KR20140045218A

KR20140045218A - Transparent chip for artificial marble, manufacturing the same and artificial marble using the same

Info

Publication number: KR20140045218A
Application number: KR1020120111479A
Authority: KR
Inventors: 임현창
Original assignee: 임현창
Priority date: 2012-10-08
Filing date: 2012-10-08
Publication date: 2014-04-16

Abstract

The present invention relates to a transparent chip for artificial marble, a method of manufacturing the same, and an artificial marble using the same.
The present invention relates to an inorganic filler based on 100 parts by weight of a resin composition comprising 60 to 90% by weight of brominated epoxy-acrylate, 5 to 20% by weight of a reactive diluent, and 5 to 20% by weight of an unsaturated polyester resin. Provided is a transparent chip for artificial marble, a method of manufacturing the same, and an artificial marble using the same, which is manufactured by mixing 5 to 25 wt%.

Description

Transparent Chip for Artificial Marble, Manufacturing the Same and Artificial Marble using The Same}

The present invention relates to a transparent chip for artificial marble, a method of manufacturing the same, and an artificial marble using the same. In more detail, the present invention relates to a transparent chip for artificial marble of high specific gravity that can obtain a sufficient specific gravity while maintaining the transparency of the chip, it is applied to artificial marble of general acrylic material, more elegant and luxurious The present invention relates to a transparent chip for artificial marble having a high specific gravity capable of manufacturing textured artificial marble, a method of manufacturing the same, and an artificial marble using the same.

Marble used for interior and exterior is divided into natural marble and artificial marble. Natural marble is processed from stones taken directly from the quarry, and artificial marble is made by hardening the stone powder to express the texture of natural marble, and is usually manufactured by mixing natural mineral with synthetic resin.

Natural marble is regarded as the finest material to decorate the space with its exquisite appearance, but its use is limited because it is limited in quantity, and it is expensive to process and transport. In order to make up for the shortcomings of such natural marble, artificial marble is used a lot nowadays.

Artificial marble has the advantage of low unit cost, light weight, and unique colors can be freely expressed compared to natural marble. Artificial marble is a synthetic compound that combines natural marble chips and minerals with acrylic, unsaturated polyester, or epoxy resin, and adds various additives or pigments to realize the texture of natural marble. Such artificial marble is largely divided into acrylic artificial marble and unsaturated polyester artificial marble.

Acrylic artificial marble has a beautiful appearance, excellent workability, is lighter than natural marble, and has excellent strength, so it is widely used for various interior materials including counter tables.

However, generally known monochromatic chip combinations have technical limitations in expressing various patterns compared to natural marble or granite.

In order to give a more refined feel to the artificial marble, it is preferable to use a transparent chip. However, the inorganic filler is used to increase the specific gravity of the chip in the manufacturing process of the transparent chip, there is a problem that the transparency of the chip is significantly reduced when using the inorganic filler.

Most of the high specific gravity transparent chips used in Korea mainly use brominated epoxy resins with high specific gravity and good transparency. However, since the hardness is lower than that of the matrix, scratches remain on the surface of the chip during sanding after manufacture of the sheet, and the interface adhesion with the matrix is poor, and the surface gloss is degraded. . In addition, the chip's impact strength is low, so cracks are generated even when used as a product.

The present invention, in order to solve the above problems, to provide a high specific gravity transparent chip for artificial marble to maintain the hardness and specific gravity of the artificial marble chip at the same level as the base material and its manufacturing method The purpose.

In addition, another object of the present invention to provide an artificial marble using a transparent chip for artificial marble as described above.

The present invention relates to an inorganic filler based on 100 parts by weight of a resin composition comprising 60 to 90% by weight of brominated epoxy-acrylate, 5 to 20% by weight of a reactive diluent, and 5 to 20% by weight of an unsaturated polyester resin. It provides a transparent chip for artificial marble, characterized in that manufactured by mixing 5 to 25% by weight.

In one embodiment, 0.2 to 2.0% by weight of the accelerator and 0.2 to 2.0% by weight of the curing agent are mixed and cured based on 100 parts by weight of the resin composition, and then crushed to produce the transparent chip for artificial marble.

In addition, the promoter is selected from the group consisting of copper, cobalt, calcium, t-butyl peroxy Maleicacid and mixtures thereof, and used as the curing agent, Methyl ethyl ketone peroxide (MEKPO), t-butyl benzonate ( TBPB) and mixtures thereof, and may be selected from one or more.

Preferably, at least one of an ultraviolet stabilizer, a polymerization inhibitor, a light diffusing agent, a coupling agent, a coloring agent, and an antioxidant may be further added to 100 parts by weight of the resin composition.

