KR20190074885A - A composition for artificial marble chips, the artificial marble chips prepared by using the composition and the artificial marble comprising the artificial marble chips - Google Patents

Abstract

The present invention relates to a composition for an artificial marble chip, the artificial marble chip manufactured with the composition for an artificial marble chip, and artificial marble including the same and, more specifically, to: a composition for an artificial marble chip which includes as a cross-linking agent any one selected from a bifunctional (meth)acrylate monomer (a1), whose glass transition temperature is -25 to 55°C and molecular weight is 330 to 1,500 g/mol, and a bifunctional (meth)acrylate oligomer (a2) whose glass transition temperature is 45 to 105°C and molecular weight is 20,000 to 120,000 g/mol, or a mixture thereof; the artificial marble chip manufactured thereby; and artificial marble including the same. The composition for an artificial marble chip, the artificial marble chip manufactured with the composition for an artificial marble chip, and artificial marble including the same are provided for excellent formability at a high temperature.

Description

FIELD OF THE INVENTION The present invention relates to a composition for artificial marble chips, an artificial marble chip produced therefrom, and artificial marbles comprising the same. BACKGROUND ART [0002]

The present invention relates to a composition for artificial marble chips, an artificial marble chip produced therefrom, and artificial marble comprising the same. More particularly, the present invention relates to a synthetic resin having a glass transition temperature of -25 to 55 占 폚 and a molecular weight of 330 to 1,500 g / ) Acrylate monomer (a1) and a difunctional (meth) acrylate oligomer (a2) having a glass transition temperature of 45 to 105 ° C and a weight average molecular weight of 20,000 to 120,000 g / mol, And an artificial marble chip produced therefrom, and an artificial marble comprising the same.

Artificial marble is made by combining natural stone powder, minerals and additives such as chips in base such as acrylic resin, unsaturated polyester resin, epoxy resin or cement, and adding additives such as pigments if necessary, It is a sieve.

Artificial marble is divided into a solid product and a granite product. Typical examples are acrylic artificial marble, unsaturated polyester artificial marble, epoxy artificial marble, melamine artificial marble , And artificial marble of the engineered stone series.

Such artificial marble has a beautiful appearance and excellent workability and is widely used as interior and exterior materials for various interior materials such as various top plate materials, dressing table, sink, counter, wall material, floor, .

For example, Korean Patent Laid-Open Publication No. 10-2015-0039913 discloses an artificial marble transparent chip composition for use in the production of artificial marble transparent chips which can realize transparency and durability is an acrylic composite, polymethyl methacrylate, unsaturated polyester, methyl Methacrylate and polyfunctional acrylic monomers.

As another example, the acrylic artificial marble disclosed in Korean Patent Laid-Open Publication No. 10-2004-0059913 can be manufactured by manufacturing an acrylic-based special chip containing chips of different colors and different sizes in the chip, classifying the acrylic- ), So that artificial marbles having patterns closer to natural stones can be realized.

However, since the artificial marble chips as described above are not sufficiently high in elongation, when the artificial marble chips are used to manufacture three-dimensional artificial marbles such as square wash basins, deep wash basins, and rounded corners, Or the artificial marble chips were cracked around the chip. Accordingly, there is an urgent need to develop a composition for an artificial marble chip having a high elongation and a high moldability, an artificial marble chip made of a composition for artificial marble chips, and an artificial marble comprising the same.

KR 10-2015-0039913 A (Apr. 14, 2014). KR 10-2004-0059913 A (2004.07.06.)

The present invention has been made to solve the above-mentioned problems, and it is an object of the present invention to provide a composition for an artificial marble chip excellent in high-temperature moldability, an artificial marble chip produced therefrom, and an artificial marble comprising the same.

(A1) having a glass transition temperature of -25 to 55 占 폚 and a molecular weight of 330 to 1,500 g / mol and a glass transition temperature of 45 (Meth) acrylate oligomer (a2) having a weight average molecular weight of 20,000 to 120,000 g / mol, or a mixture thereof.

