JPH10212177A - Porcelain tile panel with coated joint part and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To impart antifouling property and antimold property to the joint part of a porcelain tile panel with plural porcelain tiles stuck to the surface of the substrate and the joint part between the tiles by coating the surface of the joint part with a coating material. SOLUTION: The surface of the joint part of a porcelain tile panel is coated with a coating material. This coating material is preferably a coating material contg. one or more kinds of hydrolyzable silicon compds. selected from among a hydrolyzable silyl group-contg. vinyl copolymer, a hydrolyzate of organosilane and a partial condensation product of the hydrolyzate, e.g. a condensation product of a hydrolyzate of methyl triethoxysilicate as a binder or a UV-curing coating material. Titanium dioxide or zinc oxide having photocatalytic activity is preferably contained in the coating material by such an amt. that the weight concn. of the pigment is regulated to 45-85, especially 50-80 so as to improve antibacterial activity, antimold activity and deodorizing activity.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a porcelain tile panel and a method of manufacturing the same, and more particularly, to a jointed porcelain tile panel having excellent antifouling property and antifungal property and a method of manufacturing the same.

[0002]

2. Description of the Related Art Porcelain tile panels in which a porcelain square tile is fixed on a substrate with an adhesive and a cement joint material is used for joints have been widely used as a building plate material. However, the joints of the porcelain tile panel are formed of cement-based joints and are used as they are, so that dirt easily adheres to them, and mold is easily generated by using the dirt as a nutrient source. In addition, there is a problem that the external appearance tends to become dirty.

[0003]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and an object of the present invention is to provide an antifouling property.
An object of the present invention is to provide a porcelain tile panel excellent in antifungal properties and a method for producing the same.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to achieve the above object, and as a result, have found that the above object can be achieved by applying a paint to the joint surface of a porcelain tile panel. Found and arrived at the present invention. That is, the joint-coated porcelain tile panel of the present invention is a porcelain tile panel having a plurality of porcelain tiles attached to a substrate surface and joints provided between the porcelain tiles, wherein the paint is applied to the joint surface. It is characterized by being painted. Further, the method for producing a joint-coated porcelain tile panel of the present invention includes a method for coating a joint surface of a porcelain tile panel having a plurality of porcelain tiles attached to a substrate surface and joints provided between the porcelain tiles. It is characterized by painting.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. As the substrate used in the present invention, a slate plate,
Wood chip cement board, pulp cement board, asbestos cement board,
Inorganic substrates such as a lightweight aggregate-mixed cement board, a foamed concrete board, a glass fiber reinforced cement board, a calcium silicate board, a magnesium carbonate board, and other hydraulic boards. However, it is not limited to these.

[0006] In the joint-coated porcelain tile panel of the present invention, a plurality of porcelain tiles adhered to the surface of the substrate using an epoxy adhesive or the like, and joints provided between the porcelain tiles are provided. The paint is applied to the joint surface of the porcelain tile panel having the following.In the present invention, any adhesive, any porcelain tile, any joint material conventionally used in the production of the porcelain tile panel is used. Can be.

In the present invention, a lower layer coating film may be applied in advance to the joint surface to be coated with the paint. Such a lower layer coating film is an organic solvent type such as a baking type, a normal dry type, an active energy ray-curable type, an aqueous type, a conventionally known various type of paint such as a solventless type, or a substrate reinforcing primer or a urethane type, an epoxy type. , Vinyl or the like can be used alone or in combination.

In the present invention, any paint can be used as long as it is capable of forming an antifouling coating film, but a silyl group-containing vinyl copolymer having a hydrolyzable group and a hydrolyzable organosilane can be used. It is preferable to use a paint containing at least one hydrolyzable silicon compound selected from the group consisting of a decomposition product and a partial condensate of a hydrolyzate of an organosilane as a binder, or an ultraviolet-curable coating.

The silyl group-containing vinyl copolymer having a hydrolyzable group which can be used in the present invention has> C = C
<A copolymer obtained by copolymerization of at least one kind of ethylenically unsaturated monomer containing at least one group with at least one kind of a silyl group-containing monomer represented by the following general formula: : RSiX _n R ¹ in _{(3-n) (wherein,} R is a monovalent organic group containing a vinyl group, R ¹
Is an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group, and X is a group consisting of a halogen, an alkoxy, an alkoxyalkoxy, an acyloxy, a ketoximate, an amino, an acid amide, an aminooxy, a mercapto, and an alkenyloxy group. A hydrolyzable group selected,
n is an integer of 1 to 3).

