JP2003327460A - Artificial marble and production method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of producing artificial marble which has design extremely similar to that of natural stone. <P>SOLUTION: The surface of a swelled gel-like forming material which is obtained by swelling a compound having a three-dimensional cross-linked bond by a liquid monomer polymerized by radical polymerization reaction, and cracking the swelled gel to prescribed dimensions and does not substantially dissolve in the monomer, and in which the change rate of weight when perfectly dipped into the excessive monomer lies within the range of 0 to +200% is stuck with a forming material (z) in which the color difference between the color tone of the hardening material of the swelled gel-like forming material and the color tone of the hardening material when applied to the surface of the swelled gel-like forming material and hardened reaches ≥3 in a ratio of 0.01 to 30 wt.% of the total content of the forming material (z) and the swelled gel-like forming material. Then, forming is performed under heating and pressurizing. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an artificial marble and a manufacturing method thereof, and more particularly to an artificial marble having a design similar to natural stone and a manufacturing method thereof.

[0002]

2. Description of the Related Art Artificial marble is lighter in weight and has better workability than natural marble. As an alternative to natural marble, artificial marble is often used in various types of top plates such as flooring materials, wall materials, tables, kitchen tops, and vanities. It is used. Artificial marble is required to have an elegant and high-class texture resembling natural stone, and how to create the natural texture of natural stone is an important issue.

As a method for producing artificial marble, for example, natural rock powder particles and a thermosetting liquid synthetic resin are sufficiently kneaded, and the kneaded product is made into a lump having an appropriate shape and size, and the lump is formed on the surface of the lump. By attaching natural rock powder particles or pigments of different color tones and placing the thus obtained lumps of one or more tones in the mold and heating and curing under pressure, a linear pattern is formed. A method for obtaining the artificial marble has been known (see, for example, Patent Document 1).

Further, artificial marble obtained by curing a resin component mixed with a filler in advance is crushed by a hammer mill, a roll mill or the like, and made into particles of a predetermined size. A method of blending to obtain a granite-like artificial marble is known (see, for example, Patent Document 2).

As another method for reproducing a design similar to natural stone, an artificial marble having a design similar to granite is prepared by blending natural stone particles or resin particles into a matrix composed of a transparent resin and a filler. A manufacturing method is known (for example, refer to Patent Document 3).

[0006]

[Patent Document 1] Japanese Patent Publication No. 53-24447 (publication date: July 20, 1978)

[0007]

[Patent Document 2] Japanese Patent Application Laid-Open No. 2-102155 (publication date: April 13, 1990)

[0008]

[Patent Document 3] JP-A-52-952 (published date 19
(January 06, 1977)

[0009]

However, when the crushed stone of natural stone is used to obtain an artificial marble having a design similar to that of natural stone, as in the method described in Patent Document 1, there is a problem that workability is deteriorated. Further, when crushed natural stones are used, interfacial peeling is likely to occur due to insufficient adhesion between the crushed natural stones and the resin.

Further, as in the method described in Patent Document 1, a kneaded product of natural rock powder particles and a thermosetting liquid synthetic resin is formed into a lump having an appropriate shape and size, and the lump and the color tone are formed on the surface thereof. When natural rock powder particles or pigments of different types are attached and press-molded, the mass of the above kneaded material is crushed and flows by heating and pressurization. Therefore, as shown in FIG. The interface itself becomes a flow pattern without being blurred or sharp.

However, it is difficult to manufacture all artificial marble having a design similar to natural stone from a resin material without using crushed stone of natural stone.

On the other hand, when the crushed and hardened resin particles obtained by crushing the hardened resin are dispersed and hardened in the resin which becomes the matrix as in the above-mentioned Patent Document 2, a molding material which is entirely made of a resin material is used. Therefore, the problems of workability and interfacial peeling, which occur when crushed natural stone is used, are solved. However, if a large amount of pulverized and cured resin particles are mixed to obtain a desired design, the porous pulverized and cured resin particles absorb the monomer component in the resin serving as the matrix and the viscosity of the molding material becomes unstable. Or, since the fluidity is impaired and the crushed and hardened resin particles are biased and the pattern becomes unnatural, it is difficult to manufacture an artificial marble in which a desired pattern is expressed, and it is difficult to manufacture the artificial marble with 100 parts of the matrix. Generally, about 30 parts of crushed and hardened resin particles are generally mixed.

Further, the method described in Patent Document 3 is also
Having the above-mentioned problems, it is difficult to produce an artificial marble similar to natural stone in which a desired pattern is expressed, and
You can only get some monotonous granite-like artificial marble.

The present invention has been made in view of the above problems, and an object thereof is to provide an artificial marble having a design extremely similar to natural stone and a method for producing the artificial marble.

[0015]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to achieve the above object, and as a result, use a swelling gel-like molding material having a three-dimensional crosslinked structure and a crushed surface, It is found that by emphasizing the interface of the cured product when the molding material is cured, the natural stone-likeness can be expressed, and an artificial marble having a design extremely similar to that of natural stone can be produced without using crushed stone of natural stone. With
The surface formed in the gap between the surfaces of the particles having crushed surfaces, which is obtained by curing the molding material, has a color tone different from that of the particles, and if the volume is much smaller than the particles, the interface between the particles is In particular, the inventors have found that a pattern similar to the crystal structure appears and that the natural stone appearance can be expressed, and the present invention has been completed. In addition, as is often seen in natural stone, the inventors of the present invention use a cured product having a color tone different from that of a grain in a region surrounded by a vertex of a grain having a crushed surface and a plurality of grains adjacent to the grain. It has been found that the patterns are concentrated to form a natural appearance like natural stone. Furthermore, the inventors of the present application have a crushed surface, and even when adjacent grains have different color tones such as being colored in different colors, the interface between the grains is conspicuous and a pattern similar to the crystal structure is obtained. I found that I could express the character of natural stone.

That is, the artificial marble according to the present invention is
In order to solve the above problems, a granular resin cured product (Y)
And a matrix, the granular resin cured product (Y) accounts for 70 to 99% of the surface area of the artificial marble, and the matrix accounts for 30 to 1% of the surface area of the artificial marble. , And the granular resin cured products (Y) adjacent to each other have joint surfaces of shapes that substantially combine with each other, and the average adjoining ratio of the granular resin cured products (Y) is 50% or more, It is characterized in that the average aspect ratio of the granular resin cured product (Y) is 1.1 or more and 5.0 or less, and the large particle occupancy ratio is 20% or more.

In order to solve the above-mentioned problems, the artificial marble according to the present invention comprises an integrally formed aggregate of granular resin cured products (Y) having a linear crush surface, The granular resin cured products (Y) adjacent to each other,
From a cured product (Z) having a joint surface of a shape that is substantially combined with each other and having a color tone different from that of the adjacent granular resin cured product (Y), between the adjacent granular resin cured products (Y). It is characterized in that a clear streak-like interface is formed. The artificial marble preferably has a formula difference of 3 or more between the color tone of the granular resin cured product (Y) and the color tone of the cured product (Z). In the artificial marble, it is preferable that the average adjoining ratio of the granular resin cured product (Y) is 50% or more. Furthermore, the apex of the granular resin cured product (Y) formed by the crushed surface of the granular resin cured product (Y) and a plurality of granular resin cured products adjacent to the granular resin cured product (Y). The region surrounded by the product (Y) is filled with a cured product (Z) having a color tone different from that of each granular resin cured product (Y) surrounding the region, and the granular resin cured product ( Y) the average side neighborhood muscle collection rate is 50
% Or less is preferable.

In order to solve the above problems, the artificial marble according to the present invention comprises an integrally formed aggregate of granular resin cured products (Y) having a linear crush surface, The granular resin cured products (Y) adjacent to each other,
The apex of the granular resin cured product (Y), which has a joint surface of a shape substantially combined with each other, and is formed by an acute crushing surface of the granular resin cured product (Y), and the granular resin. In a region surrounded by the cured product (Y) and a plurality of adjacent granular resin cured products (Y), a cured product (Z having a color tone different from that of each granular resin cured product (Y) surrounding the region. ) Is filled.

Each of the above-mentioned artificial marbles is the above-mentioned cured product (Z).
However, it is preferable that they partially have different color tones.
The granular resin cured product (Y) preferably accounts for 70% to 99% of the surface area of each artificial marble. Furthermore, in each of the artificial marbles, the average aspect ratio of the granular resin cured product (Y) is 1.1 or more, and 5.
It is preferably 0 or less, and the large grain occupancy rate is preferably 20% or more. Further, in each of the above-mentioned artificial marbles, it is preferable that the granular resin cured products (Y) adjacent to each other have different color tones.

In order to solve the above problems, the artificial marble according to the present invention comprises an integrally formed aggregate of granular resin cured products (Y) having a linear crush surface, The granular resin cured products (Y) adjacent to each other,
A granular resin cured product (Y) that has a joining surface of a shape that is combined with each other and is directly joined and is adjacent to each other.
It is characterized in that they have different color tones and a clear interface is formed between the granular resin cured products (Y) adjacent to each other. The artificial marble has an average aspect ratio of the granular resin cured product (Y) of 1.1 or more, 5.0 or more.
It is below, and the large grain occupancy ratio is preferably 20% or more.

Further, in each of the above-mentioned artificial marbles, it is preferable that the granular resin cured product (Y) contains a metal hydroxide in a ratio of 10 to 80% by weight. Further, in each of the artificial marbles, it is preferable that the granular resin cured product (Y) has a predetermined pattern. Further, in each of the above-mentioned artificial marbles, it is preferable that the ratio of the space portion in each of the above-mentioned artificial marbles is 1% or less of the total volume.

The method for producing artificial marble according to the present invention is
In order to solve the above problems, a liquid monomer for polymerizing a compound having a three-dimensional cross-linking bond by a radical polymerization reaction (for example, a monomer (X) in the embodiment described later,
A swelling gel-like molding material obtained by crushing a swollen gel (for example, a primary reaction product mixture, a secondary reaction product mixture, etc. in the embodiments described later) swollen with a monomer (E) or the like into a predetermined size. And the surface of the swelling gel-like molding material which is substantially insoluble in the above-mentioned monomer and has a weight change rate of 0 to + 200% when completely immersed in an excess of the above-mentioned monomer. And the color difference between the color tone of the cured product of the swelling gel-like molding material and the color tone of the cured product when applied to the surface of the swelling gel-like molding material and cured (z ) Is adhered in a proportion of 0.01% by weight or more and 30% by weight or less of the total amount of the molding material (z) and the swelling gel-like molding material, and is molded under heating and pressurization. .

The method for producing artificial marble according to the present invention comprises:
In order to solve the above problems, the compound (A) is a compound having a plurality of reactive substituents selected from a hydroxyl group and a carboxyl group, and the compound (B) is a polyfunctional polyisocyanate compound, an organoaluminum compound and an alkaline earth. A compound which is at least one of a group of metal oxides, wherein at least one of the compound (A) and the compound (B) contains a trifunctional or higher functional compound, wherein the compound (A) and the compound (B) Is a liquid monomer in which a reaction compound obtained by three-dimensionally cross-linking by the reaction of the reactive substituent with the compound (B) is polymerized by a radical polymerization reaction (for example, a monomer in the embodiment described later). The swollen gel swollen by (X)), which has a measurement value using a helipass viscometer of 1,000 Pa · s or more, is crushed to a predetermined size. The color tone of the cured product of the swelling gel-like molding material on the surface of the swelling gel-like molding material and the color tone of the cured product when applied to the surface of the swelling gel-like molding material and cured. The molding material (z) having a color difference of 3 or more is adhered and heated at a ratio of 0.01% by weight or more and 30% by weight or less of the total amount of the molding material (z) and the swelling gel-like molding material. It is characterized by being molded under pressure.

In the method for producing each artificial marble, it is preferable that the molding material (z) is powder. Further, in the method for producing each artificial marble, the swelling gel-like molding material having the molding material (z) attached to its surface is spread in a mold,
After molding into a flat plate under heat and pressure, it is preferable to polish the surface of the obtained molded product.

[0025]

BEST MODE FOR CARRYING OUT THE INVENTION [Embodiment 1] An embodiment of the present invention will be described in detail below. The method for producing an artificial marble according to the first embodiment of the present invention uses a swollen gel of a predetermined size swollen with a liquid monomer that polymerizes a compound (W) having a three-dimensional cross-linking bond by a radical polymerization reaction. Surface of swelling gel-like molding material (hereinafter referred to as molding material (y)) having a predetermined degree of swelling (that is, a predetermined rate of change in weight when swollen in a monomer) obtained by crushing into And a granular resin cured product (Y) obtained by curing the swelling gel-like molding material (y) having a color tone upon curing (hereinafter,
A powdery or liquid molding material (z) having a color tone different from that of the cured product (Y)) is attached to such a degree that it covers the entire surface of the swollen gel molding material (y), and is heated and pressurized. It is a method of polymerizing the above-mentioned monomer and molding.

The swelling gel-like molding material (y) used as a raw material of the artificial marble in the present invention is a swelling gel-like molding material having a three-dimensional crosslinked structure and a crushed surface. The swelling gel-like molding material (y) does not substantially dissolve in the above-mentioned monomer, and the weight change rate when the molding material (y) is completely immersed in an excess (large amount) of the monomer is 0 to
It has a three-dimensional crosslinked structure having a crosslink density within the range of + 200%, preferably within the range of 0 to + 100%.

In the present invention, the above-mentioned weight change rate means the weight when the swelling gel-like molding material (y) is immersed in a sufficiently large amount (excess) of the above monomer at a temperature of 23 ° C. ± 2 ° C. for 24 hours. Of the swelling gel-like molding material (y) before dipping and the swelling gel-like molding material (y) after dipping the swelling gel-like molding material (y) in the monomer under the above-mentioned conditions with a wire mesh or filter paper. The weight of the swelling gel-like molding material (y) immediately after separation is compared and evaluated. In order to avoid evaporation of the monomer, the filtration should be carried out quickly and quickly, and it is necessary to remove the monomer adhering to the surface of the swelling gel-like molding material to such an extent that the monomer is removed. The numerical value in the case where the weight of the swelling gel-like molding material (y) is decreased by immersion is indicated by a minus (-),
When it increases, it is shown as plus (+), and when it does not change, it is set to 0.

That is, when the molding material (y) is completely immersed in the excess monomer, the weight change rate is 0 to + 200%.
Is within the range of 0 to 200% of the weight of the molding material (y) before immersion, when the molding material (y) is immersed in the monomer under the above conditions. Shows that the weight of the molding material (y) increases, and more specifically, when the molding material (y) is immersed in the monomer under the above conditions, it is apparently twice as much as its own weight. It shows that the weight of the molding material (y) after immersion is 3 times or less of the weight of the molding material (y) before immersion. In addition, the weight change rate is 0 to + 100%
In the range of, the appearance of weight does not change even if the molding material (y) is immersed in the monomer under the above-mentioned conditions, that is, the above-mentioned monomer is not further absorbed or absorbed. However, apparently, it absorbs only monomers up to the same weight as its own weight,
It shows that the weight of the molding material (y) after immersion is not more than twice the own weight of the molding material (y) before immersion. Here, apparently, a part of the molding material (y) is eluted in the monomer, and a part of the monomer is absorbed in the molding material (y), resulting in a change in weight thereof. Means that the offsetting result is detected as the final weight change.

The rate of change in weight of the molding material (y) is less than 0% (that is, the rate of change in weight becomes negative), that is, the molding material (y) depends on the monomer.
If the amount of a part of the compound to be eluted exceeds the amount to absorb the monomer, the three-dimensional crosslinking (crosslink density) of the molding material (y) is not sufficient and the molding material (y) is heated. When molded under pressure, the shape of the crushed surface of the particles obtained by curing the molding material (y) cannot be maintained sufficiently, and the pattern of the molded product may be partially mixed, or cloudy cloudy There is a tendency that only the pattern of can be expressed.

On the contrary, the weight change rate is + 200%.
Even if the amount exceeds a large amount, the three-dimensional crosslinked structure (crosslink density) is not sufficient, indicating that it has a low crosslinked structure that requires a large amount of monomer to reach an equilibrium state. The same problem occurs when the weight change rate is minus (-).

