JP2726245B2 - Manufacturing method of 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 method for producing a molding material suitably used for producing molded articles having various patterns such as, for example, a granite pattern, a marble pattern and a spotted pattern on the surface thereof. is there.

[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 production method for producing a molding material suitably used for producing a molded product 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 method for producing a molding material in order to achieve the above object. As a result, it has been found that a liquid monomer X which is polymerized by a radical polymerization reaction is present. A compound A having a plurality of reactive substituents, and a compound B that reacts with the compound A are combined by a reaction other than a radical reaction to form a reaction compound swollen by the monomer X ; After adding the swollen reaction compound to the monomer Y copolymerized with the monomer X , by crushing the swollen reaction compound to a predetermined size, physical properties such as mechanical strength are good, and The present inventors have found that a molding material capable of expressing a desired pattern on the surface thereof can be manufactured, and have completed the present invention.

That is, in the method for producing a molding material according to the first aspect of the present invention, the compound A is
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 , and in the presence of a liquid monomer X that is polymerized by a radical polymerization reaction, a compound A and a compound B are bonded by reacting the reactive substituent with the compound B. Te, to form a reaction compound having a three-dimensional crosslinked structure which is swollen by the monomer X, then the reaction compound moistened bulging in liquid monomer Y which is polymerized by the monomer X and the radical polymerization reaction after addition, it is characterized by crushing the reaction compound moistened bulging into a predetermined size in the presence of the monomer Y.

According to a second 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
It contains the above compound, and the compound C has a hydroxyl group and
Multiple reactive substituents selected from
Wherein compound D is a polyfunctional polyisocyanate
Compounds, organoaluminum compounds and alkaline earths
A compound that is at least one of metal oxides,
At least one of the compound C and the compound D is trifunctional or more
Wherein the compound A and the compound B are bonded by the reaction of the reactive substituent with the compound B in the presence of a liquid monomer X which is polymerized by a radical polymerization reaction. after the step of forming a reaction compound P having a three-dimensional crosslinked structure which is swollen by mer X, and P reaction compound moistened bulging, and the compound C, a said compound D, the <br/> monomer after mixing the liquid monomer Z of polymerizing by the body X and the radical polymerization reaction, crushing the reaction compound P was the swollen compound C, and compound D and the monomer predetermined size in the presence of Z while, both compounds C, the D, compound C
It is coupled by reaction with a reactive substituent and the compound D, containing crushed reacting the compound P, step a repeated one or more times to form another reaction compound Q swollen by monomer Z, then the single By radical polymerization reaction with monomers X and Z
After addition the reaction compound Q was the swell in the monomer Y polymerizing Te, the reaction compound Q was moistened bulging is characterized by crushing into a predetermined size in the presence of the monomer Y.

Hereinafter, the present invention will be described in detail. In the following description, for the sake of convenience, when it is necessary to distinguish the reaction compounds, the reaction compound P 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 compound (another reaction compound Q 2) containing the primary reaction product mixture and obtained by combining compounds C and D by a reaction other than a radical reaction is referred to as a 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 comprises a plurality of reactive compounds.
There is no particular limitation as long as the compound has a substituent . Compound C used as a raw material in the method for producing a molding material according to the present invention may contain a plurality of reactive compounds.
There is no particular limitation as long as the compound has a substituent . Examples of the compounds A and C 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). For example, as the above compound,
Polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, neopentyl glycol, trimethylolpropane, and bisphenol A; and polycarboxylic acids such as malonic acid, adipic acid, isophthalic acid, and terephthalic acid. Also, as the polymer,
Vinyl esters; unsaturated polyesters; saturated polyesters; polymers of acrylic compounds such as 2-hydroxyethyl methacrylate; copolymers of aromatic vinyl compounds such as styrene and α-methylstyrene with acrylic compounds; Can be

The compound A and the compound 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 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 obtained by reacting the compound A with a compound A.
Three-dimensional that swells due to the inclusion of a liquid, reacting with a reactive substituent
It is not particularly limited as long as it is a compound that forms a crosslinked structure with the compound A, a so-called thickening compound. The compound D used as a raw material in the method for producing a molding material according to the present invention is a compound represented by the following formula:
Three-dimensional cross-linked structure that swells due to the inclusion of liquid by reacting with
Is not particularly limited as long as it is a compound that forms with the above-mentioned compound C, that is, a so-called thickening compound. Specific examples of the compounds B and D 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 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 X 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 Z used as a raw material in the method for producing a molding material according to the present invention is a monomer X
It is not particularly limited as long as it is a liquid monomer that copolymerizes with. Further, the monomer Y used as a raw material in the method for producing a molding material according to the present invention may be a monomer Y
The monomer is not particularly limited as long as it is a monomer copolymerized with X or the monomer Z , that is, a monomer polymerized by a radical polymerization reaction.

The above-mentioned monomers X, Y and Z include various conventionally used monomers and their polymers, and specifically, for example, 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, 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.

The monomerX, MonomerYAnd monomerZ
May be the same as each other,
May be. Further separate from the secondary reaction product mixture
To form a secondary reaction product mixture
In the case, the monomer used in each stepZAre the same as each other
May be different from each other.

