JP2009228421A - Repair method for ceramic tile surface - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a simple repair method which enables a ceramic tile surface to exert excellent water absorption prevention properties, contamination resistance, etc., while taking advantage of the characteristics of an existing tile surface. <P>SOLUTION: The ceramic tile surface composed of a tile portion and a joint is repaired by coating a surface treatment liquid. The surface treatment liquid contains 0.1-50 wt.% of an alkoxysilane compound and 50-99.9 wt.% of a solvent; the alkoxysilane compound contains 90 wt.% or more of the alkylalkoxysilane compound containing a 3-12C alkyl group with an a degree of condensation of 2 or less; and the solvent contains 90 wt.% or more of an aliphatic hydrocarbon. <P>COPYRIGHT: (C)2010,JPO&INPIT

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 surface constructed for an exterior of a building or the like, it is exposed for a long time in an environment affected by sunlight, wind and rain. As a result, even if the deterioration of the tile itself has not progressed so much, deterioration such as neutralization and strength reduction tends to proceed in the joint portion.

  As a method for repairing the ceramic tile surface, a method of laminating a plurality of clear paints is proposed in JP-A-6-33565 (Patent Document 1). In the invention described in this publication, by using a clear paint, water absorption prevention can be imparted without changing the design of the existing ceramic tile surface. However, even if the ceramic tile surface obtained by such a method has a good finish immediately after coating, there is a possibility that the contamination will progress over time and the aesthetics may be impaired.

  On the other hand, Japanese Patent Application Laid-Open No. 9-287265 (Patent Document 2) describes a method of painting only joint portions of a ceramic tile surface. In the method described in this publication, a water-soluble resin for masking is applied to the joint portion of the tile and its peripheral portion, the water-soluble resin is soaked into the joint portion, and then an antifouling paint is applied around the joint portion. Then, the paint that protrudes from the tile surface is removed together with the water-soluble resin coating. According to this method, the tile portion can be unpainted and only the joint portion can be painted. However, in the method of Patent Document 2, a step of removing the coating film on the tile portion is essential, and it cannot be denied that the operation becomes complicated.

JP-A-6-33565 JP-A-9-287265

  The present invention has been made in view of such problems, and it is a simple modification that can exhibit excellent water absorption prevention, contamination resistance, etc. while making use of the characteristics of the existing tile surface with respect to the ceramic tile surface. It is intended to provide a method.

  In order to solve such problems, the present inventors have intensively studied and came up with a method of applying a specific surface treatment material to the entire surface of the ceramic tile, and completed the present invention.

That is, the method for repairing a ceramic tile surface of the present invention has the following characteristics.
1. A method of repairing a ceramic tile surface comprising a tile part and a joint part by coating with a surface treatment liquid, wherein the surface treatment liquid comprises 0.1 to 50% by weight of an alkoxysilane compound and 50 to 99.9% by weight of a solvent. The alkoxysilane compound contains 90% by weight or more of an alkylalkoxysilane compound having an alkyl group with 3 to 12 carbon atoms and a degree of condensation of 2 or less. A method for refurbishing a ceramic tile surface, comprising 90% by weight or more of hydrogen, wherein the ceramic tile surface is washed before the surface treatment liquid is applied to the entire surface of the ceramic tile surface.
2. The aliphatic hydrocarbon is an aliphatic saturated hydrocarbon having 4 or more carbon atoms. The method of repairing the ceramic tile surface described.
3. The cleaning treatment uses a cleaning agent, and the cleaning agent is an aqueous solution containing at least one selected from an inorganic acid, an organic acid, and a fluorine compound. Or 2. The method of repairing the ceramic tile surface described.

  In the present invention, the surface state, appearance, texture, etc. of the existing tile can be utilized as they are, and the water absorption prevention property of the joint part can be improved, and the neutralization of the joint part, strength reduction, efflorescence occurrence, etc. can be prevented. As a result, deterioration of the entire ceramic tile surface can be prevented. Furthermore, in the present invention, advantageous effects can also be obtained in terms of contamination resistance.

  Hereinafter, the best mode for carrying out the present invention will be described.

