JP2005290983A - Method of repairing pottery tile surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To improve appearance by making contrast between a joint part and a tile part clear while enhancing the design property of an existing tile surface to a pottery tile surface where degradation and pollution are worsened, and to impart pollution resistance, water-proofness, weatherability, and the like. <P>SOLUTION: The pottery tile surface is repaired by a first process of coloring the joint part using a colored liquid containing a pigment and/or dye, and a second process of coating the whole surface with a colored transparent paint containing a hydrolytic silyl group in a binding agent with a rate of concealment of 0.10-0.60. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for repairing a ceramic tile surface used for exterior finishing of a building or the like.

  Finishing with porcelain tiles such as porcelain tiles, porcelain tiles, semi-porcelain tiles, and porcelain tiles generally has good durability and design, so that it can protect buildings and other aesthetics. It is used favorably for improvement.

  However, in the case of a ceramic tile constructed for an exterior of a building or the like, it will be exposed for a long time in an environment affected by sunlight or wind and rain. As a result, deterioration such as reduction in gloss of the tile portion, discoloration, erosion, or neutralization or strength reduction of the joint portion proceeds. Furthermore, contamination proceeds due to airborne dust, floating pollutants such as exhaust gas, efflorescence and rust from the inside of the enclosure, and oil from the sealing material. For such ceramic tile surfaces, there is a need for refurbishment in order to restore durability, design and the like.

  As a method for refurbishing the ceramic tile surface, Patent Document 1 proposes a method of laminating a clear paint not containing a pigment. In this invention, it is said that waterproofness can be imparted without changing the design of the existing ceramic tile surface by using the clear paint.

  The present invention can be applied to a ceramic tile surface whose degree of deterioration and contamination is slight. However, improve aesthetics on surfaces that have deteriorated significantly due to long-term exposure, or on surfaces that have been significantly deteriorated and cannot be removed completely even after cleaning. Can not solve the problem of design.

  In order to cope with the problems of deterioration and contamination, there is a method of applying a colored paint to the ceramic tile surface. However, if the entire ceramic tile surface is painted with the same color, the contrast between the joint portion and the tile portion is lost, and the appearance becomes monotonous. Moreover, when the existing tile has various patterns, the patterns cannot be utilized.

JP-A-6-33565

  Therefore, the problem to be solved by the present invention is to improve the aesthetics by clarifying the contrast between the joint part and the tile part while taking advantage of the design of the existing tile face for the ceramic tile face that has deteriorated or contaminated. It is also possible to obtain a repair method that can impart stain resistance, waterproofness, weather resistance, and the like.

  In order to solve such problems, the present inventors have intensively studied and found a method of coating a specific colored transparent paint on the entire surface after coloring the joint portion using a specific coloring liquid, and completed.

That is, the method for repairing a porcelain tile surface of the present invention has the following characteristics.
1. 1st process of coloring a joint part using the coloring liquid containing a pigment and / or a dye with respect to a ceramic tile surface, the hydrolyzable silyl group is contained in the binder, and the concealment rate is 0.10 to 0.10. A method for repairing a ceramic tile surface, comprising a second step of coating the entire surface with a colored transparent paint of 0.60.
2. In the second step, a solvent composed mainly of an acrylic synthetic resin containing a hydrolyzable silyl group and an aliphatic hydrocarbon solvent having a solubility parameter of 6.5 to 9.5 that can dissolve the resin. And a transparent coloring paint having a concealment ratio of 0.10 to 0.60 is used. The method of repairing the ceramic tile surface described in 1.
3. In the second step, a non-aqueous dispersion type in which an acrylic synthetic resin containing a hydrolyzable silyl group is dispersed in a solvent mainly composed of an aliphatic hydrocarbon solvent having a solubility parameter of 6.5 to 9.5 1. A colored transparent paint containing a resin composition and having a concealment ratio of 0.10 to 0.60 is used. Or 2. The method of repairing the ceramic tile surface described in 1.
4). 1. A silicate oligomer represented by Chemical Formula 2 is contained in the colored transparent paint. Or 3. The method of repairing the ceramic tile surface described in 1.

