituent.
It is bound by the reaction with Compound B and expanded by monomer A.
A reactive compound having a moistened three-dimensional cross-linked structure is formed, and then polymerized by a radical polymerization reaction with the monomer A.
After adding the swollen reaction compound to the monomer B, the swollen reaction compound is crushed to a predetermined size and molded.
A material is obtained, and the monomer A and the monomer B are subjected to a radical polymerization reaction.
The molding material is obtained by copolymerizing
Molded article characterized in that it is. 2. 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
And compound C is a compound selected from a hydroxyl group and a carboxyl group.
A compound having a number of reactive substituents, and
Functional polyisocyanate compound, organic aluminum compound
And at least one of alkaline earth metal oxides
A liquid monomer A that is polymerized by a radical polymerization reaction.
In the presence, compound A and compound B are converted to the reactive substituent.
It is bound by the reaction with Compound B and expanded by monomer A.
Form a reaction product mixture P with a moistened three-dimensional crosslinked structure
The swollen reaction product mixture P, the compound C and the compound
Product D and a liquid monomer C copolymerized with the monomer A
After mixing, the swollen reaction product mixture P is crushed to a predetermined size.
Together with both compounds C and D with the reactive substituent of compound C
The reaction product crushed by the reaction with compound D
Another reaction swollen by monomer C, comprising the mixture P
The step of forming the product mixture Q is repeated once or more, and then the monomers A and C are polymerized by a radical polymerization reaction.
The swollen reaction product mixture Q is added to the monomer B to be combined.
After that, the swollen reaction product mixture Q is broken into a predetermined size.
To obtain a molding material, and the monomer A, the monomer B and the monomer C are subjected to radical polymerization.
The molding material is obtained by copolymerization by a combination reaction.
A molded article characterized by being obtained by molding.