The present invention is applied to a ceramic tile surface such as a building exterior.
Examples of the ceramic tile include a porcelain tile, a porcelain tile, a semi- porcelain tile, and a porcelain tile. Such a ceramic tile surface is generally formed by making a base with a base mortar on a base material, stretching ceramic tiles with a tension mortar, and filling the joints with joint mortar. Therefore, the joints between the ceramic tiles are usually in a state where the mortar is exposed.

  In the present invention, the surface treatment agent is applied to the entire surface of the ceramic tile surface including the tile portion and the joint portion. The surface treating agent in the present invention contains an alkoxysilane compound and a solvent.

  Among these, as the alkoxysilane compound, an alkylalkoxysilane compound (hereinafter simply referred to as “alkylalkoxysilane compound”) having an alkyl group having 3 to 12 carbon atoms and a degree of condensation of 1 is used as an essential component. This alkylalkoxysilane compound penetrates deeply into the joints to form a water-repellent coating, imparts water absorption prevention to the joints, and at the same time exhibits an appropriate hydrophilization action to increase the stain resistance. This greatly contributes to maintaining the aesthetics of the ceramic tile surface. Furthermore, it effectively works to suppress neutralization, strength reduction, efflorescence generation, and the like at joints.

Such an alkylalkoxysilane compound is a compound in which an alkyl group and an alkoxyl group are bonded to a silicon atom. For example, a compound represented by the following formula (1) and / or a condensate thereof can be used.
R ¹ —Si (OR ² ) ₃ (1)
(In the formula, R ¹ and R ² represent an alkyl group. R ¹ has 3 to 12 carbon atoms.)

  Specifically, examples of the compound represented by the above formula (1) include propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, and hexyltri. Methoxysilane, hexyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, nonyltrimethoxysilane, nonyltriethoxysilane, decyltrimethoxysilane, decyltriethoxysilane, undecyl Examples include trimethoxysilane, undecyltriethoxysilane, dodecyltrimethoxysilane, and dodecyltriethoxysilane. As these condensates, monomers having a condensation degree of 1 are particularly suitable in the present invention.

  As the alkylalkoxysilane compound, those having 3 to 12 (preferably 5 to 8) carbon atoms in the alkyl group are used. The alkyl group may be partially substituted with halogen or the like. When the carbon number of the alkyl group is within such a range, it is possible to achieve both excellent water absorption prevention performance at the joint and excellent performance in the stain resistance of the tile section. When the number of carbon atoms of the alkyl group is less than 3, the water absorption preventing property at the joint portion becomes insufficient. Conversely, when it exceeds 12, there is a possibility of adversely affecting the finish property, stain resistance, etc. of the tile portion.

  Examples of the alkoxyl group in the alkylalkoxysilane compound include those having 1 to 8 (preferably 1 to 4, more preferably 1 to 2) carbon atoms, and a methoxy group having 1 carbon atom is particularly preferable. If the number of carbon atoms of the alkoxyl group is such, advantageous effects in performance such as water absorption prevention can be obtained.

  The ratio of the alkylalkoxysilane compound in the alkoxysilane compound is usually 90% by weight or more (preferably 95% by weight or more, more preferably 98% by weight or more). A form in which the alkoxysilane compound is substantially composed only of the alkylalkoxysilane compound is also suitable. Examples of the alkoxysilane compound other than the alkylalkoxysilane compound include compounds whose carbon number of the alkyl group, the degree of condensation, etc. are not specified above. In the present invention, the alkylalkoxysilane compound can be controlled by reducing the ratio of such components. The effect of the silane compound can be sufficiently exhibited. When the ratio of the alkylalkoxysilane compound in the alkoxysilane compound is too low, it is difficult to obtain sufficient performance in terms of finish and stain resistance at the tile portion.

  The content ratio of the alkoxysilane compound in the surface treatment liquid is usually 0.1 to 50% by weight, preferably 1 to 30% by weight, and more preferably 2 to 20% by weight. When this content ratio is too low, the water absorption preventing property of the joint portion tends to be insufficient, and conversely, when too high, there is a possibility of adversely affecting the finishability and stain resistance of the tile portion.