On the other hand, the molding material (y) which is sufficiently crosslinked and swollen with an appropriate amount of the monomer has such a degree that the monomer is slightly absorbed even when placed in a large amount of the monomer. Almost no weight change is shown, and the weight change rate is within the range of 0 to + 200%.

Molding material (y) in the form of such a swollen gel
Is capable of appropriately flowing and molding while maintaining the shape of the crushed surface when heat-pressed.
A design very similar to natural stone, which is composed of an aggregate of granular hardened products (Y) obtained by hardening a swelling gel-like molding material (y) having a linear and sharp crushed surface as shown in FIG. It is possible to produce an artificial marble having

When obtaining the swelling gel-like molding material (y), the swelling gel used in the present invention is cut into a size that passes through the screen by a rotary blade type cutter having a screen of 7 mm set, for example. By changing the size of the screen, crushed gel particles of any size (cut gel particles) can be obtained, but in order to obtain a design similar to natural stone, use a screen of 1 mm to 20 mm. It is preferable to use crushed gel particles that have been cut. The average particle size of the crushed gel particles (grains) is preferably about 0.5 mm to 20 mm.

The compound (W) having three-dimensional cross-linking used in the swelling gel-like molding material (y) is not particularly limited, but the swelling gel swelled with the above monomer is crushed. The molecular weight and crosslink density of the compound (W) to be used so that the rate of weight change of the product satisfies the above conditions,
It is necessary that the affinity with the monomer to be used is appropriately set, whereby the viscosity and hardness of the swollen gel-like molding material obtained by swelling the compound (W) with the monomer have appropriate values. It is desirable to be set to.

Therefore, as the compound (W), the compound (A) having a plurality of reactive substituents and the compound (B) that reacts with the compound (A) are bonded by a reaction other than the radical reaction. It is desirable that the reaction compound is a product of the above. This is because it is difficult to control the viscosity and hardness of the curable resin to a suitable value when the curable resin is polymerized by radical polymerization.

The compound (A) which is a raw material of the compound (W) is not particularly limited as long as it is a compound having a plurality of reactive substituents, but a hydroxyl group or a carboxyl group as a reactive substituent is used. And the like, and compounds and polymers having two or more in one molecule. Specifically, for example, ethylene glycol, diethylene glycol, 1,
Examples thereof include polyhydric alcohols such as 4-butanediol, neopentyl glycol, trimethylolpropane and bisphenol A; and polycarboxylic acids such as malonic acid, adipic acid, isophthalic acid and terephthalic acid. As the polymer, ester polymers such as vinyl ester, unsaturated polyester and saturated polyester, (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, 2
-Copolymerization of acrylic monomers such as hydroxypropyl (meth) acrylate having functional groups such as hydroxyl groups and hydroxyl groups with acrylic monomers such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate And a copolymer of an acrylic monomer having the above functional group and an aromatic vinyl compound such as styrene or α-methylstyrene.

As the compound (B), a compound that forms a three-dimensional crosslinked structure that reacts with the reactive substituent and swells due to the inclusion of a liquid with the compound (A), a so-called thickening compound. If so, it is not particularly limited. Specific examples of the compound (B) 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 combination of the compound (A) and the compound (B) is determined so that at least one of the compound (A) and the compound (B) contains a trifunctional or higher functional compound.

The compound (W), that is, the above reaction compound, is a known method in the presence of a monomer (X) for polymerizing the compound (A) and the compound (B) by a radical polymerization reaction, if necessary. It can be obtained by reacting with. Compound (A) and compound (B)
Is, for example, depending on the use of the molded product obtained by molding the molding material (y) and the molding material (z) according to the present invention, the physical properties required for the molded product, the physical properties required at the time of molding, and the like. Therefore, they may be used in appropriate combination. That is, the compounding composition of the compound (A) and the compound (B) in the molding material (y), the amount of both used, and the like are not particularly limited.

The reaction conditions for reacting the compound (A) with the compound (B) are not particularly limited. Therefore, the above compound (A) and compound (B)
As the compound, any compound that binds by a reaction other than a radical reaction can be used. The compound (A) and the compound (B) may have a functional group that undergoes a radical reaction, such as a double bond.

When the above compounds (A) and (B) are bound by reaction, a reaction catalyst such as dibutyltin dilaurate can be used in combination.
It is not particularly limited. Also, the amount of the above catalyst used is not particularly limited. By binding the compound (A) and the compound (B), a reaction compound having a three-dimensional cross-linking bond (covalent bond and / or ionic bond) can be obtained as the compound (W).

Further, a molding material (y) is added to the above reaction compound.
It is possible to add a radical polymerization catalyst for initiating a radical polymerization during molding under heat and pressure. Examples of such radical polymerization catalysts include benzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, t-butyl peroxybenzoate, t-butyl peroxypivalate, bis (4-t-butylcyclohexyl) peroxydiene. Carbonate, diisopropyl peroxydicarbonate,
1,1-bis (t-butylperoxy) -3,3,5-
Examples thereof include organic peroxides such as trimethylcyclohexane and 2,4,4-trimethylpentyl peroxyneodecanate, but they are not particularly limited. The radical polymerization catalyst is the compound (W) and the monomer (X).
With respect to 100 parts by weight in total, it may be used within a range of 0.2 parts by weight to 2.0 parts by weight.

In addition to the above reaction compounds, fillers such as magnesium hydroxide, calcium carbonate and aluminum hydroxide; coloring agents; curing accelerators; surface treatment agents such as silane coupling agents and phosphate ester compounds; waxes and the like. Internal release agent; glass fiber having a length of about 1 mm to 6 mm, various synthetic fibers such as polyester and aramid, reinforcing agent such as carbon fiber, various additives such as metal oxide, polystyrene, polyvinyl acetate, A thermoplastic resin such as saturated polyester can be added. If necessary, additives such as an ultraviolet absorber and a flame retardant can be added to the above reaction compound.

For example, by adding a colorant to the above reaction compound, the color tone and transparency of the obtained swollen gel-like molding material (y) can be appropriately changed.

Further, for example, a swelling gel-like molding material (y) obtained by adding a filler to the reaction compound
Opacity, translucency and flame retardancy can be imparted to the molded product, and the shrinkage of the swelling gel-like molding material (y) at the time of molding and curing is small, and the surface hardness of the resulting molded product is improved. In addition, it is possible to prevent cracks.

The above-mentioned molding material (y) is a metal hydroxide of 1
It is preferably contained in a proportion of 0 to 80% by weight.
That is, the granular cured product (Y) in the obtained molded product
Preferably contains 10 to 80% by weight of metal hydroxide. As a result, it is possible to obtain a texture like natural stone and impart flame retardancy.

Thus, by adding the above-mentioned various additives and the like to the reaction compound, the reaction compound has predetermined physical properties, and
A molded product in which a desired pattern is developed can be obtained. When adding the reaction catalyst, radical polymerization catalyst, compounds such as various additives to the above reaction compound, the compound (A) and / or the compound (B) before the reaction and / or
Alternatively, compounds such as various additives are added to the monomer (X) and stirred and dispersed, and then the compound (A) and the compound (B) are added, if necessary, in the presence of the monomer (X), It can be carried out by reacting and binding.

The colorant is not particularly limited, and generally used organic and inorganic pigments can be used for the compound (A) and the compound (B). A colorant that is excellent in various properties such as weather resistance and does not adversely affect the reaction between the compound (A) and the compound (B) is preferable. The color of the colorant is not particularly limited, and may be appropriately adjusted according to the color of the desired pattern.

Further, in order to develop a more complicated and delicate pattern, several kinds of colorants having different color tones may be used together. When the colorant is added to the reaction compound, the colorant may be uniformly mixed with the reaction compound, and so that a so-called streak or cloud pattern can be formed. Two or more kinds of pre-curing compound (W) and monomer (X) in which colorants having different color tones are uniformly mixed in advance, that is, a mixture and monomer (X) of compound (A) and compound (B). ) May be mixed non-uniformly.

The addition amount (use amount) of the various additives and the synthetic resin to the reaction compound is not particularly limited, but when the colorant is added to the reaction compound, the use amount of the colorant is With respect to 100 parts by weight of the total amount of the reaction compound (compound (W)) and the monomer (monomer (X)),
It is 30 parts by weight or less, and preferably 20 parts by weight or less. Even if the amount of the colorant used exceeds 30 parts by weight, there is little difference in appearance, the effect is small, and the curing reaction of the molding material (y) is delayed, which is not desirable. When the amount of the colorant used is 20 parts by weight or less,
It is preferable because there is almost no influence on performance such as curing characteristics.

When a filler is added to the above reaction compound, the amount of the filler to be used is 100 weight% in total of the above reaction compound (compound (W)) and monomer (monomer (X)). It is desirable that the amount is 300 parts by weight or less with respect to 2 parts, and 2
It is more desirable that the amount is 00 parts by weight or less. If the amount of the above filler used exceeds 300 parts by weight, the fluidity of the molding material (y) will be impaired and the molding operation will be difficult. Further, the strength is lowered, and the flexibility is apt to be impaired. When the amount of the filler used is 200 parts by weight or less, the crushing (cutting) work is easy and the strength is high, which is more preferable.

The color tone and transparency of the obtained swelling gel-like molding material (y) can be appropriately changed by adjusting the addition amount of the colorant and the filler to be added to the above reaction compound.
As shown in FIG. 1, artificial marble with a deep (depth) appearance can be obtained.

The swelling gel-like molding material (y) according to the present invention is a swelling gel obtained by swelling a compound (W) having a three-dimensional cross-linking bond with a liquid monomer which is polymerized by a radical polymerization reaction. It is obtained by crushing to a predetermined size.

The swelling gel-like molding material (y) is prepared, for example, by mixing the compound (A) and the compound (B) with a liquid monomer (X) which is polymerized by a radical polymerization reaction. The above compounds (A) and (B) are combined by a reaction other than a radical reaction to form a reaction compound swollen with the monomer (X), and then the reaction compound is made to have a predetermined size. It can be obtained by crushing.

In this case, the compound (A), the compound (B) and the monomer (X) are mixed, and then the both compounds (A) and (B) are bonded by a reaction other than a radical reaction. As a result, a reaction compound swollen with the above-mentioned monomer (X) as a liquid monomer polymerized by a radical polymerization reaction, that is, a liquid monomer (X) inside
A cross-linked polymer gel having a three-dimensional cross-linked structure (three-dimensional network structure) that retains is obtained.

That is, when the compound (A) and the compound (B) are three-dimensionally cross-linked as described above, since the monomer (X) is present, the three-dimensional cross-linked reaction compound is present in the reaction compound. , The monomer (X) exists, and the monomer (X) undergoes a radical polymerization reaction,
It is not involved in the reaction of three-dimensional cross-linking. Therefore,
The reaction compound is swollen with the liquid monomer (X).

Even when the compound (A) and / or the compound (B) also has a radical polymerization reactive substituent, the compound (A) and the compound (B) are three-dimensionally crosslinked. Since the radical polymerization reaction is not performed at the time of binding, the monomer (X) remains unreacted. Therefore, the reaction compound composed of the compound (A) and the compound (B) is swollen by the liquid monomer (X).

The above-mentioned monomer (X) used in the present invention is not particularly limited as long as it is a liquid monomer which is polymerized by a radical polymerization reaction. Examples of the monomer (X) include various conventionally used monomers, and specific examples thereof include aromatic vinyl compounds such as styrene and α-methylstyrene; (meth) acrylic acid and Methyl (meth) acrylate, isobutyl (meth)
Examples thereof include acrylic acid compounds such as acrylate, ethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. Among these exemplified compounds, polyfunctional (meth) acrylates such as ethylene glycol di (meth) acrylate and trimethylolpropane tri (meth) acrylate can be used in combination with monofunctional monomers to improve reactivity and reactivity. Properties such as heat resistance and solvent resistance can be improved, which is desirable.

The amount of the monomer (X) used relative to the reaction compound, that is, the monomer (X) relative to the compound (W).
The amount used is not particularly limited as long as it can sufficiently swell the compound (W).
In addition, the compound (A), the compound (B) and the monomer (X)
The method of mixing with and the like are not particularly limited.

Further, the above thermoplastic resin can be added to the above reaction compound. By blending a thermoplastic resin, the shrinkage of the swelling gel-like molding material (y) during molding and curing becomes small, and the surface of the obtained molded article becomes smooth, and cracks can be prevented. it can.

When a thermoplastic resin is used, the thermoplastic resin is added to 100 parts by weight of the total amount of the above reaction compound (compound (W)) and monomer (monomer (X)). It may be added within the range of 100 parts by weight or less. If the thermoplastic resin is blended in an amount of more than 100 parts by weight, the transparency, heat resistance and water resistance of the resulting molded article may be deteriorated, which is not preferable.

In the present invention, the method for crushing a swollen gel swollen with a liquid monomer for polymerizing the compound (W) by a radical polymerization reaction, for example, the monomer (X) is not particularly limited. Instead, for example, the reaction compound swollen with the monomer (X) can be easily cut by a predetermined method such as cutting with a so-called cutter or the like. Further, for example, it can be crushed into a predetermined size by stirring or cutting in a container equipped with a medium / low speed agitator, a kneader such as a kneader, or a so-called rotary cutter. The swelling gel-like molding material (y)
Is a gel and is moderately soft, so when crushed,
The crushed surface has a so-called sharp sharp shape.

The swollen gel obtained by swelling the above-mentioned compound (W) with a liquid monomer which is polymerized by a radical polymerization reaction can be easily crushed into the above-mentioned size, and the above-mentioned weight change rate can be obtained. It has only to have a viscosity and hardness capable of maintaining the shape of the crushed surface of the swelling gel-like molding material (y) during molding. The above-mentioned viscosity depends on the composition of the above-mentioned monomer (X) and the like, but it is preferable that the value measured using a helipass viscometer is 1000 Pa · s or more, and the above-mentioned hardness is a type D durometer. The value measured using a hardness meter is preferably HDD 100 or less.

Since the swollen gel is moderately soft, it can be easily crushed with a relatively small force. In addition, since the swollen gel has an appropriate viscosity, particles crushed finer than a desired particle size are hardly generated, and therefore the yield in obtaining the particles (so-called crushing yield) Can be higher.

In the present invention, the molding material (z) used as the raw material of the artificial marble is the swelling gel-like molding material (y) alone, which is cured to a thickness of 1 cm using a flat mold. Color tone of cured product (Y) and thickness 1cm
Then, on the uncured and uncrushed molding material (y) that was cut so as to almost fill the mold, the thickness was 0.5 mm.
Difference when the molding material (z) is placed in such a manner that it is cured integrally in the mold, and the color tone of the cured material (Z) of the molding material (z) is determined by a color difference meter. The molding material is not particularly limited as long as it is 3 or more. The color difference can be easily measured based on JISK7105 by Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd.

When the color difference is less than 3, the pattern formed by the molding material (z), that is, the surfaces of the particles having crushed surfaces obtained by curing the swelling gel-like molding material (y) Boundary (interface) formed in the gap between
Is not clearly visible, and the desired design cannot be obtained.

The larger the above-mentioned color difference, the more preferable, and the molding material (z) that can finally obtain a color difference of preferably 5 or more, more preferably 7 or more, and particularly preferably 10 or more is used. The larger the color difference, the more noticeable the interface of the individual cured products (Y) when the swelling gel-like molding material (y) is cured, and the amount of the molding material (z) used should be kept as small as possible. Therefore, it is possible to suppress a decrease in physical strength and cold heat repetition strength of the obtained artificial marble. Therefore, the larger the color difference, the more preferable, and the upper limit thereof is not particularly limited. However, the color tone that can be realized is naturally limited, and at present, it is generally considered that a maximum color difference of about 150 can be realized. . Therefore, the color difference is considered to be in the range of 3 or more and 150 or less. However, the larger the color difference, the more preferable, and if a color difference of more than 150 can be obtained,
The color difference may exceed 150.

According to the present invention, on the surface of the swelling gel-like molding material (y), a powder-like or liquid-like molding for coloring the above-mentioned color difference of 3 or more so as to cover the surface. By adhering (spraying) the material (z), the interface of the cured product (Y) when the swelling gel-like molding material (y) is cured can be emphasized as shown in FIG. Can be expressed.

