JPH11148038A - Ink for forming photo-catalyst film and its production, formation of film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink used for forming photocatalyst films, capable of forming the films having uniform film qualities and sufficient performances, allowing the employment of printing devices and baking devices having good productivity and capable of being baked under conditions giving small loads to the baking devices, to provide a method for producing the ink, and to provide a method for forming the films. SOLUTION: This ink comprises at least one kind of the partial hydrolysate of an organic metal compound having a basic constituting unit of the formula: M(OH)x Ry [M is one selected from the group consisting of Ti, Sn and the like; R is one selected from the group consisting of an alkyl group, an alkoxy group and the like; (x)+(y)=(m), wherein (m) is the valency of the metal M, and (x) and (y) are each natural numbers, respectively], a high boiling point solvent comprising at least one of glycols, carbitols, and cellosolves and having a boiling point of 150-280 deg.C in an amount of 50-95 wt.% based on the ink, and an additive containing at least one of amines, organic acids, inorganic acids, β-diketones and β-ketoesters. The ink has a viscosity of 5-200 c.p.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a bacteriostatic, antibacterial, and antibacterial process which is applied to the surface of a ceramic molded product such as glass or tile, or to the surface of a metal molded product such as a metal film or a metal sheet, and baked in a post-process. The present invention relates to an ink capable of forming a photocatalytic film having effects such as deodorization, deodorization, antifogging, and self-purification, and a method for producing and forming the same.

[0002]

2. Description of the Related Art As a method for forming a photocatalytic film, a general formula M
(OH) _x R _y (M is a metal element Ti, Sn, Bi, Fe,
R is one of a group consisting of an alkyl group, an alkoxy group, an allyl group, a β-diketone chelate, and a β-ketoester chelate.
X + y = m, where m is the valence of metal M,
x and y each represent a natural number) a partial hydrolyzate of an organometallic compound represented by the following formula, a solvent for dissolving the partial hydrolyzate of the organometallic compound, amines, organic acids, inorganic acids, β-diketones Using a photocatalytic film forming solution comprising an additive such as a β-ketoester or a thickener, a film is formed by a spray method, a spin coating method, a dip method, a screen printing method, an offset printing method, a gravure printing method, or the like. There is a way.

[0003] A commonly used method is a dipping method, in which a low-boiling solvent is used as a main solvent, an object to be coated is immersed in a coating solution, and the coating is pulled up at a low speed. However, as a fundamental problem, when the object to be coated has a large area, unevenness in film thickness tends to occur, and in the case of a high refractive material, a fatal optical defect is caused. Further, there is a problem that photocatalytic films are formed on both surfaces of the object to be coated due to the method restrictions of the dipping method.

On the other hand, the method of forming a photocatalyst film by a printing method has a simple process and is very advantageous in terms of cost. Particularly, in the printing method, there is a method of printing using a thin film forming apparatus as disclosed in Japanese Patent Publication No. 3-11630 (see FIG. 1). This thin film forming apparatus includes an intaglio roll 3 rotatably supported by a support frame 2 of a base 1 and having a large number of ink cells having a depth of 1.0 to several tens μm on a surface thereof, and a surface of the intaglio roll 3 having a surface of 1.0 to 10,000 mPa · and an ink supply device 5 for supplying a low-viscosity ink of a predetermined length around the intaglio roll 3 supported by the support frame 2. And a convex portion 7 rotatably supported below the intaglio roll 3 of the support frame 2 and in contact with the intaglio roll 3, so that the ink in the ink cell is provided on the surface of the intaglio roll 3. Roll 4 for transferring the ink to the convex portion 7, and the printing roll 4 and the intaglio roll 3 supported by the support frame 2.
8 between the printing position A where the printing medium is placed and contacts the printing roll 4 on the base 1 and the retracted positions B and C separated from the printing roll 4. A platen 9 provided so as to be able to move, a printing medium driving device 10 for moving the platen 9 between the two positions, a rotation of the printing roll 4 and the platen 9
And a control device (not shown) for controlling the movement of the ink from the retreat positions B and C to the printing position A and printing the ink transferred to the convex portion 7 of the printing roll 4 on the printing medium. Have been. When a thin film forming apparatus having such a configuration is used, a photocatalytic film having a constant film thickness can be easily formed.