In addition, the reactive diluent may be selected from one or more selected from the group consisting of methyl methacrylate (MMA), styrene monomer (SM) and mixtures thereof.

In addition, the unsaturated polyester resin may be selected from the group consisting of ort type, iso type, bisphenol type, vinyl ester type, and mixtures thereof.

Preferably, the inorganic filler is at least one selected from the group consisting of silica, glass frit, and mixtures thereof. In addition, the inorganic filler may be the frit, and the glass frit may have a particle size of 0.0010 to 0.8 mm and a specific gravity of 2.0 to 3.0.

The transparent chip for artificial marble preferably has a specific gravity of 1.5 to 1.68.

In addition, according to another object of the present invention, the present invention, 60 to 90% by weight of the brominated epoxy acrylate resin, 5 to 20% by weight of reactive diluent and 5 to 20% by weight of unsaturated polyester resin by mixing 60 to 70 Melting and stirring at ° C .; (b) vacuum degassing after mixing the inorganic filler including silica or glass frit; (c) stirring and vacuum defoaming after mixing the accelerator and the curing agent; (d) pouring the cured and vacuum degassed composition in the step (c) into a mold, heating and curing; And (e) cooling the cured product cured in the step (d) and then crushing and sorting the cured product.

Preferably, after the mixing of the step (a) to increase the temperature to 60 ~ 70 ℃ to lower the viscosity, in the step (d) by increasing the temperature to 70 ~ 75 ℃ it can promote the curing.

In addition, in the step (e), after crushing the cured product, the screen size of the transparent chip may be 0.10 ~ 20mm.

In addition, the present invention provides an artificial marble comprising the above-mentioned transparent chip for artificial marble.

The present invention has the following excellent effects.

According to the production method of the present invention, a marble chip composition having a high transparency and high specific gravity glass frit applied to a high specific gravity resin, and a high specific gravity transparent chip for artificial marble having a specific gravity of 1.5 to 1.68 can do.

In addition, by applying a high specific gravity transparent chip to the artificial marble of the general acrylic material, there is an effect that can produce an artificial marble of elegant, luxurious texture closer to the natural marble.

In the present invention, the high specific gravity resin used is a mixture of brominated epoxy-acrylate (styrene) and styrene monomer (SM) having flame retardancy. An example of such a resin is K-720 (weight average molecular weight: 1500-2000) of Samwha Paint Co., Ltd. As a diluent, it can use in styrene monomer (SM) and methyl methacrylate (MMA) alternatively, or can mix and use two types.

In addition, the present invention can be used by adding an unsaturated polyester resin to the resin combination.

Specifically, in the practice of the present invention, the high specific gravity resin is mixed with 60 to 90% by weight of brominated epoxy-acrylate, 5 to 20% by weight of styrene monomer (SM) and 5 to 20% by weight of unsaturated polyester resin. Can be used.

The unsaturated polyester resin is a thermosetting resin having a molecular weight of 1000 to 3000 having a polymerizable double bond, and is prepared by condensation reaction of an α, β-unsaturated dibasic acid or a mixture of the dibasic and saturated dibasic acids with a polyhydric alcohol. Unsaturated polyester resins used in the present invention are not particularly limited in kind and specifically include ort type (e.g., those using phthalic anhydride as unsaturated acid), iso type (e.g., isophthalic acid as unsaturated acid). One or more selected from the group used, the bisphenol type (for example, bisphenol is used as the polyhydric alcohol), and the vinyl ester type (for example, modified with acrylic acid, methacrylic acid, etc.).

If the composition of the unsaturated ester resin is less than 5% by weight, there is a problem that the polymerization reaction is slowed and the workability is inferior, and if it is 25% by weight or more, the specific gravity of the transparent chip is low. When the unsaturated ester resin is used, the interfacial adhesion with the matrix is improved and the surface glossiness of the transparent chip is improved. Examples of the unsaturated polyester resins include MC-823 and MC-824 of Samwha Paint Co., Ltd.

In the present invention, with respect to 100 parts by weight of the resin composition, the promoter is selected from at least one of copper, cobalt, calcium, t-butyl peroxy Maleicacid and used 0.2 to 2% by weight. T-butyl peroxy Maleicacid has the best effect. An example of the accelerator is Chemex-MBA 25 of Hosung Kemax Co., Ltd.

In the present invention, as the curing agent, 0.2 to 2% by weight of one or more selected from Methyl ethyl ketone peroxide (MEKPO) and t-butyl peroxy benzonate (TBPB) based on 100 parts by weight of the composition is used. An example of the curing agent is Butanon M-60 of Geumjeong Akzo Nobel Co., Ltd.

