KR100728589B1 - Marble chip, method for preparing the same and artificial marble using the same - Google Patents

Abstract

A marble chip including urethane acrylate or epoxy acrylate halide based binder and resin composition is provided to be efficiently used to produce artificial marble having texture and appearance similar to engineered stone as well as favorable thermoplastic and processing properties by comprising the binder and acryl based cross-linking monomer resin composition. The marble chip is prepared by curing a resin composition comprising 10-50wt. parts of acryl based cross-linking monomer as well as 50-90wt. parts of a binder which is selected from halogenated urethane acrylate, halogenated epoxy acrylate and mixture thereof. The resin composition further includes additive selected from a group consisting of a coloring agent, a defoaming agent, a coupling agent, a UV absorber, a light diffuser, a polymerization inhibitor, a flame-retardant agent, a thermal stabilizer and mixture thereof. The halogenated urethane acrylate has number average molecular weight of 900 to 4,000 and the halogenated epoxy acrylate has number average molecular weight of 600 to 3,500.

Description

Marble Chip, Method for Preparing the Same and Artificial Marble Using the Same}

       Figure 1 shows the artificial marble surface photograph prepared in Example 5.

       Figure 2 shows the artificial marble surface photograph prepared in Example 6.

       Figure 3 shows the artificial marble surface photograph prepared in Example 9.

       Figure 4 shows the artificial marble surface photograph prepared in Example 10.

Field of invention

The present invention relates to a marble chip, a method for manufacturing the same, and an artificial marble using the same. More specifically, the present invention by applying a resin composition comprising a halogenated acrylate binder and an acrylic crosslinkable monomer to a chip expressing the pattern of artificial marble, the bonding properties with the base material and the same specific gravity and wear characteristics as the base material The present invention relates to a marble chip having a high specific gravity, a high refractive index, and a high transparency, and an artificial marble using the same.

Background of the Invention

In general, artificial marble is divided into two types, acrylic and unsaturated polyester, depending on the resin (resin). Acrylic acrylic marble has characteristics such as excellent appearance, soft texture, excellent weather resistance, etc., and the demand for various top plates and interior materials is continuously increasing.

Acrylic artificial marble is a syrup mixed with a monomer such as methyl methacrylate and polymethyl methacrylate, and a marble chip that implements an inorganic filler, color, and pattern is mixed with a polymerization initiator. After dissolution, it is usually produced by casting at an appropriate temperature.

Various kinds of marble chips are put to realize various colors and patterns of artificial marble. In particular, the appearance of artificial marble has a big influence on the value of the product due to the nature of the marble chip.

The marble chip may be hardened into a plate by a method similar to acrylic artificial marble, and then crushed to obtain various particle sizes. An acrylic material, which is the same material as the matrix, is usually used.

In recent years, transparent marble chips have been used to give the crude artificial marble a light and refined feel or to give it a jewel-like feel. Recently, the demand is increasing.

Artificial marble using a transparent marble chip that has been commercialized to date is manufactured using polymethyl methacrylate (PMMA) resin or unsaturated polyester resin as a marble chip. However, the transparent chips made of the PMMA resin or unsaturated polyester resin have a specific gravity of 1.15 to 1.24, which is lower than the specific gravity of the matrix, so that when the artificial marble is manufactured, all of the transparent chips float to the upper layer so that no surface layer is formed. There is a problem that a transparent chip does not exist or uniform chip distribution is impossible. In addition, to manufacture the artificial marble having a transparent chip distribution on the surface portion has the disadvantage that the amount of use of the chip more than about twice the base material, there is another problem that is difficult to adjust the thickness of the artificial marble.

Therefore, in order to increase the specific gravity to the level of the base metal, an inorganic filler such as aluminum trihydrate, barium sulfate, or silica should be added. However, when such an inorganic filler is added, there is a problem in that transparency is remarkably decreased.

Meanwhile, engineered stone in the form of engineered stone, which can be manufactured using natural silica minerals such as quartz, silica sand, and crystal, or transparent chips such as vitrified silica compounds such as glass or molten glass, Although there is an advantage in chip transparency, it cannot be produced in the production of acrylic artificial marble, which is a conventional continuous production method due to problems such as chip settling and chip sanding.