The present invention provides an artificial marble chip made of the composition for artificial marble chips.

The present invention provides an artificial marble comprising the artificial marble chip.

The artificial marble chip and the artificial marble comprising the composition for artificial marble chip of the present invention are excellent in high-temperature moldability, so that when the artificial marble is manufactured using the artificial marble chip, the artificial marble chip is not detached, There is an effect that the chip periphery does not crack or break.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photograph of artificial marble comprising artificial marble chips made from the composition for artificial marble chips according to Example 1 of the present invention.
2 is a photograph of an artificial marble comprising an artificial marble chip made from a composition for artificial marble chips according to Comparative Example 5 of the present invention.
3 is a schematic view of a wooden molding for testing high-temperature formability of artificial marble.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

(A1) having a glass transition temperature of -25 to 55 占 폚 and a molecular weight of 330 to 1,500 g / mol and having a glass transition temperature of 45 to 105 占 폚 (A2) having a weight average molecular weight of 20,000 to 120,000 g / mol, or a mixture thereof.

In the composition for artificial marble chips, the total content of the crosslinking agent may be 0.18 to 2.0% by weight, or 0.3 to 1.65% by weight. When the cross-linking agent is contained in an amount less than the above-mentioned range, the cross-linking density is lowered so that the absorption rate of the (meth) acrylic monomer constituting the (meth) acrylic resin syrup described later can be increased. As a result, the artificial marble chip When the artificial marble chips are contained in an amount exceeding the above range, the elongation of the artificial marble chips is low and the high-temperature formability is poor. In case of manufacturing artificial marble using such chips, There is a problem such that the chip is separated or the chip periphery is cracked.

In the present invention, bifunctional means that there are two predetermined groups containing a double bond capable of forming a bond in the curing reaction, for example, two (meth) acrylate groups.

For example, the bifunctional (meth) acrylate monomer (a1) may have a glass transition temperature of -25 to 55 占 폚 or -25 to 40 占 폚. If the glass transition temperature of the bifunctional (meth) acrylate monomer (a1) is less than the above range, the hardness of the artificial marble chips made of the composition for artificial marble chips may be lowered, and the artificial marble chips may be retracted, , The reactivity is lowered to increase the unreacted (meth) acrylate monomer (a1), and the flexural modulus of the artificial marble chip may be lowered.

The bifunctional (meth) acrylate monomer (a1) may have a molecular weight of 330 to 1,500 g / mol, or 500 to 1,300 g / mol, for example. If the molecular weight of the bifunctional (meth) acrylate monomer (a1) is less than the above-mentioned range, the curing shrinkage may become large and the heat may not be applied even if the molecular weight is too large. Lt; / RTI >

Examples of the bifunctional (meth) acrylate monomer (a1) include 1,2-ethylene glycol diacrylate, 1,12-dodotanediol di (meth) acrylate, polyethylene glycol 200 di (meth) , Polyethylene glycol 400 di (meth) acrylate, polyethylene glycol 600 di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentyl glycol di (Meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (Meth) acrylate such as ethyl isocyanurate, allyl cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) (Meth) acrylate, neopentyl glycol-modified trimethylpropane di (meth) acrylate, adamantane di (meth) acrylate, ethylene oxide modified hexahydrophthalic acid di (meth) acrylate, tricyclodecane dimethanol di Acrylate, and 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorine.

When the bifunctional (meth) acrylate monomer (a1) alone is included as the crosslinking agent, it may be contained in the composition for artificial marble chips in an amount of 0.18 to 0.7 wt%, or 0.18 to 0.5 wt%.