[0005]

However, the conventional ink composition used in the above-mentioned thin film forming apparatus has the following problems.

As a solvent, methanol, ethanol, n-
When an ink composition containing only a low-boiling solvent such as propanol, isopropanol, or n-butanol is used, when the above-described thin film forming apparatus is used, the intaglio roll 3 of the thin film forming apparatus is used.
When the ink composition is supplied to the substrate, the ink composition dries, and the ink composition cannot be transferred to a printing medium, so that a photocatalytic film cannot be formed.

[0007] In addition, when not only low-boiling solvents but also high-boiling solvents having a boiling point of 150 to 280 ° C are used in a mixture of about 3 to 20% by weight, the ink composition is supplied to the intaglio roll 3 at the same time. And drying is difficult. for example,
Even if printing is possible, when printing is performed continuously, the viscosity of the ink composition gradually increases on the intaglio roll 3, causing unevenness in the film thickness of the ink composition, and eventually causing loss of fluidity. This makes it impossible to print continuously. Therefore, it is conceivable to add a thickener such as nitrocellulose to increase the viscosity of the ink and improve the printability. However, when such a thickener is used, it is possible to print the ink composition, but the ink composition is liable to be clogged during filtration and purification of the ink. In addition, in the subsequent firing step, a careful and sufficient amount of heating conditions are required for firing and removing the thickener component, and there is also a problem of firing furnace contamination by carbon in the decomposition component. Therefore, thickeners, especially high molecular weight thickeners, should not be used as much as possible.

[0008] The conventional ink for forming a photocatalytic film is a fine particle colloid which is dispersed in an alcohol solution in a stable state and is relatively homogeneously dispersed. The film obtained using this is dense and fine. It has few holes and good crystallinity.

However, if performance as a photocatalyst film is required, it is unfortunately inappropriate. This is because the porous membrane has a larger surface area and can exhibit more photocatalytic ability.

In order to increase the surface area of the oxide film, an organic polymer material for forming a porous film, such as polyethylene glycol, which is liable to form void-like voids in the oxide film when firing in a later step is added. There is.

However, in this case, as in the case of the above-mentioned thickener, a careful and sufficient amount of heating conditions are necessary for the baking and removal of the organic polymer material component. There is also a problem of firing furnace contamination due to the above.

Accordingly, the present invention solves the above-mentioned problems, and uses a printing apparatus and a baking apparatus which are uniform in film quality and have sufficient performance and have high productivity in forming a photocatalytic film. An object of the present invention is to provide an ink for forming a photocatalyst film, a method for producing the same, and a method for forming a film, which can be carried out under conditions in which the burden on the baking apparatus is small.

[0013]

Means for Solving the Problems The ink for forming a photocatalytic film, the method for producing the same, and the method for forming a film according to the present invention have the following constitutions in order to achieve the above objects.

That is, the ink for forming a photocatalyst film of the present invention has a basic structural unit represented by the following general formula: M (OH) _x R _y (M is a metal element Ti, Sn, Bi, Fe, Zn, W, R
u is an alkyl group, an alkoxy group, an allyl group, a polyhydric alcohol alkoxy group,
x + y = m, where m is the valency of the metal M and x and y are natural numbers, and represents one of the group consisting of β-diketone chelates and β-ketoester chelates. At least one partial hydrolyzate;
A high-boiling solvent containing at least one of glycols, carbitols and cellosolves having a boiling point of 150 to 280 ° C. in the ink at 50 to 95% by weight, and amines, organic acids, inorganic acids, β-
At least one of diketones and β-ketoesters
Consists of seed-containing additives and has an ink viscosity of 5 to 200 mPas
It was configured to be:

In the method for producing an ink for forming a photocatalyst film of the present invention, the basic structural unit is represented by the following general formula: M (OH) _x R _y (M is a metal element Ti, Sn, Bi, Fe, Zn, W, R
u is a member of the group consisting of an alkyl group, an alkoxy group, an allyl group, a β-diketone chelate, and a β-ketoester chelate, and x + y = m, and m is a metal. M is a valence, x and y are natural numbers) and a partial hydrolyzate of an organometallic compound represented by the following formula: and alcohols having a boiling point of less than 30 to 150 ° C;
A low-boiling solvent containing at least one of ketones, esters, and ethers, and an additive containing at least one of amines, organic acids, inorganic acids, β-diketones, and β-ketoesters; The photocatalytic film forming solution consisting of is concentrated under a condition of room temperature to 60 ° C. or less to form a viscous solution,
Next, a high-boiling solvent containing at least one of glycols, carbitols, and cellosolves having a boiling point of 150 to 280 ° C is added to the viscous solution, and the high-boiling solvent in the ink is reduced to 50 to 95% by weight. And the ink viscosity is 5 to 200 mPa
It was configured to adjust to s.

Further, the method for forming a photocatalyst film according to the present invention comprises:
It is rotatably supported by the support frame of the base and has a depth of 1.0 to several tens.
an intaglio roll having a number of μm ink cells on its surface,
An ink supply device that supplies low-viscosity ink of 1.0 to 10,000 mPas on the surface of the intaglio roll, and an ink supply device that is provided at a predetermined location around the intaglio roll supported by the support frame and that supplies the ink supplied to the intaglio roll A doctor that holds a certain amount of ink in the ink cell by spreading the ink in the ink cell, and has a projection that is rotatably supported below the intaglio roll of the support frame and that comes into contact with the intaglio roll. A printing roll to be transferred to the convex portion, a driving device supported by the support frame to synchronously drive the printing roll 4 and the intaglio roll, and a printing position A on which the printing medium is placed and in contact with the printing roll on the base. And a platen movably provided between retreat positions B and C away from the printing roll, a printing medium driving device for moving the platen between the two positions, rotation of the printing roll and retraction of the platen Position B, C And a control device for controlling the movement of the ink to the printing position A by printing the ink transferred to the convex portion of the printing roll on a printing medium by using a thin film forming apparatus. , Wherein the ink is the photocatalytic film forming ink according to claim 1.

[0017]

Embodiments of the present invention will be described in detail with reference to the drawings.

As the partial hydrolyzate of the organometallic compound constituting the ink for forming a photocatalyst film of the present invention, one having a basic structural unit represented by the following general formula M (OH) _{x Ry} is used. Here, M is a metal element Ti,
One of the group consisting of Sn, Bi, Fe, Zn, W, and Ru, wherein R is an alkyl group, an alkoxy group, an allyl group, a polyhydric alcohol alkoxy group, a β-diketone chelate, or a β-ketoester chelate X + y = m, where m is the valence of metal M,
x and y indicate natural numbers. Specifically, Ti (O
H) ₃ CH ₃ , Ti (OH) (OiC ₃ H ₇ ) ₃ , Ti
(OH) ₃ CH ₂ CH = CH ₂ , Ti (OH) ₃ OC ₂ H ₄ O
H, Ti (OH) (CH ₃ COCHCOCH ₃ ) ₃ , Ti
(OH) (CH ₃ COCHCOOC ₂ H ₅ ) or the like can be used. Not only one kind of organometallic compound but also two or more different organometallic compounds can be used in combination.

As the high boiling solvent, at least one of glycols, carbitols and cellosolves having a boiling point of 150 to 280 ° C. is used. The high boiling point solvent is 50 ~
Must contain 95% by weight. If the content is less than 50% by weight, the ink composition is remarkably dried, for example, when printing is performed by the above-described thin film forming apparatus, and it is difficult to continuously form a photocatalytic film. If it exceeds 95% by weight, a photocatalytic film cannot be formed.

Specific examples of the high boiling solvent include ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol isoamyl ether, ethylene glycol monophenyl ether, ethylene glycol monophenyl ether acetate, and ethylene glycol monobutyl ether. Glycol benzyl ether, ethylene glycol monohexyl ether, dimethoxyethanol, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, Ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triglycol dichloride, propylene glycol, propylene glycol monobutyl ether, 1 -Butoxyethoxypropanol, propylene glycol derivatives, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, trimethylene glycol, butanediol, 1,5-pentanedio Le, hexylene glycol, octylene glycol, glyceryl monoacetate, glyceryl diacetate, glyceryl triacetate, glyceryl butyrate, glycerol ethers, glycerol-.alpha., .gamma. dichlorohydrin, 1, 2,
In addition to glycols such as 6-hexanetriol, there are carbitols and cellosolves. Among high-boiling solvents, glycols, in particular, serve as a dispersant for the organometallic compound, helping to uniformly disperse the organometallic compound.