The reason is that the MOS hardness of the acrylic compound as the base material and the silica and the silica compound as the chip showing the pattern or the pattern is different, so that the smoothness does not come out due to the difference in the sanding properties after the plate is manufactured.

Therefore, the transparent chip of artificial marble should not only have a high refractive index but also adjust the specific gravity to the same as the base material so that the chip does not sink regardless of the molding time, so that it can have a constant pattern regardless of the curing time, and the same polishing as the base material. It is required to have both flatness and smoothness at the same time after manufacturing it with artificial marble.

MEANS TO SOLVE THE PROBLEM In order to solve the said problem, by hardening the resin composition containing a halogenated acrylate binder and an acryl-type crosslinkable monomer, it is excellent in the binding force with a base material, and has the same specific gravity and the same specific gravity as the base material, and high specific gravity and high refractive index. In addition, it has begun to develop marble chips having high transparency and artificial marble using the same.

An object of the present invention is to provide a marble chip having a specific gravity of 1.50 to 1.67 and a manufacturing method thereof.

Another object of the present invention is to provide a marble chip and a method of manufacturing the same which can realize a uniform pattern regardless of curing time or molding time.

Still another object of the present invention is to provide a marble chip having excellent transparency and refractive index and a method of manufacturing the same.

It is still another object of the present invention to provide a marble chip and a method of manufacturing the same having a sanding property and a hardness of the matrix.

Still another object of the present invention is to provide a marble chip having excellent bonding force with a base material and a method of manufacturing the same.

Another object of the present invention is to provide a marble chip and a method for manufacturing the same that can exhibit a three-dimensional texture.

It is still another object of the present invention to provide a marble chip and a method of manufacturing the same, which are excellent in pigment dispersibility and binding property with matrix.

Still another object of the present invention is to provide a marble chip having excellent chemical resistance and a manufacturing method thereof.

Still another object of the present invention is to provide an artificial marble that can have the same appearance and texture as the engineered stone by applying the marble chip.

Still another object of the present invention is to provide an artificial marble capable of continuous production by applying the marble chip.

Still another object of the present invention is to provide an artificial marble having excellent thermal workability by applying the marble chip.

Still another object of the present invention is to provide an artificial marble having excellent smoothness by applying the marble chip.

The above and other objects of the present invention can be achieved by the present invention described below.

Summary of the Invention

A marble chip of the present invention is formed by curing a resin composition comprising an acrylic crosslinkable monomer and a binder selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates and mixtures thereof.

In one embodiment of the present invention, the resin composition includes 50 to 90 parts by weight of the binder and 10 to 50 parts by weight of the acrylic crosslinkable monomer. The resin composition may further include additives such as color additives, antifoaming agents, coupling agents, ultraviolet absorbers, light diffusing agents, polymerization inhibitors, and the like.

In another embodiment of the present invention, the number average molecular weight of the halogenated urethane acrylate is 900 to 4,000. The number average molecular weight of the halogenated epoxy acrylate is 600 to 3,500.

In another embodiment of the present invention, the acrylic crosslinkable monomer is methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, dodecyl (meth) acryl Laterate, octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) acrylate, meth Methoxyphenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,3-propylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, tree Ethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylate, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methyl propanediol Di (meth) acrylate, polyethylene glycol di (meth) acrylate, and the like.

In another embodiment of the present invention, the resin composition may include a styrene monomer, a halogenated styrene, vinyl toluene, diallyl terephthalate, diallyl phthalate, diallyl carbonate, divinylbenzene, alphamethylstyrene, alpha together with an acrylic crosslinkable monomer. It may further comprise a crosslinking agent consisting of methyl styrene dimer and mixtures thereof.

In another embodiment of the present invention, a marble chip may be further added to the resin composition to form a marble chip having a chip-in-chip form.

In another embodiment of the present invention, it is possible to form a marble chip having a flow pattern or a multilayer structure by using two or more kinds of resin compositions having different colors or transparency with the resin composition.

Artificial marble of the present invention includes the marble chip.

Marble chip manufacturing method of the present invention comprises the steps of preparing a resin composition by mixing an acrylic cross-linkable monomer in a binder selected from the group consisting of halogenated urethane acrylate, halogenated epoxy acrylate and mixtures thereof; Curing the resin composition to prepare a cured product; And crushing the cured product.