Examples of the above ethylenically unsaturated monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, 2-methylhexyl methacrylate, lauryl methacrylate and the like. Alkyl acrylates; vinyl aromatic hydrocarbons such as styrene, vinyl toluene and α-methylstyrene; vinyl halides such as vinyl chloride: vinylidene halides such as vinylidene chloride: butadiene;
Conjugated dienes such as isobrene; vinyl esters of saturated fatty acids having 1 to 12 carbon atoms, vinyl acetate, vinyl propionate and the like can be mentioned, and these can be used alone or in combination of two or more. Examples of the silyl group-containing monomer include γ-methacryloxypropyltrimethoxysilane, vinyltriethoxysilane, and vinyl tris (2-methoxyethoxysilane).

The above silyl group-containing vinyl copolymer having a hydrolyzable group can be obtained by copolymerizing the above-mentioned ethylenically unsaturated monomer and silyl group-containing monomer at an arbitrary ratio by a conventionally known production method. The amount of the silyl group-containing monomer is 0.5 to 25 mol%, and the amount of the ethylenically unsaturated monomer is 99.5 to 75 mol%. Preferably. The silyl group-containing vinyl copolymer has a molecular weight of 3,000 to 1,000.
It is preferably from 0000, particularly from 10,000 to 300,000.

The hydrolyzate of organosilane which can be used in the present invention is represented by the following general formula (I), (II) or (II)
It is a compound obtained by hydrolysis of an organosilane represented by I). _{^{R 2 Si (OR 3) 3}} (I) Si (OR 3) 4 (II) R 2 2 Si (OR 3) 2 (III) ( In the formulas, each of R ² is from 1 to 8 carbon atoms An organic group, R ³ is an alkyl group having 1 to 4 carbon atoms,
R ² and R ³ may be the same or different. )

Specific examples of the organic group R ^{2 in} the above general formula (I), (II) or (III) include alkyl such as methyl, ethyl, n-propyl, i-propyl and i-butyl. Group, γ-chloropropyl group, vinyl group, 3,
Examples thereof include a 3,3-trifluoropropyl group, a γ-glycidoxypropyl group, a γ-methacryloxypropyl group, a γ-mercaptopropyl group, a phenyl group, and a 3,4-epoxycyclohexylethyl group. Specific examples of the alkyl group R ³ include a methyl group, an ethyl group, and n-
Examples thereof include a propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

Specific examples of the organosilane represented by the above general formula (I) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane,
Ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, i-propyltrimethoxysilane, i-propyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, 3,3,3-trifluoropropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxy Propyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-mercaptopropyltomellitoxysilane, γ-mercaptopropyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, i-butyltrimethoxysilane, i-butyltriethoxysilane, etc. Methyltrimethoxysilane and methyltriethoxysilane are preferred.

Specific examples of the organosilane (alkyl silicate) represented by the general formula (II) include tetramethyl silicate, tetraethyl silicate, and tetra-ethyl silicate.
Examples thereof include n-propyl silicate, tetra-i-propyl silicate, tetra-n-butyl silicate, tetra-i-butyl silicate, and tetra-sec-butyl silicate.

Specific examples of the organosilane of the general formula (III) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, di-n-propyldimethoxysilane, di-n-propyl Diethoxysilane, di-i-propyldimethoxysilane, di-i-propyldiethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane and the like can be mentioned, and dimethyldimethoxysilane and diethyldiethoxysilane are particularly preferable.

The compound represented by the general formula (I), (II) or (III)
)) Is used together with the organosilanes
The mixing ratio (weight ratio) of (I) to (II) is 100: 0 to 30 in terms of organosilane (that is, (II) may not be contained), and (I) and (II) are calculated in terms of organosilane.
And the mixing ratio (weight ratio) of (III) to 100: 5
To 150, particularly preferably 100: 10 to 120. When the mixing ratio of the organosilane of the general formula (III) is larger than the above range, the formed coating film is liable to crack, and when smaller than the above range, the curability decreases, And the hardness of the coating film tends to decrease.

In the present invention, the above-mentioned general formula (I)
A partial condensate of a hydrolyzate obtained by hydrolysis of the organosilane represented by (II) or (III) can be used. The molecular weight of this partial condensate in terms of polystyrene is preferably 1,000 to 5,000, more preferably 1,
500 to 3,000. When using the above-mentioned hydrolyzate or its partial condensate, it is preferable to use a solvent solution containing a solid content of 10 to 80% by weight.