  In the surface treatment liquid of the present invention, a solvent containing 90% by weight or more of aliphatic hydrocarbon is used as a solvent for dissolving the alkylalkoxysilane compound. In the present invention, by using the above alkylalkoxysilane compound in combination with such a solvent, it is possible to maintain the appearance, texture, etc. of the tile portion and to obtain good finish. When the existing tile part is glossy, it can be finished without impairing its glossiness. Furthermore, it is possible to suppress a decrease in aesthetic appearance over time due to the adhesion of contaminants to the tile portion, and to maintain a good finished appearance over a long period of time.

As the aliphatic hydrocarbon, an aliphatic saturated hydrocarbon is preferable, and an aliphatic saturated hydrocarbon having 4 or more (more preferably 5 or more) carbon atoms is particularly preferable. Examples of such aliphatic hydrocarbons include butane (C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), hexane (C ₆ H ₁₄ ), heptane (C ₇ H ₁₆ ), and octane (C ₈ H _18). ), Nonane (C ₉ H ₂₀ ), decane (C ₁₀ H ₂₂ ), undecane (C ₁₁ H ₂₄ ), dodecane (C ₁₂ H ₂₆ ), tridecane (C ₁₃ H ₂₈ ), tetradecane (C ₁₄ H ₃₀ ), Directly such as pentadecane (C ₁₅ H ₃₂ ), hexadecane (C ₁₆ H ₃₄ ), heptadecane (C ₁₇ H ₃₆ ), octadecane (C ₁₈ H ₃₈ ), nonadecane (C ₁₉ H ₄₀ ), eicosane (C ₂₀ H ₄₂ ), etc. chain aliphatic saturated hydrocarbon, isopentane _{(C 5} H 12), 2- methyl pentane _{(C 6} H 14), 3- methylpentane _{(C 6 H 14} ), 2,2-dimethyl butane _{(C 6} H 14), 2,3- dimethylbutane _{(C 6} H 14), hexane _{(C 7} H 16 to 2-methyl), to 3-methyl hexane _{(C 7 H 16} ), 3-ethyl pentane _{(C 7} H 16), 2,2- dimethyl pentane _{(C 7} H 16), 2,3- dimethyl pentane _{(C 7} H 16), 2,4- dimethyl pentane _{(C 7 H 16} ), 3,3-dimethylpentane (C ₇ H ₁₆ ), 2,2,3-trimethylbutane (C ₇ H ₁₆ ), 2-methylheptane (C ₈ H ₁₈ ), 3-methylheptane (C ₈ H ₁₈₎ ), 2,2-dimethylhexane (C ₈ H ₁₈ ), 2,3-dimethylhexane (C ₈ H ₁₈ ), 2,5-dimethylhexane (C ₈ H ₁₈ ), 3,4-dimethylhexane ( C ₈ H _18), 2,2, - trimethylpentane _{(C 8} H 18), 2,2,4- trimethylpentane _{(C 8} H 18), 2,3,3- trimethylpentane _{(C 8} H 18), 2,3,4- trimethylpentane (C ₈ H _18), 2-methyl-octane _{(C 9} H 20), include branched aliphatic saturated hydrocarbons such as 2-methylnonane _(C 10 _{H 22).} These aliphatic hydrocarbons may be used alone or in combination of two or more.

  The ratio of the aliphatic hydrocarbon needs to be 90% by weight or more in the total solvent, but is preferably 95% by weight or more, more preferably 98% by weight or more. In the present invention, a solvent composed substantially only of aliphatic hydrocarbons is also suitable. When the ratio of the aliphatic hydrocarbon is too low, the surface treatment liquid becomes non-uniform on the tile portion during the application or drying of the surface treatment liquid, which adversely affects the finish. In addition, aesthetics are liable to deteriorate due to the adhesion of contaminants, and it is difficult to obtain sufficient performance in terms of contamination resistance.

  The content ratio of the solvent in the surface treatment liquid is usually 50 to 99.9% by weight, preferably 70 to 99% by weight, and more preferably 80 to 98% by weight. When the content ratio of the solvent is too low, there is a possibility of adversely affecting the finish properties and stain resistance of the tile portion. Conversely, when the content ratio is too high, the water absorption preventing property of the joint portion tends to be insufficient.