In one embodiment of the present invention, about 0.03 to 2.5 parts by weight of a curing agent is added to 100 parts by weight of the resin composition to cure.

In an embodiment of the present invention, the cured product is crushed to an average diameter of about 0.1 to 30 mm.

In another embodiment of the present invention, the metal is deposited on the cured product and then crushed.

In another embodiment of the present invention, the resin composition may be prepared by further adding additives such as color additives, antifoaming agents, coupling agents, ultraviolet absorbers, light diffusing agents, and polymerization inhibitors.

In another embodiment of the present invention can be manufactured in the form of a chip-in-chip by further adding a marble chip to the resin composition.

In another embodiment of the present invention, the resin composition may include a styrene monomer, a halogenated styrene, vinyl toluene, diallyl terephthalate, diallyl phthalate, diallyl carbonate, divinylbenzene, alphamethylstyrene, alpha together with an acrylic crosslinkable monomer. It can manufacture by further adding crosslinking agents, such as methylstyrene dimer.

In another embodiment of the present invention, a flow pattern or a multilayer structure may be formed using two or more kinds of resin compositions having different colors or transparency as the resin composition.

Marble chips produced according to the above method has a specific gravity in the range of 1.50 to 1.67.

Artificial marble of the present invention includes the marble chip.

Hereinafter, specific contents of the present invention will be described in detail below.

Detailed Description of the Invention

A marble chip of the present invention is formed by curing a resin composition comprising an acrylic crosslinkable monomer and a binder selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates and mixtures thereof.

The binder is 50 to 90 parts by weight, preferably 60 to 90 parts by weight, more preferably 70 to 90 parts by weight. The acrylic crosslinkable monomer is 10 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 10 to 30 parts by weight. When the content of the binder is less than 50 parts by weight, the high specific neutralization effect is lowered, and when used in excess of 90 parts by weight, the viscosity is too high, there is a problem that the workability is poor.

The binder in the present invention is selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates and mixtures thereof, of which halogenated epoxy acrylates are preferred.

The resin composition may further include conventional additives such as a color imparting agent, an antifoaming agent, a coupling agent, an ultraviolet absorber, a light diffusing agent, a polymerization inhibitor, an antistatic agent, a flame retardant, a heat stabilizer, and the like. The colorant includes inorganic or organic pigments, dyes and the like, and is 0.0001 to 10.0 parts by weight.

The number average molecular weight of the halogenated urethane acrylate is 900 to 4,000. The number average molecular weight of the halogenated epoxy acrylate is 600 to 3,500. When the molecular weight is less than the molecular weight range, the crosslinking density per unit volume is increased and becomes brittle. When the molecular weight is exceeded, the crosslinking density is low, the softening is likely to occur, and the viscosity is too high.

Specific examples of the acrylic crosslinkable monomer include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, dodecyl (meth) acrylate, and octadecyl (Meth) acrylate, methylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) acrylate, methoxyphenyl (meth) ) Acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,3- Propylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (meth) Acrylate, triethyleneglycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa ( Meth) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylic acid, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methylpropanedioldi ( Meta) acrylate, polyethylene glycol di (meth) acrylate, and the like.

In another embodiment of the present invention, the resin composition is a styrene monomer, halogenated styrene, vinyltoluene, diallyl terephthalate, diallyl phthalate, diallyl carbonate, divinylbenzene, alphamethylstyrene, alpha together with an acrylic crosslinkable monomer. It may further comprise a crosslinking agent consisting of methyl styrene dimer and mixtures thereof.

Marble chip of the present invention is to prepare a resin composition by mixing an acrylic crosslinkable monomer in a binder selected from the group consisting of a halogenated urethane acrylate, a halogenated epoxy acrylate and a mixture thereof, to cure the resin composition to prepare a cured product And it is prepared by the step of crushing the cured product.

The resin composition may include a binder and an acrylic crosslinkable monomer, and may further include additives such as colorants, antifoaming agents, coupling agents, ultraviolet absorbers, light diffusing agents, polymerization inhibitors, antistatic agents, flame retardants, and heat stabilizers. have.

