JP2001020490A - Method for repairing ceramic tile surface - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for repairing a ceramic tile surface, which can easily improve the appearance, and can impart stain-proofing property, waterproofness, moisture permeability, etc., while maintaining the design of the existing tile surface, by coating the surface which has been subjected to etching, with a transparent paint having a specific viscosity, and containing an acrylic synthetic resin with a specific mean molecular weight, the resin containing a hydrolytic silyl radical. SOLUTION: A ceramic tile surface and a surface of a joint mortar portion which undergo developed deterioration and stain, are subjected to etching. Thereafter, the surfaces are coated with a transparent paint as a binder which contains an acrylic synthetic resin with a mean molecular weight of 5,000 to 200,000, containing a hydrolytic silyl radical, and has a viscosity of 100 to 5,000 mPa.s/20 deg.C when coated. The transparent paint preferably contains a solvent mainly consisting of an aliphatic hydrocarbon-based solvent with a solubility parameter of 6.5 to 9.5, which can dissolve an acrylic synthetic resin containing a hydrolytic silyl radical. The hydrolytic silyl radical is rigidly bound to the ceramic tile surface to exert adhesiveness, and the acrylic to thereby exhibit a wet color.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for repairing a ceramic tile surface used for exterior finishing of a building or the like.

[0002]

2. Description of the Related Art Finishing with ceramic tiles such as porcelain tiles, ceramic tiles, semi-porcelain tiles, and ceramic tiles generally has good durability and design properties, so that the protection of building bodies such as buildings, Alternatively, it is used favorably for improving aesthetics.

[0003] However, in the case of a ceramic tile constructed as an exterior for a building or the like, it is exposed for a long period of time under an environment affected by sunlight, wind and rain. As a result, deterioration such as gloss reduction, fading, and erosion of the tile portion, or neutralization and strength reduction of the joint portion progress. In addition, the contamination progresses due to airborne dust, suspended pollutants such as exhaust gas, efflorescence and rust from inside the frame, and oil from the sealing material. With respect to such a ceramic tile surface, there is a need for renovation in order to restore durability, design, and the like.

[0004] As a method of repairing a ceramic tile surface,
JP-A-6-33565 proposes a method of laminating a clear paint containing no pigment. In the invention, it is stated that by using the clear paint, waterproofness can be imparted without changing the design of the existing ceramic tile surface.

The present invention is applicable to a ceramic tile surface with a small degree of deterioration or contamination. However, it is necessary to improve the aesthetics of surfaces that have been significantly degraded due to long-term exposure and have undergone significant discoloration, or those that have become so contaminated that they cannot be completely removed by washing. And the problem of design cannot be solved.

[0006] In order to deal with the problem of deterioration and contamination, there is a method of applying a coloring paint to the ceramic tile surface. However, if the entire ceramic tile surface is painted in the same color, the contrast between the joint portion and the tile portion is lost, and the appearance becomes monotonous. In addition, there is a method of applying the joint part and the tile part with paints of different colors, such as a method of masking the joint part after painting the entire tile surface and painting only the tile part, but the work process becomes complicated. If the existing tile has various patterns, the patterns cannot be utilized.

[0007]

Accordingly, the problem to be solved by the present invention is to easily and easily utilize the design of the existing tile surface on the ceramic tile surface or joint mortar portion where deterioration and contamination have progressed. It is an object of the present invention to provide a refining method that can improve aesthetics and further impart stain resistance, waterproofness, moisture permeability, weather resistance, and the like.

[0008]

Means for Solving the Problems In order to solve such problems, the present inventors have assiduously studied and, after a specific etching process, bonded to a ceramic tile surface on which deterioration or contamination has progressed. As a material, an acrylic synthetic resin having a specific average molecular weight containing a hydrolyzable silyl group is contained, and a transparent paint having a viscosity in a certain range is applied, so that the ceramic tile surface has a hydrolyzable silyl group. Formed a strong bond and exhibited excellent adhesion. Further, in the joint part, the above-mentioned acrylic synthetic resin is penetrated and hardened, and at this time, the joint part discolors as if it were wet, and the color of the coating formed on the joint part becomes black,
Finishing in a so-called wet color makes the contrast with the ceramic tile surface clear, making it easy to improve the aesthetics while making use of the design characteristics of the existing tile surface, stain resistance, waterproofness, moisture permeability, weather resistance, etc. Can be given.