The color tone of the cured product (Z) when the above-mentioned molding material (z) is applied to the surface of the above-mentioned swollen gel-like molding material (y) and cured is the color tone of the above-mentioned molding material (z). The color tone when cured to, more specifically, for example, when the molding material (z) is in the form of powder, the swelling gel-like molding material (y) The monomer (X) retained in the molding material (y) is the molding material (z)
It is a color tone when the molding material (z) is exuded and hardened. Therefore, the color tone of the cured product (Z) does not always match the color tone of the powdery molding material (z), for example, when the transparency is different.

Therefore, when selecting the molding material (z), a color sample of the molding material (z) is previously prepared according to the combination of the swelling gel-like molding material (y) and the molding material (z) to be used. It is desirable to make it.

The color tone sample of the molding material (z) may be produced, for example, by the following method. First, in the case of producing a color sample having a size of approximately 30 cm square, which is almost filled with a mold, a swelling gel-like uncured and non-crushed molding material that is cut to have a size of 29 cm square and has a thickness of 1 cm when cured. On the surface of (y), for example, the thickness when cured is 0.5 m
Apply or spray the molding material (z) in an amount of m
It may be formed by heating and pressurizing with a metal mold of cm square, and using this as a color tone sample of the molding material (z).

The molding material (z) may be semitransparent or transparent as long as the color difference is 3 or more. For example, an acrylic resin or an unsaturated polyester resin is used as the molding material (z), which is made transparent or translucent by using a resin alone or a small amount of a filler, a coloring agent, etc., and the colored swelling gel-like molding material (y) By coating and curing
It is possible to obtain a design of a colored crushed product which is separated by a transparent or translucent streak pattern.

The above molding material (z) has the color tone of the cured product (Z) of the molding material (z) in the obtained artificial marble,
It is more preferable that the cured product (Z) is used in combination so that the color difference between the cured product (Y) of the adjacent molding material (y) and the color tone of the cured product (Y) is 3 or more. Color tone of cured product (Y) and cured product (Z) adjacent to each other in the obtained artificial marble
The color difference from the color tone of can be obtained from the image obtained by digitizing the surface design of the molded artificial marble by the method described in Examples described later.

The color tone of the cured product (Y) of only the molding material (y) and the cured product (when the molding material (z) was cured on the molding material (y) by the method described in Examples below. Comparing the case where the color difference with the color tone of Z) is obtained with the case where the color difference is obtained from an image obtained by digitizing the surface design of the molded artificial marble, the latter tends to have a smaller color difference than the former. . This can be interpreted as the fact that the molding material (z) forming the interface is partially thinned and the color tone of the molding material (y) can be seen through, so that the color difference between the two is small. . Therefore, the latter color difference is 3
If it is above, it can be estimated that the color difference is 3 or more even if it measures by the former method.

As the molding material (z), a powdery material is preferably used. The powdery molding material (z) is
It is desirable that the surface of the molding material (y) can be easily coated uniformly and a beautiful streak-like design can be obtained.

The powdery molding material (z) is not particularly limited as long as it satisfies the above color difference, and specifically, for example, calcium carbonate, aluminum hydroxide, water. Fillers such as magnesium oxide and talc; inorganic pigments such as titanium oxide, zinc oxide and iron oxide; natural stone powders such as cold water sand, silica stone powder and mica powder; colored resin powders, plastics such as cuts of colored films Powder or crushed product; organic dye powder, organic pigment powder, etc., which has a powdery and unique color tone; artificial marble crushed product; the above powder is mixed with a radical polymerizable monomer such as trimethylolpropane trimethacrylate Saturated polyester resin,
A liquid opaque colorant such as a mixture dispersed in a radical-polymerizable resin such as an acrylic resin; etc. of the swelling gel-like molding material (y) attached to the surface of the swelling gel-like molding material (y) Any surface can be used without particular limitation as long as it can display the surface (interface) as a difference in color tone.

As the colored resin powder, a cured product (Y) of the swelling gel-like molding material (y) having a different color from the cured product (Y) of the swelling gel-like molding material (y) is rolled. A powder obtained by pulverizing with a pulverizer or a hammer mill may be used. That is, the molding material (z) is a cured product (Y) of the molding material (y) having a different color tone from the particles formed by curing the molding material (y) (that is, the color difference is 3 or more). It may be. In this case, the reduction in strength of the obtained molded article can be further reduced.

When a powdery molding material (z) is used as the molding material (z), the powdery molding material (z) is used.
Can also be used by dispersing it in a liquid (dispersion medium). For example, an organic pigment, an inorganic pigment, a dye or the like dispersed in a non-reactive dispersion medium can be used as the molding material (z).

As the dispersion medium for dispersing the powdery molding material (z), the dispersion medium evaporates to some extent in the mixing process of the molding material (y) and the molding material (z) and the molding process thereafter, or As long as it remains in the molding material and has little effect on the curing, it can be used without particular limitation. For example, solvents such as acetone, methyl ethyl ketone, and xylene, methyl cellosolve, dimethyl phthalate, and the like can be given.

Thus, the powdery molding material (z)
When dispersed in a non-reactive dispersion medium and used, the viscosity of the liquid containing the powdery molding material (z) is 30 Pa · s.
The following is desirable. The amount of the molding material (z) is set to the amount necessary to realize the intended design, and the amount of the dispersion medium is 30 as the viscosity of the liquid containing the molding material (z) as described above.
Select so that it is not more than Pa · s. When the viscosity of the liquid containing the molding material (z) is higher than 30 Pa · s, it takes a long time to adhere the molding material (z) to the surface of the molding material (y), resulting in poor efficiency. So undesirable.

When the above-mentioned solvent is used as the dispersion medium, the workability can be improved by increasing the amount of the solvent to reduce the viscosity of the liquid containing the molding material (z), but the total amount of the solvent is the above-mentioned molding material (z). It is desirable to set it to 20% by weight or less of y). When the total amount of the solvent exceeds 20% by weight with respect to the molding material (y), the curability of the molding material (y) to which the molding material (z) is adhered is impaired, and the moldability and physical properties are reduced. It is not preferable because the degree of reduction becomes large.

As the dispersion medium, monofunctional radically polymerizable monomers such as methyl methacrylate and styrene;
Polyfunctional radical-polymerizable monomers such as ethylene glycol di (meth) acrylate, trimethylol-ppantri (meth) acrylate, divinylbenzene; radical-polymerizable resins such as unsaturated polyester resins, vinyl ester resins, acrylic resins, etc. The reactive dispersant of can be used. In this case, the total amount of the dispersion medium is preferably 30% by weight or less of the molding material (y). When the total amount of the dispersion medium is larger than 30% by weight with respect to the molding material (y), the moldability of the molding material (y) to which the molding material (z) is attached is impaired and the physical properties are deteriorated. It is not preferable because the degree becomes large.

When the powdery molding material (z) is a non-reactive material, the powdery molding material is mixed with a monofunctional radically polymerizable monomer and a polyfunctional radically polymerizable monomer as described above. By being used by being dispersed in a body, a radical-polymerizable resin, or the like, it is possible to minimize deterioration of physical properties of a molded product obtained by curing the molding material (y) and the molding material (z).

The molding material (z) has an average particle size of 1
It is preferably 100 μm or less, and more preferably 70 μm or less, because the decrease in strength is small.

In the present invention, the amount of the molding material (z) used is such that the surface of the swelling gel-like molding material (y) can be efficiently used according to the surface area of the swelling gel-like molding material (y). 0.01 wt% of the total amount of the molding material (z) and the swelling gel-like molding material (y) so that it can be covered.
As described above, the amount is preferably set within the range of 30% by weight or less, and the upper limit thereof is more preferably 5% by weight and even more preferably 1% by weight or less.

When the amount of the molding material (z) used is less than 0.01% by weight, the surface of the swelling gel-like molding material (y) cannot be sufficiently covered, and therefore the swelling gel-like molding is performed. The interface of the cured product (Y) obtained by curing the material (y) cannot be emphasized, and there is a risk that an artificial marble having a desired design cannot be obtained. On the other hand, when the amount of the molding material (z) used exceeds 30% by weight, when the molding material (z) is a non-curable powdery molding material (z), the powdery molding is performed. The amount of the monomer (X) that oozes out into the material (z) is too small so that the powdery molding material (z) may not be sufficiently cured, and the strength of the obtained artificial marble may decrease. Further, if the amount of the molding material (z) used is too large, the interface of the cured product (Y) cannot be made conspicuous, and there is a possibility that a desired artificial marble-like design cannot be obtained.

In particular, when the amount of the molding material (z) used is 5% by weight or less, a fine streak-like line pattern is obtained, and a design very similar to natural stone can be obtained. Further, when the amount of the molding material (z) used is 1% by weight or less, the degree of decrease in physical strength and cold heat repetition strength tends to be small, which is more preferable.

The method for adhering the molding material (z) to the surface of the swelling gel-like molding material (y) is not particularly limited, but for example, the swelling gel-like molding material (y) is used. Is charged into a mixer such as a concrete mixer or a kneader, and the above molding material (z) or a liquid material in which the above molding material (z) is dispersed in the above dispersion medium is charged with stirring to mix the above molding material (z). Method of adhering to the surface of the swelling gel-like molding material (y); the swelling gel-like molding material (y) and the molding material (z) or the molding material (z) in a container such as an open drum. For example, a method in which a liquid material dispersed in a dispersion medium is charged at the same time, and the drum is rotated sideways by a drum rotating machine; a fixed amount of swelling gel-like molding material (y) is passed through the hopper, and quantitative molding is performed. Material (z Alternatively, a method of spraying or spraying a liquid material containing the molding material (z); and the like, the swelling gel-like molding material (y) and the powdery molding material (z) or the powdery material in a predetermined ratio. The method is not particularly limited as long as it is a method capable of mixing the molding material (z) with a liquid material in which the dispersion medium is dispersed. That is, the method for attaching the molding material (z) to the surface of the swollen gel-like molding material (y) is not particularly limited.

As the mixing conditions, the swelling gel-like molding material (y) and the molding material (z) are mixed with a strength such that the swelling gel-like molding material (y) is not crushed. However, there is no particular limitation. It is desirable that the molding material (z) is almost uniformly attached to the surface of the swelling gel-like molding material (y).

In the present invention, the above-mentioned molding material (z) is a powder, and the method of directly adhering the molding material (z) to the surface of the molding material (y) is to expose the surface of the molding material (y). It is desirable because it can stand up and reproduce a design similar to natural stone.

Further, the method of adhering the liquid (the liquid) in which the molding material (z) is dispersed in the dispersion medium is adhered to the surface of the molding material (y) is as follows. It is preferable in that it is easily attached, the pattern unevenness of the molded product is reduced, and the reproducibility of the design is enhanced.

Further, the molding material (z) is dispersed in a radical-polymerizable dispersion medium (that is, a monomer such as the monomer (X) which is polymerized by a radical polymerization reaction), and the molding material (y). The method of adhering to the surface of (1) is preferable because the degree of impairing the physical properties such as strength and heat resistance of the molded product is small.

According to the present invention, the swelling gel-like molding material (y) having the coloring molding material (z) attached to the surface in this manner is molded under heat and pressure to obtain a molded article. You can get artificial marble. In the present invention, a method is preferable in which the swelling gel-like molding material (y) having the molding material (z) attached to the surface thereof is spread in a mold by press molding and molded into a flat plate under heat and pressure. Used. The method of filling the swelling gel-like molding material (y) into the mold is as follows: the swelling gel-like molding material (y), that is, the swelling gel having the coloring molding material (z) attached to the surface thereof. It is preferable to use a method in which the shaped molding material (y) is dispersed and charged on the mold surface. Above all, when molding a flat plate with a uniform thickness, the cavity side of the mold is set as the lower mold, and the molding material (y) is charged substantially evenly over the entire surface of the cavity, and it is divided into several amounts beforehand. The charged molding material (y) is dispersed and charged, and the charged molding material (y) is surfaced using a suitable rod-shaped jig so that the molding material (y) has a constant height with respect to the mold surface. Is preferred.

The molding conditions for the swelling gel-like molding material (y) may be appropriately set according to the composition of the swelling gel-like molding material (y), and are not particularly limited. Although depending on the composition of the swelling gel-like molding material (y), the molding temperature (mold temperature) is generally 90 ° C. or higher,
The temperature is set to 170 ° C. or lower, preferably 100 ° C. or higher and 160 ° C. or lower. When the molding temperature is less than 90 ° C., it takes a long time to cure, or the storage stability of the molding material (y) for which a curing catalyst is selected so as to cure sufficiently at this temperature is impaired, which is not preferable. . vice versa,
Even if the temperature is higher than 160 ° C., the effect of shortening the molding time is small and, in addition, problems such as cracks and discoloration of the molded product are likely to occur, which is not preferable.

The molding pressure depends on the viscosity, fluidity and curing time of the molding material, but is generally 20 kg / cm ² or more, 10 or more.
It is preferably set to 0 kg / cm ² or less. If the molding pressure is less than 20 kg / cm ² , cracks and pinholes tend to remain in the molded product, which is not preferable. Conversely, 100
When the pressure is higher than kg / cm ² , the life of the mold is impaired, which is not preferable.

For the purpose of improving the releasability of the molded product, a resin film such as polyethylene terephthalate is preliminarily laid on the mold surface, and the molding material (z) is adhered on the resin film (y). It is also possible to charge and mold.

The molded product thus obtained can be used as it is as an artificial marble, but the swelling gel-like molding material (y), that is, the powdery molding material (z) is attached to the surface. It is preferable that the swollen gel-like molding material (y) thus spread is spread in a mold and molded into a flat plate under heat and pressure, and then the surface of the obtained molded product is polished.

The artificial marble thus obtained is formed by an aggregate of granular cured products (Y) obtained by curing the swelling gel-like molding material (y), and the swelling gel-like molding is carried out. By the molding material (z) attached to the surface of the material (y), thin streak-like line patterns (streak patterns) are obtained around the individual granular cured products (Y), and the above granular particles having a crushed surface are obtained. It has a design in which the boundary between the cured products (Y) is emphasized.

The swelling gel-like molding material (y) according to the present embodiment is such that the shape of the crushed surface at the time of heating under pressure causes the minimum deformation necessary to fill the space existing before molding. However, since the swelling gel-like molding material (y) has the above-mentioned weight change rate, viscosity, and hardness, it is kept close to each other by heating and pressing during molding. Swelling gel-like molding materials (y) that fit together are pressed against each other, and swelling gel-like molding materials (y) are adjacent to each other
The two are bonded to each other through a streak portion made of a cured product (Z) of the molding material (z) so as to be substantially combined with each other. That is, the artificial marble according to the present embodiment is adjacent to the swelling gel-like molding material (y) when the outer peripheral surface of one swelling gel-like molding material (y) adjacent to each other has a recess. On the outer peripheral surface of the other swelling gel-like molding material (y) that fits, a single convexity or a plurality of swelling gel-like molding materials (y) are gathered together, and the convex portion is shaped to substantially fit into the concave portion. Are formed.

Therefore, according to the present embodiment, the granular cured product (Y) obtained by curing the swelling gel-like molding material (y), which is calculated by the method described in Examples described later, is
The granular cured product (Y) adjacent to the granular cured product (Y)
And an average ratio of portions that are close to each other via a gap (streak portion) narrower than 20% of the average diameter obtained by averaging approximately the maximum length and the minimum length of the granular cured product (Y). It is possible to obtain an artificial marble having an average adjacency ratio of 50% or more and 100% or less, preferably 60% or more.

According to the present embodiment, the weight change rate of the swelling gel-like molding material (y) is within the range of +10 to + 200%, or the value measured using a helipass viscometer is 1,000 Pa. In the range of s or more and 150,000 Pa · s or less, or when the hardness measured by using a type D durometer hardness meter is HDD 75 or less, adjacent granular cured products (Y) are adjacent to each other. A streak pattern composed of a cured product (Z) having a color tone different from that of the cured product (Y) is formed.

