WO2009057850A1

WO2009057850A1 - Composition for coloring stone and method of coloring stone using the same

Info

Publication number: WO2009057850A1
Application number: PCT/KR2007/006171
Authority: WO
Inventors: Yang Ho Jung; Yong Joo Kim
Original assignee: Pz Global. Ltd
Priority date: 2007-10-31
Filing date: 2007-12-02
Publication date: 2009-05-07
Also published as: KR100837610B1

Abstract

This invention relates to a composition for coloring stone and a method of coloring stone using the same, and particularly to a composition for coloring stone, including, based on 100 parts by weight of the composition, 50-60 parts by weight of a color-developing agent, 0.2-4 parts by weight of a dye, 1-30 parts by weight of a binder, 0.5-15 parts by weight of a non-yellowing isocyanate-based curing agent, and 5-10 parts by weight of an additive, and to a method of coloring stone using the composition for coloring stone. In the composition for coloring stone and the method of coloring stone using the same, a reactive resin and a coloring agent penetrate into the micro pores of stone to color the stone, and then they are completely fixed into the stone through a curing reaction, thereby enabling various colors to be exhibited.

Description

COMPOSITION FOR COLORING STONE AND METHOD OF COLORING STONE USING THE SAME

Technical Field

[1] The present invention relatesto a composition for coloring stone and a method of coloring stone using the same, and more particularly, to a composition for coloring stone, which can improve the physical properties, surface colors and textures of stone, which is used as a construction material for interior and exterior use, and to a method of coloring stone, which can impart various colors to the stone using the composition. Background Art

[2] Generally, various construction materials for interior and exterior use are employed because they are suitable for use in the interior and exterior spaces of buildings in terms of functions and aesthetics. Such construction materials for interior and exterior use also function to protect buildings against environmental conditions, including wind, rain, cold and warm weather, sunlight, fire, heat, and noise, and examples thereof include timber, synthetic resin, paper, and stone.

[3] Among these construction materials for interior and exterior use, stone has been frequently used as a highly durable and environmentally friendly material. However, because stone, which is presently available, is applied without change in a natural state having an inherent texture and its own color, it cannot satisfy the demand of consumers for various colorsand textures.

[4] Thus, there have been proposed construction materials for interior and exterior use, which have colors and textures similar to natural stone and which are formed from a mixture of artificial stone powder, a colorant, and a cement adhesive in a predetermined ratio. However, these construction materialsare problematic in that the surface color is likely to fade or change with the passage of time, and dust and the colorant particles that are used are scattered during working, undesirably worsening working conditions.

[5] Further, in the case of marble, in order to mechanically process the surface thereof from a natural stateto a desired state, polishing must be conducted several times. However, such polishing not only takes a great deal of time and incurs a high cost, but also generates a large quantity of stone powder, undesirably worsening working conditions, negatively affecting the health of workers.

[6] Particularly, artificial marble is utilized as a conventional construction material for interior and exterior use. As such, artificial marble is known to be manufactured by coating the surface of general stone with a coating agent that has the appearance of marble and exhibits various colors, or by molding and curing a mixture of an epoxy resin composition with synthetic resin film color chips and a curing agent in a predetermined ratio. For example, in the case of the coating agent, Korean Patent No. 10-0342176 discloses a composition obtained by mixing an epoxy resin composition with synthetic film color chips to thus prepare a resin mixture to which a curing agent is then added, and also discloses a method of manufacturing artificial marble by applying the above composition to a predetermined thickness on the surface of a coating target and then curing it. In this case, however, the applied surface may be peeled off or become worn due to external weathering, and the surface color may fade, attributable to exposure to UV light for a long period of time, undesirably losing the originally applied color.