  The surface treatment liquid can be produced by uniformly mixing the above components by a conventional method. In the surface treatment solution, for example, a colorant, a thickener, a wetting agent, an antifreezing agent, an antiseptic, an antifungal agent, an antibacterial agent, an antibacterial agent, and a dispersion may be used, as long as the effects of the present invention are not significantly impaired. An agent, an antifoaming agent, an ultraviolet absorber, an antioxidant, a catalyst, and the like can also be mixed. In the present invention, since a practical anti-staining effect is obtained, it is not necessary to mix a photocatalyst or the like with the surface treatment liquid.

In the present invention, the surface treatment liquid is uniformly applied to the entire surface of the ceramic tile surface. A coating instrument is not specifically limited, Well-known coating instruments, such as a brush, spray, and a roller, can be used. The required amount for coating the surface treatment liquid may be appropriately set in consideration of the type and state of the ceramic tile, but is usually about 30 to 500 g / m ² (preferably 80 to 200 g / m ² ), solid In terms of minutes, it is usually about 1 to 250 g / m ² (preferably ² to 100 g / m ² ).
In the coating of the surface treatment liquid, the required amount is within the above range, and the coating can be performed in a plurality of times. In this case, the coating interval is preferably set to be relatively short, and is usually within 8 hours (preferably within 4 hours, more preferably within 2 hours).
The application and drying of the surface treatment liquid may be usually performed at room temperature. In the present invention, after coating the surface treatment liquid, it is only necessary to dry it as it is, and a process such as removing the surface treatment liquid on the tile portion is unnecessary.

  In the present invention, before the surface treatment liquid is applied, the joints or the entire tile surface is subjected to a treatment such as washing. As the cleaning treatment, a method of washing with water after applying various cleaning agents to the whole or a part of the tile surface can be employed. When washing with water, the treatment may be performed while rubbing the tile surface with a sponge or the like. After the tile surface subjected to the cleaning treatment is dried, the surface treatment liquid can be applied.

  Specifically, as the cleaning agent, an aqueous solution containing one or more selected from inorganic acids, organic acids, fluorine compounds and the like as an active ingredient is preferable. Among these, examples of the inorganic acid include hydrochloric acid, sulfuric acid, nitric acid, hydrofluoric acid, phosphoric acid, boric acid, phosphorous acid, sulfamic acid, and hypophosphorous acid. Examples of organic acids include monobasic carboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oleic acid, linoleic acid, oxalic acid, malonic acid, succinic acid, maleic acid, Dibasic carboxylic acids such as fumaric acid, itaconic acid, glutaric acid and adipic acid, lactic acid, citric acid, glycolic acid, malic acid, tartaric acid, gluconic acid, ascorbic acid, erythorbic acid and other oxycarboxylic acids, ethylenediaminetetraacetic acid Aminocarboxylic acids such as diethylenetriaminepentaacetic acid, nitrilotriacetic acid, aspartic acid and glutamic acid, sulfonic acids such as paratoluenesulfonic acid, phosphonic acids such as 1-hydroxyethylidene-1,1-diphosphonic acid and aminotrimethylenephosphonic acid Can be mentioned. Examples of the fluorine compound include hydrofluoric acid, ammonium fluoride, acidic ammonium fluoride, ammonium hydrogen fluoride, ammonium fluorosilicate, tetramethylammonium fluoride, tetraethylammonium fluoride, triethylmethylammonium fluoride, and fluorine. Trimethylhydroxyethylammonium fluoride, tetraethanolammonium fluoride, methyltriethanolammonium fluoride, and the like. These may be used in combination of two or more. In the cleaning agent, other components such as a surfactant can be appropriately mixed.

  As the cleaning agent in the present invention, an aqueous solution containing a fluorine compound is particularly suitable. An aqueous solution containing a fluorine compound and an inorganic acid and / or an organic acid is also suitable. The concentration of the fluorine compound in the cleaning agent is usually 0.001 to 3% by weight (preferably 0.005 to 1% by weight). The concentration of the inorganic acid is usually 0 to 30% by weight (preferably 1 to 20% by weight), and the concentration of the organic acid is usually 0 to 30% by weight (preferably 1 to 20% by weight). When the concentration of each component is within such a range, the tile surface is excellent in decontamination, and is suitable in terms of water absorption prevention at joints and finish of tiles.

