JP2993928B2 - Photocatalyst film forming ink, method for producing the same, and film forming method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the surface of ceramic molded products such as glass and tiles, the surface of metal molded products such as metal films and metal sheets, and the surface of heat-resistant plastics such as bismaleimide resin sheets and aramid fiber cloth. Ink that can form a photocatalytic film that provides functions such as bacteriostasis, antibacterial, deodorizing, deodorizing, antifogging, and self-purifying by applying to and baking in a later step, and a method for producing the same,
The present invention relates to a film forming method.

[0002]

2. Description of the Related Art As an ink for forming a photocatalytic film, a general formula M
(OH) _x R _y (M is a metal element Ti, Sn, Bi, F
e is one of a group consisting of an alkyl group, an alkoxy group, an allyl group, a β-diketone chelate, a β-ketoester chelate, and a hydroxycarboxylic acid ester chelate. ,
x + y = m, where m is the valence of the metal M and x and y are natural numbers) and a solvent for dissolving the partial hydrolyzate of the organometallic compound represented by Mixtures of a low-boiling solvent and a high-boiling solvent) and additives such as amines, organic acids, inorganic acids, β-diketones, β-ketoesters and thickeners are known.

[0003] The photocatalytic film-forming ink is formed into a film by a printing method because the process is simple and the cost is very advantageous. In particular, as a printing method,
There is a method of printing using a thin film forming apparatus as shown in Japanese Patent Application Laid-Open Publication No. H10 (1998) (see FIG. 1). This thin film forming apparatus includes a base 1
Is rotatably supported by the support frame 2 and has a depth of 1.0 to several tens of microns.
m, an intaglio roll 3 having a large number of ink cells on its surface;
An ink supply device 5 for supplying a low-viscosity ink of 1.0 to 10,000 mPa · s onto the surface of the intaglio roll 3, and an intaglio roll 3 provided at a predetermined location around the intaglio roll 3 supported by the support frame 2;
The ink supplied to the intaglio roll 3 is spread over the surface of the intaglio roll 3 to hold a certain amount of ink in the ink cell, and the convex which is rotatably supported below the intaglio roll 3 of the support frame 2 and comes into contact with the intaglio roll 3. A printing roll 4 having a portion 7 to transfer the ink in the ink cells to the convex portion 7 on the surface of the intaglio roll 3, a driving device 8 supported by the support frame 2 and driving the printing roll 4 and the intaglio roll 3 to rotate synchronously. A printing position A where the printing medium is placed and the printing roll 4 is placed on the base 1
And a platen 9 movably provided between retreat positions B and C separated from the printing roll 4, a printing medium driving device 10 for moving the platen 9 between the two positions, and rotation of the printing roll 4. And a control device (not shown) for controlling the movement of the platen 9 from the retracted positions B and C to the printing position A to print the ink transferred to the convex portion 7 of the printing roll 4 on the printing medium. It is configured to be. When a thin film forming apparatus having such a configuration is used, a photocatalytic film having a constant film thickness can be easily formed.

[0004]

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

Since a low-boiling solvent is used together with a high-boiling solvent as a solvent, the ink is dried when the photocatalytic film-forming ink is supplied to the intaglio roll 3, and printing is difficult. for example,
Even if you can print at the beginning, if you print continuously,
Due to the gradual increase in the viscosity of the photocatalyst film-forming ink on the intaglio roll 3, the film thickness of the photocatalyst film-forming ink becomes uneven, and eventually loses its fluidity, so that printing continues. It becomes impossible to do.

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 for forming a photocatalytic film, but clogging is likely to occur during the filtration and purification of the ink. In addition, a careful and sufficient amount of heating conditions are required for baking and removing the thickener component in the subsequent baking step,
In addition, contamination of the firing furnace by carbon in the decomposition component also poses a problem. Therefore, thickeners, especially high molecular weight thickeners,
It is better not to use it if possible.

Further, since the conventional ink for forming a photocatalytic film has the above-mentioned composition, it is dispersed in an alcohol solution in a stable state and is a relatively homogeneously dispersed fine particle colloid. The resulting film has a small surface area and a small pore diameter because it is dense and has few pores, so that the photocatalytic ability cannot be sufficiently exhibited.

In order to increase the surface area of the photocatalyst film and to increase the pore size, an organic polymer material for forming a porous film such as polyethylene glycol, which easily forms void-like voids in the photocatalyst film when baked in a later step May be added.

However, also in this case, as in the case of the above-mentioned thickener, a careful and sufficient amount of heating conditions are required to calcine and remove the organic polymer material component. The carbon contamination of the firing furnace also poses a problem.

