JP2002060651A - Metal oxide aqueous sol composition, method for forming membrane by using the same and member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal oxide aqueous sol composition capable of forming a membrane which does not show an interference color by coating on a substrate and heating, and having excellent stability with hardly causing any gelation in storage. SOLUTION: The metal oxide aqueous sol composition is a composition for forming a membrane of the metal oxide by coating on a substrate and heating, and comprises a metal oxide aqueous sol and a water-soluble polymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a metal oxide aqueous sol composition, a film forming method and a member using the same.

[0002]

2. Description of the Related Art A water-based sol is applied by spraying,
In some cases, manual coating methods such as roller coating, brush coating, and sponge coating are used.However, if the work environment is deteriorated due to contamination due to scattering of materials, evaporation of solvents, etc. Mechanical coating methods such as roll coating, curtain coating, flow coating, bar coating, dip coating, spin coating, and ultrasonic coating are more advantageous. Among them, particularly, the screen printing method, the roll coating method, and the curtain coating method are known to have excellent continuous coating properties.

[0003] However, in order to apply an aqueous sol using a screen printing method, a roll coating method, or a curtain coating method, since the aqueous sol alone has low viscosity and low thixotropy, the coating liquid drips from the mesh. In some cases, the coating may be defective, the fluidity of the coating layer may be too high and the film thickness may not be constant, or may flow out of the substrate in some cases. In addition, when the film thickness is not constant, a light reflection behavior that looks like an iridescent color called an interference color is exhibited. In particular, in the case of a metal oxide having a high refractive index (2.5 for anatase type and 2.7 for rutile type) whose layer is formed by a film represented by titanium oxide, the appearance of interference colors also becomes remarkable.

[0004] Therefore, it is necessary to increase the viscosity of the aqueous sol when performing coating by a screen printing method, a roll coating method, or a curtain coating method. Examples of the method include a method in which ethyl cellulose described in JP-A-10-183062 is used as a thickening agent, and further, silica or glass beads are added to form a mixture.
There is a method of adding a polymer compound and fillers. However, in the method of forming a film only by coating according to the above method, the substance added to increase the viscosity prevents uniform gel transition of the sol,
Interference colors are easy to appear.

On the other hand, when a polymer compound is added to an aqueous sol, the added polymer compound impairs the stability of the sol, and in some cases, the composition often gels.

[0006]

SUMMARY OF THE INVENTION The present invention is intended to provide a coating composition having a low film thickness when a low-viscosity aqueous sol is applied by a screen printing method, a roll coating method, a curtain coating method, or the like, which has excellent continuous coating properties. When using a metal oxide having a high refractive index such as titanium oxide, interference colors are likely to appear, and when a polymer compound or filler is added to increase the viscosity of an aqueous sol, the added substance is Solving the problem that uniform gel transition is hindered and interference colors are likely to appear, and the problem of sol stability being impaired when polymer compounds are added, and in some cases the composition gelling during storage, at the same time. It is an object of the present invention to provide a metal oxide aqueous sol composition, a film forming method and a member using the same.

[0007]

That is, the present invention relates to the following.

(1) A composition for forming a metal oxide film by applying it to a substrate and heating it, comprising a metal oxide aqueous sol and a water-soluble polymer. Sol composition.

(2) Two kinds of raw materials consisting of a metal oxide aqueous sol and a water-soluble polymer or an aqueous solution thereof, or a metal oxide aqueous sol, a water-soluble polymer or an aqueous solution thereof, and
The metal oxide aqueous sol composition according to (1), which is obtained by mixing three or four kinds of raw materials composed of water and / or an organic solvent.

(3) The aqueous metal oxide sol composition according to (1) or (2), comprising 0.005 to 4% by weight of a metal oxide and 0.001 to 10% by weight of a water-soluble polymer.

(4) 25 of aqueous metal oxide sol composition
The metal oxide aqueous sol composition according to (1), (2) or (3), which has a viscosity at 10 ° C of 10 to 100,000 mPa · s.

(5) The average particle diameter of the metal oxide in the metal oxide aqueous sol is 100 nm or less,
The metal oxide aqueous sol composition according to any one of (4).

(6) The aqueous metal oxide sol composition according to any one of (1) to (5), wherein the metal oxide contains titanium oxide.

(7) The aqueous metal oxide sol composition according to any one of (1) to (6), wherein the metal oxide is an anatase type titanium oxide.