  By applying the present invention to a ceramic tile surface that has deteriorated or contaminated, the design of the existing tile surface is utilized, and the contrast between the joint portion of the modified tile surface and the tile portion is clarified to improve aesthetics. Furthermore, stain resistance, waterproofness, weather resistance, and the like can be imparted.

  Hereinafter, it explains in detail with the best form for carrying out the present invention.

  The present invention is applied to a ceramic tile surface such as a building exterior. Examples of the ceramic tiles include porcelain tiles, stoneware tiles, semi- porcelain tiles, and ceramic tiles. Although the present invention can be applied to any surface finished with such a tile, an excellent effect is exerted particularly on a ceramic tile surface that has deteriorated or contaminated significantly due to long-term exposure.

  In this invention, as a 1st process, a joint part is colored using the coloring liquid (henceforth a coloring liquid) containing a pigment and / or dye. When the coloring liquid in the present invention is applied to the joint part of the ceramic tile surface to be repaired, the pigment and / or dye (hereinafter referred to as a coloring component) penetrates into the joint part, and the joint part is colored. By including this step, it is possible to finally clarify the contrast between the joint portion and the tile portion on the tile surface subjected to the repair.

  Coloring components contained in the coloring liquid include carbon black, titanium oxide, zinc oxide, ferric oxide (Bengara), lead chromate (molybdate orange), chrome lead, yellow iron oxide, ocher, ultramarine, and cobalt green. Inorganic pigments such as: azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, quinophthalone, and other organic pigments; oil-soluble dyes And dyes such as acid dyes, basic dyes, reactive dyes, and direct dyes. The content of the coloring component is not particularly limited, but is usually 0.05 to 2.0% by weight in the coloring liquid.

  In addition to coloring components, the coloring liquid used in the present invention includes various surfactants such as nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants, antifoaming agents, and anti-settling agents. An agent or the like may be contained. In addition to water, water-soluble solvents such as methanol, ethanol, isopropyl alcohol, ethylene glycol, and propylene glycol can be used as the solvent for the coloring liquid.

  The color tone of the coloring liquid may be appropriately set so that the color difference between the tile portion and the joint portion becomes larger. In the present invention, in particular, the color difference between the tile portion and the colored joint portion is 5 in ΔL value. It is preferable to set so as to be above.

  In the present invention, the method for applying the coloring liquid to the joint is not particularly limited, and for example, a brush, cloth, roller, spray, sponge, or the like can be used.

  When the coloring liquid adheres to the tile, it may be washed with water or the like. Even if the coloring liquid adheres to the tile portion, the tile portion has a lower water absorption than the joint portion and the coloring component does not easily permeate, so that the coloring component can be removed by washing. At this time, since the coloring component of the joint part penetrates into the joint part, it is difficult to be removed, and the entire tile surface can be washed with water. Further, even if the coloring component remains in the tile portion, it can be covered in the second step, so that there is no problem.

  In the present invention, it is preferable to etch the joint portion or the entire tile surface as the pretreatment of the first step. By performing the etching, it is possible to further improve the permeability and coloring property of the coloring liquid into the joint. The etching method is not particularly limited, but a solution having a sulfuric acid concentration of about 5 to 10%, a hydrochloric acid concentration of about 2 to 10%, a phosphoric acid concentration of about 10 to 20%, a quencher A solution having an acid concentration of about 3% is used as an etching agent. In addition, ammonium hydrogen fluoride, ammonium fluoride, ammonium silicofluoride aqueous solution, etc. can be used as glass etchants, so it removes pollutants from silica components in joints and etches glaze layers on ceramic tile surfaces. It is preferably used in some cases.

