JP4678280B2 - Surface treatment method for artificial marble - Google Patents

Description

  The present invention relates to a surface treatment method for applying a coating fluorine-based compound or a silicone-based compound for imparting an antifouling function to the surface of an artificial marble made of a synthetic resin.

  In recent years, artificial marble decorative boards mainly composed of thermosetting resins such as vinyl ester resins, acrylic resins and polyester resins or synthetic resins of thermoplastic resins have been widely used for wall materials and kitchen ceilings because of their excellent physical properties and high-class feeling. It is used as a board (for example, refer patent document 1).

  As an artificial marble, a resin composition in which an inorganic filler such as aluminum hydroxide is added to a thermosetting resin or a thermoplastic resin is often used, and this resin composition is formed to a predetermined thickness to suit the application. After being cut into a predetermined size, a portion corresponding to the decorative surface is polished and used as necessary.

The artificial marble produced in this way is widely used after being commercialized as a wash counter, kitchen counter, bathtub, wash bowl and the like.
JP 2001-190344 A

  Here, when artificial marble products are used in a field called watering, such as around toilets, bathrooms, kitchens, etc., dirt due to use, contamination due to detergents, dirt due to food, oil, cosmetics, etc. are easily adhered and cleaned. However, it was difficult to remove dirt even after cleaning, or dirt could not be removed even after cleaning. For these reasons, the advent of artificial marble with high antifouling performance that is difficult to get dirty and easy to remove.

  Marble is usually used as a stone material with moderate gloss on the surface, and artificial marble decorative plates are also used to polish the surface so that it has moderate gloss or for pattern expression. It was. When the surface of the artificial marble is polished, the inorganic filler contained in the resin matrix is exposed on the surface. Since this inorganic filler often has both hydrophilicity and lipophilicity, if various liquid contaminants adhere to the surface of the artificial marble decorative board, this interface is formed at the interface between the resin and the inorganic filler. There has been a problem that liquid contaminants penetrate and become difficult to remove (that is, antifouling performance is low). Further, this inorganic filler has a drawback that it is easily affected by chemicals such as bleach.

  In view of this, the present applicant provided, in Japanese Patent Application No. 2004-216294, a surface treatment method for artificial marble that makes it difficult for dirt to adhere to the surface and makes it easier to remove the adhered dirt by applying a fluororesin compound.

  However, there has been a problem in that the gloss of the surface is increased by applying the fluorine resin compound to the surface of the artificial marble, and the polishing unevenness on the surface of the artificial marble becomes easy to see.

  The present invention has been made in view of the above points. The object of the present invention is to provide a surface treatment for artificial marble that can reduce the occurrence of gloss by adding a matting material to a fluorine-based resin compound. It is an object to provide a method.

  In order to solve the above-mentioned problem, in the invention according to claim 1, at least one surface of artificial marble made of a polymer mainly composed of a thermosetting resin or a thermoplastic resin and an inorganic filler is used for matting. Applying a fluorine resin compound obtained by adding 10 to 30% by weight of a fluorine powder having a particle size of 0.1 to 20 μm obtained by pulverizing and atomizing a cross-linked solid fluorine resin to the solid content of the low molecular weight liquid fluorine resin compound It is characterized by. As a result, the surface of the artificial marble has sufficient antifouling performance, and it is possible to form a fluorine compound coating without interference fringes or smears. It can be prevented from becoming easily visible.

  In the present invention, it is possible to form a fluorine compound film having a sufficient antifouling performance on the surface of the artificial marble and free from interference fringes and smears, and also a fluorine powder for matting or It is possible to prevent the surface of the artificial marble from being glossed by the silica powder and making it difficult to see uneven polishing.

  The artificial marble in the present invention is molded from a thermosetting resin or a thermoplastic resin and an inorganic powder. As the thermosetting resin, one or more selected from vinyl ester resins, acrylic resins, and polyester resins are preferable, and as the inorganic powder, for example, calcium silicate, talc, kaolin, clay, silica, calcium carbonate, water Aluminum oxide, magnesium hydroxide, barium sulfate, calcium sulfate and the like are mentioned, but are not particularly limited. Among them, aluminum hydroxide is preferred, and aluminum hydroxide trihydrate, ie, gibbsite is more preferred. Used. The average particle size of the inorganic powder is preferably 0.1 to 100 μm, and more preferably 0.5 to 80 μm.