[7] In addition, Korean Patent No. 10-0366568 discloses a method of manufacturing artificial marble by mixing an epoxy resin composition, heated to 30-100C, with synthetic resin film color chips to prepare a mixture, which is then stirred at a reduced pressure to thus eliminate foam or water, adding the resin mixture with a curing agent to thus eliminate foam again at a reduced pressure, molding the obtained mixture using a mold, primarily curing the molded product so that it is not tacky, and then maintaining the primarily cured molded product at a predetermined temperature for a predetermined time, completely curing the molded product. Although the artificial marble manufactured using the above method satisfies the strength required for construction materials for interior and exterior use and is superior in terms of wear resistance, contraction resistance, water resistance, cold resistance and chemical resistance, the color thereof fades upon exposure to UV light for a long period of time, undesirably losing the original color thereof.

[8] Thus, there is a need for research to find a solution that is able to solve the above problems, maintain the original properties of stone without change, prevent the color of stone from fading or changing due to exposure to UV light for a long period of time, and impart various colors. Disclosure of Invention Technical Problem

[9] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and an object of the present invention is to provide a composition for coloring stone and a method of coloring stone using the same, in whbh a reactive resin and a coloring agent completely penetrate to the inside of stone to color the stone, so that various colors and textures are imparted to the surface of the stone.

[10] Another object of the present invention is to provide a composition for coloring stoneand a method of coloring stone using the same, in which a reactive resin and a coloring agent completely penetrate to the inside of stone to color the stone, so that various colors and textures are imparted to the surface of the stone, thus maMng it possible to overcome the monotone problems of conventional stone, thereby expanding the application range of the present invention not only to the construction materials for interior and exterior use but also to the decorative purposes.

[11] A further object of the present invention is to provide a composition for coloring stone and a method of coloring stone using the same, in which stone may exhibit various surface textures and colors, and, instead of a surface color conversion method through electroposition, a nano-sized reactive resin/dye mixture solution completely penetrates into the pores of stone to color the stone, and thus the reactive resin is fixed into the stone, thereby semi-permanently fixing the color into the stone to color the stone, and also the strength of the stone can be enhanced by the curing reaction of the reactive resin in the micro pores of stone. Technical Solution

[12] In order to accomplish the above objects, the present invention providesa composition for coloring stone, including, based on 100 parts by weight of the composition, 50-60 parts by weight of a color-developing agent, 0.2-4 parts by weight of a dye, 1-30 parts by weight of a binder, 0.5-15 parts by weight of a non-yellowing isocyanate-based curing agent, and 5-10 parts by weight of an additive.

[13] In the composition according to the present invention, the color-developing agent may be a mixture of an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent, as an organic solvent.

[14] In the composition according to the present invention, the aliphatic hydrocarbon solvent may be one or a mixture of two or more selected from the group consisting of methylethylketone (MEK), acetone, methylisobutylketone (MIBK), ethylacetate, buty- lacetate, cellosolve acetate, diethyleneglycol monobutyl monoether, and di- ethyleneglycol monoethyl monoether.

[15] In the composition according to the present invention, the aromatic hydrocarbon solvent may be one or a mixture of two or more selected from the group consisting of toluene, xylene, and benzene.

[16] In the composition according to the present invention, the binder may be one or a mixture of two or more selected from the group consisting of a reactive low- temperature curable urethane resin composed mainly of an acrylic polyol resin, a natural drying type cellulose acetate- or acryl-based resin, acrylic urethane, acrylic melamine, alkyd melamine, an epoxy resin-based reactive resin, and a thermosetting resin.

[17] In the composition according to the present invention, the additive may be selected from the group consisting of a penetrating agent, a UV blocking agent, an anion generating agent, and combinations thereof.

[18] In addition, the present invention provides a method of coloring stone, suitable for penetrating and fixing a coloring agent into stone, including (a) sorting natural stone, cutting it to a predetermined size, and then polishing a surface of the cut stone; (b) preparing the above-mentioned composition for coloring stone (c) immersing the stone obtained in the (a) into the composition of the (b) for 30-40 min, thus causing the coloring agent to penetrate into the stone; and (d) removing the stone immersed inthe (c) from the composition, and then subjecting the stone to washing, drying, and curing.