Further, together with the monomers X to Z , a thermoplastic resin such as polyvinyl acetate or polybutadiene may be used as a raw material of the molding material. By blending a thermoplastic resin with the monomers X to Z , shrinkage during molding and curing of the molding material is reduced, and the surface of the obtained molded article is smoothed and cracks can be prevented. . still,
When a thermoplastic resin is used, monomer X and monomer Y
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 Z. 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 a compound
A,B is reacted by a known method.
It is. The secondary reaction product mixture is a compound C,Around D
It is obtained by reacting according to known methods. this
Compound A,B,C,D is, for example, a molding material
Use of molded products obtained by
According to the properties and physical properties required at the time of molding, etc.
It is sufficient to use it. That is, the primary reaction in the molding material
Compound A to be a reaction mixture,Composition of B
And the amount of both used, as well as secondary
Compound C to be a reaction product mixture,Composition of D
Further, the usage amounts of both are not particularly limited.
Compound A,List of reaction conditions for reacting B
And compound C,The reaction conditions and the like when reacting D are particularly
It is not limited. Therefore, compound A,B,C,
D is any bond bound by a reaction other than a radical reaction
Compounds can be used. Compound A,B,
C,D is a functional group that undergoes a radical reaction, such as a double bond
May be provided.

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.

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 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, by adding the above various additives to the reaction compound, 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 above-mentioned coloring agent is not particularly limited, and the above-mentioned compounds A , B , C , and D, that is, organic and inorganic pigments generally used for the reaction compound may be used. However, a colorant which 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 a desired pattern, various patterns such as a granite pattern, a marble pattern, and 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 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.

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 X 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 Z 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) compound A, compound B and monomer X, and the method of mixing (adding) primary reaction product mixture, compound C, compound D, and monomer Z are particularly limited. It is not something to be done.

The primary reaction product mixture is charged together with the monomer Y or the monomer Z into a container equipped with, for example, a kneader such as a medium / low speed stirrer, a kneader, or a so-called rotary cutter. By being stirred, it is crushed into a predetermined size. Also, the secondary reaction product mixture, for example,
After being charged together with the monomer Y or the monomer Z into the above-described container, the mixture is stirred to be crushed into a predetermined size. Because the reaction compound is moderately soft,
The shape of the crushing surface becomes a so-called acute angle. Incidentally, the particle size of the crushed reaction compound is not particularly limited,
The range may be appropriately set according to a desired pattern.
The method of adding the reaction compound to the monomer Y or the monomer Z is not particularly limited.

The reaction compound can be easily crushed to a predetermined size and, when added to the monomer Y or the monomer Z , can maintain the shape of the crushed surface (external force). Suffices if it has a viscosity or hardness that does not cause deformation even if it is applied. The above viscosity is, for example,
Although it depends on the composition of X, Z, etc., the value measured using a helipath viscometer may be 10,000 poise or more, and the above hardness is measured using a type D durometer hardness meter. It should just be less than 100. Since the reaction compound is moderately soft, it can be easily crushed with relatively small force. Further, since the reaction compound has an appropriate viscosity, particles that are finely crushed smaller than a desired particle size are hardly generated.

Further, since the reaction compound is sufficiently swollen, even if it is added to the monomer Y or the monomer Z , the monomer Y,
It does not absorb Z. Accordingly, the viscosities of the monomers Y and Z are maintained at predetermined values, the workability of addition / mixing and the like is improved, the dispersibility of the reaction compound is improved, and the pattern is not biased.

When the above-mentioned monomer X and monomer Y are copolymerized, or when monomer X , monomer Y and monomer Z 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 X and monomer Y
100 parts by weight, or monomer X , monomer Y and monomer
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 of the total amount of Z. By copolymerizing the monomers X to Z , a molded article having a three-dimensional crosslinked structure can be obtained. The method for adding the curing agent is not particularly limited. For example, the curing agent may be added in advance to the monomer X or the monomer Z , that is, the reaction compound, or may be added to the monomer Y. May be.

[0029] Then, mica and coloring mica monomer Y, calcium carbonate, filler such as aluminum hydroxide; coloring agents;
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 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. Thus, by adding the above-mentioned various additives to the monomer Y , 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 above-mentioned colorants can be used.

The mixing (addition) ratio of the reaction compound and the monomer Y is not particularly limited, for example, according to the desired pattern or the like, may be appropriately determined, monomer Y 100 parts by weight In contrast, the reaction compound may be used within a range of about 5 parts by weight to 500 parts by weight. When a more complicated and beautiful pattern is developed, several kinds of reaction compounds 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, the monomer X ~
Since Z undergoes a copolymerization reaction, the adhesive strength at the interface between the reaction compound and the monomer Y 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.

