JPH11347482A - Production of joint part coated porcelain tile panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To embody excellent contamination resistance and mildew-proofing property by coating the joint part surface of a porcelain tile panel having plural porcelain tiles stuck to a base plate surface and the joint parts disposed between the respective porcelain tiles with a coating material by using an autodispenser by opening and closing of a solenoid valve. SOLUTION: This joint part surface of the ceramic tile panel having plural ceramic tiles stuck by using an epoxy adhesive, etc., to the surface of a base plate, such as, for example, a slate plate, and joint parts disposed between the respective ceramic tiles is coated with a coating material by using the autodispenser. The ceramic tile panel may be any panels produced by using any adhesives, ceramic tiles and joint fillers. A lower layer coating film may be previously applied on the joint part surface to be coated with the coating material. Any coating materials are usable as the coating material, insofar as the materials are capable of forming the coating films having stain-proofing properties. A coating material consisting of a hydrolyzable silicon compd. as a binder or a UV curing type coating material is more preferably used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a porcelain tile panel, and more particularly to a method for manufacturing a joint-painted porcelain tile panel having excellent stain resistance and fungicide resistance.

[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 joint portion of the porcelain tile panel is formed of a cement-based joint material and is used as it is. In addition, there has been a problem that the appearance is likely to be dirty.

[0003]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a method for producing a porcelain tile panel having excellent stain resistance and fungicide resistance. It is in.

[0004]

According to the present invention, a solenoid valve is provided on 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. Provided is a method of manufacturing a joint-coated porcelain tile panel in which a paint is applied using an auto-dispenser by opening and closing.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

The substrates used in the present invention include a slate board, a wood chip cement board, a pulp cement board, an asbestos cement board, a lightweight aggregate-mixed cement board, a foam concrete board, a glass fiber reinforced cement board, a calcium silicate board, and a magnesium carbonate board. And an inorganic substrate such as a plate or other hydraulic plate material. However, it is not limited to these.

In the present invention, a porcelain tile panel having a plurality of porcelain tiles adhered to the surface of a substrate as described above using an epoxy adhesive or the like and joints provided between the porcelain tiles. Paint is applied to the joint surface using an auto dispenser.Such a porcelain tile panel is made of any adhesive, any porcelain tile, and any joint material conventionally used in the production of porcelain tile panels. It may be manufactured using.

In the present invention, a lower coating film may be previously applied 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 a stain-resistant coating film, but a silyl group-containing vinyl copolymer having a hydrolyzable group, an organosilane It is preferable to use a paint containing at least one hydrolyzable silicon compound as a binder, or a UV-curable paint selected from the group consisting of a hydrolyzate of the above and a partial condensate of a hydrolyzate of an organosilane.

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, Alkyl acrylates such as lauryl methacrylate; vinyl aromatic hydrocarbons such as styrene, vinyl toluene and α-methylsterene; vinyl halides such as vinyl chloride: vinylidene halides such as vinylidene chloride: butadiene;
Conjugated dienes such as isoprene; 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,
Vinyl triethoxysilane, vinyl-tris (2-methoxy) ethoxysilane and the like can be mentioned.

The above silyl group-containing vinyl copolymer having a hydrolyzable group can be prepared by a conventionally known production method by mixing the above-mentioned ethylenically unsaturated monomer and silyl group-containing monomer at an arbitrary ratio. It can be produced by copolymerization. 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%. It is preferable to copolymerize. The silyl group-containing vinyl copolymer has a molecular weight of 3,000 to 1,000.
000, particularly preferably 10,000 to 300,000.

The hydrolyzate of an organosilane that can be used in the present invention is a compound obtained by hydrolyzing an organosilane represented by the following general formula (i), (ii) or (iii).

[0015] _{^{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 1 to carbon atoms There eight organic group, R ³ is alkyl group having 1 to 4 carbon atoms, R ²
And R ³ may be the same or different)

The above general formula (i), (ii) or (ii)
Specific examples of the organic group R ² in i) include an alkyl group such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an i-butyl group, a γ-chloropropyl group, a vinyl group,
3,3,3-trifluoropropyl group, γ-glycidoxypropyl group, γ-methacryloxypropyl group, γ-mercaptopropyl group, phenyl group, 3,4-epoxycyclohexylethyl group and the like. . Also,
Specific examples of the alkyl group R3 include a methyl group, an ethyl group,
n-propyl group, i-propyl group, n-butyl group, sec
-Butyl group, tert-butyl group and the like.