That is, the method for repairing a ceramic tile surface of the present invention has the following features. 1. A first step of etching the surface of the ceramic tile surface and the joint mortar portion with respect to the ceramic tile surface, and having a mean molecular weight of 500 containing a hydrolyzable silyl group as a binder.
It contains an acrylic synthetic resin of 0 to 200,000 and has a viscosity of 100 to 50,000 mPa · s / 2 at the time of coating.
A method for repairing a ceramic tile surface, comprising a second step of applying a transparent paint at 0 ° C. 2. The transparent paint forms a colored transparent film. Repair method of ceramic tile surface described in. 3. The transparent paint contains an acrylic synthetic resin containing a hydrolyzable silyl group and a solvent mainly composed of an aliphatic hydrocarbon-based solvent having a solubility parameter of 6.5 to 9.5 capable of dissolving the resin. 1. Or 2. Repair method of ceramic tile surface described in. 4. Non-aqueous dispersion type resin composition in which a transparent paint is formed by dispersing an acrylic synthetic resin containing a hydrolyzable silyl group in a solvent mainly containing an aliphatic hydrocarbon solvent having a solubility parameter of 6.5 to 9.5. Characterized by containing a substance. Or 2. Repair method of ceramic tile surface described in. 5. 2. The transparent paint contains a silicate oligomer represented by Chemical Formula 2. Or 4. Repair method of ceramic tile surface described in.

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[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail based on its embodiments. The present invention is applied to a ceramic tile surface such as a building exterior. Examples of the types of ceramic tile include porcelain tile, clay tile, semi-porcelain tile, and ceramic tile. The present invention can be applied to a surface finished with such a ceramic tile, but in particular, the ceramic tile surface and joint mortar portion are also etched on the ceramic tile surface where deterioration and contamination have significantly progressed due to long-term exposure. Construction is possible.

Although the etching method is not particularly limited, 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 1
A solution of about 0 to 20% and a solution of about 3% of citric acid concentration are used as an etching agent. Ammonium hydrogen fluoride, ammonium fluoride, ammonium fluorinated ammonium aqueous solution and the like can be used as an etching agent for glass. This is suitable for removing contaminants due to a silica component at joints and etching a glaze layer on a ceramic tile surface. These etchants should be applied to the ceramic tile surface and joints, and should be thoroughly cleaned after a certain period of time to prevent degradation residues, contaminants, and etchants from remaining on the ceramic tile surfaces and joints. is necessary.

The transparent coating used in the present invention needs to contain a binder containing a hydrolyzable silyl group.
Due to this functional group, excellent adhesion to various ceramic tile surfaces and joints is developed. Examples of the compound containing a hydrolyzable silyl group include an acrylic monomer containing a hydrolyzable silyl group, a silane coupling agent, and the like.

Specific examples of the hydrolyzable silyl group-containing acrylic monomer include γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) Acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane and the like.

The acrylic monomer containing a hydrolyzable silyl group can be used as a binder by copolymerizing the monomer with another monomer. Other monomers copolymerizable with the hydrolyzable silyl group-containing acrylic monomer include, for example, alkyl group-containing (meth) acrylates such as methyl (meth) acrylate, butyl (meth) acrylate, and cyclohexyl (meth) acrylate. A) acrylic monomers; hydroxyl-containing (meth) acrylic monomers such as 2-hydroxyethyl (meth) acrylate; ethylenically unsaturated carboxylic acids such as (meth) acrylic acid; dimethylaminoethyl (meth) acrylate Amino group-containing (meth) acrylic monomers such as: amide-containing (meth) acrylic monomers such as (meth) acrylamide; nitrile group-containing (meth) acrylic monomers such as acrylonitrile; glycidyl (meth) acrylate And epoxy group-containing (meth) acrylic monomers. In addition, aromatic hydrocarbon vinyl monomers such as styrene and methyl styrene; α, β-ethylenically unsaturated carboxylic acids such as maleic acid and itaconic acid; sulfonic acid-containing vinyl monomers such as styrene sulfonic 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;
Α-olefins such as ethylene and propylene; vinyl esters such as vinyl acetate; vinyl ethers such as methyl vinyl ether; allyl ethers such as ethyl allyl ether;