[19] The method according to the present invention may further include (e) applying a coating agent containing a UV blocking agent to a predetermined thickness on the surface of the stone, and performing low-temperature dry curing or heat curing at 150-160C for 10-30 min, after the (d).

[20] In the method according to the present invention, the coating agent may include 40 wt% of an acrylic polyol resin, 20 wt% of an isocyanate-based curing agent, 15 wt% of a fluorinated resin paint, 20 wt% of toluene, and 5 wt% of a UV blocking agent. Advantageous Effects

[21] According to the present invention, in the composition for coloring stone and the method of coloring stone using the same, a reactive resin and a coloring agent penetrate into the micro pores of stone to color the stone, and then they are completely fixed into the stone through a curing reaction, thereby realizing various colors.

[22] The composition according to the present invention penetrates and is fixedinto stone, and therefore, the stone is able to exhibit various surface textures and colors. Further, a nano-sized reactive resin/dye mixture solution completely penetrates into the stone to color the stone, and then the reactive resin is fixed into the stone, thereby semipermanently fixing the color into the stone to color the stone, and furthermore, the reactive resin is cured in the micro pores of the stone, thus enabling the enhancement of the strength of stone itself.

[23] In the case where the composition auording to the present invention penetrates and is fixed into the stone, the reactive resin and the coloring agent completely penetrate to the inside of stoneso that various colors and textures are imparted to the surface of stone, thus making it possible to overcome the monotone problems of conventional stone, thereby expanding the application range of the present invention not only to construction material for interior and exterior use but also to decorative purposes.

[24] In the composition for coloring stone and the method of coloring stone using the composition according to the present invention, stone can exhibit various colors, and the color thereof does not fade or change even upon exposure to UV light for a long period of time, thereby maintaining the originally colored stone without change.

[25] In the composition for coloring stone and the method of coloring stone using the composition according to the present invention, the colored stone may substitute for- conventional construction materials for interior and exterior use, including natural marble or artificial marble, and costs for the interior and exterior spaces of buildings may be reduced. Brief Description of the Drawings

[26] FIG. 1 is a photograph illustrating natural stone, which is sorted and cut to a predetermined size

[27] FIG. 2 is a flowchart illustrating the process of coloring stone through penetration using the composition for coloring stone, according to a first embodiment of the present invention

[28] FIG. 3 is a flowchart illustrating the process of coloring stone through penetration using the composition for coloring stone, according to a second embodiment of the present invention; and

[29] FIGS. 4 and 5 are photographs illustrating the stone, which is colored using the process of coloring stone, according to the present invention. Best Mode for Carrying Out the Invention

[30] Hereinafter, a detailed description will be given of the present invention.

[31] According to the present invention, a composition for coloring stone includes, based on 100 parts by weight of the composition, 50-60 parts by weight of a color-developing agent, 0.2-4 parts by weight of a dye, 1-30 parts by weight of a binder, 0.5-15 parts by weight of a non-yellowing isocyanate-based curing agent, and 5-10 parts by weight of an additive. [32] In the composition according to the present invention, the color-developing agent is exemplified by a mixture of an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent, as an organic solvent.

[33] The aliphatic hydrocarbon solvent is one or a mixture of two or more selected from the group consisting of methylethylketone (MEK), acetone, methylisobutylketone (MIBK), ethylacetate, butylacetate, cellosolve acetate, diethyleneglycol monobutyl monoether, and diethyleneglycol monoethyl monoether.

[34] The aromatic hydrocarbon solvent is one or a mixture of two or more selected from the group consisting of toluene, xylene, and benzene.Preferably, the aliphatic hydrocarbon solvent is exemplified by methylethylketone, acetone, methylisobutylketone, and ethylacetate, and the aromatic hydrocarbon solvent is exemplified by a toluene-containing mixture solvent.

[35] The binder is one or a mixture of two or more selected from the group consisting of a reactive low-temperature curable urethane resin composed mainly of an acrylic polyol resin, a natural drying type cellulose acetate- or acryl-basedresin, acrylic urethane, acrylic melamine, alkyd melamine, an epoxy resin-based reactive resin, and a thermosetting resin. As such, in the case of the thermosetting resin, the use of resin, composed mainly of polyvinylidene fluoride, is preferable.