Accordingly, an object of the present invention is to solve the above problems and to provide a photocatalytic film forming ink suitable for continuous printing and having an excellent photocatalytic ability, and a method for producing the same and a method for forming the same. .

[0011]

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 general formula: M (OH) _x (R ₁ ) _y (R ₂ )
_z (M is at least one member from the group consisting of metal elements Ti, Sn, Bi, Fe, W, R1 is an alkoxy group,
R2 represents at least one member selected from the group consisting of alkyl groups, allyl groups, acyl groups, ester groups, β-diketone chelates, β-ketoester chelates, and hydroxycarboxylic acid ester chelates, wherein R2 is a polyhydric alcohol or polyhydric alcohol derivative X + y + z = m, where m is the valence of the metal M, x, z
Is a natural number, and y is an integer of 0 or more), a particle of a condensate of a metal alkoxide, a solvent, and a dispersant.

In the above invention, the particles of the condensate of metal alkoxides may be configured to have a size of 1 μm or less.

In the above invention, the solvent may include at least one of polyhydric alcohols and polyhydric alcohol derivatives.

In the above invention, the dispersant may be constituted so as to contain at least one of amines, amides, organic acids, inorganic acids, β-diketones, and β-ketoesters.

Further, in the method for producing an ink for forming a photocatalytic film according to the present invention, the basic structural unit is represented by the general formula: M (R ₁ ) _a (R ₃ ) _b
(M is at least one member from the group consisting of metal elements Ti, Sn, Bi, Fe, W, and R ₁ is an alkoxy group, an alkyl group, an allyl group, an acyl group, an ester group, a β-diketone chelate, a β- R ₃ represents a monovalent alkoxy group, R ₁ and R ₃ may be the same, a + b = m, and m represents a metal M, which is at least one selected from the group consisting of keto ester chelates and hydroxycarboxylic acid ester chelates. Is a valence, a is an integer of 0 or more, b is a natural number) is mixed with at least one solvent of polyhydric alcohols and polyhydric alcohol derivatives, which is a metal alkoxide; The amount of amines, amides, organic acids, inorganic acids, β-diketones, β-ketoesters less than m in a molar ratio to the metal alkoxides It was also configured to mix simultaneously or stepwise the lower amount of water m in terms of the molar ratio to the dispersant and the metal alkoxide containing one kind.

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 mPa · s 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 transfers the ink supplied to the intaglio roll to the surface of 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 for transferring to the convex portion, a driving device supported by the support frame and synchronously driving the printing roll 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. A platen movably provided between retreat positions B and C distant from the print roll, a printing medium driving device for moving the platen between the two positions, a rotation of the print roll and a retreat position of the platen. From B and C A method for forming a photocatalytic film by printing using a thin film forming apparatus comprising: a control device for controlling the movement to the printing position A and printing the ink transferred to the convex portion of the printing roll on the printing medium. The ink was the photocatalyst film forming ink according to any one of claims 1 to 4.

[0018]

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

The particles of the condensate of metal alkoxides have the basic structural unit represented by the general formula M (OH) _x (R ₁ ) _y (R ₂ )
_Use what is _z .

Here, M is a metal element Ti, Sn, Bi,
It is at least one member from the group consisting of Fe and W. R ₁
Is an alkoxy group, an alkyl group, an allyl group, an acyl group,
An ester group, β-diketone chelate, β-ketoester chelate, and at least one selected from the group consisting of hydroxycarboxylic acid ester chelates, more specifically, a methoxy group, a methyl group, a propenyl group, an acetyl group, an acetoxy group , Acetylacetone, ethyl acetoacetate, lactic acid, tartaric acid and the like can be used. R ₂ is
It represents at least one of polyhydric alcohols and polyhydric alcohol derivatives, and more specifically, ethylene glycol, propylene glycol, hexylene glycol and the like can be used. x + y + z = m, where m is the valence of the metal M, x and z are natural numbers, and y is an integer of 0 or more. As specific examples of the basic structural unit, hydroxypropyleneglycoxide titanium bis (diethanolamine complex), hydroxyhexyleneglycoxide titanium bis (triethanolamine complex), hydroxypropyleneglycoxide titanium bis (acetylacetonate) and the like can be used. As the particles of the condensate of metal alkoxides, not only one kind but also two or more different kinds can be used in combination.

The particle size of the condensate of metal alkoxides is preferably 1 μm or less. If the thickness exceeds 1 μm, the film forming properties, smoothness, and transparency of the ink after formation of the photocatalytic film-forming ink will be poor.