  In the present invention, after performing the cleaning treatment using such a cleaning agent, the surface treatment liquid is applied, and thereby the effects such as water absorption prevention at the joint can be further enhanced. In addition, in the tile portion, it is possible to reliably prevent unevenness of the surface treatment liquid during application of the surface treatment liquid or during drying, and to obtain an effect of improving the finish.

  In the present invention, the surface containing 0.1 to 50% by weight of a tetraalkoxysilane compound as the second surface treatment liquid after coating the above-mentioned surface treatment liquid (hereinafter also referred to as “first surface treatment liquid” for convenience). The treatment liquid can be applied to the entire surface of the ceramic tile. The effect of the present invention can be further enhanced by coating the surface treatment liquid.

Among the components constituting the second surface treatment liquid, the tetraalkoxysilane compound includes a tetraalkoxysilane represented by the following formula (2) and / or a condensate thereof, or a part of the alkyl group thereof as a polyoxyalkylene group. What modified | denatured by etc. can be used.
Si (OR ³ ) ₄ (2)
(In the formula, R ³ represents an alkyl group.)

  Examples of such tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, tetraisopropoxysilane, tetra n-butoxysilane, tetraisobutoxysilane, tetra sec-butoxysilane, tetra-t- Examples thereof include butoxysilane, and those having a mixture of alkyl groups having different carbon numbers can also be used. As these condensates, those having an average degree of condensation of about 1 to 20 (preferably 2 to 10) can be used.

  As the alkoxyl group in the tetraalkoxysilane compound, those having 1 to 8 carbon atoms (preferably 1 to 4, more preferably 1 to 2) are suitable. The content ratio of the tetraalkoxysilane compound in the second surface treatment liquid is usually 0.1 to 50% by weight, preferably 0.5 to 20% by weight, and more preferably 1 to 10% by weight. By using such a tetraalkoxysilane, an excellent effect can be stably obtained.

  The second surface treatment liquid is a solution in which the above tetraalkoxysilane compound is dissolved or dispersed in a medium, and may be dispersed by an emulsifier or the like. Examples of the medium in the surface treatment liquid include a strong solvent system mainly containing an aromatic hydrocarbon solvent, a weak solvent system mainly containing an aliphatic hydrocarbon solvent, and an aqueous system mainly containing water. Various forms can be used. The content ratio of the medium in the second surface treatment liquid is usually 50 to 99.9% by weight, preferably 80 to 99.5% by weight, and more preferably 90 to 99% by weight.

  As a medium in the second surface treatment liquid, a solvent containing 90 wt% or more (preferably 95 wt% or more, more preferably 98 wt% or more) of an aliphatic hydrocarbon is suitable. A solvent composed substantially only of aliphatic hydrocarbons is also suitable. As the aliphatic hydrocarbon, an aliphatic saturated hydrocarbon is preferable, and an aliphatic saturated hydrocarbon having 4 or more (more preferably 5 or more) carbon atoms is particularly preferable. As such an aliphatic hydrocarbon, the thing similar to what was illustrated with the 1st surface treatment liquid can be used. By using such aliphatic hydrocarbons, stable effects can be obtained in terms of finish, contamination resistance, and the like.

The second surface treatment liquid may contain an alkoxysilane compound other than the tetraalkoxysilane compound. However, it is desirable to prepare such that at least 30% by weight or more of all alkoxysilane compounds in the second surface treatment liquid are the tetraalkoxysilane compounds.
In addition, the second surface treatment liquid is, for example, a resin component, a colorant, a thickening agent, a wetting agent, an antifreezing agent, an antiseptic, an antifungal agent, and an algae preventing agent within a range that does not significantly impair the effects of the present invention. , An antibacterial agent, a dispersant, an antifoaming agent, an ultraviolet absorber, an antioxidant, a catalyst, and the like may be included.
A 2nd surface treatment liquid can be manufactured by mixing these components uniformly by a conventional method. In the second surface treatment liquid, it is desirable that the resin component is not mixed so much, and the content ratio is lower than that of the tetraalkoxysilane compound in order to sufficiently exert the action of the tetraalkoxysilane compound. The content ratio of the resin component is usually less than 20% by weight (preferably 10% by weight or less), and a form not including the resin component is also suitable. Further, it is not necessary to mix a photocatalyst or the like with the second surface treatment liquid.