  The ratio of the polymer to the inorganic powder in the artificial marble matrix is preferably 50 to 500 parts by mass of the inorganic powder with respect to 100 parts by mass of the polymer. If necessary, additives such as a colorant and a pattern material may be added to the matrix of the artificial marble of the present invention. Any colorant can be used as long as it is a dye, an organic pigment, an inorganic pigment, or the like, and is usually used for an inorganic powder-containing resin molding such as artificial marble. Examples of the pattern material include, but are not particularly limited to, particles made of an organic resin or inorganic particles. Examples of the organic resin include, but are not limited to, for example, methyl methacrylate resin, polystyrene, polyvinyl chloride, polyester, epoxy resin, polyvinyl alcohol, and the like, and inorganic particles include, for example, marble particles, silica, Although mica etc. are mentioned, it is not limited to these in particular. The maximum dimension of these particles is preferably 10 mm or less, and more preferably 5 mm or less.

  Artificial marble is produced as described above. In the present invention, a low molecular weight liquid fluorine compound added with a matting material for imparting antifouling property to the surface (at least one surface) of the artificial marble is applied and penetrated. To form a film. The drying step after applying the fluorine compound may be dried at room temperature or heated. The drying process after applying the fluorine-based compound includes mica and the like, but is not particularly limited thereto. The maximum dimension of these particles is preferably 10 mm or less, and more preferably 5 mm or less.

  Fluorine resin compounds include polytetrafluoroethylene, tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene copolymer, tetrafluoroethylene / ethylene copolymer, tetrafluoroethylene and heterocyclic ring Containing fluorinated monomer copolymer, polychlorotrifluoroethylene, fluoroalkyl (meth) acrylate polymer, fluoroalkyl (meth) acrylate and other alkyl (meth) acrylate copolymer, vinylidene fluoride, vinylidene fluoride and tetra Examples include fluoroethylene copolymers, vinylidene fluoride and perfluoroalkyl vinyl ether copolymers, and the like.

  Fluorine powder having a particle size of 0.1 to 20 μm obtained by pulverizing a cross-linked solid fluororesin as a matting material is usually PTFE (polytetrafluoroethylene = tetrafluoroethylene) resin, PFA (tetrafluoroethylene). Ethylene-perfluoroalkyl vinyl ether copolymer = perfluoroalkoxy) resin, FEP (tetrafluoroethylene-hexafluoropropylene copolymer = tetrafluoroethylene-hexafluoropropylene copolymer) resin, ETFE (tetrafluoroethylene-ethylene) Copolymer = tetrafluoroethylene-ethylene copolymer) resin, PVdF (polyvinylidene fluoride = vinylidene fluoride) resin, PCTFE (polychlorotrifluoroethylene = ethylene trifluoride chloride) resin, etc. Of fluorinated resin Are those that can be used as Tsu-containing powder, which in addition to be used singly, it is also possible to use two or more thereof.

  Silica powder as a matting material is, for example, synthetic materials such as Tospearl (GE Toshiba Silicone Co., Ltd.), ACEMATT (Degussa Co., Ltd.), Mizukasil (Mizusawa Chemical Co., Ltd.), Nip Seal (Nippon Silica Industry Co., Ltd.), Shilton ( Mizusawa Chemical Industry Co., Ltd., Fine Seal (Tokuyama Soda Co., Ltd.), Cicilia (Fuji Silysia Chemical Co., Ltd.), Aerosil (Nippon Aerosil Co., Ltd.), Carplex (Shionogi Pharmaceutical Co., Ltd.), Toxeal (Tokuyama Soda Co., Ltd.) , Admafine (Admatechs Co., Ltd.), Sildex (Asahi Glass Co., Ltd.), etc., and natural systems such as Radiolite (Showa Chemical Industry Co., Ltd.), Snow Floss (Johns-Manville), Celite ( Johns-Manville) Examples include Latom (Eagle Pitcher), Silica (Central Silica), Dicalite (Grefco), Imsil (Illinois Mineral), Minucil (Pennsylvania Glass Sand). In addition, the said name is a brand name. These may be used alone or in combination of two or more.

  The fluorine powder is not soluble in a fluorine-based solvent, but the low-molecular liquid fluorine-based resin compound is soluble in a fluorine-based solvent. Examples of the fluorine-based solvent include HFE, HFPE, and PFPE, but are not particularly limited.

  Hereinafter, the present invention will be described in more detail based on examples.

  First, as a resin composition of artificial marble, vinyl ester resin (“Prominate P-311” manufactured by Takeda Pharmaceutical Co., Ltd.), aluminum hydroxide (“CW-308B” manufactured by Sumitomo Chemical Co., Ltd.), and vinyl ester resin are used. It was prepared by mixing 200 parts by mass with respect to 100 parts by mass, adding an appropriate amount of a curing agent (“Percure WO” manufactured by NOF Corporation), and mixing with a stirrer.

  This resin composition was defoamed under reduced pressure at 2666 Pa (20 Torr) for 30 minutes, poured into a mold, and the mold was heated at 90 ° C. for 70 minutes to cure the resin composition. An artificial marble molded as a thick flat plate was obtained.