(8) The metal oxide aqueous sol composition according to any one of (1) to (7), wherein the water-soluble polymer contains a cellulose derivative.

(9) The aqueous metal oxide sol composition according to (8), wherein the cellulose derivative is an etherified product and / or an esterified product of a hydroxyl group of the cellulose skeleton.

(10) The aqueous metal oxide sol composition according to (9), wherein the cellulose derivative is a derivative of hydroxypropyl cellulose.

(11) When the water-soluble polymer is a 2% by weight aqueous solution, the viscosity at 20 ° C. is 1 to 200,0.
The metal oxide aqueous sol composition according to any one of (1) to (10), which has a water pressure of 00 mPa · s.

(12) The aqueous metal oxide sol composition according to any one of (1) to (11), wherein the water-soluble polymer contains a polyoxyalkylene.

(13) The metal oxide aqueous sol composition according to (12), wherein the polyoxyalkylene is polyethylene glycol.

(14) The aqueous metal oxide sol composition according to (13), wherein the polyoxyalkylene has 1 to 200 oxyalkylene repeating units.

(15) The aqueous metal oxide sol composition according to any one of (1) to (14), wherein the organic solvent is an alcohol.

(16) The aqueous metal oxide sol composition according to (15), wherein the organic solvent is ethanol.

(17) The aqueous metal oxide sol composition according to any one of (1) to (16), wherein the organic solvent is a lactone.

(18) The aqueous metal oxide sol composition according to (17), wherein the organic solvent is γ-butyrolactone.

(19) The aqueous metal oxide sol composition according to any one of (1) to (18), wherein the organic solvent is a cellosolve.

(20) The aqueous metal oxide sol composition according to (19), wherein the organic solvent is butyl cellosolve.

(21) The content of the organic solvent in the aqueous metal oxide sol composition is 3 to 95% by weight.
0) The metal oxide aqueous sol composition according to any one of the above.

(22) Metal oxide aqueous sol 0.2 to 9
9.998% by weight, aqueous solution of water-soluble polymer 0.002 to 0.002%
Any of (1) to (21) obtained by mixing two, three or four kinds of raw materials consisting of 99.8% by weight, water 0 to 99.798% by weight and organic solvent 0 to 95% by weight. 2. The aqueous metal oxide sol composition according to item 1.

(23) It further contains at least one additive selected from the group consisting of surfactants, leveling agents, defoamers, coupling agents and preservatives.
(22) The aqueous metal oxide sol composition according to any of (22).

(24) After applying the aqueous metal oxide sol composition according to any of (1) to (23) to a substrate,
A film-forming method, wherein a film is formed by heating at 200 ° C. or higher to decompose and / or eliminate a part or all of a water-soluble polymer.

(25) The film forming method according to (24), wherein the heating is performed at a temperature of 400 ° C. or more.

(26) The film forming method according to (25), wherein the heating is performed at a temperature of 400 to 1000 ° C.

(27) The aqueous metal oxide sol composition is applied to the substrate by screen printing, roll coating or curtain coating (24) to (26).
The film forming method according to any one of the above.

(28) A member obtained by forming a film on a substrate by the film forming method according to any one of (24) to (27).

(29) The substrate is a transparent substrate (2
8) The member according to the above.

(30) The member according to (28) or (29), wherein the substrate is a glass or quartz plate.

(31) The member according to any one of (28) to (30), wherein the surface of the coating does not show interference colors.

(32) The member according to any one of (28) to (31), wherein the surface of the coating absorbs ultraviolet light.

(33) The coating is made of water purification, air purification, antifouling, antifogging, dewproofing, dripproofing, anti-icing, snowproofing, antibacterial,
The member according to any one of (28) to (32), which has at least one of functions of fungicide, algae prevention, odor prevention, and foreign matter adhesion prevention.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The metal oxide aqueous sol composition of the present invention is a composition for applying to a substrate and heating to form a metal oxide film, and contains a metal oxide aqueous sol and a water-soluble polymer. It becomes.