Specific examples of the organosilane represented by the 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-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,
Phenyltrimethoxysilane, phenyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltriethoxysilane, i-butyltrimethoxysilane, i
-Butyltriethoxysilane and the like, and methyltrimethoxysilane and methyltriethoxysilane are particularly preferable.

Specific examples of the organosilane (alkyl silicate) represented by the above general formula (ii) include tetramethyl silicate, tetraethyl silicate, tetra-n-propyl silicate, tetra-i-propyl silicate, and tetra-n- Butyl silicate, tetra-i-
Butyl silicate, tetra-sec-butyl silicate and the like can be mentioned.

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.

These general formulas (i), (ii) and (i)
When the organosilanes represented by ii) are used in combination, the mixing ratio (weight ratio) of (i) to (ii) is set to 100: 0 to 30 in terms of organosilane (that is, when (ii) is not contained). ), In terms of organosilane (i)
And the mixing ratio (weight ratio) of the total amount of (ii) to (iii)
Is preferably 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 easily cracked. On the contrary, when the mixing ratio is smaller than the above range, the curability is reduced, 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 to 5,000.
500-3000. 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, the above general formulas (i) and (i)
A hydrolyzate of organosilane represented by i) or (iii) or a partial condensate thereof is used, and water is added to perform the hydrolysis and partial condensation. The amount of water to be added is usually 0.1 to 1 to 1 equivalent of the alkoxy group of the organosilane of the general formula (i), (ii) or (iii).
It is preferably 0 mol, particularly preferably 0.15 to 0.7 mol. 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. Also,
A production accelerator may be used to produce 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) (where M is a metal such as Ti, Al, B, Zr, etc.)
⁴ is an alkyl group having 2 to 5 carbon atoms;
Is an integer of 4)

Specific examples of the compound of the general formula (iv) include tetra-i-propoxytitanium, tetra-n-butoxytitanium, tri-i-propoxyaluminum, mono-sec-butoxy-di-i-propoxyaluminum,
Examples thereof include diethoxyboron, di-n-propoxyboron, and tetra-n-butoxyzirconium, and examples of the mineral acid include hydrochloric acid and sulfuric acid. The addition amount is 0.05 parts with respect to 100 parts by weight of the organosilane.
It is preferred that the content be in the range of 2.0 to 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, titanium oxide, zinc sulfide, zinc oxide, iron oxide, graphite,
Colored inorganic pigments such as lead white, colored organic pigments such as phthalocyanine blue and benzidine yellow, extender pigments such as calcium carbonate, quartz powder, alumina, talc, precipitated barium sulfate, stainless powder, zinc powder, aluminum powder, bronze powder, Typical examples include metal powders such as mica-like iron oxide 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 ethanol and butanol.

The additives include a surface conditioner, a dispersant, an ultraviolet absorber, a thickener, an antiseptic, a fungicide, an algaecide,
Additives commonly known as paint additives, such as 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 acrylic urethane oligomers widely include those having a urethane bond in the molecule and having an unsaturated double bond capable of undergoing 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, their isomers, etc., and reaction products with polyester polyols, polyoxymethylene glycol, polyoxyethylene glycol, caprolactone boryl, trimethylolpropane, pentaerythritol, etc. Such as a reaction product of a non-yellowing polyisocyanate and a compound having a hydroxyl group and an unsaturated group, such as a compound having an isocyanate terminal, which is a compound having a hydroxyl group and an unsaturated group. As hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate There be mentioned as a typical example.

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-diethoxy-4- (p-tolylthio) benzeneazonium hexafluorophosphate, benzyldimethylketal, α-hydroxyiso Usual reaction initiators such as butyrophenone are mentioned as examples.