  In the present invention, as a second step, a colored transparent paint containing a hydrolyzable silyl group in the binder and having a concealment ratio of 0.10 to 0.60 is applied to the entire surface of the ceramic tile.

  The colored transparent paint used in the present invention needs to contain a hydrolyzable silyl group in the binder. By this functional group, excellent adhesion to various ceramic tiles and joints is expressed. Examples of the compound containing a hydrolyzable silyl group include hydrolyzable silyl group-containing acrylic monomers and silane coupling agents.

  Specific examples of the hydrolyzable silyl group-containing acrylic monomer include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, and γ- (meth) acryloxypropyl. Examples thereof include methyldimethoxysilane and γ- (meth) acryloxypropylmethyldiethoxysilane.

  The hydrolyzable silyl group-containing acrylic monomer can be used as a binder by copolymerization of the monomer with another monomer. Other monomers copolymerizable with the hydrolyzable silyl group-containing acrylic monomer include, for example, methyl group (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. ) Acrylic monomers; hydroxyl group-containing (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate; ethylenically unsaturated carboxylic acids such as (meth) acrylic acid; dimethylaminoethyl (meth) acrylate, etc. Amino group-containing (meth) acrylic monomers; amide-containing (meth) acrylic monomers such as (meth) acrylamide; nitrile group-containing (meth) acrylic monomers such as acrylonitrile; glycidyl (meth) acrylate Examples thereof include epoxy group-containing (meth) acrylic monomers. In addition, aromatic hydrocarbon vinyl monomers such as styrene and methylstyrene; α, β-ethylenically unsaturated carboxylic acids such as maleic acid and itaconic acid; sulfonic acid-containing vinyl monomers such as styrenesulfonic acid Acid anhydrides such as maleic anhydride; chlorine-containing monomers such as vinyl chloride and vinylidene chloride; hydroxyl-containing alkyl vinyl ethers such as hydroxyethyl vinyl ether; alkylene glycol monoallyl ethers such as ethylene glycol monoallyl ether; ethylene, propylene, etc. Α-olefins of vinyl acetate, vinyl esters such as vinyl acetate, vinyl ethers such as methyl vinyl ether, and allyl ethers such as ethyl allyl ether can be used.

  A silane coupling agent can be used by adding to various binders. Specific examples of the silane coupling agent include γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N- β (aminoethyl) γ-aminopropylmethyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like can be mentioned.

  The medium form of the colored transparent paint is not particularly limited, and a strong solvent system, a weak solvent system, and an aqueous system form can be used, but considering adhesiveness to the ceramic tile surface, workability, environmental hygiene, etc. Weak solvent systems are preferred.

  Examples of such weak solvent-based paints include the above-mentioned acrylic monomers containing hydrolyzable silyl groups and alkyl (meth) acrylates having an aliphatic or alicyclic alkyl group having 4 to 12 carbon atoms. A polymer formed from a monomer and another monomer containing a radical polymerizable double bond is mainly composed of an aliphatic hydrocarbon solvent having a solubility parameter of 6.5 to 9.5. A weak solvent-soluble type dissolved in a solvent or a polymer obtained by polymerizing an acrylic monomer containing a hydrolyzable silyl group as described above, having a solubility parameter of 6.5 to 9.5 Examples thereof include a non-aqueous dispersion type resin composition dispersed in a solvent containing an aliphatic hydrocarbon solvent as a main component in the presence of a resin dispersion stabilizer dissolved in the solvent, and a composite type thereof.

In particular, the above-mentioned weak solvent-soluble type or non-aqueous dispersion type resin composition can form a surface with better contamination resistance by further containing a silicate oligomer represented by Chemical Formula 3 in the composition.