The metal oxide aqueous sol used in the present invention can be used without particular limitation as long as it is a metal oxide sol using water as a solvent or a dispersion medium. As metal oxides,
Peroxides, oxides, dioxides, trioxides, tetroxides, pentoxides, hexoxides, and the like of various metals can be used without particular limitation, and may be used alone or in combination of two or more. May be used in combination. Specific examples of the metal oxide suitable for the present invention include TiO, TiO ₂ , TiO ₃ (or TiO ₃ .nH _2).
O), various titanium oxides, ZnO, SrTiO ₃ , F
e ₂ O ₃ , WO ₃ , FeTiO ₃ , RuO ₂ , LaRhO ₃ ,
CdFeO ₃ , Bi ₂ O ₃ , In ₂ O ₃ , CdO, SnO _{2 and the} like can be mentioned.

The coating formed by using the metal oxide aqueous sol composition is used for water purification, air purification, antifouling, antifogging, dewproofing, dripproofing, antifreezing, snowproofing, antibacterial, antifungal, Anti-algae, deodorant, having one or more of the functions of foreign matter adhesion prevention, also expresses good ultraviolet absorption, and is excellent in safety to the human body, as a metal oxide, TiO, Ti
Various titanium oxides such as O _{2 and} TiO ₃ (or TiO ₃ .nH ₂ O) are preferable. In particular, anatase-type titanium oxide (TiO ₂ ) is preferable for exhibiting photocatalytic ability,
The use of amorphous titanium peroxide is also preferred because it can be transferred to anatase titanium oxide by moderate heating.

In order to promote uniform gel transition of the aqueous metal oxide sol, the average particle diameter of the metal oxide is preferably 1
When the thickness is set to 00 nm or less, and when the thickness exceeds 100 nm, uniform gel transition of the metal oxide sol tends to be inhibited. Therefore, it is more preferably 50 nm or less, and still more preferably 2 nm or less.
0 nm or less. The average particle size of the metal oxide is preferably 0.1 nm or more, more preferably 1 nm or more. The particle size was determined by diluting the metal oxide aqueous sol 100 times with distilled water, dropping the sample on a sample holding mesh sheet, and drying the sample.
It can be obtained by observing with a transmission electron microscope under the condition of 00 kV. For example, the average particle diameter can be obtained from the average of 100 particles within a certain range.

The amount of the metal oxide in the metal oxide aqueous sol is not particularly limited, but is 0.01 to 5% by weight because of the handleability of the metal oxide aqueous sol and the stability of the metal oxide aqueous sol. It is preferably in the range of 0.1 to 3% by weight, more preferably 0.5 to 2% by weight. Further, the content of the metal oxide in the metal oxide aqueous sol composition is preferably 0.005 to 4% by weight, more preferably 0.1 to 3% by weight, and still more preferably 0.1 to 3% by weight. 3 to 2% by weight.

The water-soluble polymer used in the present invention is not particularly limited as long as it can be dissolved, hydrated, suspended and dispersed in water to increase the viscosity of the aqueous sol. For example, first, as the natural water-soluble polymer, potato, potato,
Starch from tapioca, wheat, corn starch, etc.
Mannan, seaweed, seaweed, galactan, sodium alginate, trolloom, gum arabic, gum gum, gum arabic and other plant mucilage, dextrin, levan etc.
Examples include proteins such as albumin, soy protein, and collagen. Examples of the semi-synthetic water-soluble polymer include cellulose derivatives such as viscose, methylcellulose, ethylcellulose, propylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, carboxymethylcellulose, soluble starch, carboxymethylstarch, And starches such as aldehyde starch. Examples of the synthetic water-soluble polymer include polyvinyl alcohol, polyvinyl ether, polyvinyl methyl ether, polyvinyl pyrrolidone, polyacrylate, polyoxyalkylene such as an ethylene oxide adduct of polyethylene glycol and polypropylene glycol, and derivatives thereof. . Upon use, one or more kinds can be used.

Further, if necessary, dissolve in water, hydrate,
Acrylic resin, polyester resin, melamine resin, urea resin, polyamide resin, polyimide resin, epoxy resin, phenol resin, ketone resin, polyurethane resin, fluorine resin, which can be suspended and dispersed to increase the viscosity of the aqueous sol, One or two of silicone resins and their resins such as silicone, amine and epoxy modified resins;
More than species can be used.

Among the above-mentioned various water-soluble polymers, the cellulose derivative can be sufficiently adjusted in viscosity by adding a small amount thereof. This is useful because a coating film can be formed and an appearance having excellent transparency can be obtained. In this sense, the cellulose derivative is preferably an etherified product and / or an esterified product of a hydroxyl group, and the oxyalkylene-modified cellulose derivative is more useful because it has a low thermal decomposition temperature and little residue after decomposition. Among them, the hydroxypropylcellulose derivative is preferable because it can maintain the leveling property and the transparency of the coating film when heated, because of its characteristic of being thermoplastic among the cellulose derivatives.