The second surface treatment liquid is uniformly applied to the entire surface of the ceramic tile surface. The coating of the second surface treatment liquid may be usually performed for 1 hour to 10 days, preferably 3 hours to 7 days after the application of the first surface treatment liquid. A coating instrument is not specifically limited, Well-known coating instruments, such as a brush, spray, and a roller, can be used. The required amount for coating the second surface treatment liquid may be set as appropriate in consideration of the type and state of the ceramic tile, but is usually 10 to 300 g / m ² (preferably 30 to 150 g / m ² ). About 0.1 to 150 g / m ² (preferably 0.3 to 75 g / m ² ) in terms of solid content. The application and drying of the second surface treatment liquid may be usually performed at room temperature.

  As described above, in the present invention, by using a specific surface treatment liquid, it is possible to obtain a finish that exhibits water repellency at the joints of the ceramic tile surface and hydrophilicity at the tiles, preventing water absorption and stain resistance. It is possible to exert an excellent effect in the above. The mechanism of action is not clear, but the properties of the joint and the tile are completely different, so the permeability, reactivity, orientation, etc. of the alkoxysilane compound at each site are also different. Presumed to be played.

  Examples are given below to clarify the features of the present invention.

(Manufacture of surface treatment liquid)
Surface treatment liquids 1 to 9 were produced by mixing the following raw materials at a weight ratio shown in Table 1.
Alkoxysilane compound 1: Hexyltrimethoxysilane (condensation degree 1)
Alkoxysilane compound 2: Hexyltriethoxysilane (condensation degree 1)
Alkoxysilane compound 3: butyltrimethoxysilane (condensation degree 1)
Alkoxysilane compound 4: Hexyltrimethoxysilane (condensation degree 3)
Alkoxysilane compound 5: Hexyltrimethoxysilane (condensation degree 6)
・ Solvent 1: Mixture of aliphatic hydrocarbons with 9 or more carbon atoms ・ Solvent 2: Aliphatic hydrocarbon solvent (containing 30% by weight of aromatic hydrocarbons)
-Solvent 3: Aromatic hydrocarbon solvent (aromatic hydrocarbon 100% by weight)

[I. Test 1]
Example 1
After the surface treatment solution 1 is spray-coated on the entire surface at a required amount of 80 g / m ² on a test base material consisting of cement mortar in the joint and the tile part in porcelain tile, the standard condition (temperature 23 ° C, relative The surface treatment solution 1 was dried for 1 hour at a humidity of 50%, and then sprayed again on the entire surface with the required amount of 80 g / m ² . Then, it was dried for 24 hours in a standard state. The following test was performed on the test plate obtained by the above method. The results are shown in Table 2. In Example 1, good results could be obtained in any test.

-Finishing The appearance of the tile after painting was observed. The evaluation was performed in three stages (A>B> C) where “A” was defined as “A” indicating that there was no abnormality in the drying process and the texture and gloss after drying were unchanged.
-Water absorption prevention A test plate was fixed vertically, and water was continuously sprayed to the test plate using a hose for 1 minute. Under the present circumstances, the water-repellent condition and color change in a joint part were observed. The evaluation was performed in five stages (A> A ′>B> B ′> C) where “A” is a sample having high water repellency and no color change.
-Contamination resistance After the test plate was installed vertically outdoors and exposed for one month outdoors, the appearance of the test plate was observed. The evaluation was performed in three stages (A>B> C) where “A” is defined as no contamination.
-Contact angle The contact angle of the tile part was measured about the test board after evaluating the said contamination | pollution resistance test. As a measuring device, a static contact angle measuring device CA-D type (manufactured by Kyowa Interface Science Co., Ltd.) was used, and the average value was calculated at five locations. The evaluation was performed in three stages, with “A” being a contact angle with respect to water of less than 50 °, “B” being 50 ° or more and less than 70 °, and “C” being 70 ° or more.