When the molding material (y) harder than the molding material (y) is used, that is, the weight change rate of the swelling gel-like molding material (y) is 0 to less than + 10%, or the helipass viscosity is The value measured using a meter is 150,00
If it exceeds 0 Pa · s, or if the hardness is HDD
When it is larger than 75 and HDD 100 or less, the molding material (z) is extruded from between the swelling gel-like molding materials (y) adjacent to each other by the pressure at the time of molding, and the extruded molding material (z) is Surrounded by the vertices of the swelling gel-like molding material (y) generated by crushing the swelling gel and a plurality of swelling gel-like molding materials (y) adjacent to the swelling gel-like molding material (y) By flowing and entering into the region (space), the flat parts of the particles, that is, the side parts of the granular cured product (Y), which are linear crushed surfaces generated by the crushing of the swollen gel, are adjacent to each other. The granular cured product (Y) has a joint surface of a shape in which the cured products (Y) are directly joined to each other, and the apex portion of the granular cured product (Y), that is, the apex of the granular cured product (Y). , Adjacent to the granular cured product (Y) In a region surrounded cured product of the number of granular and (Y) a result, the artificial marble having a design in which the cured product of the molding material (z) (Z) is filled is obtained.

When crushed natural stones or crushed and hardened resin particles obtained by crushing a hardened resin are used, the crushed natural stones and crushed and hardened resin particles are obtained because their shape is maintained during molding. Artificial marble does not have a shape in which adjacent particles are substantially combined with each other,
For example, grains come into point contact with each other via a matrix or the like. Therefore, when crushed natural stone or crushed and hardened resin particles are used, it is not possible to obtain artificial marble having the above-mentioned average adjoining ratio.

Further, since the swelling gel-like molding material (y) according to the present embodiment substantially maintains the shape of the crushed surface during pressurization and heating, it is integrally molded and has a linear shape. It is possible to obtain an artificial marble having a design composed of an aggregate of granular resin cured products (Y) having a crushed surface. In the artificial marble according to the present embodiment, the average aspect ratio of the granular resin cured product (Y) measured by the method described in Examples described later is 1.1 or more and 5.0 or less, and the long side The large particle occupancy ratio, which indicates the ratio of particles having a size of 1 mm or more to the surface area, is 20% or more and 100% or less.

The ratio of the granular resin cured product (Y) in the artificial marble according to the present embodiment to the surface area of the artificial marble is in the range of 70 to 99%, and the granular resin cured product (Y Other than the above), the proportion of the streak portion made of the cured product (Z) of the molding material (z) in the surface area of the artificial marble is 30 to 1%.
Within the range of.

In the present invention, portions other than grains are called a matrix or a matrix portion. Therefore,
In the present embodiment, a portion other than the granular resin cured product (Y) is called a matrix or a matrix portion.
The artificial marble according to the present embodiment is formed by the molding material (z) attached to the surface of the swelling gel-like molding material (y).
The structure has a structure in which thin streak-shaped line patterns (streak patterns) made of the cured product (Z) of the molding material (z) are formed as a matrix between adjacent granular resin cured products (Y). . Therefore, in the artificial marble according to the present embodiment, a thin streak-shaped line pattern (streak pattern) portion made of the cured product (Z) of the molding material (z) corresponding to the matrix portion of the conventional artificial marble is provided. In particular, it is called a streak portion.

Further, in the artificial marble according to the present embodiment, there is no visually distinguishable void or space portion, and the ratio of the space portion in the obtained artificial marble is 1% or less of the total volume. is there.

When a lump of the kneaded material used in the conventional method for producing artificial marble is used in place of the swelling gel-like molding material (y), the above-mentioned kneaded material is pressed and heated. Since the lumps are crushed and flow, as shown in FIG. 2, the boundaries between the lumps, that is, the interfaces are not blurred and do not have a sharp shape, and the interfaces themselves have a flow pattern and have a linear fracture surface. It is not possible to obtain an artificial marble having a design made of an aggregate of granular resin cured products (Y).

As described above, the artificial marble obtained by the manufacturing method according to the present embodiment is a grain having a crushed surface, that is, the above-mentioned powder formed in the gap between the surfaces of the individual molding materials (y). The boundary surface formed by the body-shaped molding material (z) has a color tone different from that of the particles, and the volume thereof is smaller than the volume of the particles, so that a sharp interface is formed as shown in FIG. It consists of an aggregate of grains that have, the boundaries between grains are emphasized by a color tone different from that of grains, which is unprecedented,
It has a design very similar to the crystal structure of natural stone.

That is, the artificial marble according to the present embodiment comprises an aggregate of granular resin cured products (Y) integrally formed and having a linear crushing surface. The article (Y) has a joint surface of a shape that is substantially combined with each other, and between the adjacent granular resin cured products (Y), the adjacent granular resin cured products (Y) are present.
It has a design in which a streak-like clear interface made of a cured product (Z) having a color tone different from that is formed. In the artificial marble, the granular resin cured product (Y) and the cured product (Z) do not mix with each other and form a clear interface.

As described above, the above-mentioned artificial marble is composed of the cured resin product (Y) in granular form and the matrix (streak pattern portion) other than the cured product (Y) in granular form. More specifically, The granular resin cured product (Y) occupies 70 to 99% of the surface area of the artificial marble, and the matrix occupies 30 to 1% of the surface area of the artificial marble. Resin cured products (Y) of
It has a joint surface of a shape which is substantially combined with each other, and the average adjoining ratio of the granular resin cured product (Y) is 50% or more,
The average aspect ratio of the granular resin cured product (Y) is 1.
The ratio is 1 or more and 5.0 or less, and the large grain occupancy ratio is 20% or more.

Moreover, according to the present embodiment, the artificial marble having such a design can be obtained without using crushed natural stone. Therefore, according to the present embodiment, it is possible to provide an artificial marble which does not have the problems of workability and interfacial peeling as in the case of using crushed natural stone, and which has an extremely similar design to natural stone. .

Further, in the present embodiment, as described above, by using the swelling gel as the patterning material, that is, the swelling gel-like molding material (y), the size and thickness of the swelling gel and the depth of the interface can be obtained. Depending on the above, the color of the above grain looks different.

The swelling gel-like molding material (y) may be used in a single color, or a plurality of colors (a plurality of types) of swelling gel-like molding material (y) colored in different colors may be used.
The artificial marble shown in FIG. 1 uses, as its raw material, a swelling gel-like molding material (y) of a plurality of colors colored in different colors. Further, as the swelling gel-like molding material (y),
By using the transparent swelling gel-like molding material (y) together with the colored swelling gel-like molding material (y), an artificial marble more like natural stone can be obtained. The transparent swelling gel-like molding material (y) can be easily obtained, for example, by adding no filler or coloring agent to the above-mentioned reaction compound.

Further, when the desired pattern is more complicated, for example, the compound (A) and the compound (B) are combined by a reaction other than the radical reaction in the presence of the monomer (X) to form a simple compound. A reaction compound (primary reaction product mixture) swollen by the monomer (X) is formed, and then this primary reaction product mixture is ground to a desired particle size, and then the compound (C), the compound (D), and the radical polymerization reaction are carried out. The pulverized product is mixed with a monomer (E) to be polymerized, and the compound (C) and the compound (D) are bonded by a reaction other than a radical reaction, and a reaction compound swollen by the monomer (E) (secondary compound By repeating the step of forming the reaction product mixture) once or more, it is possible to obtain an artificial marble having grains in the grains.

As described above, since the above-mentioned primary reaction product mixture is sufficiently swollen (the weight change rate is in the range of 0 to + 200%), even if it is added to the monomer (E), the monomer ( E)
It does not absorb a large amount. Therefore, the viscosity of the mixture of the compound (C), the compound (D) and the monomer (E) is maintained at a predetermined value, workability such as addition and mixing is improved, and the mixture of the primary reaction product is obtained. Has good dispersibility and the pattern is not biased. The primary reaction product mixture, when added to the monomer (E), has such a viscosity and hardness that the shape of the crushed surface can be maintained, so that a desired pattern can be exhibited. it can. Therefore, the secondary reaction product mixture has a predetermined pattern derived from the primary reaction product mixture. Accordingly, the secondary reaction product mixture thus obtained is used as a swelling gel-like molding material (y), that is, a liquid-state monomer for polymerizing the compound (W) having a three-dimensional crosslinking bond by a radical polymerization reaction. By using it as a swollen gel swollen by the body, it is possible to obtain an artificial marble having a more three-dimensional effect and a more complicated and beautiful pattern.

The above-mentioned primary reaction product mixture can be obtained by reacting the compound (A) and the compound (B) by a well-known method as described above. The secondary reaction product mixture can be obtained by reacting the compound (C) and the compound (D) by a well-known method. These compound (A), compound (B), compound (C), and compound (D) are appropriately selected depending on, for example, the purpose of the artificial marble finally obtained so that the physical properties required for the purpose can be obtained. It may be used in combination. That is, the compounding composition of the compound (A) and the compound (B) to be a primary reaction product mixture, the amount of both used, and the compound (C) and the compound (D) to form a secondary reaction product mixture. )
The compounding composition, the amount used of both, and the like are not particularly limited. Further, the reaction conditions and the like when reacting the compound (A) and the compound (B), and the reaction conditions and the like when reacting the compound (C) and the compound (D) are not particularly limited. Absent.

As the above compound (C), the compound (A)
Compounds similar to can be used. The compound (A) and the compound (C) may be the same as or different from each other. Furthermore, 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, and
They may be different from each other.

As the compound (D), the same compounds as the compound (B) can be used. The compound (B) and the compound (D) may be the same as or different from each other. Furthermore, 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, or
They may be different from each other.

Therefore, also in the case of producing an artificial marble using the above-mentioned secondary reaction product mixture, compound (A), compound (B), compound (C), compound (D)
Can be any compound that binds by a reaction other than a radical reaction. The compound (A), the compound (B), the compound (C), and the compound (D) may have a functional group that undergoes a radical reaction, such as a double bond.

When molding the swelling gel-like molding material (y), when filling the mold with the swelling gel-like molding material (y) having the molding material (z) attached to the surface thereof. In addition, for example, a swelling gel-like molding material (y) having a whitish color tone
And swelling gel-like molding material (y) having a blackish color tone are arranged in a streak pattern, etc., swelling gel-like molding material (y) having different color tone is arranged in advance so that a desired pattern is obtained, that is, It may be spread over the entire surface of the mold and molded into a flat plate shape.

As a result, it is possible to obtain an artificial marble having another pattern, for example, a large flow pattern, when viewed in a wide range.

When a swelling gel-like molding material (y) of a plurality of colors colored in different colors is used as the swelling gel-like molding material (y) as described above, the molding material (z) is , The color tone of the cured product (Y) obtained by curing only the swelling gel-like molding material (y), which is used most, and the molding material (z) placed on the above molding material (y) and integrally cured. The color difference with the color tone of the cured product (Z) of the above molding material (z) may be selected to be 3 or more.
Preferably, 5 of all molding materials (y) used as raw materials
It is preferable to select the molding material (z) so that the color difference is 3 or more with respect to 0% by weight or more of the molding material (y), and to obtain a cured product of all molding materials (y) used as raw materials. Most preferably, the molding material (z) is selected so that the color difference is 3 or more.

Further, in the present invention, the molding material (z)
As a plurality of types of molding materials (z) having different color tones are prepared in advance, these are simultaneously attached to the surface of the molding material (y),
If the mixing work necessary for the adhesion is completed to the extent that the respective colors are not completely mixed, the stripe pattern forming the interface is multicolored and a partially mixed stripe pattern can be obtained.

Also, by preparing a plurality of types of molding materials (y) coated with molding materials (z) of different colors and mixing these non-uniformly at the time of molding, the streak pattern of the interface to be formed. Is multicolored and a partially mixed streak pattern can be obtained.

Furthermore, when the molding material (z) is attached to the surface of the molding material (y), the molding material (z) is made into a liquid state,
The viscosity of the molding material (y) is considerably higher than that of the molding material (z), specifically, the weight change rate of the swelling gel-like molding material (y) is in the range of 0 to + 100%, or The value measured using a helipass viscometer is 10,000.
Pa · s or higher, or the hardness measured using a type D durometer hardness meter is HDD 15 or higher, HDD
100 or less, the viscosity of the molding material (z) is 10P
In the case of a · s or less, the molding material (z) flows and enters the space formed between the molding materials (y),
A characteristic design is easily formed. That is, a plurality of grains are likely to be aggregated to form a large space portion, a streak pattern is large near the apex of the grains, and grains are likely to be dense in a flat portion of the grains that are relatively easily deformed by pressure during molding. Become a design.
When viewed with a design in which the surface is polished, a streak pattern is concentrated on the apexes of the grains, and grains are densely gathered on the side portions of the grains to obtain a design in which a thin streak pattern is formed. Such designs are often found in natural stones, and are one of the elements that make up the natural appearance.

The concentration of the streak pattern at the apex portion of the grain can be evaluated by the average side neighborhood streak assembly rate described in the examples described later. When this value is 50% or less, it is a natural stone close to natural stone. It is desirable because a design with a unique appearance can be obtained.

As described above, according to the present embodiment, when the molding material (z) is attached to the surface of the molding material (y), the molding material (z) is made into a liquid state and By virtue of the fact that the viscosity is considerably higher than that of the molding material (z), it is composed of an aggregate of granular resin cured products (Y) integrally formed and having a linear crushing surface, and is adjacent to each other. The resin cured products (Y) of (1) have joint surfaces of shapes that are substantially combined with each other, and the granular resin cured products (Y) are formed by the sharply crushed surfaces of the granular resin cured products (Y). In the region surrounded by the apex of Y) and the granular resin cured product (Y) adjacent to the granular resin cured product (Y), each granular resin cured product (Y) surrounding the region. To obtain an artificial marble filled with a cured product (Z) having a color tone different from It can be.

The artificial marble obtained by the method according to the present embodiment is lighter in weight than natural marble and has a workability (cutting,
It has excellent qualities such as polishing, adhesion, etc., and is very similar to natural stone, and has a high-quality feel, and is suitable for use on various top plates such as flooring, wall materials, tables, kitchen tops, and vanities. .

[Embodiment 2] Another embodiment of the present invention will be described in detail below. In the present embodiment, the same components as those described in the first embodiment will be designated by the same reference numerals, and the description thereof will be omitted.

The artificial marble according to the present embodiment is composed of an aggregate of granular resin cured products (Y) integrally formed and having a linear crushing surface. Y) each have a joint surface of a shape that is substantially combined with each other, and are directly joined, and the granular resin cured products (Y) adjacent to each other are colored in different colors from each other. It has a configuration in which a clear interface is formed between the granular resin cured products (Y) having different color tones and adjacent to each other.

The artificial marble according to the present embodiment is the swelling gel-like molding material (y) of a plurality of colors (a plurality of types) having different color tones, such as being colored in different colors, as a raw material in the first embodiment. It can be obtained by molding under heat and pressure without using the molding material (z) attached to the surface of the molding material (y).

The above-mentioned molding material (y) used as a raw material is obtained by three-dimensionally cross-linking the compound (W), for example, the compound (A) and the compound (B), as described in the first embodiment. By adding, for example, a colorant or a filler to the resulting reaction compound and adjusting the addition amount of the colorant or the filler to be added, the color tone and transparency can be appropriately changed. Further, by using the transparent swelling gel-like molding material (y) together with the colored swelling gel-like molding material (y) as the above-mentioned swelling gel-like molding material (y), an artificial marble more like natural stone can be obtained. Obtainable. The transparent swelling gel-like molding material (y) can be easily obtained, for example, by adding no filler or coloring agent to the above-mentioned reaction compound.

Furthermore, also in the present embodiment, when the desired pattern is more complicated, for example, in the presence of the monomer (X), the compound (A) and the compound (B) are subjected to other than radical reaction. The reaction is combined to form a reaction compound (primary reaction product mixture) swollen by the monomer (X), and the primary reaction product mixture is then crushed to a desired particle size to obtain a compound (C), a compound (D). ), And the pulverized product are mixed with the monomer (E) which is polymerized by a radical polymerization reaction, and the compound (C) and the compound (D) are bonded by a reaction other than the radical reaction to form a monomer (E). By repeating the step of forming the swollen reaction compound (secondary reaction product mixture) once or more, it is possible to obtain an artificial marble having grains in the grains.