[0049] Among the water-soluble polymers, polyoxyalkylene is preferable because of obtaining appropriate flow characteristics. In particular, polyethylene glycol is preferable because it has a high effect of changing the thixotropic degree when combined with a cellulose derivative.

The number of oxyalkylene repeating units of the polyoxyalkylene is determined by the necessary viscosity, similarly to the viscosity of the water-soluble polymer, and is not limited, but sufficient viscosity can be adjusted by adding a small amount. Therefore, it is preferably from 1 to 200, and if it exceeds 200, the viscosity becomes too high with a small amount, and it is difficult to adjust. For this reason, 2 to 100 is preferable, and 3 to 70 is more preferable.

The viscosity of the water-soluble polymer is determined by rheological items such as required viscosity and thixotropic degree, and is not limited. However, since the viscosity can be sufficiently adjusted by adding a small amount,
20 ° C., 2% by weight aqueous solution, 1 to 200,000 mPa
S is preferable, and if it is less than 1 mPa · s, sufficient viscosity cannot be obtained even if the amount of addition is increased, and 200,000 mPa · s
Above s, the viscosity becomes too high with a small amount, making it difficult to adjust.
For this reason, 2 to 100,000 mPa · s is preferable,
3 to 50,000 mPa · s is more preferable.

The molecular weight of the water-soluble polymer is not particularly limited and preferably exhibits the above viscosity under the above conditions. For example, the weight average molecular weight measured by gel permeation chromatography in terms of standard polystyrene is 20.
0 to 5,000,000, preferably 500
More preferably, it is で 1,000,000.

When an aqueous solution of a water-soluble polymer is used for preparing the metal oxide aqueous sol composition of the present invention, the concentration of the water-soluble polymer is preferably 0.001 to 50% by weight, more preferably 0.5 to 50% by weight. It is desirable to use a 10% by weight aqueous solution.

The content of the water-soluble polymer in the aqueous metal oxide sol composition of the present invention is determined by the balance between the required viscosity and the storage stability of the aqueous metal oxide sol composition, and is limited. Although there is no, for the metal oxide aqueous sol composition,
0.001 to 10% by weight is preferred, and 0.001% by weight
If it is less than 10%, sufficient viscosity cannot be obtained, and if it exceeds 10% by weight, the viscosity becomes too high to adjust easily, and the stability of the aqueous metal oxide sol composition may be significantly impaired. In addition, it may take a considerable time to decompose and / or eliminate part or all of the water-soluble polymer by heating after applying the metal oxide aqueous sol composition to the substrate. Therefore, the content is preferably 0.005 to 5% by weight, and
01 to 3% by weight is more preferred.

In preparing the aqueous metal oxide sol composition of the present invention, the above-mentioned aqueous metal oxide sol and aqueous solution are adjusted to adjust the solubility of the water-soluble polymer and the viscosity of the aqueous metal oxide sol composition. In addition to the water-soluble polymer, water and / or an organic solvent can be further mixed as a solvent or a dispersion medium.
The organic solvent may be used by being mixed in advance with an aqueous solution of a water-soluble polymer.

The organic solvent that can be used in the present invention is one that enhances the solubility of the water-soluble polymer, has good miscibility with water, and does not impair the storage stability of the aqueous metal oxide sol composition. Although there is no limitation, alcohols having a high vapor pressure such as ethanol, methanol, and isopropanol may be used to improve the drying property of the coating film.
Species or two or more can be used. From the viewpoint of odor and safety, ethanol is particularly preferred.

Organic solvents suitable for improving the coating workability of the aqueous metal oxide sol composition include cellosolves such as butyl cellosolve and ethyl cellosolve having a low vapor pressure, and methyl carbitol, ethyl carbitol and butyl carbitol. Lactones such as carbitols and γ-butyrolactone can be mentioned, and one or more of these can be used. Among them, γ-butyrolactone and butyl cellosolve are particularly preferable because they can suppress the partial drying of the metal oxide aqueous sol composition during handling and maintain good storage stability of the metal oxide aqueous sol composition.