In an embodiment of the present invention, a curing agent may be used when curing the resin composition. As the curing agent, benzoyl peroxide, lauroyl peroxide, bis (4-tertarybutylcyclohexyl) peroxydicarbonate, etc. may be used, but is not limited thereto. The curing agent is cured by adding 0.03 to 2.5 parts by weight of the curing agent, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin composition. The curing method is not particularly limited, and may be cured in a heat source condition of 50 to 180 ℃. In order to control the curability, an amine or sulfonic acid compound may be added together with the curing agent or a saponified salt of copper, cobalt, potassium, calcium, zirconium, and zinc may be added.

In an embodiment of the present invention, the cured product is crushed to an average diameter of 0.1 to 30 mm. The shredding method can be easily carried out by those skilled in the art.

In another embodiment of the present invention, a metal such as aluminum or silver is deposited on the cured product and then crushed. Thus, when the metal chip is deposited and the crushed marble chip is added to the artificial marble, it can be more three-dimensional and produce a jewelry-like effect.

In another embodiment of the present invention, a marble chip may be further added to the resin composition. The marble chip may be transparent, translucent, or opaque, and a mixture thereof may be used. As the marble chip added to the resin composition, the marble chip prepared in the present invention may be used, and a marble chip obtained by pulverizing an ordinary acrylic or unsaturated ester artificial marble may be used. In this way, the marble chip obtained by further adding the marble chip to the resin composition, curing and pulverizing is in the form of a chip-in-chip, and can produce more various patterns.

In another embodiment of the present invention, the resin composition may be a styrene monomer, bromostyrene, vinyltoluene, diallyl terephthalate, diallyl phthalate, diallyl carbonate, divinylbenzene, alphamethylstyrene, together with an acrylic crosslinkable monomer. Crosslinking agents, such as alpha methyl styrene dimer, can be added further.

In another specific example of this invention, the said resin composition uses 2 or more types of resin compositions from which a color and transparency differ. As a result, it is possible to form a flow pattern or a multi-layer structure on the high specific gravity marble chip. For example, after preparing two or more kinds of resin compositions having different colors from each other, and simultaneously injecting the two or more kinds of resin compositions into a curing conveyor belt, a cured product formed with a flow pattern is formed, and when it is pulverized, a flow pattern is formed. Marble chips can be manufactured. The said 2 or more types of resin can use the said transparent resin composition and an opaque resin composition.

Marble chips produced according to the method of the present invention have a specific gravity in the range of 1.50 to 1.67, preferably 1.57 to 1.64.

Artificial marble of the present invention includes the marble chip.

The artificial marble is prepared by curing the curable composition mixed with the marble chip and the resin syrup prepared in a conventional manner. As the resin syrup, an acrylic resin or an unsaturated polyester type may be used, and preferably, an acrylic resin. The curable composition may further include inorganic fillers or conventional additives such as calcium carbonate, aluminum hydroxide, silica, alumina, barium lactate, magnesium hydroxide, and the like. It can be easily carried out by a person who has.

Since the artificial marble of the present invention uses a marble chip having a specific gravity of 1.50 to 1.67, a uniform pattern can be realized regardless of a curing time or a molding time, and continuous production is possible.

The surface texture of the artificial marble using the marble chip can produce a surface texture similar to that of the engineered stone and has excellent workability. Therefore, the countertop of the sink countertop of the kitchen, the countertop of the vanity table, the reception desk of a bank and a general store can be used. It can be applied to a wide range of tops and decorative articles.

In addition, the artificial marble can be pulverized and used as a marble chip of a chip Hengtae, a chip having a transparent chip formed therein.

The invention can be better understood by the following examples, which are intended to illustrate the invention and are not intended to limit the scope of protection defined by the appended claims.

Example

Example  1 to 4: Marble Chip  Produce

Example 1

0.2 parts by weight of benzoyl peroxide and 100 parts by weight of benzoyl peroxide and 100 parts by weight of a resin composition consisting of 85 parts by weight of a urethane bromide acrylate, 5 parts by weight of bromostyrene and 10 parts by weight of methyl methacrylate, and bis (4-tertarybutylcyclohexyl) peroxydicarbo 0.5 parts by weight of nate was mixed, cured at 50 ° C., and then crushed to prepare a high specific gravity marble chip having a specific gravity of 1.597.