Also in this embodiment, as described in the first embodiment, the above-mentioned primary reaction product mixture is sufficiently swollen (the weight change rate is within the range of 0 to + 200%). Even if it is added to (E), it does not absorb a large amount of the monomer (E). Therefore, the viscosity of the mixture of the compound (C), the compound (D) and the monomer (E) is maintained at a predetermined value, workability such as addition and mixing is improved, and the mixture of the primary reaction product is obtained. Has good dispersibility and the pattern is not biased. The primary reaction product mixture, when added to the monomer (E), has such a viscosity and hardness that the shape of the crushed surface can be maintained, so that a desired pattern can be exhibited. it can. Therefore, the secondary reaction product mixture has a predetermined pattern derived from the primary reaction product mixture. Accordingly, the secondary reaction product mixture thus obtained is used as a swelling gel-like molding material (y), that is, a liquid-state monomer for polymerizing the compound (W) having a three-dimensional crosslinking bond by a radical polymerization reaction. By using it as a swollen gel swollen by the body, it is possible to obtain an artificial marble having a more three-dimensional effect and a more complicated and beautiful pattern.

When the swelling gel-like molding material (y) is molded, when the swelling gel-like molding material (y) is filled in the mold, for example, a swelling gel-like molding having a whitish color tone is obtained. By arranging the molding material (y) and the swelling gel-like molding material (y) having a dark color tone in a streak pattern, the swelling gel-like molding material (y) having different color tones can be obtained in advance with a desired pattern. May be arranged, that is, spread over the entire surface of the mold and molded into a flat plate shape. This makes it possible to obtain an artificial marble having another pattern, for example, a large flow pattern, when viewed in a wide range.

As the molding material (y), a molding material (y) having a different color tone is used in place of the molding material (Z) in Embodiment 1, and a swelling gel-like molding material is based on JIS K7105. The color tone of the cured product (Y) obtained by curing only (y) using a flat plate-shaped mold to a thickness of 1 cm, and the uncured product cut to a thickness of 1 cm so that the mold is almost filled. The molding material (y) that has not been crushed in step 1, that is, the molding material (y) of the first layer, as the molding material (y) of the second layer, has a thickness of 0.5 mm.
Molding material (y) having a different color tone from the molding material (y) of the layer
And the color tone of the cured product (Y) of the second layer molding material (y) when cured integrally in the mold is 3 or more when determined by a color difference meter. It is preferable to use them in combination. The color difference is preferably 5 or more, more preferably 7 or more, and further preferably 10 or more.

Further, it is more preferable to use the molding material (y) in combination so that the color difference between the cured products (Y) of the molding materials (y) adjacent to each other in the obtained artificial marble is 3 or more. . The color difference between the cured products (Y) of the molding materials (y) adjacent to each other in the obtained artificial marble is the same as the cured product (Y) of the molding materials (y) and the molding material (z) adjacent to each other in the obtained artificial marble. The surface design of the molded artificial marble can be determined from the digitized image in the same manner as the color difference with the cured product (Z) of (1).

According to this embodiment, by selecting the combination of the molding materials (y) to be used so that the granular resin cured products (Y) adjacent to each other have different color tones from each other, The interface between the cured products (Y) when the swelling gel-like molding material (y) is cured can be clarified, and the natural stone-likeness can be expressed.

The artificial marble according to this embodiment is also
As described in the first embodiment, the swelling gel-like molding material (y) used as a raw material can be obtained as a molded product by molding under heat and pressure, preferably by press molding. That is, in the present embodiment, the molding method of the swelling gel-like molding material (y) includes a plurality of colors of swelling gel-like molding material (y) having different color tones such as being colored in different colors. Is preferably used, and the resulting mixture is spread in a mold and press-formed into a flat plate under heat and pressure. As a method for filling the mold with the swelling gel-like molding material (y), a method of dispersing and charging the swelling gel-like molding material (y) on the mold surface is suitable. In particular, when molding a flat plate having a uniform thickness, as described in the first embodiment, the cavity side of the mold is set to the lower mold, and the molding material (y) is charged substantially uniformly on the entire cavity surface. Molding material (y) pre-divided into several quantities so that
It is preferable to disperse and charge, and to level the surface of the charged molding material (y) using an appropriate rod-shaped jig so that the molding material (y) has a constant height with respect to the mold surface. Is.

The molding conditions for the swelling gel-like molding material (y) may be appropriately set according to the composition of the swelling gel-like molding material (y), and are not particularly limited. Although depending on the composition of the swelling gel-like molding material (y), the molding temperature (mold temperature) is generally 90 ° C. or higher and 170 ° C. or lower, as described in the first embodiment. Is set in the range of 100 ° C. or higher and 160 ° C. or lower. Further, although the molding pressure depends on the viscosity of the molding material, the fluidity, and the curing time, as described in the first embodiment,
Generally, it is preferably set to 20 kg / cm ² or more and 100 kg / cm ² or less.

For the purpose of improving the releasability of the molded product, a resin film such as polyethylene terephthalate may be previously laid on the mold surface, and the molding material (y) may be charged on the resin film for molding. It is possible.

The molded product thus obtained can be used as it is as an artificial marble, but the swollen gel molding material (y) is spread in a mold and molded into a flat plate under heat and pressure. After that, it is preferable to polish the surface of the obtained molded product.

The artificial marble thus obtained according to the present embodiment is formed by an aggregate of granular hardened products (Y) obtained by hardening the swelling gel-like molding material (y), Due to the molding materials (y) having different tones,
A design very similar to the crystal structure of natural stone, in which the granular hardened products (Y) adjacent to each other have different color tones, and the boundaries between the granular hardened products (Y) having the crushed surface are clearly distinguished, Have Moreover, according to the present embodiment, the artificial marble having such a design can be obtained without using crushed natural stone.

The swelling gel-like molding material (y) according to the present embodiment is such that the shape of the crushed surface at the time of heating and pressurizing causes the minimum deformation necessary to fill the space existing before molding. However, since the swelling gel-like molding material (y) has the above-mentioned weight change rate, viscosity, and hardness, it is kept close to each other by heating and pressurization during molding. The swelling gel-like molding materials (y) are pressed against each other, are slightly deformed so as to fill the space between the swelling gel-like molding materials (y), and are joined together in a form in which they are assembled together. Therefore, the artificial marble obtained in the present embodiment also forms an interface where the granular resin cured products (Y) are in continuous contact with each other in a shape in which they are combined with each other.

According to the present invention, it is possible to provide an artificial marble which does not have the problems of workability and interfacial peeling as in the case of using crushed natural stone and which has a design extremely similar to natural stone.

Further, the swelling gel-like molding material (y) according to the present embodiment is also integrally molded because the shape of the crushed surface is generally maintained during heating under pressure.
It has a design composed of an aggregate of granular resin cured products (Y) having a linear crushed surface, and the average aspect ratio of the granular resin cured products (Y) is 1.1 or more and 5.0 or less. The large particle occupancy ratio, which indicates the ratio of particles having a long side of 1 mm or more to the surface area, is 20% or more and 100% or less.

Furthermore, the artificial marble according to the present embodiment also has no voids or spaces that can be visually identified, and the ratio of the spaces in the obtained artificial marble is 1% or less of the total volume. Is.

The artificial marble according to the present embodiment, like the artificial marble described in the first embodiment, is lighter in weight and excellent in workability than natural stone, and has an elegant and high-quality texture that is extremely similar to natural stone. It is preferably used for various top plates such as floors, wall materials, tables, kitchen tops, and vanities.

The present invention is not limited to the above-described embodiments, but various modifications can be made within the scope of the claims, and the technical means disclosed in the different embodiments can be combined appropriately. Such embodiments are also included in the technical scope of the present invention.

[0151]

The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these. In addition, "part" described in Examples and Comparative Examples means "part by weight".

Grains and streaks (matrix) occupying the surface area of the artificial marble obtained in the following examples
, Average adjoining ratio, average aspect ratio, large grain occupancy ratio, average side neighborhood muscle assembly ratio, ratio of space portion in artificial marble, viscosity / hardness of reaction product, and color difference were measured by the following methods.

(Ratio of grain portion and streak portion (matrix portion) occupying the surface area of the artificial marble) From the uniform portion of the surface design of the formed article, 5 cm × 5
The range of cm was read by a scanner and used as an image file.
The obtained image file is processed by image processing software (Photoshop, Ad
obe) and processed as follows. (1) First, the color tone was converted so as to emphasize the difference in color tone between the grain portion made of the granular resin cured product (Y) and the streak portion. At this time, in order to facilitate the next binarization work, the grain portion or streak portion of the obtained image was selected by the above image processing software, and the tone was converted into a single color. (2) After that, the image data was binarized so that the image was divided into a grain portion and a streak portion. By this operation, the streak part is converted to black and the grain part is converted to white (or vice versa). At this time, so that the image is divided at the boundary between the grain portion and the streak portion,
The threshold value was set. For reference, the surface pattern of the artificial marble obtained in Example 2 is shown in FIG. 6, and the surface pattern of the artificial marble obtained by performing image processing of FIG. 6 in order to obtain the proportion of the grain portion and the streak portion in the surface area of the artificial marble is obtained. The binarized image is shown in FIG. (3) Next, by examining the histogram of the above image and determining the ratio of the white and black areas to the total surface area respectively, the ratio of the grain portion and the streak portion to the total surface area of the obtained molded product is calculated. I asked. The ratio of the matrix portion to the total surface area of the obtained molded product can be determined in the same manner as the ratio of the streak portion to the total surface area of the obtained molded product.

(Average Adjacency Ratio) The average adjacency ratio is 5c from the uniform portion in the surface design of the formed product.
It was calculated by the following method using an image file obtained by reading a range of m × 5 cm with a scanner. (1) First, an image in a range of 5 cm × 5 cm read by a scanner was printed, and from the printed image, one substantially largest grain (a granular resin cured product) was selected. (2) The substantially maximum length of the selected grains was measured and this was used as the major axis. In addition, the substantially minimum length of the selected grains was measured, and this was defined as the minor axis. (3) The average value of the major axis and the minor axis was determined, and this was used as the average diameter. (5) The distance between the selected grain and the grain adjacent to the grain (the portion forming the streak pattern) is 20 times the average diameter of the selected grain.
A portion narrower than 100% was searched for, and the periphery of the selected grain in this portion was colored with a color not shown on the image (red in the following examples). The above-described operation was performed one by one for all the grains adjacent to the selected grain on the entire outer circumference of the selected grain. (6) The length of the colored portion and the length of the entire outer circumference of the selected grain are obtained from the printed image, and the ratio of the length of the colored portion to the entire outer circumference is obtained, whereby the selected grain is The ratio (adjacent ratio) of the region adjacent to the grain and adjacent to the grain was calculated. (7) From the printed image, determine the adjacency ratio for the next largest grain after the grain selected previously, repeat this operation,
Data were obtained for a total of 10 grains. (8) The obtained 10 data were averaged and this was taken as the average adjacency ratio.

(Average Aspect Ratio) The average aspect ratio was calculated by using an image file obtained by reading a range of 5 cm × 5 cm with a scanner from a uniform portion in the surface design of the formed product, It was calculated by the method shown below. (1) First, print an image in the area of 5 cm x 5 cm read by the scanner, and from the printed image, select the largest grain
I selected one. (2) The substantially maximum length of the selected grains was measured and this was used as the major axis. In addition, the substantially minimum length of the selected grains was measured, and this was defined as the minor axis. (3) The major axis / minor axis was calculated as the aspect ratio. (4) From the printed image, the aspect ratio of the next largest particle after the previously selected particles was determined, and this operation was repeated to obtain data on a total of 10 particles. (5) The obtained 10 pieces of data were averaged, and this was taken as the average aspect ratio.

(Large grain occupancy ratio) The large grain occupancy ratio is 5c from the uniform portion in the surface design of the formed product.
It was calculated by the following method using an image file obtained by reading a range of m × 5 cm with a scanner. (1) First, of the images in the area of 5 cm × 5 cm read by the scanner, the image in the arbitrary area of 3 cm × 3 cm was selected on the screen. (2) On the screen, all particles having a long side of 1 mm or more were selected and colored with a color not on the screen (red in the following examples). At this time, when the color tone of the grain was clearly different from the surrounding streak pattern or grain, the range of the grain portion was selected based on the color tone difference, and then the selected region was colored red. On the other hand, when the boundary (outer periphery) of the grain was unclear, the interface between the grain portion and the streak portion was manually selected, the range of the grain portion was selected, and then the selected region was colored red. (3) Select an area other than the colored area,
It was colored in a color different from the previously colored red (blue in the following examples). (4) The area of the red-colored area and the area of the blue-colored area were determined from the histogram, and the ratio of the red-colored area to the total colored area was calculated.

(Average Side Neighborhood Muscle Collection Rate) The average side neighborhood muscle collection rate was obtained by reading a range of 5 cm × 5 cm with a scanner from a uniform portion in the surface design of the formed product. It was calculated by the method described below using the image file. (1) First, the obtained image file is processed by image processing software (Phot
The color tone was converted so as to emphasize the difference in color tone between the grain portion made of the granular resin cured product (Y) and the streak portion. At this time, in order to easily perform the next binarization work, the grain portion or the streak portion of the obtained image was selected by the image processing software and converted into a monotone. (2) After that, the image data was binarized so that the image was divided into a grain portion and a streak portion. By this work,
The streak part is converted to black, and the grain part is converted to white (or vice versa). At this time, the threshold value was set so that the image was divided at the boundary between the grain portion and the streak portion. (3) The binarized image obtained in this manner was printed, and one grain having the maximum size was selected from the printed binarized image. (4) From the entire circumference of the selected grain, make as sharp an angle as possible
About 6 locations were selected and used as vertices. (5) From the entire circumference of the selected grains, the same number of sides as the vertices selected in (4) above, which consist of linear crushed surfaces, were selected from the portion close to the straight line. (6) The substantially maximum length of the selected grains was measured, and this was used as the major axis. In addition, the substantially minimum length of the selected grains was measured, and this was defined as the minor axis. The average value of the major axis and the minor axis was calculated, and this was taken as the average diameter. (7) At the apex of the selected grain, a circle having a diameter of 20% of the average diameter was drawn around the apex, and the area of the streak portion included in the circle was determined. (8) The work of (7) above was carried out for all the selected vertices, and the total was calculated to be the area of the muscle near the vertices. (9) On the other hand, on the side of the selected grain, draw a circle having a length that is 20% of the average diameter calculated above, including this side as the diameter of the circle, and draw the area of the streak part included in this circle. I asked. (10) The work of (9) above was carried out for all the selected sides, and the total was calculated to be the area of the muscle near the sides. (11) From the muscle areas near the vertices and the muscle areas near the edges obtained in this way, the muscle aggregation rate near the edges (%) = the muscle area near the edges / the muscle area near the vertices × 100 Was calculated. (12) From the printed binarized image, the above-mentioned neighborhood neighborhood muscle assembly rate was determined for the grain next to the grain selected previously, and this operation was repeated to obtain data on a total of 10 grains. (13) The obtained 10 pieces of data were averaged, and this was taken as the average side neighborhood muscle assembly rate.

(Ratio of Space in Artificial Marble) The ratio of space in the artificial marble was measured by the following method. (1) First, a specific gravity was measured by cutting out a portion without voids or spaces from the molded artificial marble. It was confirmed that the cut artificial marble had no voids or voids by cutting the artificial marble into small pieces after measuring the specific gravity. (2) Next, an arbitrary portion of the artificial marble was cut out and the specific gravity was measured. (3) The ratio of the space portion was calculated by comparing the two specific gravity values obtained in (1) and (2) above. For example, when the specific gravity of the void-free portion, that is, the specific gravity of the cut artificial marble is 1.82 and the specific gravity of any portion of the artificial marble is 1.80, the ratio of the space portion is (1.82-1 .80) /1.82×100=1.1, it can be estimated that the spatial portion is about 1%. When the proportion of the space portion calculated by the above method is less than 1%, it was determined that the proportion of the space portion in the artificial marble was 0%. Therefore, if there is no significant difference between the two specific gravities obtained in (1) and (2) above, it can be estimated that there is no space. A specific gravity bottle was used for the measurement of the specific gravity in the above (1) and (2).