Further, by using a high-boiling solvent having a boiling point of 150 to 280 ° C., a leveling effect can be obtained by evaporating the solvent in a stepwise manner, and the drying of the photocatalytic film can be prevented.

As the low-boiling solvent, at least one of alcohols, ketones, esters and ethers having a boiling point of less than 30 to 150 ° C. is used. Specifically, methanol, ethanol, n-propanol, isopropanol, 2-propanol, n-butanol, isobutanol, secondary butanol, tertiary butanol, secondary amyl alcohol, 3-pentanol, tertiary amyl alcohol, fusel Alcohols such as oils, ketones such as acetone, methyl acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, diethyl ketone, ethyl-n-butyl ketone, and formic acid Methyl, ethyl formate, propyl formate, n-butyl formate, isobutyl formate, amyl formate, methyl acetate, ethyl acetate, acetic acid
n-propyl, isopropyl acetate, -n-butyl acetate,
Esters such as isobutyl acetate, sec-butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, di-n-propyl ether, diisopropyl ether, 1,2-butylene oxide, dioxane, trioxane, 2-methyl There are ethers such as furan, tetrahydrofuran, tetrahydropyran, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,1-dimethoxymethane, and 1,1-diethoxyethane.

The low-boiling solvent is preferably composed mainly of alcohol, and the proportion of the ester or ketone in the low-boiling solvent is preferably 15% by weight or less. If the content exceeds 15% by weight, the convex portions are deteriorated, which causes various problems such as pinholes and lack of smoothness.

As the additive, at least one of amines, organic acids, inorganic acids, β-diketones, and β-ketoesters which act as a stabilizer is used. In addition, a drying regulator such as N, N'-dimethylformamide and dimethylacetamide can be added.
One or more of these may be used in combination. The additive is contained in the material, but may be further added after the viscous solution obtained by concentrating the photocatalytic film-forming gel is concentrated.

In order to obtain an ink for forming a photocatalyst film, a solution for forming a photocatalyst film comprising the above-mentioned organometallic compound, a low-boiling solvent and an additive is concentrated at room temperature to 60 ° C. or lower to form a viscous solution. Thereafter, a high boiling solvent is added as a diluting solvent. If the temperature is lower than room temperature, the condensation polymerization reaction does not easily proceed, while if it exceeds 60 ° C., the condensation polymerization product does not dissolve in the high boiling point solvent.

When the photocatalytic film-forming solution is treated under the conditions of room temperature to 60 ° C. or less, the site of the metal hydrate of the partial hydrolyzate undergoes a heterogeneous low-density polycondensation reaction, resulting in a viscous solution. Conceivable. The presence of the heterogeneous polycondensate, which is considered to constitute this viscous solution, facilitates the formation of pores when fired in a subsequent step, and provides an oxide film having a large surface area. Further, since the solution is in a viscous state, the range of selecting a high boiling point solvent to be added in the next step can be appropriately selected, and the viscosity of the ink can be easily adjusted.

By adding a high-boiling solvent to the viscous solution, the high-boiling solvent in the ink is adjusted to 50 to 95% by weight and the ink viscosity is adjusted to 5 to 200 mPa · s. When the viscosity is less than 5 mPa · s, dripping and unevenness in film thickness on the coated surface are remarkable, and it is difficult to obtain a uniform resistance value or film thickness. On the other hand, if the viscosity exceeds 200 mPas, the desired film thickness can be obtained by adjusting the depth of the intaglio roll, but the amount of ink transferred at one time increases, and it is difficult to control the film thickness of the obtained film. Become. Further, the leveling property of the printed photocatalyst film is deteriorated, and it is difficult to obtain a smooth film.

In the present invention, instead of adding a thickener to adjust the viscosity of the ink, the viscosity is adjusted by adding a high-boiling solvent to a viscous solution obtained by concentrating the photocatalytic film forming solution. To improve printability.