Example 2

To 100 parts by weight of a resin composition consisting of 80 parts by weight of brominated epoxy acrylate, 5 parts by weight of styrene monomer and 15 parts by weight of methyl methacrylate, 0.01 part by weight of phthalocyanine green was added as a color imparting agent, and 0.2 parts by weight of benzoyl peroxide as a curing agent and bis ( The same procedure as in Example 1 was carried out except that 0.2 part by weight of 4-tert-butylcyclohexyl) peroxydicarbonate was mixed. The marble chip had a specific gravity of 1.595 and was green.

Example 3

0.2 parts by weight of benzoyl peroxide and 100 parts by weight of benzoyl peroxide and bis (4-tertylbutylcyclohexyl) peroxydicarbonate in 100 parts by weight of a resin composition consisting of 85 parts by weight of brominated epoxy acrylate, 5 parts by weight of styrene monomer and 10 parts by weight of methyl methacrylate. The same procedure as in Example 1 was carried out except that 0.2 parts by weight were mixed. The specific gravity of the manufactured marble chip was 1.624.

Example 4

A mixture of 0.2 parts by weight of benzoyl peroxide and 0.5 parts by weight of bis (4-tertarybutylcyclohexyl) peroxydicarbonate in 100 parts by weight of a resin composition consisting of 85 parts by weight of brominated epoxy acrylate and 15 parts by weight of methyl methacrylate. Except that was carried out in the same manner as in Example 1. The specific gravity of the manufactured marble chip was 1.618.

Comparative Example 1

90 parts by weight of urethane bromide acrylate, 10 parts by weight of styrene monomer, 0.2 parts by weight of benzoyl peroxide and 0.5 parts by weight of bis (4-tertarybutylcyclohexyl) peroxydicarbonate were mixed. Was carried out in the same manner as in Example 1. The marble chip had a specific gravity of 1.601.

Comparative Example 2

80 parts by weight of brominated epoxy acrylate and 20 parts by weight of styrene monomer were mixed with 0.2 parts by weight of benzoyl peroxide and 0.5 parts by weight of bis (4-tertylbutylcyclohexyl) peroxydicarbonate. And it was carried out in the same manner as in Example 1. The specific gravity of the manufactured marble chip was 1.583.

Comparative Example 3

Except that the mixture of 2 parts by weight of trimethyl propane triacrylate, 0.1 parts by weight of normal dodecyl mercaptan and 1.0 parts by weight of benzoyl peroxide to 100 parts by weight of a syrup made by dissolving polymethyl methacrylate in methyl methacrylate. It carried out similarly to Example 1. The specific gravity of the manufactured marble chip was 1.183.

Comparative Example 4

It carried out similarly to Example 1 except having mixed 100 weight part of unsaturated polyester resins (Aekyung Chemical Co., Ltd., TP-145X) and 1.0 weight part of benzoyl peroxides. The specific gravity of the manufactured marble chip was 1.203.

Comparative Example 5

Example 1 except 100 parts by weight of a vinyl ester resin (DION-9120, manufactured by Aekyung Chemical Co., Ltd.), and 1.0 part by weight of benzoyl peroxide, prepared by mixing 60 parts by weight of epoxy acrylate oligomer and 40 parts by weight of styrene monomer. Was performed in the same manner. The specific gravity of the manufactured marble chip was 1.194.

Example  5 to 8: artificial marble

Example 5

180 parts by weight of aluminum hydroxide, 2 parts by weight of trimethylpropanetriacrylate, 0.1 part by weight of normaldodecyl mercaptan, 0.1 part by weight of an antifoaming agent and a dispersant, respectively, in 100 parts by weight of a syrup made by dissolving polymethylmethacrylate in methyl methacrylate. 50 parts by weight of the transparent chip prepared in Example 1 was added to the composition in which 1.0 parts by weight of benzoyl peroxide was mixed, and stirred well, followed by curing at a temperature of 60 ° C. by a continuous molding method to prepare artificial marble. The prepared artificial marble surface photograph is shown in FIG.

Example 6

The same procedure as in Example 5 was carried out except that the colored transparent chip prepared in Example 2 was used. The prepared artificial marble surface photograph is shown in FIG. 2.

Example 7

The same procedure as in Example 5 was carried out except that the chip prepared in Example 3 was used.