In the present invention, it is preferable to use 5 to 25% by weight of the inorganic filler with respect to 100 parts by weight of the resin composition. In general, the use of inorganic fillers decreases transparency and increases specific gravity. Transparent chips formed of 100% resin have excellent transparency. However, the hardness is weaker than the matrix (Matrix) has a disadvantage that the scratching phenomenon occurs on the chip surface during sanding (Sanding). In addition, since the impact strength of the transparent chip is low as a product, cracks are generated even when used as a product, and thus there is a problem that durability is poor. This problem can be solved by using an appropriate amount of inorganic filler with good transparency. As the inorganic filler, one or more of silica and glass frit may be selected or mixed, but the most effective inorganic filler is glass frit. When less than 5% by weight, the specific gravity of the transparent chip is lowered, and when it exceeds 25% by weight, the transparency of the transparent chip is inferior.

The glass frit refers to a fragment or powder of glass pulverized by blending raw materials such as silica, feldspar, borax and melting at high temperature, followed by quenching. The glass frit has a specific gravity of 2.0 to 3.0 and a particle size of 0.0010 to 0.8 mm. An example of such glass frit is CF-0005-30A manufactured by Frit Japan.

In this invention, 0.01-0.5 weight% of ultraviolet stabilizers can be used with respect to 100 weight part of resin compositions, As an example of a ultraviolet stabilizer, Tinuvin-327 is mentioned. In addition, antioxidant can use 0.02-0.5 weight% with respect to 100 weight part of resin compositions, As an example, Iganox-1010 is mentioned.

In the present invention, the polymerization inhibitor may be used in an amount of 0.002 to 0.006% by weight based on 100 parts by weight of the resin composition, and for example, may be selected from parabenzenequinone and dibetayl patabenzenequinone. If necessary, a crosslinking agent may be added, and the amount of the crosslinking agent is preferably 0.2 to 3% by weight based on 100 parts by weight of the resin composition, and may be selected from dimethacrylate, ethylene glycol dimethacrylate, and triethylene glycol alone or two kinds. It can be used over.

In the present invention, a dye or a pigment is used as the colorant, but only a dye may be used alone. Pigments made of toners can be used to improve dispersibility. The amount used may be 0.001 to 0.5% by weight based on 100 parts by weight of the resin composition. As the amount of the coloring agent increases, the transparency of the chip is inhibited, so it is preferable to use the coloring agent in a small amount as possible.

Hereinafter, a method of manufacturing a high specific gravity transparent chip will be described in detail.

60 to 90% by weight of brominated epoxy-acrylate, 5 to 20% by weight of styrene monomer (SM), and 5 to 20% by weight of unsaturated polyester resin are placed in a reactor equipped with a stirrer, a thermometer, and a vacuum degassing apparatus. Put it in. Since the mixed resin has a very high viscosity, the mixture is melted at 60 to 70 ° C. for at least 2 hours while supplying nitrogen or air to lower the viscosity to allow stirring. 5-25 wt% of glass frit was added to 100 weight parts of the resin composition in a mixed resin having a low viscosity, and vacuum degassing was performed for 30 minutes. 2.0 wt% and 0.2 ~ 2.0 wt% of Methyl ethyl ketone peroxide are added as a curing agent, followed by mixing and vacuum degassing for 5 minutes.

Thereafter, the composition is cast to a mold to cure. At this time, the temperature of the mold is heated to 70 ~ 75 ℃. When curing is completed, additional heat treatment at 80 ° C. for 3 hours results in fully cured cured resin. After cooling the cured product at room temperature, it is crushed by a grinder and the size of the chip is separated by a separator as necessary. The size of the transparent chip is preferably about 0.15 ~ 10 mm in particle size to facilitate the application to the product of artificial marble.

The present invention can be better understood through the following examples, but the present invention is not limited to the following examples.

90% by weight of brominated epoxy-acrylate and 10% by weight of styrene monomer (SM) (e.g., 91% by weight of Samwha Paint Co., Ltd.) and unsaturated polyester resin ( For example, 9 wt% of MC-824 of Samwha Paint Co., Ltd. is placed in a reactor equipped with a stirrer. If the viscosity is low enough to be melted by stirring while maintaining at 60 ~ 70 ℃ for more than 2 hours, 10 wt% of glass frit (for example, CF-0005-30A of Nippon Frit Co., Ltd.) is added and vacuum degassed for 20 minutes. To 100 parts by weight of the resin composition, 1.0 wt% of t-butyl peroxy maleicacid (e.g., chemex-BMA 251 of Hyosung Kemax Co., Ltd.) was added and Methyl ethyl ketone peroxide (e.g. After adding 1.0% by weight of Nobel Butanon M-60), mix and vacuum degassing for 5 minutes. The mixture is poured into a mold and cured after heating to a temperature of 70 ~ 75 ℃.