In the present invention, a hydrolyzate of organosilane represented by the above general formula (I), (II) or (III) or a partial condensate thereof is used. Add water. The amount of water to be added is generally 0.1 to 1.0 mol, particularly 0.15 to 0.7 mol, per equivalent of the alkoxy group of the organosilane of the general formula (I), (II) or (III). Is preferred. If the number of moles of water is less than the above range, storage stability tends to be poor, and if the number of moles of water is more than the above range, curing and drying tends to be slow. Further, a production accelerator may be used for producing such a partial condensate of organosilane.

As such an accelerator, a compound represented by the following general formula (IV) or a mineral acid can be used. M (OR ⁴ ) _X (IV) In the general formula (IV), M is a metal such as Ti, Al, B, Zr, R ⁴ is an alkyl group having 2 to 5 carbon atoms, and x is 2 -4.

Specific examples of the compound of the general formula (IV) include
Tetra-i-propoxytitanium, tetra-n-butoxytitanium, tri-i-propoxyaluminum, mono-s
ec-butoxy-di-i-propoxyaluminum, diethoxyboron, di-n-propoxyboron, tetra-
Examples thereof include n-butoxyzirconium and the like, and examples of mineral acids include hydrochloric acid and sulfuric acid. The addition amount is 0.05 to 100 parts by weight of the organosilane.
It is preferred to be in the range of 2.0 parts by weight.

In the present invention, these hydrolyzable silicon compounds can be used alone or in combination of two or more. The coating composition containing a hydrolyzable silicon compound as a binder, which can be used in the present invention, can be used by blending various pigments, organic solvents, additives, and the like, if necessary.

As the pigment, a pigment generally used for paints can be used as it is. Specifically, coloring inorganic pigments such as titanium oxide, zinc sulfide, zinc white, iron oxide, graphite, lead white, coloring organic pigments such as phthalocyanine blue and benzidine yellow, calcium carbonate, quartz powder, alumina, talc, sedimentation Typical examples thereof include extender pigments such as neutral barium sulfate, and metal powders such as stainless powder, zinc powder, aluminum powder, bronze powder, and mica powder.

Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone; Representative examples include alcohol solvents such as butanol. Also,
As additives, surface conditioners, dispersants, ultraviolet absorbers,
Additives commonly known as paint additives, such as thickeners, preservatives, fungicides, anti-algal agents, and reaction control catalysts, may be mentioned.

The UV-curable coating material that can be used in the present invention contains a UV-polymerizable compound and a photoinitiator as essential components. As the ultraviolet polymerizable compound, a compound having an unsaturated double bond capable of radical polymerization in a molecule can be used. Specifically, relatively low molecular weight polyester resin, alkyd resin, polyether resin, acrylic resin, epoxy resin, urethane resin, silicone resin, polybutadiene resin, acrylic oligomer or prepolymer, acrylic urethane oligomer, and 2-ethylhexyl (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dipropylene glycol mono (meth) acrylate, (meth) acrylamide, N-vinylpyrrolidone, triethylene glycol di (meth) acrylate, A typical example is a single or mixture of reactive monomers such as trimethylolpropane tri (meth) acrylate and dipentaerythritol hexane (meth) acrylate.

The above-mentioned acrylic urethane oligomers widely include those having a urethane bond in the molecule and having an unsaturated double bond capable of radical polymerization and having an average molecular weight of several hundreds to several tens of thousands and having a viscous state at room temperature. For example, an oligomer obtained by reacting a polyisocyanate with a (meth) acrylic acid ester having a hydroxyl group, a polyether-based acrylic urethane oligomer, a polyester-based acrylic urethane oligomer, a polybutadiene-based acrylic urethane oligomer, and the like can also be mentioned.

Specifically, toluene diisocyanate,
Hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, xylene diisocyanate, isomers thereof and the like, polyester polyol, polyoxymethylene glycol, polyoxyethylene glycol, caprolactone polyol,
A reaction product of a polyisocyanate (especially preferably a non-yellowing type polyisocyanate) such as a compound having an isocyanate terminal, which is a reaction product with trimethylolpropane, pentaerythritol, or the like, and a compound having a hydroxyl group and an unsaturated group is included. No. Representative examples of the compound having a hydroxyl group and an unsaturated group include hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, and glycidyl (meth) acrylate.

As the UV-polymerizable compound, cationic ring-opening polymerization type vinyl-2-ethylhexyl ether, vinyl decyl ether, 1,2-epoxycyclohexane,
Dicyclopentadienedioxide, sorbitol polyglycidyl ether and the like can also be used.