The silane coupling agent can be used by adding it to various binders. As the silane coupling agent, specifically, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropylmethyltriethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, N- β (aminoethyl) γ-aminopropylmethyltriethoxysilane,
γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane and the like.

The transparent coating used in the present invention must have an average molecular weight of the binder of 5,000 to 200,000 and a viscosity of the coating at the time of coating of 100 to 50,000 mPa · s / 20 ° C. When the average molecular weight of the binder is lower than 5,000, the permeability to joints becomes good, but the stain resistance, waterproofness, moisture permeability, and the like of the coating formed on the ceramic tile surface are improved.
Coating properties such as weather resistance will be degraded. Conversely, if the average molecular weight of the binder is higher than 200,000, the permeability to the joint decreases, and the coating formed on the joint does not have a sufficient wet color, so that the contrast with the ceramic tile surface becomes clear. hard. On the other hand, with respect to the viscosity of the paint, if it is lower than 100 mPa · s / 20 ° C.,
This causes sagging during painting on the ceramic tile surface, leading to a reduction in painting workability. In addition, 50,000 mPa · s / 20
If the temperature is higher than ° C, the application of the paint to the grooved joints becomes insufficient, and it becomes difficult to simultaneously finish the ceramic tile surface and the joints with a single coating. Also, as described above, even when the average molecular weight of the binder is within the specified range, the penetration of the transparent paint into the joint portion is not sufficient, and similarly, when the molecular weight of the binder is out of the range, the joint portion has The wet color does not appear sufficiently, and the contrast between the ceramic tile surface and the joint is difficult to be clear. In addition, the viscosity of the transparent paint in the present invention was measured by a BH-type rotational viscometer, 20 r.
Viscosity in pm. (Guidance value at 4th rotation)

The medium form of the transparent paint is not particularly limited, and a strong solvent type, a weak solvent type and an aqueous type can be used.
In consideration of the adhesion to the ceramic tile surface, workability, environmental hygiene, and the like, a weak solvent containing an aliphatic hydrocarbon solvent as a main component is preferable.

As such a weak solvent-based coating material, an acrylic monomer having a hydrolyzable silyl group and an aliphatic or alicyclic alkyl group having 4 to 12 carbon atoms (meth) Polymers formed from alkyl acrylate monomers and other monomers containing radically polymerizable double bonds are mainly composed of aliphatic hydrocarbon solvents having solubility parameters of 6.5 to 9.5. A solubility parameter of 6.5 to 9 that does not dissolve a weak solvent-soluble type dissolved in a solvent as a component or a polymer obtained by polymerizing the acrylic monomer containing a hydrolyzable silyl group described above. Non-aqueous dispersion type resin compositions which are dispersed in a solvent containing an aliphatic hydrocarbon-based solvent as a main component in the presence of a resin-based dispersion stabilizer dissolved in the solvent. At this time, the non-aqueous dispersion type resin composition, if the molecular weight of the resin-based dispersion stabilizer falls within the range of the above-mentioned average molecular weight, forms a wet color by permeation at joints, and as a whole formed film. Is excellent in weather resistance and waterproofness.