As the solvent, those used in ordinary inks may be used. For example, ethylene glycol,
Diethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, 1,2,6-hexanetriol, glyceryl monoacetate, and the like can be used.

[0023] A high boiling point solvent such as isophorone, anone, methyl cellosolve, ethyl cellosolve, butyl cellosolve, butyl cellosolve acetate, carbitol acetate and butyl carbitol may be contained.

Further, a low boiling point solvent may be contained. The content of the low boiling solvent is preferably 40% or less. The reason is that when the ratio of the low boiling solvent exceeds 40% by weight, the ratio of the high boiling solvent becomes less than 60%, and when printing is performed by the above-described thin film forming apparatus, the ink for forming the photocatalytic film is remarkably dried. This makes it difficult to form a metal oxide film.

Examples of the low-boiling solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, secondary amyl alcohol, 3-pentanol, and tertiary amyl alcohol; , Methyl acetone, methyl ethyl ketone, ketones such as methyl-n-propyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl formate, ethyl formate, propyl formate, n-butyl formate, isobutyl formate, methyl acetate, ethyl acetate , N-propyl acetate, isopropyl acetate, acetic acid
Esters such as n-butyl, isobutyl acetate, methyl propionate, ethyl propionate, methyl butyrate, ethyl butyrate, di-n-propyl ether, diisopropyl ether, 1,2-butylene oxide, dioxane, trioxane, 2-methylfuran , Tetrahydrofuran,
There are ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, 1,1-dimethoxymethane, and 1,1-diethoxyethane.

As the dispersant, those used for ordinary inks may be used. For example, ethanolamine,
Amines such as diethanolamine; amides such as N, N'-dimethylformamide (DMF); organic acids such as acetic acid and lactic acid; inorganic acids such as nitric acid; β-diketones such as acetylacetone and benzoylacetone; Β-ketoesters and the like can be used. In addition, a surfactant such as an ethylene oxide adduct, a polyethylene oxide polypropylene oxide copolymer, or polyoxyethylene nonylphenol ether may be contained.

In the ink for forming a photocatalyst film having such a structure, since a particle of a hydrolyzate of a specific metal alkoxide or a condensate thereof is used, the photocatalyst film is hardly dense, and a metal oxide film having photocatalytic ability is used. It is suitable as. This is because a porous film having a large surface area is easily formed, the pore diameter becomes large, and relatively large organic substances are easily contacted. Further, even if the drying speed of the coating film is increased, the film hardly breaks.

In order to obtain an ink for forming a photocatalyst film, the following method is preferred.

First, a solvent is mixed with metal alkoxides.

As the metal alkoxides, those having a basic structural unit of the general formula M (R ₁ ) _a (R ₃ ) _b are used.

Here, M is a metal element Ti, Sn, Bi,
It is at least one member from the group consisting of Fe and W. R ₁
Is an alkoxy group, an alkyl group, an allyl group, an acyl group,
It represents at least one member from the group consisting of ester groups, β-diketone chelates, β-ketoester chelates, and hydroxycarboxylic acid ester chelates. R ₃ represents a monovalent alkoxy group, and more specifically, methoxide, ethoxide, i-propoxide, t-butoxide and the like can be used. R ₁ and R ₃ may be the same, a + b = m, m is the valence of the metal M, a is an integer of 0 or more, and b is a natural number.

As the solvent, at least one of polyhydric alcohols and polyhydric alcohol derivatives as metal alkoxides is used. More specifically, the boiling point is 130-280 ° C
Alcohols having a divalent or higher hydroxyl group, such as glycol solvents, trihydric alcohol monoester solvents, and the like. Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol,
Examples include dipropylene glycol, trimethylene glycol, butanediol, 1,5-pentanediol, hexylene glycol, octylene glycol, and 1,2,6-hexanetriol. Polyhydric alcohol derivatives include glyceryl monoacetate.

Next, amines, amides, organic acids, and the like in an amount less than m in a molar ratio to the metal alkoxides,
A dispersant containing at least one of inorganic acids, β-diketones, and β-ketoesters, and water in a molar ratio of less than m to the metal alkoxide are mixed simultaneously or stepwise.

Here, the mixing of the dispersant and water is performed when the particle size of the condensate of metal alkoxides is 1 μm.
m or less.

First, a dispersant is mixed to disperse the aggregated particles, and then water is mixed and partially hydrolyzed to reduce the particle size of the condensate of metal alkoxides to 1 μm.
m or less can be obtained.