  The colored transparent paint used in the present invention needs to have a concealment ratio of 0.10 to 0.60 (preferably 0.15 to 0.40). When the concealment ratio is within such a range, the aesthetics can be improved while taking advantage of the design of the existing ceramic tile surface, and the tile and joints are resistant to contamination, waterproof, weather resistance, etc. Can be granted. If the concealment rate is less than 0.10, the fading and contamination cannot be recovered and a beautiful appearance cannot be obtained. If the concealment ratio is larger than 0.60, the contrast between the tile portion and the joint portion becomes unclear, the design property of the existing tile surface is lost, and the entire tile may have a monotonous appearance.

The concealment rate in the present invention is a value measured according to JIS K 5400 7.2. Specifically, a test piece obtained by applying 150 μm of a coating material used at the time of painting (diluted coating material when diluted) to a concealment rate test paper, and drying it for 48 hours in a temperature 20 ° C. and humidity 65% environment. About the following formula,
Hiding ratio = (luminous reflectance of paint film on black ground) / (luminous reflectance of paint film on white ground)
It is a value represented by

  What is necessary is just to set suitably the color tone of the colored transparent coating material used for this invention in the range of the concealment rate of 0.10-0.60 according to the color pattern of the existing ceramic tile used as the object of repair. In this case, the pigment used is inorganic such as titanium oxide, zinc oxide, carbon black, ferric oxide (Bengara), lead chromate (molybdate orange), yellow lead, yellow iron oxide, ocher, ultramarine, cobalt green, etc. Organic pigments such as pigments, azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine, and quinophthalone can be used. It is also possible to use extender pigments such as heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate, barium carbonate, white carbon, diatomaceous earth.

  In addition, additives such as plasticizers, antiseptics, antifungal agents, antifoaming agents, leveling agents, pigment dispersants, anti-settling agents, anti-sagging agents, ultraviolet absorbers, and antioxidants are used alone in colored transparent paints. Or it can mix | blend in combination.

  It does not specifically limit as a coating method of a colored transparent coating material, Well-known coating methods, such as brush coating, spray coating, and roller coating, can be used.

Coat-weight when painting a colored transparent paint may be appropriately set by the kind of material and the substrate to be coated, ^{usually, 0.1kg / m 2 ~0.3kg / m} 2 about coat-weight It is desirable to paint with. By applying the colored transparent paint in such a coating amount, a beautiful appearance can be obtained while taking advantage of the design of the existing tile surface.

  Examples and Comparative Examples are shown below to clarify the features of the present invention.

(Example 1)
The tile surface was made of cement mortar and tiled tea color porcelain tiles. The base material is coated with a coloring liquid consisting of carbon black, an anionic surfactant, and water and having a carbon black content of 0.3%, then washed with water and dried at room temperature. It was. Here, ΔL between the colored joint and the tile was measured and found to be 16.7. Next, using the raw materials shown in Table 1, paint 1 prepared by blending in Table 2 was applied with a wool roller at a coating amount of 0.2 kg / m ² and dried at room temperature. As a result, the contrast between the tile portion and the joint portion became clear, and the aesthetics of the entire tile surface was also dramatically improved.

(Example 2)
A test was conducted in the same manner as in Example 1 except that the paint 2 was used in place of the paint 1. As a result, the contrast between the tile part and the joint part became clear, and the aesthetics of the entire tile surface was dramatically improved.

(Example 3)
A test was conducted in the same manner as in Example 1 except that the paint 3 was used in place of the paint 1. As a result, the contrast between the tile portion and the joint portion became clear, and the aesthetics of the entire tile surface was dramatically improved.

Example 4
A test was conducted in the same manner as in Example 1 except that the paint 4 was used in place of the paint 1. As a result, the contrast between the tile portion and the joint portion became clear, and the aesthetics of the entire tile surface improved dramatically.

(Example 5)
A test was conducted in the same manner as in Example 1 except that the paint 5 was used in place of the paint 1. As a result, the contrast between the tile part and the joint part became clear, and the aesthetics of the entire tile surface was dramatically improved.