(Viscosity / Hardness of Reaction Product) A Helipass viscometer (manufactured by Brookfield UK) was used to measure the viscosity of the reaction product. A D type durometer hardness meter (manufactured by Toyo Seiki Co., Ltd.) was used to measure the hardness of the reaction product.

(Color Difference) The color difference between the color tone of the cured product of the crushed material and the color tone of the cured material of the molding material (z) was measured by using the molding material before crushing as a flat plate mold (length 30 cm × width 30 cm, The height (thickness) can be varied) and the color tone when cured to a thickness of 1 cm, and the thickness of 1 cm on the molding material cut to fill the mold substantially The color difference from the color tone of the above molding material (z) when the molding material (z) is placed so that the distance becomes 0.5 mm and is integrally cured in the mold is measured according to JIS K7105 using a color difference meter. It was carried out by measuring based on. As the color difference meter, a Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd. was used.

The color difference between the color tone of the cured product of the crushed product and the color tone of the cured product of the molding material (z) forming the streaks in the obtained molded product (artificial marble) is the same as that of the obtained molded product. It was determined based on the following method from the image obtained by digitizing the surface design. Two colors (a1,
b1, L1) and (a2, b2, L2) are measured,
The color difference ΔE is expressed by the following equation ΔE = {(Δa) ² + (Δb) ² + (ΔL) ² } ^1/2 (wherein Δa = a1-a2, Δb = b1-b2, ΔL =
L1-L2 is shown).

On the other hand, when an image is digitized and input by a scanner or a digital camera, color information about each pixel of the input image can be obtained. Usually this value is (R, G,
It is given by the numerical value of B) and represents the degree of color development of red, green and blue, respectively. When inputting with a scanner, digital camera, or the like, the brightness and color tone as a whole are often deviated due to the conditions of digitization, and it is difficult to obtain absolute color information. Therefore, in the present invention, the color difference between the cured product of the crushed product and the cured product of the molding material (z) in the obtained molded product is determined from the image obtained by digitizing the surface design of the obtained molded product. It was evaluated by the relative color difference which can be evaluated simply.

When data of (R, G, B) is obtained for one point of the input image, the following equation a = 106.0 × (R ^1/3 −G ^1/3 ) b = 42.34 × (G ^{1 / 3−} B ^1/3 ) L = 25.29 × G ^{1 /} 3−18.38 The above data can be converted into the value of (a, b, L).

However, (R, G,
Since the numerical value of B) is from 0 to the maximum value (for example, 255) defined on the image software, it is desirable to correct this value using a white standard plate or the like. For example, a pure white standard plate having (a, b, L) values of (0, 0, 97) has (R, G, B) values of (97, 97, respectively).
97). When this standard plate is captured as an image by a digital camera and the color information and (R, G, B) values of the pure white portion are obtained, and the respective values are (180, 200, 190), each value is 97. Therefore, it is preferable to multiply by 97/180, 97/200, and 97/190 to correct the respective values. If the photographing conditions are different, it is desirable that the standard data is photographed again and the numerical value of this correction data is obtained again.

Example 1 A copolymer of styrene and 2-hydroxyethyl methacrylate in 70 parts of methyl methacrylate (manufactured by Sekisui Chemical Co., Ltd., trade name: LMSH)
(200) 30 parts was added, the mixture was heated to 40 ° C. and stirred for 2 hours to prepare a syrup. To 100 parts of this syrup, 4 parts of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX), 0.01 part of dibutyltin dilaurate, 1,1-bis (t-butylperoxy)- 3,3,5-Trimethylcyclohexane (Nippon Yushi Co., Ltd., trade name: Perhexa 3M)
0.5 part, aluminum hydroxide (Sumitomo Chemical Co., Ltd., trade name: CW-325B) 160 parts, white toner (Dainichi Seika Kogyo Co., Ltd., trade name: AT-3) 1.0
Parts were added, and the mixture was stirred and mixed using a mixer, and then degassed in vacuum to obtain a mixture. This mixture was poured into a box-shaped container and allowed to react for a whole day and night to obtain a swollen gel-like (jelly-like) white soft reaction product (a).

The obtained reaction product (a) was cut into a brick-like block with a knife, and a rotary blade type high speed cutter (manufactured by Nishimura Kikai Seisakusho: high speed crusher HS-35) cuts the average particle size to 4
The particles were cut into mm particles to obtain a white crushed material (1).

A swelling gel-like black soft reaction product was produced in the same manner except that the toner used was changed to 0.8 part of a black toner (manufactured by Dainichiseika Kogyo KK, trade name: AT-256). The product (b) was obtained. The obtained reaction product (b) was cut in the same manner as the reaction product (a) to obtain a black crushed product (2).

Further, a swelling gel-like brown soft reaction product (in the same manner as described above) was used except that the toner used was changed to 1 part of a brown toner (manufactured by Dainichiseika Kogyo Co., Ltd., trade name: AT-96). c) was obtained. The obtained reaction product (c) was cut in the same manner as the reaction product (a) to obtain a brown crushed product (3).

The viscosities of the reaction product (a), the reaction product (b), and the reaction product (c) measured with a helipass viscometer are 135,000 Pa · s, 125,000, respectively.
The values were 0 Pa · s and 140,000 Pa · s. Also,
The above reaction product (a), reaction product (b), reaction product (c) measured using a type D durometer hardness meter
Hardness of HDD 20, HDD 15, HDD
It was 35.

Next, 50 parts of the crushed material (1), 5 parts of the crushed material (2), and 45 parts of the crushed material (3) were charged into an open drum, and titanium oxide (commercially available from Ishihara Sangyo Co., Ltd. Name: R-820) 0.3 part was added, the lid was closed, and the mixture was rotated for 30 minutes with a drum rotating machine to mix the crushed materials of each color, and on the surface thereof, as the molding material (z) according to the present invention. Of titanium oxide was evenly applied. JIS
Based on K7105, Co manufactured by Nippon Denshoku Industries Co., Ltd.
The color tone of the cured product of the crushed product (1) measured by the lor Measuring System, that is, the color tone of the cured product of the reaction product (a) and the surface of the reaction product (a) were applied and cured. At this time, the color difference from the color tone of the cured product of titanium oxide is 8.0, that of the cured product of the crushed product (2), that is, the color tone of the cured product of the reaction product (b) and the reaction product (b). The color difference from the color tone of the cured product of titanium oxide when applied to the surface of (4) and cured is 25, that of the cured product of the crushed product (3), that is, the cured product of the reaction product (c). The color difference between the color tone and the color tone of the cured product of titanium oxide when applied to the surface of the reaction product (c) and cured was 12.

The rate of weight change was measured when the crushed material obtained as described above was swollen in a monomer polymerized by a radical polymerization reaction. 10 g of the crushed product was weighed, placed in a glass bottle containing 100 g of methyl methacrylate and tightly capped, and then allowed to stand in a thermostat controlled at 23 ° C. ± 2 ° C. for 24 hours, then, After filtering with a 50-mesh wire gauze, quickly spread it on filter paper, absorb the methyl methacrylate adhering to the surface on the plain filter paper, transfer it to a glass petri dish, and weigh it, it was 14.5 g, weight change The rate was + 45%.

Then, subsequently, the mixture of the crushed material was
Spread evenly in a flat mold controlled at 120 ° C, heat and pressurize at a pressure of 70 kg / cm ² for 10 minutes to cure, and obtain a flat plate of uniform thickness (thickness 13 mm). It was

After sanding (polishing) the surface of this flat plate for about 1 mm and polishing it by buffing, a white stone pattern on a white, black or brown granular background with a vivid white streak pattern is a natural stone. An artificial marble with a pattern very similar to that of the design was obtained. The white streak pattern is formed along the grain surface at an acute angle, and there is no part like the conventional resin products where the edges are blurred due to mixing, and a molded product with a novel design (artificial marble )was gotten.

In the obtained molded product, the proportion of the grain portion in the surface area was 75%, and the proportion of the streak portion in the surface area was 25%. Further, the average adjacency ratio in the molded product is 60%, the average aspect ratio is 2.5, the large particle occupancy ratio is 70%, the ratio of the space portion in the artificial marble is 0%, and the crushing obtained from the image of the artificial marble. The color difference between the color tone of the cured product of the product (1) and the color tone of the cured product of titanium oxide is 6.6, and the color difference between the color tone of the cured product of the crushed product (2) and the color tone of the cured product of titanium oxide is 21, The color difference between the color tone of the cured product of the crushed product (3) and the color tone of the cured product of titanium oxide was 8.5. The surface pattern of the artificial marble obtained in this example is shown in FIG.

[Comparative Example 1] Unsaturated polyester resin (manufactured by Nippon Shokubai Co., Ltd., trade name: Epolak N-36) 15
Part, calcium carbonate (manufactured by Nitto Koka Kogyo Co., Ltd., trade name: NS-100) 35 parts, Shirakan Suiseki (manufactured by Nitto Koka Kogyo Co., Ltd., trade name: # 70), and 1 part benzoyl peroxide. Was kneaded and solidified into a spherical shape of about 10 mm, and 0.5 part of titanium oxide powder (manufactured by Ishihara Sangyo Co., Ltd., trade name: R-820) was sprinkled on the mixture to form a comparative molding material (I ) Got.

The molding material (I) was mixed at a mold temperature of 100.
When a mold was filled and molded in the same manner as in Example 1 except that the temperature was changed to 0 ° C., a molded product having a translucent background with a streaky white pattern was obtained. The streak pattern was partially dispersed and mixed due to the flow at the time of molding, a clear sharp surface pattern was not obtained, and the appearance was different from natural stone.

Further, the weight change rate was determined in the same manner as in Example 1 except that the above-mentioned molding material hardened into a spherical shape of about 10 mm was used and the monomer was changed to a styrene monomer. It dissolved in the monomer, leaving only the powder. That is, all of the added resin (15 parts of unsaturated polyester resin) is dissolved, and 35 parts of calcium carbonate and 5 parts are added.
Only 0 parts of Shirasuiseki remained as a non-prototype powder. That is, the weight change rate of the above molding material is −15.
%Met.

When the ratio of the space portion in the obtained molded product (artificial marble) was measured, it was 0%. In addition, the obtained molded product does not have a clear granular pattern. Therefore, it is necessary to measure the ratio of the particle portion and the matrix portion in the surface area of the molded product, the average adjacency ratio, the average aspect ratio, and the large grain occupancy ratio. I couldn't.

[Comparative Example 2] Commercial artificial marble (manufactured by N & L Marble Co., Ltd., trade name: Marves Celes G-07)
The ratio of the grain part and the matrix part to the surface area of
The average adjacency ratio, the average aspect ratio, the large grain occupancy ratio, and the ratio of the space portion in the artificial marble were measured by the methods described above. As a result, in the artificial marble, the proportion of the grain portion in the surface area was 45%, and the proportion of the matrix portion other than the grain portion in the surface area was 55%. The average adjoining ratio in the above-mentioned molded product was 10%, the average aspect ratio was 1.5, the large particle occupying ratio was 32%, and the ratio of the space portion in the artificial marble was 0%. The surface pattern of the commercially available artificial marble is shown in FIG. 4, and the binarized image thereof is shown in FIG.

Example 2 The brown reaction product (c) prepared in Example 1 was used, using the rotary blade high-speed cutter used in Example 1, and changing the diameter of the screen to obtain an average particle size. Two
mm crushed product (4), brown crushed product (5) having an average particle size of 4 mm, and brown crushed product (6) having an average particle size of 7 mm were obtained.

The measurement was carried out using a helipath viscometer,
The reaction product (c), which is a block for crushed chips, has a viscosity of 140,000 Pa · s and a hardness of HDD 3
It was 5.

Next, 20 parts of the crushed material (4), 30 parts of crushed material (5), and 50 parts of crushed material (6) were charged into an open drum in the same manner as in Example 1, and titanium oxide (Ishihara Sangyo (Trade name: R-820, manufactured by Co., Ltd.) was added, and in the same manner as in Example 1, titanium oxide as the molding material (z) according to the present invention adhered to the surface, A mixture of different brown crushed products was obtained. JIS K710
Color Measur manufactured by Nippon Denshoku Industries Co., Ltd.
crushed materials (4) to (6) measured by Ining System
The color tone of the cured product of the above, that is, the color difference between the color tone of the cured product of the above reaction product (c) and the color tone of the cured product of titanium oxide when applied on the surface of the above reaction product (c) and cured. 1
It was 1. In addition, the weight change rate of the crushed material measured in the same manner as in Example 1, that is, the reaction product (c)
The weight change rate of was 45%.

A mixture of the above-mentioned crushed material having titanium oxide adhered to the surface was molded in the same manner as in Example 1 to obtain a flat plate having a uniform thickness. The surface of this flat plate was polished in the same manner as in Example 1, and as a molded product, an artificial marble having a pattern of white streaks in the background of brown grains and a pattern very similar to the design of natural stone was obtained. Was given.

The ratio of the area of the grain portion to the area of the streak portion of the obtained molded product was streak portion 3 with respect to grain portion 29, and the ratio of the grain portion to the surface area was 91%. The ratio of the part to the surface area was 9%. The molded product was densely packed with particles, and there were no voids or spaces that could be visually discerned. The average adjacent ratio in the above-mentioned molded product is 70%, the average aspect ratio is 1.8, the large grain occupancy ratio is 60%, the ratio of the space portion in the artificial marble is 0%,
Each brown crushed product obtained from the image of artificial marble (4)
The color difference between the color tone of the cured product of (6) and the color tone of the cured product of titanium oxide was 8.2. As described above, the surface pattern of the artificial marble obtained in this example is shown in FIG. 6, and its binarized image is shown in FIG. 7.

Example 3 Example 1 was repeated except that 0.5 part of dark red toner (manufactured by Dainichiseika Kogyo KK, trade name: AT TS999) was used in place of the white toner used in Example 1. Similarly, a swollen gel-like (jelly-like) dark red soft reaction product (d) was obtained.

The obtained reaction product (d) was cut in the same manner as in Example 1 to obtain a crushed product (7) of dark red having an average particle size of 4 mm. The viscosity of the reaction product (d), which is a block for crushed chips, was 140,000 Pa · s, and the hardness was HDD 35, which was measured using a helipass viscometer.

Next, 100 parts of syrup prepared in the same manner as in Example 1, 4 parts of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX), 0.01 part of dibutyltin dilaurate. ,
1,1-bis (t-butylperoxy) -3,3,5-
Trimethylcyclohexane (Nippon Yushi Co., Ltd., trade name: Perhexa 3M) 0.5 part, aluminum hydroxide (Sumitomo Chemical Co., Ltd., trade name: CW-325B)
100 parts of white toner (manufactured by Dainichiseika Kogyo Co., Ltd., trade name: AT-3) was mixed with 3.0 parts and then divided into two, and one of them was further black toner (Dainichi Seika Kogyo Co., Ltd.). (Trade name: AT-256) manufactured by Nippon Kayaku Co., Ltd. was added, and the mixture was stirred and mixed, and then both were vacuum degassed to obtain a white mixture (i) and a gray mixture (ii). 5 parts of this white mixture (i) and 5 parts of gray mixture (ii) were weighed and lightly mixed so as not to mix them completely, and a white mottled pattern was obtained as the molding material (z) according to the present invention. A mixture (iii) was obtained.
Based on JIS K7105, the color tone of the cured product of the crushed product (7) measured by Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd. and the color of the cured product applied to the surface of the crushed product (7) and cured. The color difference from the color tone of the cured product of the white mixture (i) was 89, and the color tone of the cured product of the crushed product (7) and the gray mixture (when applied to the surface of the crushed product (7) and cured ( The color difference from the color tone of the cured product of ii) is 92.
Met. The weight change rate of the crushed material (7) measured in the same manner as in Example 1 was + 45%.

Subsequently, the white mottled mixture (ii
i) and 100 parts of the crushed material (7) were put into an open drum, covered with a lid and rotated with a drum rotator for 2 minutes to stir. After that, the obtained mixture was taken out and placed in a box-shaped container, and left in it for a day and night to be thickened to obtain a block-shaped molding material (e).