In addition, water is first mixed and partially hydrolyzed,
Next, by mixing a dispersant to disperse the aggregated particles, it is possible to obtain a photocatalyst film-forming ink having a particle size of a condensate of a metal alkoxide of 1 μm or less.

Further, a dispersing agent is mixed to disperse the aggregate particles, and at the same time, water is mixed and partially hydrolyzed to form a photocatalyst having a particle size of a condensate of metal alkoxides of 1 μm or less. A film forming ink can be obtained.

Examples of the dispersant include amines such as ethanolamine and diethanolamine, amides such as N, N'-dimethylformamide (DMF), organic acids such as acetic acid and lactic acid, inorganic acids such as nitric acid, and acetylacetone.
There are β-diketones such as benzoylacetone and β-ketoesters such as ethyl acetoacetate. One or more of these may be used in combination.

Thus, an ink for forming a photocatalyst film can be obtained. The ink for forming a photocatalyst film has properties suitable as an ink due to a solvent and a dispersant mixed in the process of producing the ink for forming a photocatalyst film.

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 and the intaglio roll, and a printing roll for mounting the printing medium and mounting 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; Rotation of the table and the retreat position B of the surface
It is preferable to use a thin film forming apparatus comprising a control device for controlling the movement from C to the printing position A and printing the ink transferred to the convex portion of the printing roll on the printing medium.

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

The photocatalyst film thus obtained exhibits excellent properties for the following reasons.

Since metal alkoxides are treated in a solution of the above-mentioned polyhydric alcohols or polyhydric alcohol derivatives, the condensation reaction causes multiple alcohol decompositions, resulting in irregular, irregular and high molecular weight alcohols. Form metal compounds.

Therefore, even if the metal compound is stabilized with a dispersant and then subjected to a hydrolysis treatment, there is no significant change in the shape of the generated fine particles. Even if the metal compound is hydrolyzed and then stabilized with a dispersant, there is no significant change in the shape of the generated fine particles. Even if the metal compound is stabilized by a dispersant and subjected to a hydrolysis treatment at the same time, there is no significant change in the shape of the generated fine particles.

The ink for forming a photocatalyst film of the present invention uses fine particles of irregular, irregular and high molecular weight as particles of a condensate of a metal alkoxide, and thus is suitable as a metal oxide film having photocatalytic activity.

Further, since the ink for forming a photocatalyst film contains polyhydric alcohols and polyhydric alcohol derivatives having hygroscopicity, the printed film has hygroscopicity. It is presumed that the moisture-absorbing water is involved in the decomposition-condensation reaction and the oxide film-forming reaction of the basic constituent units of the photocatalytic film-forming ink, and has a promoting effect of forming a crystal structure and pores having excellent photocatalytic ability.

[0048]

EXAMPLES Example 1 Titanium tetraisopropoxide 6.4 as a metal alkoxide in 11.2 g of propylene glycol as a solvent
g was added and stirred to aggregate to form a slurry.

Next, diethanolamine as a dispersant
2.0 g was added to obtain a translucent organometallic compound particle dispersion.

Next, 0.4 g of water was added, and the mixture was sufficiently stirred and reacted to obtain a solution containing a partial hydrolyzate of titanium tetraisopropoxide.

Thus, the TiO ₂ solid content of about 9.2
% And a viscosity of about 50 mPa · s to obtain 20 g of an ink for forming a photocatalyst film.

Next, the ink for forming a photocatalytic film was coated with SiO ₂ by 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 the glass substrate is preliminarily dried on a hot plate, the glass substrate is fired at a rate of 3 ° C./min to 500 ° C. using a conveyor-type firing furnace.
By cooling from 500 ° C. to room temperature, a photocatalytic film having a thickness of 1200 ° was obtained.

The photocatalytic activity of the photocatalyst film thus obtained was evaluated based on the change in concentration due to the 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 0.0008% for Example 1. Therefore, the dye concentration after 24 hours was 0.0008%, and had excellent photocatalytic performance.

Comparative Example 1 Titanium tetraisopropoxide (5 g) as a metal alkoxide was completely dissolved in 30 g of anhydrous ethanol as a low boiling point solvent, and 4 g of diethanolamine was added as a dispersant 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.

The same glass substrate as in Example 1 was dip-coated on a 25 mm × 70 mm glass plate at a dip rate of 100 cm / min, and the process of baking at 500 ° C. was repeated three times. 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 Example 1. further,
In Comparative Example 1, coating and firing had to be repeated many times to obtain a predetermined film thickness, which was troublesome.