(Example 6)
For the same substrate as in Example 1, after applying a coloring liquid consisting of carbon black, an anionic surfactant, and water and having a carbon black content of 0.1% on the joint, it was washed with water, Dry at room temperature. Here, ΔL between the colored joint and the tile was measured and found to be 7.6. Next, the coating material 6 shown in Table 2 was applied at a coating amount of 0.2 kg / m ² with a wool roller and dried at room temperature. As a result, the contrast between the tile portion and the joint portion became clear, and the aesthetics of the entire tile surface was also dramatically improved.

(Example 7)
A 5% ammonium fluoride aqueous solution was applied to the same substrate as in Example 1 while rubbing with a sponge, and the entire tile surface was etched and then washed with water. Next, a coloring liquid composed of carbon black, an anionic surfactant, and water and having a carbon black content of 0.1% was applied to the joint, washed with water, and dried at room temperature. Here, ΔL between the colored joint and the tile was measured and found to be 9.1. Furthermore, the coating material 6 shown in Table 2 was applied at a coating amount of 0.2 kg / m ² with a wool roller and dried at room temperature. As a result, the contrast between the tile portion and the joint portion became clear, and the aesthetics of the entire tile surface was also dramatically improved.

(Comparative Example 1)
The entire tile was washed with water and dried on the same substrate as in Example 1. Here, ΔL between the joint portion and the tile portion was measured and found to be 3.2. Next, the coating material 1 shown in Table 2 was applied at a coating amount of 0.2 kg / m ² with a wool roller and dried at room temperature. In the tile surface thus obtained, the contrast between the tile portion and the joint portion has become unclear.

(Comparative Example 2)
For the same substrate as in Example 1, after applying a coloring liquid consisting of carbon black, an anionic surfactant, and water and having a carbon black content of 0.1% on the joint, it was washed with water, Dried. Here, ΔL between the colored joint and the tile was measured and found to be 7.6. Next, the coating material 7 shown in Table 2 was applied at a coating amount of 0.2 kg / m ² with a wool roller and dried at room temperature. The tile surface thus obtained was exposed to contamination remaining in the tile portion, resulting in poor aesthetics.

(Comparative Example 3)
For the same substrate as in Example 1, after applying a coloring liquid consisting of carbon black, an anionic surfactant, and water and having a carbon black content of 0.2% to the joint, it was washed with water, Dried. Here, ΔL between the colored joint and the tile was measured and found to be 12.5. Next, the paint 8 shown in Table 2 was applied with a wool roller at a coating amount of 0.2 kg / m ² and dried at room temperature. In the tile surface thus obtained, the contrast between the tile portion and the joint portion becomes unclear, resulting in a monotonous finish.

Claims (4)

  1st process of coloring a joint part using the coloring liquid containing a pigment and / or a dye with respect to a ceramic tile surface, the hydrolyzable silyl group is contained in the binder, and the concealment rate is 0.10 to 0.10. A method for repairing a ceramic tile surface, comprising a second step of coating the entire surface with a colored transparent paint of 0.60.   In the second step, a solvent composed mainly of an acrylic synthetic resin containing a hydrolyzable silyl group and an aliphatic hydrocarbon solvent having a solubility parameter of 6.5 to 9.5 that can dissolve the resin. The method for refurbishing a ceramic tile surface according to claim 1, wherein a colored transparent coating material containing γ and having a concealment ratio of 0.10 to 0.60 is used.   In the second step, a non-aqueous dispersion type in which an acrylic synthetic resin containing a hydrolyzable silyl group is dispersed in a solvent mainly composed of an aliphatic hydrocarbon solvent having a solubility parameter of 6.5 to 9.5 The method for repairing a ceramic tile surface according to claim 1 or 2, wherein a colored transparent paint containing a resin composition and having a concealment ratio of 0.10 to 0.60 is used. The method for repairing a ceramic tile surface according to claim 2 or 3, wherein the colored transparent paint contains a silicate oligomer represented by Chemical Formula 1.