The composition for artificial marble chips contains the bifunctional (meth) acrylate-based monomer (a1) in a content within the range described above, thereby allowing the thermosetting reaction to proceed sufficiently. In the artificial marble chip prepared from the composition for artificial marble chips, It is possible to effectively prevent the migration phenomenon caused by the presence of the reaction monomer. For example, when unreacted monomers are present in the composition for artificial marble chips, yellowing may occur on the surface of artificial marble chips produced from the composition for artificial marble chips over time, It may deteriorate the quality of the artificial marble included.

The bifunctional (meth) acrylate oligomer (a2) may have a glass transition temperature of 45 to 105 ° C or 45 to 90 ° C, for example. When the glass transition temperature of the bifunctional (meth) acrylate oligomer (a2) is lower than the above range, the hardness is lowered to give a rubber feeling. If the glass transition temperature is higher than the above range, the artificial marble chips may be deformed.

The bifunctional (meth) acrylate oligomer (a2) may have a weight average molecular weight of 20,000 to 120,000 g / mol, or 30,000 to 110,000 g / mol, for example. The weight average molecular weight can be measured by gel permeation chromatography (GPC), which is a known method. If the weight average molecular weight of the bifunctional (meth) acrylate oligomer (a2) is less than the above range, the viscosity may be lowered and non-uniformity may occur due to the precipitation of the inorganic material. Internal bubbles due to development can occur.

Examples of the bifunctional (meth) acrylate oligomer (a2) include, for example, polydimethyl (meth) acrylate oligomer, polydiethyl (meth) acrylate oligomer, polyethyleneglycol di (meth) acrylate oligomer and polyurethane di (Meth) acrylate oligomer.

When the (meth) acrylate oligomer (a2) is included alone as the crosslinking agent, it may be contained in the artificial marble chip composition in an amount of 0.05 to 1.0% by weight, or 0.18 to 0.9% by weight.

The composition for artificial marble chips contains the bifunctional (meth) acrylate oligomer (a2) in a content within the range described above to sufficiently accelerate the thermosetting reaction. In the artificial marble chip prepared from the artificial marble chip composition, It is possible to effectively prevent the migration phenomenon caused by the presence of the reaction oligomer.

When the composition for artificial marble chips contains both the bifunctional (meth) acrylate monomer (a1) and the bifunctional (meth) acrylate oligomer (a2) as the crosslinking agent, the bifunctional (meth) The total content of the acrylate-based monomer (a1) and the bifunctional (meth) acrylate-based oligomer (a2) may be in the range of 0.30 to 1.7 wt%, or 0.35 to 1.4 wt% The artificial marble chip may not be separated or detached in the artificial marble, so that the periphery of the artificial marble chip may not be split.

The composition for artificial marble chips may further comprise a bifunctional (meth) acrylate-based monomer (a3) having a glass transition temperature of 45 to 55 ° C and a molecular weight of 150 to 220 g / mol as the crosslinking agent.

The glass transition temperature of the bifunctional (meth) acrylate monomer (a3) may be 45 to 55 ° C, or 47 to 53 ° C. If the glass transition temperature of the bifunctional (meth) acrylate monomer (a3) is less than the above range, the artificial marble chips made of the composition for artificial marble chips and the artificial marble comprising the artificial marble chips may be removed, The bending elastic modulus of the artificial marble may be lowered and the workability may be deteriorated such that the back surface of the artificial marble is cracked by a woodworking machine or the like.

If further comprise a crosslinking agent having a glass transition temperature within the above range, the artificial marble, artificial marble chips is made of chip composition has a flexural modulus be 700-1000kg / mm ^2, or 750-950kg / mm ^2. The artificial marble chip has a flexural modulus in the above range, so that the artificial marble including the artificial marble chip can be easily cut, cut and sanded.

The content of the bifunctional (meth) acrylate monomer (a3) The molecular weight may be from 150 to 220 g / mol, or from 170 to 210 g / mol. When the molecular weight of the bifunctional (meth) acrylate monomer (a3) is less than the above range, it may be difficult to ensure high-temperature moldability. If the molecular weight exceeds the above range, the reactivity is lowered, have.