The obtained block-shaped molding material (e) was
The same flat mold as in Example 1 was used to cure in the same manner as in Example 1, and the surface was sanded by about 1 mm.
Then, as a molded product, dark red particles,
At the grain boundary, an artificial marble was obtained in which a streak pattern composed of white to gray mottled patterns and partially colored in different colors was expressed.

The ratio of the grain portion of the obtained molded article to the surface area was 79%, and the proportion of the streak portion to the surface area was 21.
%Met. In addition, the molded product is densely packed with particles,
There were no voids or spaces that could be visually identified. The average adjacency ratio in the molded product is 90%, the average aspect ratio is 1.8, the large particle occupancy ratio is 71%, the ratio of the space portion in the artificial marble is 0%, and the crushed material obtained from the image of the artificial marble (7 The color difference between the color tone of the cured product of () and the color tone of the cured product of the mixture (iii) was 84 in the white part of the cured product of the mixture (iii) and 70 in the gray part. The surface pattern of the artificial marble obtained in this example is shown in FIG. 8 and its binarized image is shown in FIG.

Example 4 In Example 1, the amount of hexamethylene diisocyanate trimer used was increased from 4 parts to 8 parts, and instead of the white toner, a dark red toner (manufactured by Dainichiseika Kogyo Co., Ltd. Name: AT TS999) 0.5
A swollen gel-like (jelly-like) dark red soft reaction product (f) was obtained in the same manner as in Example 1 except that parts were used.

The reaction product (f) thus obtained was crushed in dark red (8) having an average particle diameter of 10 mm by changing the diameter of the screen using the rotary blade color high speed cutter used in Example 1. A dark red crushed material (9) having an average particle diameter of 4 mm and a dark red crushed material (10) having an average particle diameter of 2 mm were obtained. The viscosity of the reaction product (f), which is a block for crushed chips, measured by using a helipass viscometer was 160,000 or more (measurement limit). The hardness was HDD 50.

On the other hand, 75 parts of methyl methacrylate and polymethyl methacrylate (manufactured by Sumitomo Chemical Co., Ltd.,
Acrylic syrup was prepared by mixing 25 parts of trade name: Sumipex EX) at 40 ° C. for 6 hours. Black toner on this acrylic syrup (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name:
AT-256) 3 parts and 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane (NOF Corporation, trade name: Perhexa 3M).
5 parts were added and mixed to obtain a black syrup (x). The viscosity of the black syrup (x) was 0.5 Pa · s.

Next, 50 parts of the crushed material (8), 30 parts of crushed material (9), 20 parts of crushed material (10), and 15 parts of black syrup (x) were charged into a small concrete mixer for 10 minutes. By stirring and mixing, a mixture of crushed pieces of dark red having different sizes, to the surface of which the black syrup (x) as the molding material (z) of the present invention was attached, was obtained. Based on JIS K7105, the color tone of the cured product of the crushed products (8) to (10) measured by Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd., that is, the cured product of the reaction product (f). The color difference between the color tone and the color tone of the cured product of the black syrup (x) when applied on the surface of the reaction product (f) and cured was 75. In addition, the weight change rate of the crushed material measured in the same manner as in Example 1, that is, the weight change rate of the reaction product (f) was + 20%.

A mixture of the crushed product having the black syrup (x) attached to the surface was cured in the same manner as in Example 1 by using the same flat plate-shaped mold as in Example 1, and the surface was about 1 m.
When removed by m sanding (polishing), an artificial marble having a beautiful design similar to natural stone, having dark red grains and black streak patterns formed at the grain interfaces, was obtained as a molded product. In this artificial marble, the area of the streak pattern in the part where the apexes of the particles are gathered is larger than the streak pattern in the side part of the particle, and a characteristic design in which there are many matrices in the gaps between the corners of the particle is formed.

The particle portion of the obtained molded product occupies 78% of the surface area, and the streak portion occupies 22% of the surface area.
%Met. In addition, the molded product is densely packed with particles,
There were no voids or spaces that could be visually identified. The average adjacent ratio in the molded product is 60%, the average aspect ratio is 2.2, the large particle occupancy ratio is 60%, the ratio of the space portion in the artificial marble is 0%, and the dark red of each of the dark reds obtained from the image of the artificial marble. The color difference between the color tone of the cured products of the crushed products (8) to (10) and the color tone of the cured product of the black syrup (x) was 66. In addition, the neighborhood peripheral muscle assembly rate in the above-mentioned molded product was 35%. The surface pattern of the artificial marble obtained in this example is shown in FIG.

[Example 5] 100 parts of syrup prepared in the same manner as in Example 1, 4 parts of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX), dibutyltin dilaurate 0. 01
Part, 1,1-bis (t-butylperoxy) -3,3,
5-trimethylcyclohexane (manufactured by NOF CORPORATION)
Product name: Perhexa 3M 0.5 part, Aluminum hydroxide (Sumitomo Chemical Co., Ltd. product name: CW-325
B) 180 parts of beige toner (Dainichi Seika Kogyo Co., Ltd., trade name: Beige NSB64) mixed with 0.05 parts, and a dark red crushed product (9) with an average particle diameter of 4 mm prepared in Example 4 ) 10 parts were added, and the mixture was stirred and mixed using a mixer, and then degassed in vacuum to obtain a mixture. This mixture was poured into a box-shaped container and allowed to react for one day and night to obtain a swollen gel-like (jelly-like) beige-colored soft reaction product (g) containing brown (dark red) grains.

Using the reaction product (g) obtained, the rotating blade color high-speed cutter used in Example 1 was used, and the diameter of the screen was changed to obtain beige particles (11) with brown particles having an average particle size of 7 mm. , Beige particles with brown particles having an average particle size of 4 mm (1
2), brown beige particles with an average particle size of 2 mm (13)
Got

The measurement was performed using a helipass viscometer,
The reaction product (g), which is a block for crushed chips, has a viscosity of 140,000 Pa · s and a hardness of HDD 4
It was 0.

Next, 40 parts of beige particles (11) with brown particles having an average particle diameter of 7 mm, 20 parts of beige particles with brown particles having an average particle diameter of 4 mm (12), beige particles with brown particles having an average particle diameter of 2 mm ( 13) 40 parts, and 0.2 part of titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: R-820) were put into an open drum in the same manner as in Example 1, and then on the surface in the same manner as in Example 1. A mixture of beige particles with brown particles having different sizes and having titanium oxide as the molding material (z) according to the present invention attached was obtained. Color measuring by Nippon Denshoku Industries Co., Ltd. based on JIS K7105
The color difference between the color tone of the cured product of the brown particles and the color tone of the cured product of titanium oxide when applied to the surface of the brown particle and cured, measured by System, is 45. The color difference from the color tone of the cured product of titanium oxide when applied to the surface of the beige particles and cured was 21. The rate of change in weight of the beige particles with brown particles, that is, the rate of change in weight of the reaction product (g), measured in the same manner as in Example 1, was + 40%.

A mixture of the above-mentioned brown particles and beige particles having different sizes and having titanium oxide adhered to the surface was cured in the same manner as in Example 1 by using the same flat plate-shaped mold as in Example 1 to obtain the surface. Was removed by sanding (polishing) about 1 mm, and as a molded product, brown particles were scattered in beige particles, and there were white stripes on the edges. I was able to obtain the artificial marble of.

The particle portion of the obtained molded product occupies 72% of the surface area, and the streak portion occupies 28% of the surface area.
%Met. In addition, the molded product is densely packed with particles,
There were no voids or spaces that could be visually identified. The average adjoining ratio in the molded product is 55%, the average aspect ratio is 2.5, the large grain occupancy ratio is 50%, the ratio of the space portion in the artificial marble is 0%, and the beige with brown particles obtained from the image of the artificial marble. The color difference between the color tone of the cured product of the particles (11) to (13) and the color tone of the cured product of titanium oxide is 43 in the brown part of the cured product of the brown particles (11) to (13), a beige color. It was 20 in parts. The surface pattern of the artificial marble obtained in this example is shown in FIG.

Example 6 In place of the white toner used in Example 1, 0.2 parts of black toner (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: AT-256), beige toner (Dainichi Seika Kogyo Co., Ltd.) Made by company, product name: Beige NSB64) 0.
In the same manner as in Example 1 except that 8 parts and 1 part of dark red toner (manufactured by Dainichiseika Kogyo Co., Ltd., trade name: AT TS999) were used, respectively, in the form of a swollen gel (jelly),
A black soft reaction product (h), a brown (beige) color soft reaction product (i), and a red (dark red) color soft reaction product (j) were obtained.

The reaction products (h) to (j) thus obtained were crushed in black with an average particle diameter of 7 mm by using the rotary blade color high speed cutter used in Example 1 and changing the diameter of the screen. (14), black crushed material (15) having an average particle diameter of 4 mm, black crushed material (16) having an average particle diameter of 2 mm, and average particle diameter of 7 mm
Brown crushed product (17), brown crushed product having an average particle size of 4 mm (18), brown crushed product having an average particle size of 2 mm (19),
Red crushed material with an average particle size of 7 mm (20), average particle size of 4 m
m red crushed material (21) and red particle crushed material (22) having an average particle diameter of 2 mm were obtained. The above reaction product (h), which is a block for crushed chips, measured using a helipass viscometer
The viscosities of (j) to 140,000 Pa · s and the hardness of HDD 35 were respectively.

25 parts of the crushed material (14),
3 parts of crushed material (15), 2 parts of crushed material (16), crushed material (1
7) 25 parts, crushed material (18) 0 part, crushed material (19) 5
Parts, crushed material (20) 35 parts, crushed material (21) 5 parts, crushed material (22) 0 parts, and titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: R-820) 0.1. Parts were added and mixed for 10 minutes with a Resicon mixer to obtain a mixture of multicolor particles having different sizes and having titanium oxide as the molding material (z) according to the present invention adhered to the surface. JISK710
Color Measur manufactured by Nippon Denshoku Industries Co., Ltd.
54, the color difference between the color tone of the cured product of the black crushed product and the tone of the cured product of titanium oxide when applied to the surface of the black crushed product and cured, as measured by an ing system. The color difference between the color tone of the cured product of the product and the color tone of the cured product of titanium oxide when applied and cured on the surface of the brown crushed product is 82, and the color tone of the cured product of the red crushed product and the color of the red product The color difference from the color tone of the cured product of titanium oxide when applied to the surface of the crushed product and cured was 125. The rate of change in weight of each of the crushed materials, which was measured in the same manner as in Example 1, that is, the rate of change in weight of the reaction products (h) to (j) was + 45%.

A mixture of the above-mentioned multicolor particles having different sizes of titanium oxide adhered to the surface was cured in the same manner as in Example 1 by using the same flat plate-shaped mold as in Example 1, and the surface was coated with After 1 mm sanding (polishing) and removing, a beautiful natural stone-like product consisting of large, medium and small multi-colored particles composed of three color particles of red and black brown and white streaky pattern parts as a molded product. We were able to obtain artificial marble.

The ratio of the grain portion of the obtained molded article to the surface area was 90%, and the proportion of the streak portion to the surface area was 10.
%Met. In addition, the molded product is densely packed with particles,
There were no voids or spaces that could be visually identified. The average adjacency ratio in the molded product is 65%, the average aspect ratio is 1.8, the large grain occupancy ratio is 80%, the ratio of the space portion in the artificial marble is 0%, and the black crushing is obtained from the image of the artificial marble. The color difference between the color tone of the cured product (black grains) and the color tone of the titanium oxide cured product is 52, and the color difference between the color tone of the cured product (brown grain) of the brown crushed product and the color tone of the titanium oxide cured product. 72. The color difference between the color tone of the cured product (red particles) of the red crushed product and the color tone of the cured product of titanium oxide was 121. The surface pattern of the artificial marble obtained in this example is shown in FIG.
Shown in.

[Example 7] 100 parts of syrup prepared in the same manner as in Example 1, 4 parts of hexamethylene diisocyanate trimer (manufactured by Nippon Polyurethane Industry Co., Ltd., trade name: Coronate HX), dibutyltin dilaurate. 01
Part, 1,1-bis (t-butylperoxy) -3,3,
5-trimethylcyclohexane (manufactured by NOF CORPORATION)
Product name: Perhexa 3M) 0.5 part, blue toner (manufactured by Sumika Color Co., Ltd., product name: Blue KR-5E382)
In the same manner as in Example 1, 0.05 parts were mixed to obtain a transparent and pale blue colored soft reaction product (k).

The reaction product (k) thus obtained was colored transparent and light blue by changing the diameter of the screen by using the rotary blade color high speed cutter used in Example 1 and having an average particle diameter of 2 m.
A crushed product (23) of m was obtained. The reaction product (k), which is a block for crushed chips, had a viscosity of 40,000 Pa · s and a hardness of H, measured using a helipass viscometer.
It was DD 15.

Next, 100 parts of the white crushed material (1) having an average particle diameter of 4 mm used in Example 1 and the crushed material (23) 1 were used.
Parts, iron black (manufactured by Dainichiseika Kogyo Co., Ltd., trade name: Black-1), 0.1 parts, were put into an open drum in the same manner as in Example 1, and in the same manner as in Example 1, the surface was covered with a book. A mixture of crushed materials of two colors having different sizes, to which iron black as the molding material (z) according to the invention was attached, was obtained. JIS K710
Color Measur manufactured by Nippon Denshoku Industries Co., Ltd.
color of the cured product of the crushed product (1) measured by an ing system, that is, the color tone of the cured product of the reaction product (a) obtained in Example 1 and the surface of the reaction product (a). The color difference from the color tone of the cured product of iron black when cured by the above is 52, and the color tone of the cured product of the crushed product (23), that is, the color tone of the cured product of the reaction product (k) and the above The color difference from the color tone of the iron black cured product when applied to the surface of the reaction product (k) and cured was 31. Further, the weight change rate of the crushed material (23) measured in the same manner as in Example 1, that is, the weight change rate of the reaction product (k) is +.
It was 45%.

A mixture of the above-mentioned crushed products having iron black adhered to the surface and having different sizes was cured in the same manner as in Example 1 by using the same flat plate-shaped mold as in Example 1, and the surface was about 1 mm.
When removed by sanding (polishing), a beautiful natural stone-like artificial marble with a black streak pattern formed on the ground with white particles partially mixed with transparent blue particles as a molded product. I was able to get

The ratio of the grain portion of the obtained molded product to the surface area was 70%, and the proportion of the streak portion to the surface area was 30.
%Met. In addition, the molded product is densely packed with particles,
There were no voids or spaces that could be visually identified. The average adjacency ratio in the molded product is 50%, the average aspect ratio is 2.0, the large grain occupancy ratio is 40%, the ratio of the space portion in the artificial marble is 0%, and the crushed material ( Color difference between the color tone of the cured product (white particles) of 1) and the color tone of the cured product of iron black, and the crushed product (23)
The color difference between the color tone of the cured product (transparent pale blue particles) and the color tone of the iron black cured product was 16. The surface pattern of the artificial marble obtained in this example is shown in FIG.

[Embodiment 8] A swollen gel-like (jelly-like) white soft material was obtained in the same manner as in Example 1 except that the amount of the white toner was changed from 1.0 part to 0.1 part. The reaction product (l) was obtained.

The obtained reaction product (l) was cut in the same manner as in Example 1 to give a white crushed product (2
4) was obtained. The viscosity of the reaction product (l), which is a block for crushed chips, measured by a helipass viscometer is 1
The hardness was 40,000 Pa · s and the hardness was HDD 35.

Next, 100 parts of the crushed material (24), iron black (manufactured by Dainichiseika Kogyo Co., Ltd., trade name: Black-1)
0.3 part was put into an open drum in the same manner as in Example 1, and in the same manner as in Example 1, a crushed product having iron black as the molding material (z) according to the present invention attached to the surface was obtained. . J
Based on IS K7105, the color tone of the cured product of the crushed material (24) measured by Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd., that is, the color tone of the cured product of the reaction product (l) and the reaction. The color difference from the color tone of the cured product of iron black when applied on the surface of the product (l) and cured was 59. The rate of change in weight of the crushed product (24) measured in the same manner as in Example 1, that is, the rate of change in weight of the reaction product (l) was + 45%.

The crushed material (24) with iron black adhered to the surface
Was cured in the same manner as in Example 1 using the same flat plate-shaped mold as in Example 1, and the surface was removed by sanding (polishing) by about 1 mm. We were able to obtain a beautiful natural stone-like artificial marble with a black streaky pattern formed on it.