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. It is desired that the transparent spherical glass beads having a center particle diameter of 100 μm or less have the function of transmitting light energy into the coating film, and satisfy the following conditions.

(A) The central particle size is 100 μm or less, preferably 10 to 60 μm. The center particle diameter is 100 μm
It does not affect the curability of the coating even if it exceeds
Glass beads are 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. 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, but since the light transmittance of the coating film tends to substantially decrease when the center particle size is small, the center particle size is preferably in the range of 10 to 60 μm. preferable. (B)
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 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 to the inside of the coating film. It becomes possible, and also in the case of a thin film coating, it becomes possible to add a large amount of coloring pigment,
It becomes possible to form a thin coating film having high hiding power.

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. It should be noted that even if the center particle size exceeds 100 μm, there is no effect on the curability of the coating film, but 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, when the center particle size is small, the transmittance of the coating film tends to substantially decrease. Is desirable. When it is desired to form a thin film having a thickness of about 30 μm or less, it is preferable to use a glass powder having a central particle diameter of 10 μm or less.

The shape of the glass powder is preferably spherical when a thick film of several tens μm to several hundred μm is formed, while a thin film of several μm to several tens μm is formed. In this case, the shape may be irregular.

The materials of the transparent spherical glass beads and the transparent glass powder which 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 ultraviolet-curable coating material which can be used in the present invention can be used by blending various kinds of pigments, organic solvents or additives, if necessary, with the coating composition described above. The same ones shown in the coating composition using a hydrolyzable silicon compound as a binder can be used.

Titanium oxide and zinc oxide which can be incorporated into 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 is Pigmen Weight
Concentration (pigment weight concentration), which is calculated by the following equation.

PWC = [weight of pigment content (%)] / [weight of the national form in paint (%)] × 100 If PWC is less than 45, the photocatalytic effect is not sufficiently exhibited. Conversely, if it exceeds 85, the film formability is reduced, and cracking and peeling of the coating film are liable to occur.

The 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. If the replacement ratio is less than 10% by weight, no replacement effect is observed. Conversely, if it exceeds 50% by weight, the photocatalytic effect will be reduced, which is not preferable.

In the present invention, the above-described 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, acrylic acid or methacrylic acid alkyl ester copolymer emulsion resin, bisphenol type epoxy emulsion resin, polyamide resin, aliphatic polyamine curing agent, inorganic powder, cement, pigment, water By applying an undercoating paint containing any component selected from the above and the like to form an undercoating film, the effects aimed at in the present invention can be further improved.

As a coating method for applying the undercoat paint as described above to the joint surface of the porcelain tile panel, brush painting,
Conventionally practiced methods such as roll coating, air spray, airless spray, electrostatic spray, and jet ink printer coating in which required portions are masked can be used as they are.

As a method of coating only the joints, even if the spray coating is performed aiming at the joints, it is inevitable that the spray scatters around the joints, and a clean finished appearance cannot be obtained. Also, covering the area around the joint and brushing the joint is unsuitable as an industrial production method. Therefore, in the present invention, a coating method in which a paint is applied to the joint surface of the porcelain tile panel using an auto dispenser is employed. In the present invention, after mixing the above components, the mixture is filtered and purified using a filter having a pore size of about 1/10 or less of the diameter of the nozzle in the auto dispenser used in the method of the present invention. It is preferable to use a paint obtained by the above method.

The viscosity of the paint used in the present invention is from 1 to 100.
It is preferably 00 mPa · S (20 ° C.). If the viscosity of the paint is out of this range, the paint discharged from the nozzle may not be easily formed into a normal dot-shaped paint droplet, which is not preferable. Also, as other properties of the paint,
It is preferable that the surface tension is 20 to 70 mN / m (20 ° C.) and the specific gravity is 0.8 to 3.

In the present invention, a conventionally known auto dispenser can be used as the auto dispenser, and the control method thereof may be continuous coating or indirect dot-like coating.