The (meth) acrylate monomer (a3) may be, for example, ethylene glycol di (meth) acrylate.

In addition, the bifunctional (meth) acrylate monomer (a3) may be included in the composition for artificial marble chips in an amount of 0.05 to 0.3% by weight, or 0.10 to 0.25% by weight.

When the composition for artificial marble chips contains the bifunctional (meth) acrylate-based monomer (a3) in the content within the above range, the artificial marble chips produced from the composition for artificial marble chips and the artificial marble comprising them The artificial marble has an excellent workability such that the back surface is not broken during the processing.

The composition for artificial marble chips may further include one or more selected from (meth) acrylic resin syrups, inorganic fillers, initiators, defoamers, coupling agents, and pigments.

The (meth) acrylic resin syrup may be prepared by stirring a composition for a syrup containing a (meth) acrylic monomer and a (meth) acrylic polymer resin at 50 to 70 ° C for 20 to 40 minutes.

Examples of the (meth) acrylic monomer include a monomer having an alkyl group (meth) acrylate, a monomer having a hydroxyl group (meth) acrylate, a monomer having a carboxyl group (meth) acrylate and a monomer having a nitrogen And at least one selected from the group consisting of

The (meth) acrylic polymer resin may be one obtained by polymerizing the (meth) acrylic monomer.

The (meth) acrylic resin syrup may have a viscosity at 25 ° C of 500 to 3,000 cps or 800 to 2,000 cps, for example. If the viscosity of the (meth) acrylic resin syrup is less than the above range, the physical properties and shrinkability of the cured product may be deteriorated. If the viscosity exceeds the above range, the handling of the syrup becomes difficult or the defoaming efficiency may be lowered.  

The (meth) acrylic resin syrup may be contained in the composition for artificial marble chips in an amount of 25 to 45% by weight or 30 to 40% by weight. When the (meth) acrylic resin syrup is contained in the above-mentioned range, cracks do not occur in the artificial marble chips as a cured product, and the deterioration of the surface quality, in which the artificial marble chips made of the composition for artificial marble chips have a plastic surface feel, It may not occur.

The inorganic filler may include, for example, at least one selected from calcium carbonate, aluminum hydroxide, alumina, magnesium hydroxide, and silica, but is not limited thereto.

The inorganic filler may have an average particle diameter of 10 to 80 占 퐉 or 20 to 70 占 퐉 as predetermined particles. The average particle diameter can be measured using, for example, SEM / TEM equipment. When the average particle diameter of the inorganic filler is less than the above range, the monomer absorption rate increases due to the roughness of the surface of the inorganic filler, the viscosity increases and product formation may be difficult. When the average particle diameter exceeds the above range, Precipitation and separation of the inorganic filler and the composition for artificial marble chips may occur.

 The inorganic filler may be included in an amount of 45 to 70% by weight or 50 to 65% by weight, for example, in the composition for artificial marble chips. When the inorganic filler is included in the above range, there is no deterioration of quality and cracks may not occur in the process of manufacturing artificial marble chips.

The initiator may be, for example, a peroxide-based initiator. Specific examples thereof include peroxides such as benzoyl peroxide, lauroyl peroxide, butyl hydroperoxide, cumyl hydroperoxide, or azo compounds such as azobisisobutyronitrile Can be used. The initiator may, for example, be included in the composition for the artificial marble chip in an amount of 0.1 to 10% by weight, but is not limited thereto.

The defoaming agent may include, for example, a silicone type, a non-silicone type defoaming agent, or a mixture thereof. The antifoaming agent may be included in the artificial marble chip composition in an amount of, for example, 0.1 to 10% by weight, but is not limited thereto.

As the coupling agent, for example, a silane coupling agent such as 3- (trimethoxycycyl) propyl (meth) acrylate, vinyltrimethoxysilane, and vinyltriethoxysilane may be used. The coupling agent may be included in the composition for artificial marble chips in an amount of, for example, 0.1 to 10% by weight, but is not limited thereto.

Examples of the pigment include inorganic pigments, organic pigments, dyes, and the like. Specific examples thereof include reddish brown pigments such as iron oxide, yellow pigments such as iron hydroxide, green pigments such as chromium oxide, gray pigments such as sodium aluminosilicate, white pigments such as titanium oxide, and black pigments such as carbon black. A usual one used can be used. The pigment may be included in the composition for artificial marble chips in an amount of, for example, 0.1 to 10% by weight, but is not limited thereto.

The composition for artificial marble chips may have a viscosity of 4,000 to 10,000 cps, or 5,000 to 8,000 cps. If the viscosity of the composition for artificial marble chips is less than the above range, the (meth) acrylic resin syrup and the inorganic filler can be separated from each other due to the difference in specific gravity. When the viscosity exceeds the above range, It is difficult to produce, and the thickness of the plate for chips may be defective.

The artificial marble chip according to the present invention is obtained by pouring the composition for artificial marble chips into a mold, curing the mixture at 70-100 ° C for 10 minutes to 30 minutes to produce a flat plate for artificial marble chips, .

The artificial marble chip may have a particle diameter of 100 to 2.5 meshes, or 40 to 3.5 meshes, for example. If the particle diameter of the artificial marble chips is within the above range, artificial marble can be produced without causing deterioration of the appearance by the artificial marble chips and cracking between the artificial marble chips and the composition for artificial marble and without decreasing the flowability.

The artificial marble comprising artificial marble chips according to the present invention may comprise from 6 to 18% by weight or from 8 to 16% by weight of said artificial marble chips.

If the artificial marble chip is included in the range below the range, the appearance efficiency of the appearance effect by the artificial marble chip may deteriorate. If the artificial marble chip is included in the range above, the formability may be deteriorated.

(Meth) acrylic resin syrup, 45 to 65% by weight of an inorganic filler, 0.14 to 1.6% by weight of a crosslinking agent, 0.1 to 10% by weight of an initiator, 0.1 to 10% by weight of an antifoaming agent By weight or 8 to 20 parts by weight of the artificial marble chips in 100 parts by weight of the artificial marble slurry comprising 10 to 10% by weight of a binder, 0.1 to 10% by weight of a coupling agent, and 0.1 to 10% have.

The components of the artificial marble slurry may be the same as those of the composition for artificial marble chips, and the viscosity range of the artificial marble slurry may be the same as the viscosity range of the composition for artificial marble chips.

The artificial marble comprising the artificial marble chip according to the present invention can be manufactured by pouring the artificial marble composition into a mold and then curing at 70-100 ° C for 10 minutes to 30 minutes.

The artificial marble including the artificial marble chips may have an elongation of 80% or more. The elongation may be measured using a tensile machine (Instron 8872, equipped with a 160 ° C heating chamber). Since the artificial marble has the elongation in the above range, the high-temperature formability is excellent, so that even when the body is molded into a three-dimensional shape, the problem of cracking or popping on the surface can be effectively prevented.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

1. Manufacture of artificial marble chips

Example 1

(Meth) acrylate (LG Chem, IH830) and methyl (meth) acrylate (purified gold, EP Grade) were mixed in a weight ratio of 28:72 and stirred at 60 ° C for 30 minutes to obtain Resin syrup (viscosity 1000 cps, 25 캜) was prepared.

Subsequently, 0.5 part by weight of polyethylene glycol 400 di (meth) acrylate (MIWA, M280) having a glass transition temperature of -25 to 30 DEG C and a molecular weight of 598 g / mol as a crosslinking agent was added to 38 parts by weight of the (meth) acrylic resin syrup, (Viscosity 5,000 cps at 25 캜) containing 60 parts by weight of inorganic filler, 0.3 part by weight of an initiator, 0.3 part by weight of a defoaming agent, 0.4 part by weight of a coupling agent and 0.5 part by weight of a black pigment.

The composition for artificial marble chips was poured into a mold and cured at 90 ° C. for 30 minutes or less to produce a plate for artificial marble chips. The plate for artificial marble chips was crushed to prepare artificial marble chips having a particle size of 100 to 2.5 mesh Respectively.

Example 2

Except that 0.8 part by weight of polyethylene glycol di (meth) acrylate oligomer (BNTM, BNO-2H) having a glass transition temperature of 45 to 55 DEG C and a weight average molecular weight of 53,000 g / mol as a crosslinking agent was used alone. An artificial marble chip was prepared in the same manner

Example 3

0.05 part by weight of a polyethylene glycol di (meth) acrylate oligomer (BNTM, BNO-2H) having a glass transition temperature of 45 to 55 DEG C and a weight average molecular weight of 53,000 g / mol as a crosslinking agent and a glass transition temperature of -25 to 30 DEG C and 598 g 0.4 g of a polyethylene glycol 400 di (meth) acrylate (MIWON, M280) having a molecular weight of 100 g / mol was used as a starting material.

Example 4

0.3 part by weight of polyethylene glycol 400 di (meth) acrylate (Miwa, M280) having a glass transition temperature of -25 to 30 占 폚 and a molecular weight of 598 g / mol as a crosslinking agent, a glass transition temperature of 45 to 55 占 폚 and a weight 0.05 part by weight of a polyethylene glycol di (meth) acrylate oligomer (BNTM, BNO-2H) having an average molecular weight and an ethylene glycol di (meth) acrylate having a glass transition temperature of 45 to 55 占 폚 and a molecular weight of 198 g / , M221) were used in place of 0.1 parts by weight of the polyimide precursor.

[Comparative Example]

Comparative Example 1

An artificial marble chip was prepared in the same manner as in Example 1, except that 0.5 part by weight of trimethylolpropane tri (meth) acrylate (MIWA, M301), which is a trifunctional monomer, was used alone as a crosslinking agent

Comparative Example 2

An artificial marble chip was prepared in the same manner as in Example 1, except that 0.5 part by weight of phenol ethoxy acrylate (MIWON, M140), which is a monofunctional monomer, was used alone as a crosslinking agent.

Comparative Example 3

As a crosslinking agent, trifunctional oligomer, penta-tri-triol triacrylate (Miwon, M340) 0.5 part by weight was used alone to prepare an artificial marble chip.

Comparative Example 4

As a crosslinking agent, a monofunctional oligomer (Miwon, PU320) 0.5 An artificial marble chip was prepared in the same manner as in Example 1, except that the weight was used alone.

Comparative Example 5

Except that 0.5 part by weight of ethylene glycol di (meth) acrylate (MIWA, M221) having a glass transition temperature of 45 to 55 DEG C and a molecular weight of 198 g / mol as a crosslinking agent was used alone, A marble chip was produced.

Comparative Example 6

Except that 0.5 parts by weight of bisphenol Aethoxy 30 diacrylate (MWN, M2300), which is a bifunctional (meth) acrylate monomer having a glass transition temperature of -57 DEG C and a molecular weight of 1,200 g / mol, An artificial marble chip was produced in the same manner as in Example 1.

Comparative Example 7

0.5 part by weight of bifunctional (meth) acrylate monomer tris (2-hydroxyethyl) isocyanurate diacrylate (MIWON, M2370) having a glass transition temperature of 131 DEG C and a molecular weight of 370 g / mol was used as a crosslinking agent An artificial marble chip was produced in the same manner as in Example 1. [

Comparative Example 8

(Meth) acrylate oligomer butadiene diacrylate (MIWON, MB2012) having a glass transition temperature of 55 占 폚 and a molecular weight of 6,400 g / mol as a crosslinking agent were used in the same manner as in Example 1 Artificial marble chips were prepared.

Comparative Example 9

(Meth) acrylate oligomer (LG Chem, 828M) having a glass transition temperature of 65 占 폚 and a molecular weight of 200,000 g / mol as a crosslinking agent were used alone, Chip.

Comparative Example 10

Except that 0.8 parts by weight of a bifunctional (meth) acrylate oligomer (LG Chem, G50) having a glass transition temperature of 40 占 폚 and a molecular weight of 35,000 g / mol was used alone as a crosslinking agent, Chip.

Comparative Example 11

(Meth) acrylate oligomer (LG Chem, G110) having a glass transition temperature of 108 DEG C and a molecular weight of 40,000 g / mol as a crosslinking agent, 0.8 part by weight were used alone to prepare an artificial marble chip.

2. Manufacture of artificial marble

(Meth) acrylate (LG Chem, IH830) and methyl (meth) acrylate (purified gold, EP Grade) were mixed in a weight ratio of 28:72 and stirred at 60 ° C for 30 minutes to obtain Resin syrup (viscosity 1000 cps, 25 캜) was prepared.

Subsequently, to 38 parts by weight of the (meth) acrylic resin syrup, 0.4 part by weight of polyethylene glycol 400 di (meth) acrylate (MIWA, M280) having a glass transition temperature of -25 to 30 DEG C and a molecular weight of 598 g / An artificial marble slurry (viscosity of 5000 cps, 25 캜) was prepared containing 60 parts by weight of filler, 0.3 part by weight of initiator, 0.3 part by weight of defoamer, 0.4 part by weight of coupling agent, and 0.6 part by weight of white pigment.

100 parts by weight of the artificial marble slurry was mixed with 11 parts by weight of the artificial marble chips prepared in Examples 1 to 4 and Comparative Examples 1 to 11, and the artificial marble composition was cured at 90 ° C within 30 minutes to prepare artificial marble.

Test Example

Test Example 1: High temperature moldability

Each of the artificial marbles according to Examples 1 to 4 and Comparative Examples 1 to 11 was heated for 180 minutes and then subjected to a drawing process at a predetermined curvature radius under the conditions of 25 and 70 MPa using a 1 ton press apparatus, And then pressed and pressed on a wooden mold having a rectangular tube shape. Specifically, the depth formed in each of the above molded products is 142 mm, and is a sharp-edged wooden shape having an angle of 45 degrees. The outer diameter of the horizontal portion is bent by 90 degrees to 83 mm and the outer diameter of the central round portion is bent to 18 mm (see FIG.

By observing the round part and the horizontal part of the molded product visually, when the artificial marble chip or the artificial marble surface around the chip had no cracks or peaks, it was evaluated as being excellent in high temperature formability and was marked as "O" When cracks or peaks appear on the surface, it was evaluated as inferior in high-temperature formability and indicated as "X ".

High temperature formability Example 1 O Example 2 O Example 3 O Example 4 O Comparative Example 1 X Comparative Example 2 X Comparative Example 3 X Comparative Example 4 X Comparative Example 5 X Comparative Example 6 X Comparative Example 7 X Comparative Example 8 X Comparative Example 9 X Comparative Example 10 X Comparative Example 11 X

As shown in Table 1, it was confirmed that the artificial marble of Examples 1 to 4 was excellent in high-temperature moldability (see Fig. 1).

On the other hand, a monofunctional (meth) acrylate monomer or oligomer (Comparative Example 2, Comparative Example 4) was used in the case of using a trifunctional (meth) acrylate monomer or oligomer as a crosslinking agent (Comparative Example 1 and Comparative Example 3) It can be confirmed that the high-temperature formability is inferior to the examples in all cases.

In addition, the artificial marble of Comparative Example 5 is a crosslinking agent which is inferior in high-temperature moldability to Examples by using a bifunctional (meth) acrylate-based monomer having a glass transition temperature of -25 to 55 캜 and a molecular weight of less than 330 g / mol (See FIG. 2).

In the case of using a bifunctional (meth) acrylate-based monomer having a glass transition temperature of less than -25 ° C or more than 55 ° C and a molecular weight of from 330 to 1,500 g / mol (Comparative Example 6, Comparative Example 7) It can be confirmed that the high-temperature moldability is inferior to that of

When a bifunctional (meth) acrylate oligomer having a weight average molecular weight of less than 20,000 g / mol or more than 120,000 g / mol was used as a crosslinking agent (Comparative Example 8, Comparative Example 9 It is confirmed that the high temperature moldability is inferior to the Examples.

In the case of using a bifunctional (meth) acrylate oligomer having a glass transition temperature of less than 45 占 폚 or more than 105 占 폚 and a weight average molecular weight of 20,000 to 120,000 g / mol as a crosslinking agent (Comparative Example 10 and Comparative Example 11) It can be confirmed that the high-temperature moldability is inferior to that of

Claims (12)

(Meth) acrylate monomer (a1) having a glass transition temperature of -25 to 55 占 폚 and a molecular weight of 330 to 1,500 g / mol and a glass transition temperature of 45 to 105 占 폚 and a weight average molecular weight of 20,000 to 120,000 (meth) acrylate oligomer (a2) having a weight-average molecular weight of less than 1,000 g / mol, or a mixture thereof. The method according to claim 1,
Wherein the cross-linking agent is included in the composition for the artificial marble chip in an amount of 0.18 to 2.0% by weight. The method according to claim 1,
The (meth) acrylate monomer (a1) may be at least one selected from the group consisting of 1,2-ethylene glycol diacrylate, 1,12-dodotanediol di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, (Meth) acrylate, polyethylene glycol 600 di (meth) acrylate, neopentylglycol adipate di (meth) acrylate, hydroxyl puivalic acid neopentyl glycol di (meth) , Dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, ethylene oxide modified di (meth) acrylate, di (meth) acryloxyethyl isocyanurate , Allyl cyclohexyl di (meth) acrylate, tricyclodecane dimethanol (meth) acrylate, dimethylol dicyclopentanedi (meth) acrylate, ethylene oxide di (Meth) acrylate, adamantane di (meth) acrylate, and tricyclodecane dimethanol di (meth) acrylate, neopentyl glycol-modified trimethylpropane di , And 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorine. The method according to claim 1,
Wherein the bifunctional (meth) acrylate oligomer (a2) is selected from the group consisting of a polydimethyl (meth) acrylate oligomer, a polydiethyl (meth) acrylate oligomer, a polyethylene glycol di (meth) acrylate oligomer and a polyurethane di And at least one member selected from the group consisting of an alkaline earth metal hydroxide and a lyotropic oligomer. The method according to claim 1,
Wherein the crosslinking agent further comprises a difunctional (meth) acrylate-based monomer (a3) having a glass transition temperature of 45 to 55 DEG C and a molecular weight of 150 to 220 g / mol. 6. The method of claim 5,
Wherein the bifunctional (meth) acrylate monomer (a3) comprises ethylene glycol di (meth) acrylate. The method according to claim 1,
Wherein the composition for artificial marble chips further comprises one or more selected from the group consisting of (meth) acrylic resin syrups, inorganic fillers, initiators, defoamers, coupling agents and pigments. An artificial marble chip made from the composition for the artificial marble chip of any one of claims 1 to 7. 9. The method of claim 8,
Wherein the artificial marble chip has a particle size of 100 to 2.5 mesh. 10. The method of claim 9,
Artificial marble comprising said artificial marble chips. 11. The method of claim 10,
Wherein the artificial marble comprises 6 to 18% by weight of the artificial marble chips. 11. The method of claim 10,
Wherein the artificial marble comprises 0.14 to 1.6 wt% of a crosslinking agent.

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