Examples of the photoinitiator include benzoin, benzophenone and their esters, benzoyl peroxide,
Azobisisobutyronitrile, diphenyl disulfide, N-methyldiethanolamine, acylphosphine oxide, 2,5-dietoxin-4- (p-tolylthio) benzeneazonium hexafluorophosphate, benzyldimethylketal, α-hydroxyisobutyrophenone And the like.

The ultraviolet-curable coating material that can be used in the present invention may contain transparent spherical glass beads having a central particle diameter of 100 μm or less and / or transparent glass powder. In view of the fact that the transparent spherical glass beads having a center particle diameter of 100 μm or less have a function of transmitting light energy into the inside of the coating film, it is desired to satisfy the following conditions. (A) The central particle size is 100 μm or less, preferably 10 to 6
0 μm. It should be noted that even if the center particle size exceeds 100 μm, the coating film curability is not affected, but glass beads are conspicuous in the resulting coating film, giving rise to roughness and the like. Also, physical properties such as tensile strength are reduced. On the other hand, the lower limit of the center particle size is not particularly limited. However, when the center particle size is small, the light transmittance of the coating film tends to substantially decrease.
It is preferred to be within the range of μm. (B) It is transparent and spherical. The spherical glass beads function as a lens and have an effect of increasing the transmittance. The glass beads that can be used in the present invention can be used without any particular limitation as long as they satisfy the above conditions.

The transparent glass powder having a center particle diameter of 100 μm or less has a function of imparting abrasion resistance and the like to the obtained coating film and transmitting light energy into the coating film. Can be formed, and a large amount of a coloring pigment can be added even in the case of a thin film coating film, so that a thin film coating film having high hiding power can be formed. It is desired that the transparent glass powder satisfies the following conditions in order to give the coating film the above function.

The central particle size is 100 μm or less, preferably 0.5 to 60 μm. The center particle diameter is 100 μm
It does not affect the curability of the coating even if it exceeds
The glass powder is conspicuous in the resulting coating film, giving rise to roughness and the like, which is not preferable in terms of the appearance of the coating film. In addition, physical properties such as tensile strength are reduced. On the other hand, the lower limit of the center particle size is not particularly limited. However, as the center particle size decreases, the transmittance of the coating film tends to substantially decrease.
It is desirable that the thickness be in the range of 5 to 60 μm. When a thin film of about 30 μm or less is desired, the central particle size is
It is preferable to use the following glass powder. In addition, about the shape of a glass powder, when forming a thick film coating of several tens μm to several hundreds μm, it is preferable that the glass is spherical, while when forming a thin film coating of several μm to several tens μm, May be amorphous.

Examples of the material of the transparent spherical glass beads and the transparent glass powder that can be used in the present invention include soda lime glass, soda lime / lead glass, potassium / lead glass, potassium / soda / lead glass, and borosilicate glass. Specific examples include high-alumina glass, potassium-soda-barium glass, and the like. In particular, low-alkali glass is desirable because of its good hydrolysis resistance. In addition, low-pressure mercury lamps, high-pressure mercury lamps, metal halide lamps,
Carbon arc lamps, xenon lamps, chemical lamps and the like can be used.

The UV-curable coating composition which can be used in the present invention can be used by blending various pigments, organic solvents or additives as necessary with the above-described coating composition. As the pigment, a pigment commonly used for paints can be used as it is. Specifically, coloring inorganic pigments such as titanium oxide, zinc sulfide, zinc white, iron oxide, graphite, lead white, coloring organic pigments such as phthalocyanine blue and benzidine yellow, calcium carbonate, quartz powder, alumina, talc, sedimentation Typical examples thereof include extender pigments such as neutral barium sulfate, and metal powders such as stainless powder, zinc powder, aluminum powder, bronze powder, and mica powder.

Examples of the organic solvent include hydrocarbon solvents such as toluene and xylene; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone;
Representative examples include alcohol solvents such as methanol, ethanol, and butanol. As additives, additives commonly known as paint additives such as surface conditioners, dispersants, ultraviolet absorbers, thickeners, preservatives, fungicides, antialgal agents, reaction control catalysts and the like can be used. No.