In order to form a photocatalyst film by a printing method using the ink for forming a photocatalyst film of the present invention, a large number of ink cells having a depth of 1.0 to several tens μm, which are rotatably supported by a support frame of a base and have a depth of 1.0 to several tens μm, are formed on the surface. An intaglio roll having, an ink supply device for supplying a low viscosity ink of 1.0 to 10,000 mPas to the surface of the intaglio roll, and an intaglio roll provided at a predetermined position around the intaglio roll supported by the support frame and supplied to the intaglio roll A doctor that spreads the ink on the surface of the intaglio roll to hold a certain amount of ink in the ink cell, and has a convex portion that is rotatably supported below the intaglio roll of the support frame and contacts the intaglio roll. A printing roll for transferring the ink in the ink cell to the convex portion, a driving device supported by the support frame for synchronously driving the printing roll 4 and the intaglio roll, and a printing medium placed on the base and printing on the base A platen movably provided between a printing position A in contact with the printing roll and retracted positions B and C distant from the printing roll; a printing medium driving device for moving the platen between the two positions; A control device for controlling the rotation of the roll and the movement of the platen from the retracted positions B and C to the printing position A to print the ink transferred to the convex portions of the printing roll on the printing medium. It is preferably used.

FIG. 1 is a perspective view showing a thin film forming apparatus applicable to the photocatalytic film forming ink of the present invention. In the figure, 1 is a base, 2 is a support frame, 3 is an intaglio roll, 4
Is a printing roll, 5 is an ink supply device, 6 is a doctor, 7
Denotes a convex portion, 8 denotes a driving device, 9 denotes a surface plate, and 10 denotes a printing medium driving device.

The photocatalyst film forming ink of the present invention can be used by a die coater coating method or a roll coater coating method by appropriately selecting a solvent.

[0032]

Example 1 Titanium tetraisopropoxide (5 g) as an organometallic compound was completely dissolved in 30 g of anhydrous ethanol as a low boiling point solvent, and 4 g of diethanolamine was added as a stabilizer to obtain a uniform transparent liquid. Next, 0.3 g of water was added, and the mixture was sufficiently stirred and reacted to obtain an ethanol solution containing a partial hydrolyzate of titanium tetraisopropoxide. Next, the mixture was concentrated by removing the ethanol solvent at 30 mmHg and 55 ° C. using an evaporator, and at the stage where a viscous solution was obtained, 25 g of hexylene glycol was added as a high-boiling-point solvent, and the mixture was stirred uniformly to obtain a TiO ₂ solid. As a result, 35 g of a photocatalyst film forming ink having a viscosity of about 35 mPa · s and a viscosity of about 35 mPa · s was obtained.

This ink for forming a photocatalytic film was composed of a partially hydrolyzed product of titanium tetraisopropoxide, hexylene glycol and diethanolamine, and the content of hexylene glycol in the ink was 71% by weight.

Then, the ink for forming a photocatalytic film was coated with a SiO ₂ coat of 300 mm × 3 using a thin film forming apparatus (Angstroma® (registered trademark) in-line type manufactured by Nissha Printing Co., Ltd.).
Printing was performed twice consecutively on a 00 mm × 1.1 mm soda glass substrate.

After preliminarily drying the glass substrate on a hot plate, the glass substrate is fired at a rate of 3 ° C./min to 500 ° C. using a conveyer type firing furnace, and subsequently in a conveyor type firing furnace.
By cooling from 500 ° C. to room temperature, a photocatalyst film having a thickness of 900 ° was obtained.

The photocatalytic activity of the photocatalyst film thus obtained was evaluated by a change in concentration due to decomposition of the dye in the aqueous dye solution.

The above glass substrate was cut into a size of 10 mm × 35 mm, and a dye having excellent light resistance (SANDOZ SANDOLAN manufactured by Sando Co., Ltd.)
MILL.BLUE N-BL)
After irradiating ultraviolet light from the film surface side with V black light (wavelength peak 365 nm, 8W × 2), the concentration of the dye was measured by a calibration curve. The dye concentration before irradiation is 0.0050
%, Example 1 was 0.0050%, and the dye concentration after irradiation for 24 hours was 0.0049% for the reference and 0.0011% for Example 1. Therefore, the dye concentration after 24 hours was 0.0011%, and had excellent photocatalytic performance.