(Example 2)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 2 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Example 2, good results could be obtained in any test.

(Example 3)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 3 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Example 3, good results could be obtained in any test.

Example 4
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 4 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Example 4, generally good results could be obtained.

(Example 5)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 5 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Example 5, generally good results could be obtained.

(Comparative Example 1)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 6 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Comparative Example 1, the surface treatment liquid was repelled during the coating process, and spotted contamination was observed in the stain resistance test. In the contact angle measurement, the variation depending on the measurement location was large.

(Comparative Example 2)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 7 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Comparative Example 2, the surface treatment liquid was repelled during the coating process, and spotted contamination was observed in the stain resistance test. In the contact angle measurement, the variation depending on the measurement location was large.

(Comparative Example 3)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 8 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Comparative Example 3, the gloss of the tile portion was lowered.

(Comparative Example 4)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 9 was used instead of the surface treatment liquid 1. The test results are shown in Table 2. In Comparative Example 4, the gloss of the tile part was lowered, and the stain resistance and hydrophilicity of the tile part were insufficient.

(Comparative Example 5)
The test substrate itself (no coating) was tested in the same manner as in Example 1. The test results are shown in Table 2. In Comparative Example 5, the water absorption preventing property was inferior.

[II. Test 2]
(Example 6)
Apply a 0.6% by weight aqueous solution of ammonium fluoride to the entire surface of the test substrate (the joint is made of cement mortar and the tile is made of ocher porcelain tile). After leaving for 30 seconds, it was washed with water while rubbing with a sponge. After drying for 24 hours under standard conditions, after spray coating the entire surface of the surface treatment liquid 1 in the required amount 80 g / m ^2, dried for 1 hour at standard conditions, then the same surface treatment liquid 1 in the required amount 80 g / m ² The entire surface was sprayed again. Then, it was dried for 24 hours in a standard state. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 3. In Example 6, good results were obtained in any test, and it was possible to restore the aesthetic appearance of the soiled tile surface and maintain the aesthetic appearance.

(Example 7)
A mixed aqueous solution of 0.5% by weight of ammonium fluoride, 3% by weight of phosphoric acid, and 10% by weight of lactic acid was applied to the entire test substrate as in Example 6, left for about 30 seconds, and then rubbed with a sponge. Washed with water. After drying for 24 hours under standard conditions, after spray coating the entire surface of the surface treatment liquid 1 in the required amount 80 g / m ^2, dried for 1 hour at standard conditions, then the same surface treatment liquid 1 in the required amount 80 g / m ² The entire surface was sprayed again. Then, it was dried for 24 hours in a standard state. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 3. In Example 7, good results were obtained in any of the tests, and it was possible to restore the aesthetic appearance of the dirty tile surface and maintain the aesthetic appearance.

(Example 8)
A mixed aqueous solution of 3% by weight of phosphoric acid and 10% by weight of lactic acid was applied to the entire test substrate as in Example 6, and allowed to stand for about 30 seconds, and then washed with water while rubbing with a sponge. After drying for 24 hours under standard conditions, after spray coating the entire surface of the surface treatment liquid 1 in the required amount 80 g / m ^2, dried for 1 hour at standard conditions, then the same surface treatment liquid 1 in the required amount 80 g / m ² The entire surface was sprayed again. Then, it was dried for 24 hours in a standard state. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 3. In Example 8, generally good results could be obtained, but Examples 6-7 were better in terms of water absorption prevention.

Example 9
A 0.6 wt% ammonium fluoride aqueous solution was applied to the entire test substrate as in Example 1, and allowed to stand for about 30 seconds, and then washed with water while rubbing with a sponge. After drying for 24 hours at standard conditions, the surface treatment liquid 4 in the required amount 80 g / m ² was spray-coated on the entire surface, dried for 1 hour at standard conditions, then the same surface treatment liquid 4 in the required amount 80 g / m ² The entire surface was sprayed again. Then, it was dried for 24 hours in a standard state. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 3. In Example 9, good results could be obtained in any test. The water absorption preventing property was better than that of Example 4.