Next, a coating method for applying a paint to the joint surface of the porcelain tile panel by using an auto dispenser will be specifically described based on an embodiment using an auto dispenser by opening and closing a solenoid valve. A porcelain tile panel having a plurality of porcelain tiles attached to the substrate surface and joints provided between the porcelain tiles is placed on a conveyor and transported forward. A dispensable valve of an auto dispenser is provided above the conveyor, and a plurality of nozzles having a diameter of 0.1 to 0.4 mm are provided in the auto dispensable valve over the entire width of the conveyor. It is provided in a parallel arrangement downward at a pitch of 5 mm.

It should be noted that the auto-dispensable valve may be single and correspond to the width of the conveyor, but a plurality of auto-dispensable valves may be arranged side by side according to the size of the porcelain tile panel. The good thing is, of course. In order to send the paint in the paint tank to the auto-dispensable valve, connect the auto-dispensable valve with the pump, and through the relief valve,
Connect with paint tank.

Also, a storage unit for storing data corresponding to the position of the joint to be coated and the length of the joint, a control unit (computer) for issuing a control signal to the valve control device based on the data input from the storage unit, and a projector A phototube sensor provided with a photodetector on both sides of the porcelain tile panel transport path on the compare is provided, the passage of the porcelain tile panel is sensed by the phototube sensor, and a detection signal is transmitted to the control unit. An encoder is connected to the drive roll of the compare, and a pulse is transmitted to the control unit at a minimum rotation angle of, for example, 360/2000 degrees. Although the above description is of a system in which the auto-dispensable valve is fixed, it is also possible to adopt a system in which the control operation is performed in the width direction or the traveling direction of the porcelain tile panel.

Next, an example of the method of the present invention for coating the joint of a porcelain tile panel with an auto dispenser including such a control system will be described. When the porcelain tile panel is conveyed on the conveyor at a speed of 1 to 60 m / min, preferably 3 to 45 m / min, the photoelectric tube sensor detects that the front end of the porcelain tile panel has reached a predetermined position on the conveyor. , And transmits the signal to the control unit. on the other hand,
With the operation of the conveyor, a pulse is transmitted from the encoder to the control unit.

The control unit starts counting the pulses based on the signal from the photoelectric tube sensor, and when the number of pulses reaches a preset value stored in advance, thereafter, the control unit responds to the number of pulses received within a predetermined range (time). Above, the position of the joint to be painted,
Data corresponding to the joint length is read from the storage unit, and a control signal (command signal) based on the data is sequentially transmitted to the valve control device, whereby the valves are individually controlled to open and close by the valve control device.

As a result, the paint is fed into the auto-dispensable valve at a pressure of 0.1 to 0.5 kg / cm ² , is discharged from the nozzle when the valve is opened, and paints the joint based on the data. I do. Further, a device for rotating the porcelain tile panel by 90 ° is installed in the conveyor, and after the porcelain tile panel is rotated by 90 °, the joint is applied in the vertical and horizontal directions by performing the same coating method as described above. In addition, since the surface of the porcelain tile panel and the tip of the nozzle have a distance of about 0.5 to 4 cm, they do not contact each other. Can be painted without any trouble. In the present invention,
In this way, the joints of the porcelain tile panel are painted by the auto dispenser.

[0056]

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 attached to a straight plate using an epoxy adhesive, two by two in the vertical and horizontal directions, and the joint width between the tiles was set to 2 mm. Into the joints, a cement-based base conditioner, Extractor No. 5 (trade name, manufactured by Dainippon Paint Co., Ltd.) was embedded so as to be lower than the tile surface by 2 mm to obtain a porcelain tile panel specimen.

(2) An automatic liquid dispenser (trade name: JB1113) manufactured by I & J Fastener Co., Ltd. was used as a coating machine. Nozzle No. 21 and a space between the porcelain tile panel were 5 mm and the primary pressure was 2 kg / cm. ^2. Implemented under the condition of a porcelain tile panel transfer speed of 10 m / min.