The water serving as the solvent or the dispersion medium preferably does not contain impurities such as ions in terms of the stability and the film forming property of the aqueous metal oxide sol composition of the present invention. Exchange water is preferred, and distilled water is more preferred.

The content of the organic solvent in the metal oxide aqueous sol composition is preferably from 0 to 95% by weight to adjust the solubility of the water-soluble polymer and the viscosity of the metal oxide aqueous sol composition. It is preferable to secure the balance of storage stability of the aqueous metal oxide sol. If it exceeds 95% by weight, the stability of the metal oxide aqueous sol composition may be significantly impaired. For this reason, 3 to 95% by weight is preferable, and 1 to 5% by weight.
0% by weight is more preferable, 2 to 30% by weight is more preferable, and 5 to 15% by weight is particularly preferable. The content of water in the metal oxide aqueous sol composition is from 4.994 to 99.
994% by weight, preferably 50 to 99% by weight.
Is more preferable, and 80 to 95% by weight is further preferable.

In the metal oxide aqueous sol used for preparing the metal oxide aqueous sol composition of the present invention, a water-soluble polymer or an aqueous solution thereof, and three or four kinds of raw materials comprising water and / or an organic solvent, The ratio of the metal oxide aqueous sol is 0.2 to
99.998% by weight, preferably 10 to 90% by weight.
%, More preferably 30 to 70% by weight. When an aqueous solution of a water-soluble polymer is mixed, the amount used is 0.002% of the total raw material.
To 99.8% by weight, preferably 0.5 to 50%.
It is more preferable to set the weight%. In addition, the above two types,
The amount of water mixed as one of the three or four types of raw materials is preferably 0 to 99.798% by weight, more preferably 0 to 80% by weight, and more preferably 1 to 5% by weight of all the raw materials.
More preferably, it is 0% by weight. In addition, the content of water and / or the organic solvent in the obtained metal oxide aqueous sol composition is preferably 85 to 99.994% by weight, and preferably 90 to 99.9% by weight in total. Is more preferable. In particular, the metal oxide aqueous sol composition contains 30 to 99.9% by weight of water, preferably 70 to 97% by weight,
More preferably 80 to 95% by weight, organic solvent 0 to 70% by weight, preferably 3 to 70% by weight, further preferably 3 to 70% by weight.
It is desirable to contain about 30% by weight.

The aqueous metal oxide sol composition of the present invention further comprises a surfactant, a leveling agent,
Additives such as antifoaming agents, coupling agents, preservatives and the like can be contained.

Examples of the surfactant that can be used in the present invention include sulfonic acid polyoxyethylene alkyl phenyl ether ammonium salt, sulfonic acid polyoxyethylene alkyl phenyl ether sodium salt, fatty acid sodium soap, fatty acid californite, and the like.
Sodium dioctyl sulfosuccinate, alkyl sulfate, alkyl ether sulfate, alkyl sulfate soda salt, alkyl ether sulfate soda salt, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether sulfate soda salt, alkyl sulfate TEA salt, polyoxyethylene alkyl ether sulfate TEA salt, 2-
Sodium ethylhexyl alkyl sulfate, sodium acylmethyltaurate, sodium lauroylmethyltaurate, sodium dodecylbenzenesulfonate, disodium lauryl sulfosuccinate, disodium sodium sodium polyoxyethylenesulfosuccinate, polycarboxylic acid, oleoyl sarcosine, amide Ether sulfate, lauroyl sarcosinate, sulfo FA
Anionic surfactants such as ester sodium salt; polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxy Ethylene alkyl ester,
Polyoxyethylene alkyl phenol ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene laurate, polyoxyethylene stearate, polyoxyethylene alkyl phenyl ether, polyoxyethylene oleate, sorbitan alkyl ester, poly Oxyethylene sorbitan alkyl ester, polyether-modified silicone, polyester-modified silicone, sorbitan laurate, sorbitan stearate, sorbitan palmitate, sorbitan oleate, sorbitan sesquioleate, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan stearate,
Polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan oleate, glycerol stearate, polyglycerin fatty acid ester, alkylalkylolamide, lauric acid diethanolamide, oleic acid diethanolamide, oxyethylene dodecylamine, polyoxyethylene dodecylamine, poly Nonionic surfactants such as oxyethylene alkylamine, polyoxyethylene octadecylamine, polyoxyethylene alkyl propylene diamine, polyoxyethylene oxypropylene block polymer, polyoxyethylene stearate; dimethyl alkyl betaine, alkyl glycine, amido betaine, imidazoline Amphoteric surfactants such as octadecyldimethylbenzylammonium chloride, Dimethylbenzylammonium chloride, tetradecyldimethylbenzylammonium chloride, dioleyldimethylammonium chloride, 1-hydroxyethyl-2-alkylimidazoline quaternary salt, alkylisoquinolinium bromide, polymer amine, octadecyltrimethylammonium chloride, alkyltrimethyl Ammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, behenyltrimethylammonium chloride, alkylimidazoline quaternary salt, dialkyldimethylammonium chloride, octadecylamine acetate, tetradecylamine acetate, alkylpropylenediamine acetate, didecyldimethyl Cationic such as ammonium chloride Surface active agents, and the like. These may be used in combination or alone or in combination. The content of the surfactant in the metal oxide aqueous sol composition is preferably 0.001 to 5% by weight, and more preferably 0.01 to 2% by weight.