[III. Test 3]
(Example 10)
The surface treatment liquid 1 was spray coated on the entire surface of the test substrate similar to that of Example 1 at a required amount of 120 g / m ² and then dried in a standard state for 3 hours. Next, the surface treatment liquid 10 (a mixture of tetramethoxysilane condensate (average condensation degree 4) and solvent 1, weight ratio 2:98) is spray-coated on the entire surface at a required amount of 50 g / m ² and is 24 hours under standard conditions. Dried. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 4. In Example 10, good results could be obtained in any test.

(Example 11)
The surface treatment liquid 1 was spray coated on the entire surface of the test substrate similar to that of Example 1 at a required amount of 120 g / m ² and then dried in a standard state for 3 hours. Subsequently, the surface treatment liquid 11 (a mixture of tetramethoxysilane condensate (average condensation degree 8) and solvent 1, weight ratio 2:98) is spray-coated on the entire surface at a required amount of 50 g / m ² and is 24 hours under standard conditions. Dried. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 4. In Example 11, good results could be obtained in any test.

Example 12
The surface treatment liquid 1 was spray coated on the entire surface of the test substrate similar to that of Example 1 at a required amount of 120 g / m ² and then dried in a standard state for 3 hours. Next, the surface treatment liquid 12 (a mixture of tetramethoxysilane condensate (average condensation degree 4) and solvent 1, weight ratio 4:96) is spray-coated on the entire surface at a required amount of 50 g / m ² and is 24 hours under standard conditions. Dried. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 4. In Example 12, good results could be obtained in any test.

(Example 13)
The surface treatment liquid 4 was spray coated on the entire surface of the test substrate similar to Example 1 at a required amount of 120 g / m ² and then dried in a standard state for 3 hours. Subsequently, the surface treatment liquid 10 was spray-coated on the entire surface at a required amount of 50 g / m ² and dried in a standard state for 24 hours. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 4. In Example 13, good results could be obtained in any test.

(Example 14)
The surface treatment liquid 5 was spray coated on the entire surface of the test substrate similar to Example 1 at a required amount of 120 g / m ² and then dried in a standard state for 3 hours. Subsequently, the surface treatment liquid 10 was spray-coated on the entire surface at a required amount of 50 g / m ² and dried in a standard state for 24 hours. The test plate obtained by the above method was tested in the same manner as in Example 1. The results are shown in Table 4. In Example 14, good results could be obtained in any test.

[IV. Test 4]
Each raw material was mixed by the usual method by the weight ratio shown in Table 5, and the surface treatment liquids 13-14 were manufactured.

(Example 15)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 13 was used instead of the surface treatment liquid 1. The test results are shown in Table 6. In Example 15, although it was a little inferior compared with Examples 1-3, the favorable result was able to be obtained in general.

(Comparative Example 6)
The test was performed in the same manner as in Example 1 except that the surface treatment liquid 14 was used instead of the surface treatment liquid 1. The test results are shown in Table 6. In Comparative Example 6, the texture and gloss after drying were not uniform. In the contact angle measurement, the variation depending on the measurement location was large.

Claims (3)

A method of repairing a ceramic tile surface comprising a tile part and a joint part by coating with a surface treatment liquid,
The surface treatment liquid contains 0.1 to 50% by weight of an alkoxysilane compound and 50 to 99.9% by weight of a solvent,
The alkoxysilane compound contains 90% by weight or more of an alkylalkoxysilane compound having 3 to 12 carbon atoms in the alkyl group and a condensation degree of 2 or less.
The solvent contains 90% by weight or more of aliphatic hydrocarbons,
A method for refurbishing a ceramic tile surface, wherein the ceramic tile surface is cleaned before the surface treatment liquid is applied to the entire surface of the ceramic tile surface.   The method for repairing a ceramic tile surface according to claim 1, wherein the aliphatic hydrocarbon is an aliphatic saturated hydrocarbon having 4 or more carbon atoms. The cleaning treatment uses a cleaning agent,
The method for repairing a ceramic tile surface according to claim 1 or 2, wherein the cleaning agent is an aqueous solution containing at least one selected from an inorganic acid, an organic acid, and a fluorine compound.