Example 8

The same procedure as in Example 5 was carried out except for using the chip prepared in Example 4.

Comparative Example 6

The same procedure as in Example 5 was carried out except that the chip prepared in Comparative Example 1 was used.

Comparative Example 7

The same procedure as in Example 5 was carried out except that the chip prepared in Comparative Example 2 was used.

Comparative Example 8

The same procedure as in Example 5 was carried out except that the chip prepared in Comparative Example 3 was used.

Comparative Example 9

The same process as in Example 5 was carried out except that the chip prepared in Comparative Example 4 was used.

Comparative Example 10

The same procedure as in Example 5 was performed except that the chip prepared in Comparative Example 5 was used.

Evaluation of the artificial marbles of Examples 5 to 8 manufactured from the marble chips of Examples 1 to 4 and Comparative Examples 6 to 10 manufactured from the chips of Comparative Examples 1 to 5 is shown in Table 1 below.

Property evaluation method in the above was carried out in the following manner.

(1) Chemical resistance: 1.0 N concentration of hydrochloric acid and 1.0 N concentration of ammonia was used to evaluate the surface after immersion for 48 hours at 25 ° C.

(2) Refractive index: It measured by ABBE refractometer (3T) under 25 degreeC temperature conditions.

(3) Smoothness: The smoothness of the interface between the chip and the base metal after sanding was visually evaluated.

(4) Sanding property: The appearance of the chip after sanding with sandpaper was visually evaluated.

(5) Concave: The interface between the chip and the matrix is cracked, or the chip is decayed and evaluated visually.

(6) Thermal processability: When the artificial marble was heated at 180 ° C. for 20 minutes and subjected to curved surface processing, the minimum radius at which chips were not protruded or cracked was measured.

As shown in Table 1, Examples 5 to 8 were good in all the physical properties evaluation, and even in the heat processability to the curved surface of the radius 150 MM. Comparative Examples 6 and 7 show the results of chip cracking and high thermal workability in high specific gravity or sanding properties. Comparative Example 8 had the best result in the thermal workability, but the transparent chip distribution was not constant at the shear plane. In addition, since the refractive index was low, the texture such as quartz could not be represented, and thus it was impossible to produce the engineered stone. In Comparative Example 9, the chip distribution was poor, and the occurrence of the concave phenomenon and the thermal workability were the lowest, and the chemical resistance of the chip was poor. Comparative Example 10 is not applicable to continuous production because the shear chip distribution is not constant.

Example 9 Preparation of Artificial Marble Containing Marble Chips in Chip-In-Chip Form

10 parts by weight of a marble chip having a size of 0.01 to 5 mm obtained by crushing acrylic artificial marble was added to the resin composition of Example 2, and then cured and pulverized to prepare a marble chip. The manufactured marble chip had a chip-in-chip form with colored chips inside the chip, and artificial marble was manufactured in the same manner as in Example 5 using the marble chip. The prepared artificial marble surface photograph is shown in FIG. 3.

Example 10 Preparation of Artificial Marble Containing Marble Chips with Flow Streaks

In the resin composition of Example 1, a resin composition (a) in which 0.1 parts by weight of carbon black was added as a color imparting agent was prepared, and a resin composition (b) in which 0.1 parts by weight of iron oxide red was added thereto as a color imparting agent, respectively. The resin compositions (a) and (b) were simultaneously injected into the belt at the same ratio to obtain a cured product having a flow pattern. After grinding to 0.1 to 30 mm to prepare a marble chip having a flow stripe, artificial marble was manufactured in the same manner as in Example 5 using the marble chip. The prepared artificial marble surface photograph is shown in FIG. 4.