In particular, in the above-mentioned weak solvent-soluble type or non-aqueous dispersion type resin composition, a surface having more excellent stain resistance can be formed by further containing a silicate oligomer represented by Chemical Formula 3 in the composition. Becomes

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The transparent paint used in the present invention is desirably colorless and transparent because the purpose is to utilize the design of the existing ceramic tile surface. However, the transparent paint is such that it does not completely cover the design of the existing ceramic tile surface. It does not prevent that it is colored. In particular, depending on the degree of coloration, a design superior to existing ceramic tiles may be exhibited in combination with the design of ceramic tiles. Examples of pigments used in this case include inorganic oxides such as titanium oxide, zinc oxide, carbon black, ferric oxide (bengala), lead chromate (molybdate orange), graphite, yellow iron oxide, ocher, ultramarine, cobalt green, and the like. Organic pigments such as azo, naphthol, pyrazolone, anthraquinone, perylene, quinacridone, disazo, isoindolinone, benzimidazole, phthalocyanine and quinophthalone pigments can be used. Also, heavy calcium carbonate, clay, kaolin, talc, precipitated barium sulfate,
It is also possible to use extenders such as barium carbonate, white carbon, diatomaceous earth and mica, and interference titanium mica having dichroism.

In the transparent paint, additives such as a plasticizer, an antiseptic, a fungicide, an antifoaming agent, a leveling agent, a pigment dispersant, an anti-settling agent, an anti-sagging agent, an ultraviolet absorber, and an antioxidant. Can be used alone or in combination.

The method for applying the transparent paint is not particularly limited, and known coating methods such as brush coating, spray coating, roller coating and the like can be used.

The amount with paint when painting the clearcoat 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 coating It is desirable to apply the coating at the applied amount. By painting with such a coating amount, while utilizing the design of the existing tile surface,
This is because a beautiful appearance can be obtained.

In the present invention, the surface of the joint mortar portion becomes porous by the etching in the first step. Originally, the joint mortar surface was porous at the time of ceramic tile construction, but the porous part was lost due to the deposition of contaminants during repair, but the surface part of the joint mortar is removed by etching Therefore, the porous surface is restored. Such a porous surface is
Then, the specific acrylic synthetic resin containing the hydrolyzable silyl group to be applied is promoted to penetrate into the joint mortar portion, and the joint mortar portion becomes wet color in combination with the specific physical properties of the acrylic synthetic resin. On the other hand, the surface of the ceramic tile is appropriately roughened by etching, and has an effect of improving adhesion to a specific acrylic synthetic resin.

[0025]

EXAMPLES Examples and comparative examples are shown below to further clarify the features of the present invention.

(Example 1) Joints made of cement-colored mortar, tiles made of brown-colored porcelain tile,
An aged tile surface was used as a base material. A 5% aqueous solution of ammonium fluoride was applied to the substrate while rubbing it with a sponge, the entire tile surface was etched, washed with water, dried, and then the raw materials shown in Table 1 were used. Apply 0.2k of the prepared transparent paint with a wool roller
It was painted in g / ^{m 2.}

(Examples 2 to 5) On the same base material as in Example 1
On the other hand, similarly, the raw materials shown in Table 1 were used, and the distribution shown in Table 2 was used.
The colored transparent paint prepared by combining
Coating amount 0.2kg / m ²Painted.

(Comparative Example 1) The same base material as in Example 1 was washed with the whole tile with water, and the transparent coating material prepared according to the composition shown in Table 2 was mixed with a wool roller using the raw materials shown in Table 1. Coating was performed at a coating amount of 0.2 kg / m ² .

(Comparative Examples 2 to 5) A 5% aqueous solution of ammonium fluoride was applied to the same substrate as in Example 1 by rubbing with a sponge, the entire tile surface was etched, washed with water, and dried. Using the raw materials shown in Table 1, the transparent paint prepared according to the composition shown in Table 2 was applied with a wool roller at a coating amount of 0.2 kg / m ² .