Example 2 As in Example 1, anhydrous ethanol 30 was used as the low boiling point solvent.
6.5 g of titanium tetra-t-butoxide as an organometallic compound was completely dissolved in g, and 4 g of diethanolamine was further added as a stabilizer to obtain a uniform transparent liquid. Next, 0.3 g of water was added, and the mixture was sufficiently stirred and reacted to obtain an ethanol solution containing a partial hydrolyzate of titanium tetra-t-butoxide. Next, use an evaporator to
g, concentrated at 55 ° C. by removing the ethanol solvent to form a viscous solution, 5 g of ethylene glycol and 15 g of hexylene glycol as a high-boiling solvent were added, and the mixture was stirred uniformly to obtain a TiO ₂ solid content of 5.6% and a viscosity of about 5.6%. 35 g of an ink for forming a photocatalyst film of 38 mPa · s was obtained.

This ink for forming a photocatalytic film is composed of a partial hydrolyzate of titanium tetra-t-butoxide, hexylene glycol, ethylene glycol and diethanolamine, and the content of hexylene glycol in the ink is 57%.
% By weight.

The photocatalytic activity of the photocatalyst film thus obtained was evaluated in the same manner as in Example 1 by the change in concentration in the aqueous dye solution due to the decomposition of the dye.

The above glass substrate was cut into a size of 10 mm × 35 mm, and a dye having excellent light resistance (SANDOZ SANDOLAN manufactured by Sando Co., Ltd.)
MILL.BLUE N-BL)
After irradiating ultraviolet light from the film surface side with V black light (wavelength peak 365 nm, 8W × 2), the concentration of the dye was measured by a calibration curve. The dye concentration before irradiation is 0.0050
%, Example 2 was 0.0050%, and the dye concentration after irradiation for 24 hours was 0.0049% for the reference and 0.0012% for Example 2. Therefore, the dye concentration after 24 hours was 0.0012%, and had excellent photocatalytic performance.

Comparative Example 1 In the same manner as in Example 1, the synthesis proceeded to the stage before the concentration to obtain an ethanol solution containing a partial hydrolyzate of titanium tetraisopropoxide.

This ethanol solution was dip-coated on a glass substrate 25 mm × 70 mm in the same manner as in Example 1 at a dip rate of 100 cm / min. I got The photocatalytic activity of the photocatalyst film thus obtained was evaluated in the same manner as in Example 1 by the change in concentration due to the decomposition of the dye in the aqueous dye solution. The dye concentration before irradiation was 0.0050% for the reference, and 0.2% for Comparative Example 1.
The dye concentration after irradiation for 24 hours was 0.0049% for the reference and 0.0020% for Comparative Example 1. Therefore, the dye concentration after 24 hours was 0.0020%, and the photocatalytic performance was inferior to Examples 1 and 2. Further, in Comparative Example 1, it was necessary to repeat coating and firing several times in order to obtain a predetermined film thickness, which was troublesome.

Comparative Example 2 In the same manner as in Example 1, the synthesis proceeded to the stage before the concentration to obtain an ethanol solution containing a partial hydrolyzate of titanium tetraisopropoxide. To this solution was directly added 25 g of hexylene glycol as a high-boiling solvent without concentration, and the mixture was stirred uniformly to obtain 64 g of a photocatalyst film forming ink having a TiO2 solid content of about 3%.

When the ink for forming a photocatalyst film was printed in the same manner as in Example 1, after printing several sheets, the ink composition on the intaglio roll dried and could not be continuously printed.

[0046]

Since the present invention has the above-described structure, it has the following effects.

Since the ink for forming a photocatalyst film of the present invention has a suitable drying property and does not dry immediately upon printing, it has a high film thickness accuracy on the same printing medium and can be printed even when repeatedly printed. The thickness of each printed body is high and the printability is excellent.

Further, since it does not contain a high molecular weight thickener for adjusting the viscosity, the ink has excellent filterability and is easy to handle, and the load on the firing conditions is reduced.