The product cured by Example 1 was transparent and colorless.

Example 1 Tinuvin-327 0.04% by weight, 0.3% by weight of crosslinking agent, and 0.02% by weight of Iganox-1010 as antioxidant were further used in the composition.

Comparative Example

To the mixture of 90% by weight of unsaturated polyester resin and 10% by weight of glass frit, 0.9% by weight of t-butyl peroxy maleicacid was added as an accelerator, and a transparent chip was prepared using 0.9% by weight of Methyl ethyl ketone peroxiden M-60 as a curing agent. .

Specific gravity and refractive index of the product cured by each Example was measured and summarized in Table 1. The refractive index was measured using an Abbe refractometer.

division importance Refractive index Example 1 1.62 1.56 Example 2 1.61 1.56 Comparative Example 1.26 1.55

According to the present invention, by using an inorganic filler having excellent transparency to a high specific gravity resin, it is possible to produce a transparent chip for artificial marble having a good transparency at a specific gravity of 1.5 to 1.68.

Claims

5 to 25 weights of inorganic fillers based on 100 parts by weight of a resin composition comprising 60 to 90 weight% of brominated epoxy-Acrylate, 5 to 20 weight% of reactive diluent, and 5 to 20 weight% of unsaturated polyester resin Transparent chip for artificial marble, characterized in that the mixture was prepared by%.

The method according to claim 1,
0.2 to 2.0% by weight of the accelerator and 0.2 to 2.0% by weight of the curing agent by mixing with respect to 100 parts by weight of the resin composition, and then crushed, wherein the transparent chip for artificial marble.

3. The method of claim 2,
The accelerator is selected from the group consisting of copper, cobalt, calcium, t-butyl peroxy maleicacid and mixtures thereof, and the curing agent is Methyl ethyl ketone peroxide (MEKPO), t-butyl benzonate (TBPB). And at least one selected from the group consisting of a mixture thereof, wherein the transparent chip for artificial marble is used.

The method according to claim 1,
At least one of an ultraviolet stabilizer, a polymerization inhibitor, a light diffusing agent, a coupling agent, a coloring agent, and an antioxidant is added to 100 parts by weight of the resin composition.

The method according to claim 1,
The reactive diluent is methyl methacrylate (MMA), styrene monomer (SM) and a transparent chip for artificial marble, characterized in that at least one selected from the group consisting of.

The method according to claim 1,
The unsaturated polyester resin is an artificial marble transparent chip, characterized in that at least one selected from the group consisting of ort type, iso type, bisphenol type, vinyl ester type and mixtures thereof.

7. The method according to any one of claims 1 to 6,
The inorganic filler is a transparent chip for artificial marble, characterized in that at least one selected from the group consisting of silica (Slika), glass frit (Glass Frit) and mixtures thereof.

The method of claim 7, wherein
As the inorganic filler, the glass frit is used, and the glass frit has a particle size of 0.0010 to 0.8 mm and specific gravity of 2.0 to 3.0.

The method of claim 7, wherein
Transparent chip for artificial marble, characterized in that the specific gravity is 1.5 ~ 1.68.

(a) mixing 60-90% by weight of brominated epoxy acrylate resin, 5-20% by weight of reactive diluent and 5-20% by weight of unsaturated polyester resin to melt and stir at 60-70 ° C;
(b) vacuum degassing after mixing the inorganic filler including silica or glass frit;
(c) stirring and vacuum defoaming after mixing the accelerator and the curing agent;
(d) pouring the cured and vacuum degassed composition in the step (c) into a mold, heating and curing; And
(e) crushing and sorting after cooling the cured product cured in the step (d);
Method of manufacturing a transparent chip for artificial marble comprising a.

11. The method of claim 10,
After the mixing in step (a) to increase the temperature to 60 ~ 70 ℃ to lower the viscosity,
Method of producing a transparent chip for artificial marble, characterized in that to promote the curing by increasing the temperature to 70 ~ 75 ℃ in the step (d).

11. The method of claim 10,
In the step (e), after crushing the cured product, the size of the transparent chip is selected, the manufacturing method of the transparent chip for artificial marble, characterized in that 0.10 ~ 20mm.

Artificial marble comprising a transparent chip for artificial marble according to any one of claims 1 to 6.