[0030]

[Table 1]

[0031]

[Table 2]

After coating and curing for one week, the appearance of the tile surface was evaluated. The appearance of the tile surface after coating and after 6 months of exposure was also evaluated. The evaluation was as follows. The results are shown in Table 3. (1) Contamination recovery (after one week) ○: Contamination is recovered △: Contamination is recovered slightly ×: Contamination is not recovered (2) Contrast (after one week and six months) ◎: With tile surface The contrast between the joint and the joint is very clear. ○: The contrast between the tile and the joint is clear. Δ: The contrast between the tile and the joint is slightly unclear. ×: The contrast between the tile and the joint is unclear. ) Finishing property (after one week and six months) ：: Very good clarity and smoothness on the tile surface. ：: Clearness and smoothness are good on the tile surface. Δ: Clearness and smoothness are slightly inferior on the tile surface. ×: Very poor sharpness and smoothness on the tile surface,
May cause sagging. (4) Weather resistance (after 6 months) ：: swelling and peeling of coating film on tile surface and joint
No discoloration. Δ: Swelling, peeling, or discoloration of the coating film slightly occurred on the tile surface or joint. ×: Any of swelling, peeling, and discoloration of the coating film significantly occurred on the tile surface or joint portion. (5) Stain resistance (after 6 months) ：: No contamination is observed on the tile surface and joints. ：: No contamination is observed on the tile surface. Δ: Slight contamination is observed on the tile surface and joints. ×: Remarkable contamination is seen on the tile surface and joints.

[0033]

[Table 3]

(Results) From Table 3, all the tests in the examples showed good results. In particular, in Examples 3 to 5, the contrast between the tile surface and the joint portion was excellent, and the finish was very excellent in sharpness and smoothness. In Example 5, the stain resistance of the tile surface and the joint after 6 months was also excellent. On the other hand, in Comparative Example 1, since there was no etching step, the permeability of the transparent paint was poor at the joints, and the degree of wet color was low, resulting in poor contrast. Also, the adhesion to the ceramic tile surface was insufficient. In Comparative Example 2, since the molecular weight of the transparent paint was high, penetration into joints was poor, and as in Comparative Example 1, the result was inferior in contrast and adhesion. Comparative Example 3 was insufficient in adhesion to the ceramic tile surface because of the acrylic urethane resin. In Comparative Example 4, since the viscosity of the transparent paint was high, the permeability at the joints was poor, and as in Comparative Example 1, the result was inferior in contrast and adhesion. Comparative Example 5
Causes sagging at the time of painting because the viscosity of the transparent paint is low,
As a result, the finish was very poor.

[0035]

According to the present invention, the aesthetic appearance can be easily and easily improved by using a single coating film on the ceramic tile surface on which deterioration or contamination has progressed, while utilizing the design property of the existing tile surface.
Furthermore, stain resistance, waterproofness, moisture permeability, weather resistance, and the like are imparted, and the contrast between the joint portion and the tile portion of the renovated tile surface can be made clearer.

Claims (5)

[Claims] A first step of etching the surface of the ceramic tile surface and the joint mortar portion with respect to the ceramic tile surface;
As a binder, it contains an acrylic synthetic resin having an average molecular weight of 5,000 to 200,000 containing a hydrolyzable silyl group, and has a viscosity of 100 to 50,000 mPa ·
A method for repairing a ceramic tile surface, comprising a second step of applying a transparent paint at s / 20 ° C. 2. The method according to claim 1, wherein the transparent paint forms a colored transparent film. 3. A transparent paint comprising, as a main component, an acrylic synthetic resin containing a hydrolyzable silyl group and an aliphatic hydrocarbon-based solvent having a solubility parameter of 6.5 to 9.5 capable of dissolving the resin. The method for repairing a ceramic porcelain tile surface according to claim 1 or 2, wherein the method comprises the step of: 4. An acrylic synthetic resin having a hydrolyzable silyl group as a transparent coating, having a solubility parameter of 6.5 to 6.5.
3. The method for repairing a ceramic tile surface according to claim 1 or 2, comprising a non-aqueous dispersion type resin composition dispersed in a solvent mainly containing an aliphatic hydrocarbon solvent of 9.5. . 5. The method for repairing a ceramic tile surface according to claim 3, wherein the transparent paint contains a silicate oligomer represented by Chemical Formula 1. Embedded image