[36] The additive is selected from the group consisting of a penetrating agent, a UV blocking agent, an anion generating agent, and combinations thereof. Particularly useful is a mixture of a penetrating agent and a UV blocking agent. Used in the present invention, the penetrating agent is Z-6341 Silane, available from Dow Corning, and various types of penetrating agent and UV blocking agent may be used depending on the end use.

[37] As the dye used in the present invention, any commercial dye product may be used so long as it can be dissolved in an organic solvent, and examples thereof include ORICO and ORIMAX from Orient Chemical, and NEOJAPON from BASF, Germany.

[38] Using the composition for coloring stone as mentioned above, a method of coloring stone, sάtablefor penetrating and fixing a color into the stone, is described below, with reference to the appended drawings.

[39] FIG. 2 is a flowchart illustrating the process of coloring stone through penetration using the composition for coloring stone, according to a first embodiment of the present invention, and FIG. 3 is a flowchart illustrating the process of coloring stone through penetration using the composition for coloring stone, according to a second embodiment of the present invention.

[40] As shown in FIG. 2, natural stone, which can be seen in FIG. 1, is sorted and is cut to a predetermined size, after which the surface of the cut stone is polished (SlOO).

[41] The composition having the above properties for coloring the stone is prepared

(S200).

[42] The stone prepared at step SlOO is immersed into the composition prepared at step S200 for 30-40 min, so that the coloring agent penetrates into the stone (S300), after which the stone is removed from the composition, washed, dried, and cured, thus fixing a desired color to the stone (S400).

[43] The stone manufactured through the above process is capable of exhibiting various colors depending on the color of a dye constituting the coloring agent. In the present invention, because the coloring agent penetrates and is fixed into the stone to thus realize various colors, unlike conventional surface coating, the stone does not undergo surface scratching, color changes due to external weathering, and decoloration or discoloration due to exposure to UV light.

[44] According to the present invention, in order to minimize decoloration and discoloration due to UV light, coating of the surface of the stone, obtained at step S400, with a coating agent containing a UV blocking agent or an anion generating agent for imparting healthful effects and disinfecting effects (S500) and performing low- temperature dry curing or heat curing at 150- 160C for 10-30 min (S600) may be further conducted.

[45] The coating agent includes 40 wt% of an acrylic polyol resin, 20 wt% of an isccyanate-based curing agent, 15 wt% of fluorinated resin paint, 20 wt% of toluene, and 5 wt% of a UV blocking agentor an anion generating agent. In this case, the coating agent preferably has the same color as the color that penetrates and is fixed into the stone. Mode for the Invention

[46] A better understanding of the present invention may be obtained through the following example, which is set forth to illustrate, but is not to be construed as the limit of the present invention.

[47] Example

[48] The coloring composition and the coating agent for surfxe coating after coloring the stone were prepared as follows.

[49] Table 1 [Table 1] [Table ]

[50] * Coloring Composition [51] Table 2 [Table 2] [Table ]

[52] * Coating Agent [53] [54] Natural granite was cut to a predetermined size (e.g., width 100 mm x length 100 mm x thickness 20 mm) and was then polished, after which the cut granite was immersed into the prepared coloring composition for 40 min to cause the coloring agent to penetrate into the granite. After 40 min, the granite was removed from the composition, and then the surface thereof was washed, dried at room temperature, and aired at 120C for 20 min, thus fixing the coloring agent into the micro pores of the granite. The coating agent, prepared as above, was applied to a predetermined thickness on the surface of the colored granite, and then dry cured at low temperatures, thereby manufacturing a specimen.

[55] From FIG. 4, the stone thus obtained can be seen to have been completely colored. In particular, as shown in FIG. 5, it can be seen that the inside of the stone was colored.

[56] The weather resistance, water resistance, and chemical resistance of the colored stone were tested. The test methods and the test results were as follows.

[57] ( 1 ) Weather Resistance Test

[58] The test for allowing the colored stone to stand under conditions of a) 20 2C, 1 hour, b) 60 2C, relative humidity of 905%, 6 hours, and c) -30 2C, 6 hours was repeated 5 times, after which whether gloss and color were changed was observed. As the results thereof, there was no change in gloss or in color.

[59] (2) Water Resistance Test

[60] The colored stone was tested axording to KS F 4601 : 2001. As the results thereof, the absorption rate was determined to be 0.1%.

[61] * Absorption Rate (%) = (absorbed stone weight - dried stone weight)/dried stone weight x 100

[62] Q) Chemical Resistance Test

[63] - A spot test was conducted for 1 hour using a liquid bleacher (Yuhanrox), after which whether gloss and color were changed was observed. As the results thereof, there was no change in gloss or in color.

[64] - The same test as in the test using the liquid bleacher was conducted using 50% powdery detergent(Super-Ti), after which whether gloss and color were changed was observed. As the results thereof, there was no change in gloss or in color.

[65] - The same test as in the test using the liquid bleacher was conducted using a hydrochloric acid solution (pH 2), after which whether gloss and color were changed was observed. As the results thereof, there was no change in gloss or in color.

[66]

Claims

[1] A composition for coloring stone, comprising, based on 100 parts by weight of the composition, 50-60 parts by weight of a color-developing agent, 0.2-4 parts by weight of a dye, 1-30 parts by weight of a binder, 0.5-15 parts by weight of a non-yellowing isocyanate-based curing agent, and 5-10 parts by weight of an additive.

[2] The composition for coloring stone according to claim 1 , wherein the color- developing agent is a mixture of an aliphatic hydrocarbon solvent and an aromatic hydrocarbon solvent, as an organic solvent.

[3] The composition for coloring stone according to claim 2, wherein the aliphatic hydrocarbon solvent is one or a mixture of two or more selected from a group consisting of methylethylketone (MEK), acetone, methylisobutylketone (MIBK)₁ ethylacetate, butylacetate, cellosolve acetate, diethyleneglycol monobutyl monoether, and diethyleneglycol monoethyl monoether.

[4] The composition for coloring stone according to claim 2, wherein the aromatic hydrocarbon solvent is one or a mixture of two or more selected from a group consisting of toluene, xylene, and benzene.

[5] The composition for coloring stone according to claim 1, wherein the binder is one or a mixture of two or more selected from a group consisting of a reactive low-temperature curable urethane resin composed mainly of an acrylic polyol resin, a natural drying type cellulose acetate- or acryl-based resin, acrylic urethane, acrylic melamine, alkyd melamine, an epoxy resin-based reactive resin, and a thermosetting resin.

[6] The composition for coloring stone axording to claim 1, wherein the additive is selected from a group consisting of a penetrating agent, a UV blocking agent, an anion generating agent, and combinations thereof.

[7] A method of coloring stone, suitable for penetrating and fixing a coloring agent into stone, comprising:

(a) sorting natural stone, cutting it to a predetermined size, and then polishing a surface of the cut stone

(b) preparing the composition for coloring stone of any one of claims 1 to 6;

(c) immersing the stone, obtained in the (a),into the composition for coloring stone, prepared in the (b), for 30-40 min, thus causing the coloring agent to penetrate into the stone; and (d) removing the stone, immersed in the (c), from the composition for coloring stone, and then subjecting the stone to washing, drying, and curing.

[8] The method of coloring stone according to claim 7, further comprising (e) applying a coating agent containing a UV blocking agent to a predetermined thickness on the surface of the stone, and performing low-temperature dry curing or heat curing at 150-160C for 10-30 min, after the (d).

[9] The method of coloring stone according to claim 8, wherein the coating agent comprises 40 wt% of an acrylic polyol resin, 20 wt% of an isccyanate-based curing agent, 15 wt% of a fluorinated resin paint, 20 wt% of toluene, and 5 wt% of a UV blocking agent.