  After this artificial marble board is surface-polished with a nonwoven fabric abrasive (manufactured by Sumitomo 3M Co., Ltd.), a low-molecular liquid fluororesin ("Fluorosurf" produced by Fluoro Technology Co., Ltd.) has a boiling point of 80 ° C to 150 ° C (standard 100) Fluorine resin compound dissolved at a concentration of 3% (1% to 5%) in a fluorine solvent composed of HFPE (hydrofluoropolyether) prepared at ℃. Alternatively, a coating material produced by adding a predetermined ratio of silica powder to the solid content of the fluororesin compound is applied by spraying or something like a brush, dried at room temperature, and the coating is applied to the surface. Formed.

  The gloss of the artificial marble subjected to this surface treatment was targeted to be less than 10 at 60 °, and 10 or more were not allowed.

  Moreover, antifouling property was evaluated about the artificial marble which performed this surface treatment. The antifouling property is the difference in color before and after the test after boiling in 500 ml of water using tea (tea pack made by Lipton), dropping it on the surface of artificial marble (packing) and leaving it to wash for 24 hours. Evaluation was performed by measuring. The boundary of the presence or absence of antifouling property was a color difference of 1.0.

Further, the finished appearance was confirmed, and it was evaluated whether there was any deposit of matte material, uneven coating, or the like.
<Test conditions>
In Example 1, 10% of fluorine powder made of PTFE was added to the solid content of the fluororesin compound.

  In Example 2, 30% of fluorine powder made of PTFE was added to the solid content of the fluororesin compound.

  In Example 3, 20% of fluorine powder made of PFA was added to the solid content of the fluororesin compound.

  In Example 4, 20% of fluorine powder made of FEP was added to the solid content of the fluororesin compound.

  In Example 5, 2% of the above-mentioned “Tospearl” as silica powder was added to the solid content of the fluororesin compound.

  In Example 6, 20% of the above-mentioned “Tospearl” as silica powder was added to the solid content of the fluororesin compound.

  In Example 7, 10% of the above “ACEMATT” was added as a silica powder with respect to the solid content of the fluororesin compound.

  In Comparative Example 1, the matte material was not added to the fluororesin compound.

  In Comparative Example 2, 8% of fluorine powder made of PTFE was added to the solid content of the fluororesin compound.

  In Comparative Example 3, 35% of fluorine powder made of PTFE was added to the solid content of the fluororesin compound.

  In Comparative Example 4, 1% of the above-mentioned “Tospearl” as silica powder was added to the solid content of the fluororesin compound.

  In Comparative Example 5, 25% of the above-mentioned “Tospearl” as silica powder was added to the solid content of the fluororesin compound.

  Table 1 shows the test conditions and evaluation results of Examples 1 to 6, and Table 2 shows the conditions and evaluation results of Comparative Examples 1 to 6.

<Test results>
In each of Examples 1 to 7, the gloss was able to be lowered while maintaining the antifouling property when the 60 ° gloss was less than 10.

  Moreover, it turned out that a silica powder (Example 1- Example 4) needs less addition amount than a fluorine powder (Example 5-Example 7). The reason for this is that the particle size of the fluorine powder is 1 μm or less as the primary particle size, whereas the silica powder has a large particle size of 2 to 12 μm, so that a small amount can be added to appear on the surface. Conceivable. However, since the antifouling property of silica itself is inferior to that of fluorine, it cannot be added in a large amount.

  In Comparative Example 1 (without matting material), there is no problem with antifouling properties, but the gloss is high and polishing unevenness is easily noticeable.

  In Comparative Example 2 (fluorine powder is insufficient), the gloss reduction is small and the polishing unevenness is easily noticeable.

  In Comparative Example 3 (excessive fluorine powder), the gloss and antifouling properties have reached the target, but the fluorine powder is deposited on the surface and can be removed by finger touch.

  In Comparative Example 4 (silica powder is insufficient), the gloss reduction is small and the polishing unevenness is easily noticeable.

  In Comparative Example 5 (excessive silica powder), the gloss reached the target, but the antifouling property decreased due to the influence of silica appearing on the surface.

  As described above, the artificial marble decorative board coated by adding fluorine powder or silica powder as a matting material to the fluororesin compound of the present invention has improved water and oil repellency due to the antifouling coating film on the surface, Gloss can be lowered while exhibiting excellent stain resistance.

Claims (1)

Particle size of 0.1 to 20 μm obtained by pulverizing cross-linked solid fluororesin for matting and atomizing on at least one surface of artificial marble made of a polymer mainly composed of thermosetting resin or thermoplastic resin and an inorganic filler. surface treatment how the artificial marble, characterized by comprising applying a fluororesin compound added 10 to 30% by weight relative to the fluorine powder low molecular liquid fluororesin compound solids.