Titanium oxide and zinc oxide which can be incorporated in the coating composition of the present invention are known as photocatalysts having antibacterial activity, antifungal activity and deodorizing activity. In the present invention,
The above titanium oxide or zinc oxide has a PWC of 45
To 85, preferably 50 to 80 in the paint. Here, PWC means Pigment Weight Concentra
(weight concentration of pigment), which is calculated by the following equation. PWC = [weight of pigment content (%)] / [weight of total solids in paint
(%)] × 100 When the PWC is less than 15, the photocatalytic effect is not sufficiently exhibited. Conversely, if it exceeds 85, the film-forming properties decrease, and cracks and peeling of the coating film are liable to occur, which is not preferable.

Further, titanium oxide or zinc oxide having photocatalytic activity may be replaced with at least one selected from the group consisting of activated carbon, silica gel, zeolite and calcium phosphate in an amount of 10 to 50% by weight of the above amount. It is possible. Examples of the calcium phosphate include α-tricalcium phosphate, β-tricalcium phosphate, tetracalcium phosphate, octacalcium phosphate, and hydroxyapatite, with hydroxyapatite being particularly preferred. When the replacement ratio is less than 10% by weight, no replacement effect is observed. Conversely, if the content exceeds 50% by weight, the photocatalytic effect is undesirably reduced.

In the present invention, the above paint is applied to the joint surface of a porcelain tile panel having a plurality of porcelain tiles attached to the substrate surface and joints provided between the porcelain tiles. However, prior to such coating, copolymerization of acrylic acid or alkyl methacrylate emulsion resin, bisphenol-type epoxy emulsion resin, polyamide resin, aliphatic polyamine curing agent, inorganic powder, cement, pigment, water, etc. By applying an undercoat containing any component selected from the above to form an undercoat film, the effects aimed at in the present invention can be further improved.

As a coating method for applying the above-mentioned paint to the joint surface of the porcelain tile panel, there are conventional paint methods such as brush painting, roll painting, air spray, airless spray, and electrostatic spray which are performed by masking required portions. The method generally used can be adopted as it is.

[0040]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” and “%” are based on weight. <Example 1> (1) Two 10 cm square porcelain tiles were stuck on a straight plate by using an epoxy adhesive in a vertical and horizontal direction, and the joint width between the tiles was set to 2 mm. In this joint, glaze Gen No. 5 (trade name, manufactured by Dainippon Paint Co., Ltd.), which is a cement-based base conditioner, is embedded so as to be 2 mm lower than the tile surface.
A porcelain tile panel specimen was used.

(2) A coating was prepared by diluting 100 parts of V silicon (trade name, acrylic silicone resin coating, manufactured by Dainippon Paint Co., Ltd.) with 10 parts of a special thinner. (3) Mask the periphery of the joint of the porcelain tile panel of the above (1) with a masking tape, and apply the above (2) with a brush.
Was painted. This step was performed twice so that the coating amount was 100 g / m ² , the layers were coated, and dried at room temperature for 2 weeks.

(4) Stain resistance test: As a stain resistance test, a contaminant (A) obtained by kneading 1 part of carbon black with 100 parts of water or kneading 1 part of carbon black with 100 parts of salad oil. The contaminant (B) was applied to the joints of the tiles with a brush and dried at 20 ° C. for 24 hours.
Washing with a brush with running water, this process was repeated 5 times. The state of the stain was visually observed and evaluated according to the following criteria. ：: complete removal of dirt, ○: removal of almost all dirt, Δ: removal of only a part of dirt, ×: complete removal of dirt.

(5) Antifungal test: The test piece was placed on a potato dextrose agar medium, and both the test piece and the agar medium were inoculated with spores of Alitanaria (black mold). The culture was performed at 30 ± 1 ° C. and a relative humidity of 80 to 90% for one week. Thereafter, the surface was visually observed and evaluated according to the following criteria. ：: No mold was observed at joints. ○: Slight mold was observed at joints. Δ: Mold was observed at joints but not significant. ×: Mold was noticeably generated at joints. .

Further, the joints were wiped off with gauze moistened with water, and the degree of removal of mold was visually observed, and evaluated according to the following criteria. ◎: No mold stains were observed at all, ：: Almost completely removed, Δ: Partial removal residue was observed, ×: Not removed. The results of each evaluation were as shown in Table 1.

<Example 2> 40 parts of methyltriethoxysilicate and 54 parts of isopropyl alcohol were stirred and mixed at 40 ° C.
Of 5.7 parts of water was added dropwise over 90 minutes. After the completion of the dropwise addition, the mixture was further stirred at 40 ° C. for 4 hours.
A solution of the hydrolyzed condensate of 0% methyltriethoxysilicate was obtained. The polystyrene equivalent weight average molecular weight of the condensate was 10,000. Specimens were prepared in the same manner as in Example 1 except that this condensate solution was used as a paint.
It was painted similarly and evaluated similarly. The results of each evaluation were as shown in Table 1.