(3) Acrylic silicone resin AM1532
(Kanebuchi Chemical Co., Ltd., trade name: acrylic silicone resin containing hydrolyzed silyl group, solid content concentration 50%) 20 parts of titanium oxide and 5 parts of xylene are added to 20 parts, and glass beads are appropriately added. A paint dispersion was prepared. 50 parts of an acrylic silicone resin YC3623 (manufactured by Kanegafuchi Chemical Co., Ltd., trade name: acrylic silicone resin containing a hydrolyzed silyl group, solid content concentration 50%) are added. The beads were removed to obtain a paint base material. The curing agent BT1 was added to 100 parts of the main agent.
20S (manufactured by Kanegafuchi Chemical Co., Ltd., trade name: tin-based catalyst)
The solution was diluted with 0 parts, further diluted with 40 parts of xylene and 10 parts of butyl acetate, and continuously applied at a coating pressure of 0.3 kg / cm ² .

(4) The direction of the joint of the porcelain tile panel obtained in (1) and the direction and position of the compare belt are adjusted,
Using the paint of the above (3), coating was carried out under the conditions of the above (2) and (3), and dried at room temperature for 2 weeks.

<Evaluation method> (Stain resistance test) A contaminant (A) obtained by kneading 1 part of carbon black with 100 parts of water or a contaminant obtained by kneading 1 part of carbon black with 100 parts of salad oil ( B) is applied to tile joints with a brush, dried at 20 ° C. for 24 hours, and then washed with a brush while flowing water.
I returned the line. The state of the stain was visually observed and evaluated according to the following criteria.

◎: Completely removes dirt. ○: Removes most dirt. △: Partly removes dirt. ×: Dirt is not removed at all.

(Test for Antifungal Property) A 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). Culture is 30
The test was performed at ± 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 the joints. ：: Mold was slightly observed at the joints. ：: Mold was observed at the joints but was not significant. X: Mold was significantly observed at the joints. Further, the joints were wiped off with gauze moistened with water, and the degree of removal of mold was visually observed, and evaluated based on the following criteria.

◎: No mold stains were observed at all. ほ ぼ: Almost completely removed. ：: Removal residue was partially observed. X: 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 size: 0.7 μm, specific surface area: 170 m). ² / g) 160 parts, xylene 10 parts and isopropyl alcohol 10 parts were added to form a coating. 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. Also, the PWC of this paint
Is 75.

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 dried at 20 ° C. for 24 hours. Irradiated at an intensity of 4.0 mW / cm ² for 1 hour, washed with a brush while further flowing water, and the condition 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 and 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 introduction pipe. 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 added dropwise over 10 minutes. 3
After an hour, the mixture was cooled to room temperature and neutralized to pH 8 with ammonia to obtain an emulsion having a solid content of 48%. A test piece was prepared in the same manner as in Example 1 except that a mixture obtained by stirring and mixing 50 parts of ethylene glycol monobutyl ether and 50 parts of ion-exchanged water with the emulsion was added as a film-forming aid, and the resulting mixture was used as a paint. And paint in the same way,
It was evaluated similarly. 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. Table 1 shows the results of each evaluation.
As shown in FIG.

[0073]

[Table 1]

As is clear from Table 1, Example 1 of the present invention
In the cases of Nos. To 4, excellent stain resistance and fungicide resistance were achieved by coating the joints. However, in the case of Comparative Example 1 which was an emulsion paint and Comparative Example 2 where no joint was applied, there was a problem in stain resistance and mold resistance.

[0075]

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 (3)

[Claims] A paint is applied to a joint surface of a porcelain tile panel having a plurality of porcelain tile panels attached to a substrate surface and joints provided between the porcelain tiles by using an auto dispenser by opening and closing a solenoid valve. A method of manufacturing a joint-painted porcelain tile panel, characterized by painting a tile. 2. The coating material is at least one selected from the group consisting of a hydrolyzable silyl group-containing vinyl copolymer, a hydrolyzate of an organosilane, and a partial condensate of a hydrolyzate of an organosilane. The method for producing a joint-painted porcelain tile panel according to claim 1, wherein a paint using a hydrolyzable silicon compound as a binder or an ultraviolet-curable paint is used. 3. A pigment having a weight concentration (PWC) of titanium oxide or zinc oxide having photocatalytic activity of 45 to 8 as a coating material.
3. The coating composition according to claim 1, wherein the paint is used in an amount of 5.
3. The method for producing a joint-painted porcelain tile panel according to item 1.