[0032] As described above, in the method of manufacturing a molding material according to the present embodiment, the presence of monomer X, with a compound A and compound B is bound by a reaction other than a radical reaction, by the monomer X Forming a swollen primary reaction product mixture,
Next, the swollen primary reaction product mixture is added to the monomer Y copolymerized with the monomer X, and then 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 Z , the swollen primary reaction product mixture is reduced to a predetermined size. And the above both compounds C 1 ,
The D and is bound by a reaction other than a radical reaction, a monomer
The step of forming a secondary reaction product mixture swollen by X and Z is repeated at least once, and then the swollen secondary reaction product mixture is added to the monomer Y copolymerized with the monomers X and Z. Thereafter, the swollen secondary reaction product mixture is crushed to a predetermined size. Since the reaction compound is moderately soft, it can be easily crushed with relatively small force. Further, since the reaction compound has an appropriate viscosity, particles that are finely crushed smaller than a desired particle size are hardly generated.

[0033] Since the reaction compound is sufficiently swollen, never absorb the monomer Y, and Z be added to the monomer Y or monomer Z. Accordingly, the viscosities of the monomers Y and Z are maintained at predetermined values, the workability of addition / mixing and the like is improved, the dispersibility of the reaction compound is improved, and the pattern is not biased. When the reaction compound is added to the monomer Y or the monomer Z , the reaction compound has a viscosity or hardness that can maintain the shape of the crushed surface, so that a desired pattern can be expressed. it can. Therefore, for example, the above method (a 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 compound. 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, it is possible to easily and easily produce a molded article having a three-dimensional effect, for example, an artificial stone having an appearance resembling natural stone such as granite, granite, and marble. be able to. In addition, when the molding material is cured and molded, the monomers X to Z undergo a copolymerization reaction, so that the adhesive strength at the interface between the reaction compound and the monomer Y 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.

[0034]

According to the above-mentioned method, a molding material having good physical properties such as mechanical strength and capable of expressing 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.

[0035]

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 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 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 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 with each other, 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 Z was mixed with 25 parts of a styrene-2-hydroxyethyl methacrylate copolymer (trade name: LMSH200, manufactured by Sekisui Chemical Co., Ltd.) as the compound 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, a polymethyl methacrylate 30 parts,
70 parts of methyl methacrylate as monomer Y and ethylene glycol dimethacrylate: by mixing (Kyoeisha Chemical Co., Ltd. trade name: Light Ester EG) 3.0 parts, 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, the mixture was 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 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 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.

In the artificial stone, as shown in FIG. 1, a crushed secondary reaction product mixture 2 is dispersed in a dough 3 made of a cured product of a monomer Y. 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 2 100 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 (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. 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 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 that was not thickened (monomer X ).

Next, 30 parts of polymethyl methacrylate,
Mixing 70 parts of methyl methacrylate as monomer Y 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, 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 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 is clear from the results of Examples 1 and 2, the reaction compound is appropriately soft and can be easily crushed with a relatively small force. Also,
Since the obtained reaction compound has a moderate viscosity,
It can be seen that particles crushed finer than the 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.

[0052]

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. There is an effect that the material for use can be easily and easily manufactured. And 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 method, a molded article with a rich three-dimensional effect, for example, granite or granite,
An artificial stone or the like having an appearance resembling natural stone such as marble can be easily and easily manufactured.

[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 compound) 2 Secondary reaction product mixture (reaction compound) 3 Fabric (cured product of monomer Y )

Claims (4)

(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
Wherein compound A and compound B are converted to the reactive substituents in the presence of a liquid monomer X polymerized by a radical polymerization reaction .
Be coupled by reaction with a compound B, to form a reaction compound having a three-dimensional crosslinked structure which is swollen by the monomer X, then liquid monomer to be polymerized by the monomer X and the radical polymerization reaction after addition the reaction compound moistened bulging body Y, the production method of molding material characterized by crushing the reaction compound moistened bulging into a predetermined size in the presence of the monomer Y. 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
The compound A and the compound
Wherein at least one of the product B contains a trifunctional or higher functional compound
Wherein 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
And less of the compound C and the compound D
One of them contains a compound having three or more functions, and in the presence of a liquid monomer X polymerized by a radical polymerization reaction, compound A and compound B are converted to the reactive substituent.
Be coupled by reaction with a compound B, after the step of forming a reaction compound P having a three-dimensional crosslinked structure which is swollen by the monomer X, and P reaction compound moistened bulging, and the compound C, the compound D
When, after mixing the liquid monomer Z which is polymerized by the monomer X and the radical polymerization reaction, a predetermined reaction compound P was the swollen compound C, in the presence of compounds D and monomer Z And the two compounds C and D are combined by reacting the reactive substituent of compound C with compound D to form a monomer Z containing the crushed reaction compound P. another reaction compound Q a step of repeating one or more times to form swollen by, and then, the monomer X, reacting the compound was the swell in the monomer Y to heavy <br/> case by Z a radical polymerization reaction Q And then crushing the swollen reaction compound Q to a predetermined size in the presence of the monomer Y. 3. The reaction between the reactive substituent and the compound B 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. 3. The method for producing a molding material according to claim 1, wherein: 4. The reaction between the reactive substituent and the compound D 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. 3. The method for producing a molding material according to claim 2, wherein: