KR20180110941A - Artificial marble composition and artificial marble using the same - Google Patents

Abstract

Provided is an artificial marble composition which contains an acrylic resin, an acrylic monomer, and an inorganic filler which is modified by a silane coupling agent represented by chemical formula 1, SiRX(OR′)4-x. According to the present invention, the artificial marble composition has excellent stain resistance and significantly improved easy-clean effects.

Description

ARTIFICIAL MARBLE COMPOSITION AND ARTIFICIAL MARBLE USING THE SAME [0001]

Artificial marble composition and artificial marble using the same.

Recently, artificial marble is used as a substitute for natural marble, and has various characteristics such as softness, soft texture, excellent processability and excellent durability. Due to such physical properties of artificial marble, it can be used for interior and exterior materials for construction such as sinks, wash basins, bathtubs, banks and general counters, and various counter tops, thresholds, furniture, .

Common properties required in these various applications are excellent stain resistance. Accordingly, various methods for improving the stain resistance of artificial marble have been researched.

One embodiment of the present invention provides an artificial marble composition having a high water contact angle, which can impart excellent stain resistance and significantly improved Easy-clean effect.

In one embodiment of the present invention, there is provided an artificial marble composition comprising an acrylic resin, an acrylic monomer, and an inorganic filler, wherein the inorganic filler is modified by a silane coupling agent represented by formula (1).

In another embodiment of the present invention, artificial marble is provided which is a cured product of said artificial marble composition.

The artificial marble composition can impart excellent stain resistance, and artificial marble, which is a cured product of the artificial marble composition, can have a high water contact angle, excellent stain resistance and remarkably improved easy-clean effect.

BRIEF DESCRIPTION OF THE DRAWINGS The above and other features and advantages of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings in which: These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art to which the invention pertains. Only.

In one embodiment of the present invention, there is provided an artificial marble composition comprising an acrylic resin, an acrylic monomer, and an inorganic filler, wherein the inorganic filler is modified by a silane coupling agent represented by the following formula (1).

[Chemical Formula 1]

SiRX (OR ^' ) 4-x

In Formula 1, at least one of R is a substituted or unsubstituted alkyl group having 8 to 18 carbon atoms; Or a substituted or unsubstituted heteroalkyl group having 8 to 18 carbon atoms; each R ^' is independently an alkyl group having 1 to 2 carbon atoms; Or a heteroalkyl group, and x is an integer of 1 to 3.

The artificial marble composition can impart a high water contact angle, excellent stain resistance and a significantly improved Easy-clean effect.

The acrylic resin may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl And combinations thereof. The term " polymer "

The weight average molecular weight (Mw) of the acrylic resin may be about 60,000 to about 15. Since the acrylic resin has a weight average molecular weight in the above range, sieving is facilitated by mixing with an acrylic monomer, and artificial marble produced therefrom can exhibit excellent bending strength and impact resistance.

Specifically, the acrylic resin may affect the basic physical properties of artificial marble. The acrylic resin has a weight average molecular weight (Mw) within the above range, so that it can be easily dissolved in the acrylic monomer contained in the artificial marble composition to form a syrup. The artificial marble produced using the syrup can have high bending strength and impact resistance, is easy to cut, and can realize excellent physical properties that do not break even when the artificial marble is dropped at a height of about 1 m or more.

The artificial marble composition may include about 200 parts by weight to about 500 parts by weight of the acrylic monomer based on 100 parts by weight of the acrylic resin, so that the viscosity of the artificial marble composition can be appropriately controlled. The acrylic monomer and the inorganic filler are mixed well so that the physical properties of the artificial marble, which is a cured product of the artificial marble composition, can be excellent and uniform. Specifically, when the content of the acrylic monomer is less than the above range, the viscosity of the artificial marble composition may become high and the handling property may deteriorate. When the content exceeds the above range, the curing property and shrinkage of the artificial marble composition The properties may be deteriorated, and there may be a problem that the physical property distribution is not uniform.

The acrylic monomer contained in the artificial marble composition may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) (Meth) acrylate, and combinations thereof.

The artificial marble composition includes an inorganic filler. The inorganic filler can prevent shrinkage during curing of the artificial marble composition, improve surface smoothness, impart high hardness, and increase weight have.

The inorganic filler may be included in an amount of about 100 to about 700 parts by weight based on 100 parts by weight of the acrylic resin. Specifically, the inorganic filler may be contained in an amount of about 400 to about 700 parts by weight based on 100 parts by weight of the acrylic resin. For example, when the content of the inorganic filler is less than the above range, there is a problem of hardening shrinkage, and when the content exceeds the above range, the impact resistance may be lowered.

 The average particle size of the inorganic filler may be from about 10 탆 to about 100 탆. By having the above-mentioned average particle size, the inorganic filler can be appropriately dispersed in the artificial marble composition, and the viscosity of the artificial marble composition containing the inorganic filler can be appropriately controlled and the physical properties can be maintained uniformly.

Specifically, the inorganic filler may include one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica, alumina, and combinations thereof. For example, the artificial marble composition may include an inorganic filler containing a hydroxyl group or crystal water such as aluminum hydroxide, magnesium hydroxide, etc., and may have excellent flame retardancy.

The inorganic filler is surface-modified with a silane coupling agent, thereby increasing the compatibility with the acrylic resin and improving the mechanical strength and the like of the artificial marble.

The silane coupling agent is represented by the following formula (1).

[Chemical Formula 1]

SiRX (OR ^' ) 4-x

In Formula 1, at least one of R is a substituted or unsubstituted alkyl group having 8 to 18 carbon atoms; Or a substituted or unsubstituted heteroalkyl group having 8 to 18 carbon atoms; each R ^' is independently an alkyl group having 1 to 2 carbon atoms; Or a heteroalkyl group, and x is an integer of 1 to 3.

Since the inorganic filler is surface-modified with the silane coupling agent, a high water contact angle, excellent stain resistance and a remarkably improved easy-clean effect can be imparted to the artificial marble composition containing the inorganic filler.

In this specification, an easy-clean effect means ease of cleaning after the contaminants have adhered.

The silane coupling agent is a substituted or unsubstituted alkyl group having 8 to 18 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 8 to 18 carbon atoms. The silane coupling agent has a long straight chain structure within the above range, so that it can have a high water contact angle, excellent stain resistance and a significantly improved Easy-clean effect.

For example, when the R has a carbon number less than the above range, the water contact angle is lowered, and the stain resistance to which the contaminants are not adhered may be lowered. When R is in the range exceeding the above range, the steric hindrance between the silane coupling agent becomes large, and the density of the silane coupling agent treated on the surface of the inorganic filler may be lowered. Therefore, the compatibility between the acrylic resin and the inorganic filler may be lowered, so that even though the inorganic filler is modified by the silane coupling agent, sufficient physical properties can not be obtained. In addition, a side effect that the stain resistance is lowered may occur, and an easy-clean effect may not be obtained.

Specifically, the substituted alkyl group having 8 to 18 carbon atoms and the substituted heteroalkyl group having 8 to 18 carbon atoms are each an alkyl group having a carbon number of 8 to 18 and a heteroalkyl group having a carbon number of 8 to 18, A substituent selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a mercapto group, a vinyl group, an epoxy group, a glycidyl group, an amino group, a methacrylic group, a phenyl group, a ureido group, a halogen group and combinations thereof.

The substituted or unsubstituted heteroalkyl group having 8 to 18 carbon atoms may contain oxygen (O) or nitrogen (N) in the main chain. For example, it has a long linear structure including one to three of oxygen (O) or nitrogen (N), has a high water contact angle, has excellent stain resistance and a significantly improved Easy- .

For example, the silane coupling agent may be a substituted or unsubstituted alkyl group having 8 to 18 carbon atoms, when x in Formula 1 is 2 or more; Or a substituted or unsubstituted R 8 other than a heteroalkyl group having 8 to 18 carbon atoms may be each independently selected from methyl, ethyl, propyl, isopropyl or butyl.

The silane coupling agent is an alkyl group having 1 to 2 carbon atoms; Or an alkoxy group having R 'as a heteroalkyl group. For example, from 2 to 3 alkoxy groups.

The silane coupling agent having the alkoxy group can easily form a bond with an inorganic filler. Thus, the adsorption of contaminants to the interface of the inorganic filler can be suppressed, and even when the contaminants are attached, they can be easily wiped off with water, washing water or the like. As a result, it is possible to increase the easy-clean effect which allows the contaminants to be easily removed.

The heteroalkyl group may include oxygen (O) or nitrogen (N) in the main chain.

For example, the silane coupling agent may be selected from the group consisting of octyltriethoxy silane, n-decyltriethoxysilane, dodecylmethyldiethoxysilane, dodecyltriethoxysilane, ), (HEPTADECAFLUORO-1,1,2,2-TETRA-HYDRODECYL) TRIETHOXYSILANE, (heptadecafluoro 1, 2-tetra- 1,1,2,2-Tetra-HYDRODECYL TRIMETHOXYSILANE), HEXADECYLTRIETHOXYSILANE (Hexadecyltriethoxysilane)

N-octadecylmethyldiethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, n-octadecylmethyldimethoxysilane, ), n-octadecyltriethoxysilane, octyldimethylsiloxymethylsilane, octadecyltrimethoxysilane, octadecyltrimethoxysilane, tridecafluoro-1,1,2,2-tetra (TRIDECAFLUORO-1,1,2,2-TETRAHYDRO-OCTYL) TRIETHOXYSILANE, and combinations thereof.

The amount of the silane coupling agent may be about 0.5 to about 20 parts by weight based on 100 parts by weight of the inorganic filler. The silane coupling agent is contained in an amount within the above range to give an appropriate compatibility between the inorganic filler and the resin to give excellent physical properties, to increase the water contact angle, to significantly improve the easy-clean effect Can be given. Specifically, when the content of the silane coupling agent is less than the above range, the water contact angle is lowered and the easy-clean effect is lowered. When the content exceeds the above range, Or the cross-linking density is too high, which is not efficient.

The inorganic filler may be surface-modified with a silane coupling agent by a wet method or a dry method. The wet method means a method in which a silane coupling agent is dispersed in a solvent to form a slurry state, and an inorganic filler is added to the solution in which the inorganic filler is directly or diluted. The dry method refers to a method in which an inorganic filler is sprayed with a solution of a silane coupling agent directly or by diluting with water while stirring with a mixer.

The artificial marble composition may further include one additive selected from the group consisting of decoration chips, crosslinking agents, polymerization initiators, catalysts, and combinations thereof.

The decoration chip may be prepared by mixing a monochromatic resin composition or a resin composition of different colors. The kind of the chip is not particularly limited, and for example, a resin or a chip made of a natural material can be used.

The decoration chip may include one selected from the group consisting of an acrylic resin, an epoxy resin, a polyester resin, and a combination thereof.

In the case of using the natural material for the decoration chip, the usual materials in this field can be used. Examples of the natural material include mother-of-pearl, stone, quartz, charcoal, loess, magnet, fragrance, pearl, Powder, and the like, and is not particularly limited thereto.

The cross-linking agent is a multifunctional acrylic monomer having an intramolecular copolymerizable double bond and cross-linking with an acrylic resin. The cross-linking agent is selected from the group consisting of ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol Is selected from the group consisting of dimethacrylate, trimethylolpropane trimethacrylate, 1,6-hexanediol dimethacrylate, polybutylene glycol dimethacrylate, neopentyl glycol dimethacrylate, and combinations thereof. One can be included.

The polymerization initiator may be an organic peroxide such as benzoyl peroxide, diacyl peroxide such as dicumyl peroxide, butyl hydroperoxide, hydroperoxide such as cumyl hydroperoxide, t-butyl peroxymaleic acid, t-butyl hydroperoxide , t-butyl hydroperoxy butyrate, acetyl peroxide, lauroyl peroxide, azobisisobutyronitrile, azobisdimethyl valeronitrile, t-butyl peroxyneodecanoate, t-amyl peroxy 2 - ethyl hexanoate, and combinations thereof.

The catalyst may be selected from the group consisting of organic amines, organic metal salt catalysts, and combinations thereof.

The artificial marble composition may have a viscosity of about 5Ps to about 200Ps at 25 < 0 > C. Specifically, it may have a viscosity of about 10Ps to about 120Ps. By having the above-mentioned viscosity of the artificial marble composition, the flowability of the artificial marble composition in the artificial marble production process can be improved, and thus the mass productivity of artificial marble can be improved. Further, the artificial marble produced from the artificial marble composition may be free from warping or bubbling, and thus can produce high quality artificial marble.

In another embodiment of the present invention, artificial marble is provided which is a cured product of said artificial marble composition. The artificial marble is a cured product of the above-mentioned artificial marble composition, has a high water contact angle, can have excellent stain resistance and remarkably improved Easy-clean effect.

Specifically, the artificial marble may have a water contact angle of from about 95 [deg.] To about 105 [deg.]. The artificial marble has a high water contact angle in the above range, and when the contaminant touches it, it does not penetrate and may flow down, and the contaminants may not adhere well. The artificial marble has an easy-clean effect that is easily cleaned even when contaminants are attached. Further, the artificial marble can maintain the above characteristics even after a long time has elapsed.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

< Example  And Comparative Example >

Manufacturing example  1-1

100 parts by weight of aluminum hydroxide, 5 parts by weight of octyltriethoxy silane, 100 parts by weight of isopropyl alcohol as an organic solvent, 5 parts by weight of distilled water and 0.5 part by weight of acetic acid as an organic acid were precipitated, The precipitate was separated and sufficiently dried at 90 ° C to 120 ° C. The dried aluminum hydroxide was dispersed in distilled water and floated on the water surface to confirm that the surface treatment was completed.

Manufacturing example  1-2

100 parts by weight of aluminum hydroxide and 5 parts by weight of octyltriethoxy silane were mixed and dispersed in a mixer having a sufficient shear force and sufficiently dried at 90 to 120 ° C. The dried aluminum hydroxide was dispersed in distilled water and floated on the water surface to confirm that the surface treatment was completed.

Manufacturing example  2

Surface-modified aluminum hydroxide was prepared in the same manner as in Preparation Example 1-1 except that 5 parts by weight of n-dodecyltriethoxy silane was used as the silane coupling agent.

Manufacturing example  3

The surface-modified aluminum hydroxide was prepared in the same manner as in Preparation Example 1-1 except that 5 parts by weight of methacryloxypropyltrimethoxysilane was used as the silane coupling agent.

Manufacturing example  4

The surface-modified aluminum hydroxide was prepared in the same manner as in Preparation Example 1-1 except that 5 parts by weight of docosyltriethoxysilane was used as the silane coupling agent.

Example  One

100 parts by weight of polymethyl methacrylate having a weight average molecular weight of 90,000, 300 parts by weight of methyl methacrylate, and 600 parts by weight of surface-modified aluminum hydroxide of Production Example 1-1 were mixed to prepare a resin composition having a viscosity of 70 Ps.

The resin composition was cured in an oven at 60 ° C to 90 ° C to prepare artificial marble.

Example  2

Artificial marble was prepared in the same manner as in Example 1 except that the surface-modified aluminum hydroxide of Production Example 1-2 was used as an inorganic filler.

Example  3

Artificial marble was prepared in the same manner as in Example 1, except that the surface-modified aluminum hydroxide of Production Example 2 was used as an inorganic filler.

Comparative Example  One

An artificial marble was prepared in the same manner as in Example 1, except that aluminum hydroxide not surface-modified with a silane coupling agent was used.

Comparative Example  2

Artificial marble was prepared in the same manner as in Example 1, except that the surface-modified aluminum hydroxide of Production Example 3 was used as an inorganic filler.

Comparative Example  3

Artificial marble was prepared in the same manner as in Example 1 except that the surface-modified aluminum hydroxide of Production Example 4 was used as an inorganic filler.

<Evaluation>

Experimental Example  1: Water Contact angle

Distilled water was dropped on the artificial marble specimens of the examples and comparative examples, and the shape of the droplets was measured by a CCD camera using a contact angle meter OCA-15 (Dataphysics) The angle with the surface was measured. The results are shown in Table 1.

Experimental Example  2: Easy- clean (Easy-clean)

The name pens were painted on the artificial marble surfaces of the examples and comparative examples and then cleaned with ethanol. Then, the residual state of the namepen was compared. At this time, when the surface of the artificial marble was visually observed, it was judged to be good when there was no trace, and when it was found to be trace. The results are shown in Table 1.

Water contact angle (°) Easy-clean Example 1 100 Good Example 2 98 Good Example 3 103 Good Comparative Example 1 85 Bad Comparative Example 2 87 Bad Comparative Example 3 103 Bad

As shown in Table 1, Example 1, which is a cured product of an artificial marble composition modified by a silane coupling agent represented by a compound having at least one alkyl group having 8 to 18 carbon atoms in Formula 1, And exhibits an excellent easy-clean effect. On the other hand, in the case of Comparative Example 3 in which the number of carbon atoms exceeded the above range, the contact angle of water is high, but the effect of iscleaning is rather low.

Claims (14)

An acrylic resin, an acrylic monomer, and an inorganic filler,
The inorganic filler may be modified with a silane coupling agent represented by the following formula
Artificial marble composition:
[Chemical Formula 1]
SiRX (OR ^' ) 4-x
In Formula 1, at least one of Rs is a substituted or unsubstituted alkyl group having 8 to 18 carbon atoms; Or a substituted or unsubstituted heteroalkyl group having 8 to 18 carbon atoms,
Each R ^' is independently an alkyl group having 1 to 2 carbon atoms; Or a heteroalkyl group,
And x is an integer of 1 to 3.
The method according to claim 1,
The substituted alkyl group having 8 to 18 carbon atoms and the substituted heteroaryl group having 8 to 18 carbon atoms are each an alkyl group having 8 to 18 carbon atoms and a heteroalkyl group having 8 to 18 carbon atoms,
A structure having one substituent selected from the group consisting of an alkyl group having 1 to 5 carbon atoms, a mercapto group, a vinyl group, an epoxy group, a glycidyl group, an amino group, a methacrylic group, a phenyl group, a ureido group, a halogen group, An artificial marble composition.
The method according to claim 1,
The substituted or unsubstituted C2-C18 heteroalkyl group may be, for example,
(O) or nitrogen (N) in the main chain
Artificial marble composition.
The method according to claim 1,
The acrylic resin may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl And combinations thereof. &Lt; RTI ID = 0.0 &gt;
Artificial marble composition.
The method according to claim 1,
The acrylic monomer may be at least one selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, glycidyl &Lt; / RTI &gt; and combinations thereof.
Artificial marble composition.
The method according to claim 1,
Wherein the inorganic filler comprises one selected from the group consisting of aluminum hydroxide, magnesium hydroxide, calcium carbonate, silica, alumina, a catalyst, and combinations thereof
Artificial marble composition.
The method according to claim 1,
And 100 to 700 parts by weight of the inorganic filler relative to 100 parts by weight of the acrylic resin
Artificial marble composition.
The method according to claim 1,
The content of the silane coupling agent is 0.5 to 20 parts by weight relative to 100 parts by weight of the inorganic filler
Artificial marble composition.
The method according to claim 1,
The inorganic filler preferably has an average particle diameter of from 10 탆 to 100 탆
Artificial marble composition.
The method according to claim 1,
A coating composition, a decorative chip, a crosslinking agent, a polymerization initiator, and combinations thereof
Artificial marble composition.
11. The method of claim 10,
Wherein the chip comprises one selected from the group consisting of an acrylic resin, an epoxy resin, a polyester resin, and combinations thereof
Artificial marble composition.
The method according to claim 1,
Having a viscosity of from 5Ps to 200Ps at 25 &lt;
Artificial marble composition.
An artificial marble which is a cured product of the artificial marble composition according to any one of claims 1 to 12.
14. The method of claim 13,
Having a water contact angle of 95 ° to 105 °
Artificial marble