The present invention has a high specific gravity of 1.50 to 1.67, it is possible to implement a uniform pattern regardless of the curing time or molding time, excellent transparency and refractive index, sanding properties and morse hardness is the same as the matrix (matrix), Not only has excellent binding force, but also can exhibit a three-dimensional texture, and excellent pigment dispersibility and binding with the matrix, there is no concave phenomenon, and provides a marble chip with excellent chemical resistance and a manufacturing method thereof. By applying the chip, it can have the same appearance and texture as the engineered stone, and it has the effect of providing the artificial marble which is capable of continuous production and is excellent in heat processing and smoothness.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (19)

A marble chip formed by curing a resin composition comprising a binder and an acrylic crosslinkable monomer, wherein the binder is selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates, and mixtures thereof. The marble chip of claim 1, wherein the resin composition comprises 50 to 90 parts by weight of the binder and 10 to 50 parts by weight of the acrylic crosslinkable monomer. The method of claim 1, wherein the resin composition further comprises an additive, the additive is a colorant, antifoaming agent, coupling agent, ultraviolet absorber, light diffusing agent, polymerization inhibitor, antistatic agent, flame retardant, heat stabilizer and mixtures thereof Marble chip, characterized in that selected from the group consisting of. The marble chip of claim 1, wherein the number average molecular weight of the halogenated urethane acrylate is 900 to 4,000, and the number average molecular weight of the halogenated epoxy acrylate is 600 to 3,500. According to claim 1, wherein the acrylic crosslinkable monomer is methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, oxyl (meth) acrylate, dodecyl (meth) acrylate , Octadecyl (meth) acrylate, methylcyclohexyl (meth) acrylate, isobonyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, chlorophenyl (meth) acrylate, methoxy Phenyl (meth) acrylate, bromophenyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,2-propylene glycol (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1 , 3-propylene glycol (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, diethylene glycol di (Meth) acrylate, triethylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa ( Meth) acrylate, ethoxyethoxyethyl acrylate, epoxy acrylate of glycidyl methacrylic acid, 1,6-hexanediol di (meth) acrylate, glycerin tri (meth) acrylate, methylpropanedioldi ( Marble chip, characterized in that selected from the group consisting of meth) acrylate, polyethylene glycol di (meth) acrylate and mixtures thereof. The method of claim 1, wherein the resin composition further comprises a crosslinking agent together with an acrylic crosslinkable monomer, the crosslinking agent is a styrene monomer, bromostyrene, vinyltoluene, diallyl terephthalate, diallyl phthalate, diallyl carbonate, Marble chip, characterized in that selected from the group consisting of divinylbenzene, alphamethylstyrene, alphamethylstyrene dimer and mixtures thereof.       The marble chip according to claim 1, wherein a marble chip is further added to the resin composition to form a chip-in-chip form.       The marble chip of claim 1, wherein the resin composition uses a plurality of resin compositions different in color or transparency.         Artificial marble comprising a marble chip of any one of claims 1 to 8. Preparing a resin composition by mixing an acrylic crosslinkable monomer with a binder selected from the group consisting of halogenated urethane acrylates, halogenated epoxy acrylates, and mixtures thereof; Curing the resin composition to prepare a cured product; And Crushing the cured product; Marble chip manufacturing method characterized in that consisting of. The marble chip manufacturing method according to claim 10, wherein 0.03 to 2.5 parts by weight of a curing agent is added to 100 parts by weight of the resin composition to cure. The method of claim 10, wherein the cured product is a marble chip manufacturing method, characterized in that crushing to an average diameter of 0.1 to 30 mm. The method of claim 10, wherein the metal is deposited on the cured product and then crushed. The method of claim 10, wherein the resin composition further comprises an additive, the additive is a colorant, antifoaming agent, coupling agent, ultraviolet absorber, light diffusing agent, polymerization inhibitor, antistatic agent, flame retardant, heat stabilizer and mixtures thereof Marble chip manufacturing method, characterized in that selected from the group consisting of. 11. The method of claim 10, The marble chip manufacturing method characterized in that the addition of the marble chip to the resin composition to produce a chip-in-chip form. The method of claim 10, wherein the resin composition further comprises a crosslinking agent together with the acrylic crosslinkable monomer, the crosslinking agent is a styrene monomer, halogenated styrene, vinyltoluene, diallyl terephthalate, diallyl phthalate, diallyl carbonate, dial A method for producing a marble chip, characterized in that selected from the group consisting of vinylbenzene, alphamethylstyrene, alphamethylstyrene dimer and mixtures thereof. The method of claim 10, wherein the resin composition is a marble chip manufacturing method using a plurality of resin compositions of different colors or transparency. A marble chip manufactured by the manufacturing method of any one of claims 10 to 17 and having a specific gravity of 1.50 to 1.67. Artificial marble comprising a marble chip of claim 18.

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