At first glance, the above-mentioned artificial marble seems to have a larger matrix portion as compared with the artificial marbles obtained in the other examples, but this is because the amount of the white toner in the grain portion is small and the amount of white toner is small. This is because a black streak pattern is partially visible in the ground part consisting of grains. The grain part of the obtained molded product occupies 70% of the surface area, and the streak part occupies 30% of the surface area. It was The molded product was densely packed with particles, and there were no voids or spaces that could be visually discerned. The average adjacency ratio in the molded product is 50%, the average aspect ratio is 2.0, the large grain occupancy ratio is 40%, the ratio of the space portion in the artificial marble is 0%, and the crushed material ( The color difference between the color tone of the cured product (white particles) of 24) and the color tone of the iron black cured product was 48. The surface pattern of the artificial marble obtained in this example is shown in FIG.

Example 9 In Example 1, 0.1 parts of a brown toner (manufactured by Dainichiseika Kogyo KK, trade name: AT-829) and a yellow toner were used in place of the white toner in the obtained syrup. (Product name: A manufactured by Dainichi Seika Kogyo Co., Ltd.
T-1195) except that 0.05 part each was added.
The mixture was stirred and mixed and degassed in vacuo in the same manner as in Example 1 to obtain a beige mixture (iv).

Further, 0.5 part of the toner to be used is red toner (manufactured by Dainichiseika Kogyo KK, trade name: ATTS999) and brown toner (manufactured by Dainichi Seika Kogyo KK, trade name: A).
T-829) A reddish brown mixture (v) was obtained in exactly the same manner except that the amount was changed to 0.5 part.

Then, in the same box-shaped container as used in Example 1, first, the beige mixture (iv) described above was added.
20 mm thick, and then 2 mm thick red-brown mixture (v) described above was slowly poured so as not to mix the two as much as possible, and the 20 mm beige mixture (iv) 2), a 2 mm reddish brown mixture (v) was layered on top of the above) to obtain a layered (2 layers) mixture. Then, in the same manner, from above the two-layer mixture,
mm of beige mixture (iv) is poured over it,
The above-mentioned reddish brown mixture (v) having a thickness of 2 mm was injected, and this operation was further continued to give a total of 4 layers of beige mixture (iv) and 4 layers of reddish brown mixture (v). An alternating layered mixture was obtained. Finally, 150 mm of a beige mixture (iv) was slowly poured onto this layered mixture, and the mixture was left to stand overnight for reaction to occur, and beige layers and reddish brown layers were alternately laminated. A soft reaction product (m) in the form of a swollen gel was obtained.

The obtained reaction product (m) was cut in the same manner as in Example 1, and the beige mixture (iv) was used as the base.
A crushed product with a pattern (25) having an average particle size of 7 mm in which a reddish brown mixture (v) was mixed in a flow pattern in the ground was obtained.

The viscosity of the reaction product (m) measured using a helipass viscometer was 125,000 Pa · s. The hardness of the reaction product (m) measured using a type D durometer hardness meter was HDD 17.

Next, the crushed product with a pattern (25) was placed in an open drum in the same manner as in Example 1, and further titanium oxide (manufactured by Ishihara Sangyo Co., Ltd., trade name: R-820).
0.3 part was added, and in the same manner as in Example 1, a patterned beige crushed product (26) having titanium oxide as the molding material (z) according to the present invention attached to the surface was obtained. .
The beige mixture (iv) is left to stand for a whole day and night to react, and the reaction product (n) is cured to obtain a color tone of the cured product and the reaction product (n) is coated on the surface. The color difference from the color tone of the cured product of titanium oxide when cured was 7.4. Further, the color tone of the cured product obtained by curing the reaction product (o) obtained by allowing the red-brown mixture (v) to stand for one day and reacting, and applying it to the surface of the reaction product (o). The color difference with the color tone of the cured product of titanium oxide was 76 when cured. The color difference is J
Based on ISK7105, it was measured by Color Measuring System manufactured by Nippon Denshoku Industries Co., Ltd. Further, the weight change rate of the crushed material (25) measured in the same manner as in Example 1, that is, the weight change rate of the reaction product (m) was + 45%.

The crushed product (26) having titanium oxide adhered to its surface was cured in the same manner as in Example 1, and the surface was removed by sanding (polishing) for about 1 mm. We were able to obtain artificial marble with a beautiful design, similar to natural stone, with a partially reddish brown pattern and white streaks around beige grains.

The particle portion of the obtained molded product occupies 91% of the surface area, and the streak portion occupies 9% of the surface area.
Met. The molded product was densely packed with particles, and there were no voids or spaces that could be visually identified. The average adjacency ratio in the molded product was 90%, the average aspect ratio was 2.1, the large particle occupation ratio was 85%, and the ratio of the space portion in the artificial marble was 0%. The color difference between the beige color of the cured product of the product (m) and the color tone of the cured titanium oxide (white) is 10, and the color tone of the reddish brown part of the cured product of the reaction product (m) Color difference with the color tone of the cured product of titanium oxide (white) is 7
It was 8. The surface pattern of the artificial marble obtained in this example is shown in FIG. 15, and its binarized image is shown in FIG.

[Embodiment 10] A swollen gel-like soft material of 5 colors of black, brown, beige, ash and white was prepared in the same manner as in Embodiment 1 except that the toner was changed as shown in Table 1. A reaction product was obtained. Each of the obtained reaction products was cut in the same manner as in Example 1 to obtain crushed products (grains) of 5 colors having an average particle size of 4 mm.

The viscosities of the respective reaction products measured with a helipass viscometer are 125,000 Pa · s (black), 140,000 Pa · s (brown), 140,00, respectively.
0Pa ・ s (Beige), 125,000Pa ・ s
(Gray) and 135,000 Pa · s (white).
Further, the hardness of each reaction product measured using a type D durometer hardness meter is, in order, HDD (black) 1
5, HDD 35, HDD 35, HDD 15, HD
It was D20.

Next, molding was carried out in the same manner as in Example 1 except that 20 parts of each crushed material of each color described above was mixed without using an additive for forming a streak pattern. It was That is, the mixture of the crushed materials of the respective colors described above was cured in the same manner as in Example 1 by using the same flat plate-shaped mold as in Example 1, and the surface was removed by sanding (polishing) by about 1 mm. As a result, an artificial marble having a characteristic natural stone-like appearance in which grains of black, brown, beige, ash, and white are mixed can be obtained as a molded product.

In the above-mentioned molded product, the average aspect ratio was 1.8, the proportion of large grains occupied was 97%, and the proportion of the space portion in the artificial marble was 0%. The ratio of the particle portion of the obtained molded product to the surface area was 100%, the molded product was densely packed with particles, and there was no visually discernible void or space. The rate of change in weight of the crushed material of each color, which was measured in the same manner as in Example 1, that is, the rate of change in weight of the reaction product of each color, was + 45%. The surface pattern of the artificial marble obtained in this example is shown in FIG.

[0230]

[Table 1]

[0231]

EFFECTS OF THE INVENTION According to the present invention, by using the above-mentioned swelling gel-like molding material, when heat and pressure molding is performed,
The shape of the crushed surface can be maintained. Further, according to the present invention, on the surface of the swelling gel-like molding material, the color tone of the cured product of the swelling gel-like molding material, and when applied to the surface of the swelling gel-like molding material and cured. Molding material (z) for coloring having a color difference of 3 or more from the color tone of the cured product
By adhering in the above proportion, the interface of the cured product when the swelling gel-like molding material is cured can be emphasized, and the natural stone-likeness can be expressed.

Therefore, according to the present invention, a fine streak-like line pattern is formed around the granular resin cured product (Y) obtained by curing the swelling gel-like molding material having a linear crushing surface. However, there is an effect that it is possible to provide a method for producing an artificial marble having a design extremely similar to natural stone, in which the boundary between the granular resin cured products (Y) is emphasized by a color tone different from that of the particles.

The artificial marble according to the present invention thus obtained is composed of an aggregate of the granular resin cured products (Y) integrally formed and having a linear crush surface as described above. , The granular resin cured products (Y) adjacent to each other have a joint surface of a shape that is substantially combined with each other,
A design in which a linear streaky interface made of a cured product (Z) having a color tone different from that of the adjacent granular resin cured product (Y) is formed between the adjacent granular resin cured products (Y). Have

The artificial marble according to the present invention thus obtained is composed of the granular resin cured product (Y) and the matrix as described above, and the granular resin cured product (Y) is , The matrix occupies 70 to 99% of the surface area of the artificial marble, the matrix occupies 30 to 1% of the surface area of the artificial marble, and the granular resin cured products (Y) adjacent to each other, The above-mentioned granular resin cured product (Y) having joint surfaces that are substantially combined with each other
Of 50% or more, the average aspect ratio of the granular resin cured product (Y) is 1.1 or more and 5.0 or less, and the large grain occupancy ratio is 20% or more. .

Further, the artificial marble according to the present invention is composed of an aggregate of granular resin cured products (Y) integrally formed and having a linear crushing surface as described above, and is adjacent to each other. The resin cured products (Y) of (1) have joint surfaces of shapes that are substantially combined with each other, and the granular resin cured products (Y) are formed by the sharply crushed surfaces of the granular resin cured products (Y). In the region surrounded by the apex of Y) and the granular resin cured product (Y) adjacent to the granular resin cured product (Y), each granular resin cured product (Y) surrounding the region. It has a design in which a cured product (Z) having a color tone different from that is filled.

Therefore, according to the present invention, there is provided a method for producing an artificial marble having a design extremely similar to natural stone, in which the boundary between the granular resin cured products (Y) is emphasized by a color tone different from that of the particles. There is an effect that can be done.

Further, according to the present invention, as the swelling gel-like molding material (y), a plurality of colors (a plurality of types) of swelling gel-like molding material (y) having different color tones such as being colored in different colors are used. By using the above-mentioned molding material (y) without adhering the molding material (z) to the surface of the molding material (y) and molding under heating and pressing as it is, thereby hardening the granular resin having a linear crush surface. Granular resin cured product (Y) having a joint surface of a shape in which mutually adjacent granular resin cured products (Y) are formed of an aggregate of objects (Y) and are directly bonded to each other. It is possible to obtain artificial marble having a design in which (Y) have different color tones and a clear interface is formed between the granular resin cured products (Y) adjacent to each other.

Therefore, according to the present invention, since the granular resin cured products (Y) adjacent to each other have different color tones, the interface between the granular resin cured products (Y) adjacent to each other is emphasized. It is possible to provide a method of manufacturing an artificial marble having a design extremely similar to that of natural stone.

[Brief description of drawings]

FIG. 1 is a diagram showing a surface pattern of an artificial marble obtained by using a method for manufacturing an artificial marble according to an embodiment of the present invention.

FIG. 2 is a diagram showing a surface pattern of a conventional artificial marble.

3 is a diagram showing a surface pattern of the artificial marble obtained in Example 1. FIG.

FIG. 4 is a diagram showing a surface pattern of a commercially available artificial marble shown in Comparative Example 2.

5 is a diagram showing a binarized image obtained by performing image processing on FIG. 4. FIG.

6 is a diagram showing a surface pattern of the artificial marble obtained in Example 2. FIG.

7 is a diagram showing a binarized image obtained by performing image processing on FIG. 6;

8 is a diagram showing a surface pattern of the artificial marble obtained in Example 3. FIG.

9 is a diagram showing a binarized image obtained by performing image processing on FIG. 8. FIG.

10 is a diagram showing a surface pattern of the artificial marble obtained in Example 4. FIG.

11 is a diagram showing a surface pattern of the artificial marble obtained in Example 5. FIG.

12 is a diagram showing a surface pattern of the artificial marble obtained in Example 6. FIG.

13 is a diagram showing a surface pattern of the artificial marble obtained in Example 7. FIG.

14 is a diagram showing a surface pattern of the artificial marble obtained in Example 8. FIG.

15 is a diagram showing a surface pattern of the artificial marble obtained in Example 9. FIG.

16 is a diagram showing a binarized image obtained by performing image processing on FIG.

17 is a diagram showing a surface pattern of the artificial marble obtained in Example 10. FIG.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Masaaki Chatan             Osaka Prefecture Ibaraki City Ekimae 1-2-10 No.             And L Marble Co., Ltd. F term (reference) 4J002 CK02W CK02X CK02Y DE139                       DE146 FD097 FD098 FD099                       GL02

Claims (6)

[Claims] 1. A cured resin (Y) in the form of particles and a matrix, wherein the cured resin (Y) in the form of particles constitutes 70 to 99% of the surface area of the artificial marble, and a matrix. Is 30 to 1% of the surface area of the artificial marble
And the granular resin cured product (Y) adjacent to each other
Each of them has a joint surface of a shape which is substantially combined with each other, and the average adjoining ratio of the granular resin cured product (Y) is 50.
% Or more, the average aspect ratio of the granular resin cured product (Y) is 1.1 or more and 5.0 or less, and the large particle occupancy ratio is 2
Artificial marble characterized by being 0% or more. 2. An integrally formed aggregate of granular resin cured products (Y) having a linear crushing surface, and the granular resin cured products (Y) adjacent to each other are substantially formed. A streak formed of a cured product (Z) having a color tone different from that of the granular resin cured product (Y) adjacent to each other, which has a joint surface of a shape to be combined with each other Artificial marble characterized by the formation of a clear interface. 3. An integrally formed aggregate of granular resin cured products (Y) having a linear crushing surface, and the granular resin cured products (Y) adjacent to each other are substantially formed. The apex of the granular resin cured product (Y), which has a joint surface having a shape to be combined with each other and is formed by an acute crushing surface of the granular resin cured product (Y), and the granular resin cured product ( Y) and a plurality of granular resin cured products (Y) adjacent to each other are filled with a cured product (Z) having a color tone different from that of each granular resin cured product (Y) surrounding the region. Artificial marble that is characterized by being. 4. An integrally molded aggregate of granular resin cured products (Y) having a linear crushing surface, and adjacent granular resin cured products (Y) are combined with each other. It has a shaped joint surface and is directly joined, and the granular resin cured products (Y) adjacent to each other have different color tones, and the granular resin cured products (Y) adjacent to each other are clearly defined. Artificial marble characterized by the formation of various interfaces. 5. A swelling gel-like molding material obtained by crushing a swelling gel obtained by swelling a compound having a three-dimensional cross-linking bond with a liquid monomer which is polymerized by a radical polymerization reaction into a predetermined size. The weight change rate when completely immersed in an excess amount of the above-mentioned monomer is 0 which is not substantially dissolved in the above-mentioned monomer.
The color tone of the cured product of the swelling gel-like molding material on the surface of the swelling gel-like molding material, which is within the range of + 200%, and when the surface of the swelling gel-like molding material is applied and cured. Molding material (z) having a color difference of 3 or more from the color tone of the cured product
Is attached at a rate of 0.01% by weight or more and 30% by weight or less of the total amount of the molding material (z) and the swelling gel-like molding material, and molding is performed under heating and pressurization. Marble manufacturing method. 6. A compound (A) is a compound having a plurality of reactive substituents selected from a hydroxyl group and a carboxyl group, and a compound (B) is a polyfunctional polyisocyanate compound,
A compound which is at least one of an organoaluminum compound and an alkaline earth metal oxide, the compound (A)
And at least one of the compounds (B) contains a tri- or higher functional compound, and the compounds (A) and (B) are three-dimensionally cross-linked by the reaction between the reactive substituent and the compound (B). The reaction compound formed by swelling is a swollen gel swollen with a liquid monomer that is polymerized by a radical polymerization reaction, and the swollen gel measured with a helipass viscometer is 1,000 Pa · s or more. On the surface of the swelling gel-like molding material obtained by crushing to a size of, and the color tone of the cured product of the swelling gel-like molding material, and when it is applied to the surface of the swelling gel-like molding material and cured. The molding material (z) having a color difference of 3 or more from the color tone of the cured product is 0.0 of the total amount of the molding material (z) and the swelling gel-like molding material.
A method for producing an artificial marble, which comprises adhering at a ratio of 1% by weight or more and 30% by weight or less and molding under heating and pressurization.