Comparative Example 2 As in Comparative 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 dispersant 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. To this solution was directly added 25 g of hexylene glycol as a high boiling point solvent without concentration, and the mixture was stirred uniformly to obtain 64 g of a photocatalyst film forming ink having a TiO ₂ 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 for forming a photocatalyst film on the intaglio roll dried and could not be continuously printed. Was.

[0060]

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

The ink for forming a photocatalyst film of the present invention has an appropriate drying property and does not dry immediately during printing, so that the same printing medium has high film thickness accuracy and can be coated even when repeatedly printed. The thickness of each printed body is high and the printability is excellent.

The photocatalyst film obtained by the photocatalyst film forming ink of the present invention has a porous structure and excellent photocatalytic ability. Even if an organic polymer material for forming a porous film is added, only a small amount is required.

Further, since it does not contain a high molecular weight thickening agent for adjusting the viscosity, the ink has excellent filterability and is easy to handle, and has little adverse effect on firing conditions and contamination of the firing furnace.

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.

The method for forming a photocatalyst 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

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B01J 35/02 B01J 35/02 J 37/02 301 37/02 301M (56) References JP-A-9-315839 (JP, A JP-A-9-248467 (JP, A) JP-A-10-167727 (JP, A) JP-A-10-204323 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C09D 11/00-11/20 C03C 17/22-17/27 C09D 1/00-1/12

Claims (6)

(57) [Claims] The basic structural unit is represented by the following general formula: M (OH) _x (R ₁ ) _y (R ₂ ) _z (M is at least one of the group consisting of metal elements Ti, Sn, Bi, Fe, W) There, R ₁ represents an alkoxy group, an alkyl group, an allyl group, an acyl group, an ester group, beta-diketone chelate, beta-keto ester chelate, at least one selected from the group consisting of hydroxy-carboxylic acid ester chelate, R ₂ is Represents at least one of polyhydric alcohols and polyhydric alcohol derivatives,
x + y + z = m, where m is the valence of the metal M, x and z are natural numbers, and y is an integer of 0 or more), a particle of a condensate of metal alkoxides, a solvent, and a dispersant. An ink for forming a photocatalytic film, comprising: 2. Particles of a condensate of a metal alkoxide are
The photocatalyst film forming ink according to claim 1, which has a size of 1 µm or less. 3. The ink for forming a photocatalyst film according to claim 1, wherein the solvent contains at least one of polyhydric alcohols and polyhydric alcohol derivatives. 4. The photocatalyst according to claim 1, wherein the dispersant contains at least one of amines, amides, organic acids, inorganic acids, β-diketones, and β-ketoesters. Ink for film formation. 5. The basic units are represented by the following general formula _{M (R 1) a (R} 3) b (M is at least one selected from the group consisting of metal elements Ti, Sn, Bi, Fe, W, R 1 Represents at least one selected from the group consisting of an alkoxy group, an alkyl group, an allyl group, an acyl group, an ester group, a β-diketone chelate, a β-keto ester chelate and a hydroxycarboxylic acid ester chelate, and R ₃ represents a monovalent alkoxy group. R ₁ and R ₃ may be the same, and a + b = m, m is a valence of metal M, a is an integer of 0 or more, and b is a natural number. At least one solvent selected from the group consisting of polyhydric alcohols and polyhydric alcohol derivatives, and then adding amines, amides, and organic acids in a molar ratio less than m to the metal alkoxides. The method according to claim 1, wherein the dispersant containing at least one of inorganic acids, β-diketones, and β-ketoesters and the metal alkoxide are mixed simultaneously or stepwise with water in an amount less than m in a molar ratio of less than m. ~ Claim 4
A method for producing an ink for forming a photocatalyst film, comprising obtaining the ink for forming a photocatalyst film according to any one of the above. 6. 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 driving device for synchronously driving the roll and the intaglio roll, and moving between a printing position A on which the printing medium is placed and in contact with the printing roll on the base and retreating positions B and C away from the printing roll. Yes A platen provided to the printer, a printing medium drive for moving the platen between the two positions, and printing by controlling the rotation of the printing roll and the movement of the platen from the retracted positions B and C to the printing position A. 5. A method for forming a photocatalytic film by printing using a thin film forming apparatus comprising a control device for printing ink transferred to a convex portion of a roll on a printing medium, wherein the ink is any one of claims 1 to 4. A method for forming a photocatalyst film, which is the ink for forming a photocatalyst film according to any one of the above.