Example 3 Lucene # 300 as a paint
Specimens were prepared and coated in the same manner as in Example 1, except that after coating with Enamel E500 (trade name, manufactured by Dainippon Paint Co., Ltd., UV curable paint), the coating was cured by UV irradiation. And evaluated similarly. The results of each evaluation were as shown in Table 1.

Example 4 100 parts of the hydrolyzed condensate solution obtained in Example 2 was mixed with titanium oxide SSP-20 (trade name, manufactured by Sakai Chemical Industry Co., Ltd., average particle diameter 0.7 μm, specific surface area 170 m). ² / g) 160 parts, xylol 10 parts and isopropyl alcohol 10 parts were added to form a paint. To this, 0.1 part of a curing accelerator (dibutyltin laurate) was added. Except that this was used as a paint, a test piece was prepared and painted in the same manner as in Example 1. Regarding the stain resistance, the contaminant (A) or the contaminant (B) was applied to the joints of the tiles with a brush by the method of Example 1, and was applied at 20 ° C.
After drying for 4.0 hours using a black light.
Irradiation was carried out for 1 hour at an intensity of mW / cm ² , and further washing with a brush was carried out while flowing water. The state of the stain was visually observed and evaluated in the same manner as in Example 1. Other characteristics were evaluated in the same manner as in Example 1. The results of each evaluation were as shown in Table 1.

Comparative Example 1 450 parts of ion-exchanged water, ethylene oxide 20 of p-nonylphenol were placed in a reaction vessel equipped with a temperature controller, an irrigating stirrer, a reflux condenser, a supply vessel, a thermometer, and a nitrogen inlet tube. 5 parts of a 35% aqueous solution of the sodium salt of a sulfuric acid half ester of a molar adduct, and p-
20 parts of a 20% aqueous solution of 25 mol of nonylphenol ethylene oxide adduct was added and maintained at 80 ° C., and 2.5 parts of potassium persulfate was added thereto. After 5 minutes, 230 parts of butyl acrylate, 230 parts of styrene and 5 parts of acrylic acid were added. Was added dropwise over 3 hours. Thereafter, a solution prepared by dissolving 1 part of potassium persulfate in 30 parts of ion-exchanged water was dropped over 10 minutes. After 3 hours, the mixture was cooled to a greenhouse and neutralized to pH 8 with ammonia to obtain an emulsion having a solid content of 48%. A test specimen was prepared in the same manner as in Example 1 except that a mixture of 50 parts of ethylene glycol monobutyl ether and 50 parts of ion-exchanged water was added to the emulsion as a film-forming aid, and the resulting mixture was used as a paint. , And similarly evaluated. The results of each evaluation were as shown in Table 1.

<Comparative Example 2> Evaluation was made in the same manner as in Example 1 except that the joint was not coated. The result of each evaluation is the first
As shown in the table.

[0050]

As is clear from Table 1, in the case of Examples 1 to 4 of the present invention, excellent stain resistance and fungicide resistance were achieved by coating the joints. However, Comparative Example 1 which is an emulsion paint and Comparative Example 2 where the joint was not coated
In the case of (1), there was a problem in stain resistance and mold resistance.

[0052]

According to the present invention, since the paint is applied to the joint surface of the porcelain tile panel, a joint-painted porcelain tile panel excellent in stain resistance and antifungal property can be obtained.

Claims (4)

[Claims] 1. A porcelain tile panel having a plurality of porcelain tiles adhered to a substrate surface and joints provided between the porcelain tiles, wherein a paint is applied to the joint surface. Joints painted porcelain tile panel. 2. A coating material comprising: a hydrolyzable silyl group-containing vinyl copolymer; a hydrolyzate of an organosilane;
And at least one hydrolyzable silicon compound selected from the group consisting of a hydrolyzate of organosilane and a partial condensate thereof. Item 7. The joint-painted porcelain tile panel according to item 1. 3. A coating material containing titanium oxide or zinc oxide having photocatalytic activity in such an amount as to have a PWC of 45 to 85. 3. The coating material according to claim 1, wherein Jointed painted porcelain tile panel. 4. A paint is applied to a joint surface of a porcelain tile panel having a plurality of porcelain tiles attached to a substrate surface and joints provided between the porcelain tiles. 4. The method for producing a joint-painted porcelain tile panel according to item 2 or 3.