Further, the method for producing an ink for forming a photocatalyst film of the present invention can easily obtain the above-described ink for forming a photocatalyst film.

In addition, during the production of the ink, it is concentrated at a temperature of 60 ° C. or less to form a viscous solution in which a low-density condensation reaction occurs, so that the photocatalytic ability can be obtained without adding an organic polymer material for forming a porous film. It has an effective porous structure, and even when added, a small amount of addition is sufficient.

Further, the method for forming a photocatalytic film according to the present invention comprises:
It is possible to perform printing with high film thickness accuracy on the same printing medium and high film thickness accuracy even when printing is performed repeatedly on the same printing medium, and it is excellent in continuous printability.

[Brief description of the drawings]

FIG. 1 is a perspective view showing a thin film forming apparatus applicable to a photocatalyst film forming ink of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base 2 Support frame 3 Intaglio roll 4 Printing roll 5 Ink supply device 6 Doctor 7 Convex part 8 Drive device 9 Surface plate 10 Printed object drive device

Claims (3)

[Claims] The basic structural unit is represented by the following general formula: M (OH) _x R _y (M is a metal element Ti, Sn, Bi, Fe, Zn, W, R
u is an alkyl group, an alkoxy group, an allyl group, a polyhydric alcohol alkoxy group,
x + y = m, where m is the valency of the metal M and x and y are natural numbers, and represents one of the group consisting of β-diketone chelates and β-ketoester chelates. At least one partial hydrolyzate;
A high-boiling solvent containing at least one of glycols, carbitols and cellosolves having a boiling point of 150 to 280 ° C. in the ink at 50 to 95% by weight, and amines, organic acids, inorganic acids, β-
At least one of diketones and β-ketoesters
Consists of seed-containing additives and has an ink viscosity of 5 to 200 mPas
An ink for forming a photocatalyst film, which is: 2. The basic structural unit is represented by the following general formula: M (OH) _x R _y (M is a metal element Ti, Sn, Bi, Fe, Zn, W, R
u is a member of the group consisting of an alkyl group, an alkoxy group, an allyl group, a β-diketone chelate, and a β-ketoester chelate, and x + y = m, and m is a metal. M is a valence, x and y are natural numbers) and a partial hydrolyzate of an organometallic compound represented by the following formula: and alcohols having a boiling point of less than 30 to 150 ° C;
A low-boiling solvent containing at least one of ketones, esters, and ethers, and an additive containing at least one of amines, organic acids, inorganic acids, β-diketones, and β-ketoesters; The photocatalytic film forming solution consisting of is concentrated under a condition of room temperature to 60 ° C. or less to form a viscous solution,
Next, a high-boiling solvent containing at least one of glycols, carbitols, and cellosolves having a boiling point of 150 to 280 ° C is added to the viscous solution, and the high-boiling solvent in the ink is reduced to 50 to 95% by weight. And the ink viscosity is 5 to 200 mPa
s. A method for producing an ink for forming a photocatalyst film, wherein the method is adjusted to be s. 3. An intaglio roll rotatably supported by a support frame of a base and having a large number of ink cells having a depth of 1.0 to several tens μm on its surface, and a low viscosity ink of 1.0 to 10,000 mPa · s on the surface of the intaglio roll. And a doctor that is provided at a predetermined position around the intaglio roll supported by the support frame and spreads the ink supplied to the intaglio roll on the surface of the intaglio roll to hold a certain amount of ink in the ink cell. A printing roll that is rotatably supported below the intaglio roll of the support frame and has a convex portion that comes into contact with the intaglio roll, and transfers the ink in the ink cells to the convex portion on the surface of the intaglio roll; A drive device for synchronously rotating the roll 4 and the intaglio roll, and a printing position A on which the printing medium is placed and in contact with the printing roll on the base, and a retracted position B, C separated from the printing roll. Move A platen provided with the platen, a printing medium driving device for moving the platen between the two positions, and controlling the rotation of the print roll and the movement of the platen from the retracted positions B and C to the print position A. The photocatalyst film according to claim 1, wherein the photocatalyst film is formed by printing using a thin film forming apparatus including a control device that prints the ink transferred to the convex portion of the printing roll on a printing medium. A method for forming a photocatalytic film, which is a forming ink.