Examples of the leveling agent that can be used in the present invention include diacetone alcohol, ethylene glycol monomethyl ether, 4-hydroxy-4-
Methyl-2-pentanone, dipropylene glycol, tripropylene glycol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, propylene glycol monomethyl ether, 1-propoxy-2-propanol, dipropylene glycol monomethyl ether, dipropylene glycol Propylene glycol monoethyl ether, tripropylene glycol monoethyl ether and the like can be mentioned, and these can be used alone or in combination of two or more. The content of the leveling agent in the metal oxide aqueous sol composition is preferably 0.001 to 5% by weight, more preferably 0.01 to 2% by weight.

Examples of the antifoaming agent which can be used in the present invention include polyether-modified polysiloxane, silicones, polyglycols, ethylene oxide-propylene oxide copolymer, paraffin-based mineral oil and hydrophobic component. Emulsions, higher alcohols such as octanol and lauryl alcohol, tributyl phosphate and the like can be mentioned, and these can be used alone or in combination of two or more. The content of the antifoaming agent in the metal oxide aqueous sol composition is preferably 0.001 to 1% by weight, more preferably 0.01 to 0.05% by weight.

Examples of the coupling agent that can be used in the present invention include vinyltrichlorosilane, vinyltris (β-methoxyethoxy) silane, vinyltrimethoxysilane, vinyltriethoxysilane, and (γ-methacryloxypropyl) trisilane. Methoxysilane, (γ-methacryloxypropyl) triethoxysilane, β-
(3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- Aminopropyltrimethoxysilane,
γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropyltriethoxysilane, N- (β-aminoethyl) -Γ-aminopropylmethyldimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, N-
Phenyl-γ-aminopropyltrimethoxysilane, N
-Phenyl-γ-aminopropyltriethoxysilane,
Silane coupling agents such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-chloropropyltriethoxysilane, vinyltrichlorotitanium, vinyltris (β-methoxyethoxy) Titanium, vinyltrimethoxytitanium, vinyltriethoxytitanium, (γ-methacryloxypropyl) trimethoxytitanium, (γ-methacryloxypropyl) triethoxytitanium, β- (3,4-epoxycyclohexyl) ethyltrimethoxytitanium, β -(3,4-epoxycyclohexyl) ethyltriethoxytitanium, γ-glycidoxypropyltrimethoxytitanium, γ-glycidoxypropyltriethoxytitanium, γ-aminopropyltrimethoxytitanium, γ-aminopro Le triethoxy titanium, N
-(Β-aminoethyl) -γ-aminopropyltrimethoxytitanium, N- (β-aminoethyl) -γ-aminopropyltriethoxytitanium, N- (β-aminoethyl)
-Γ-aminopropylmethyldimethoxytitanium, N-
(Β-aminoethyl) -γ-aminopropylmethyldiethoxytitanium, γ-aminopropylmethyldimethoxytitanium, N-phenyl-γ-aminopropyltrimethoxytitanium, N-phenyl-γ-aminopropyltriethoxytitanium, γ- Mercaptopropyltrimethoxytitanium, γ-mercaptopropyltriethoxytitanium, γ-
Examples include titanium coupling agents such as chloropropyltrimethoxytitanium and γ-chloropropyltriethoxytitanium, and these can be used alone or in combination of two or more. The content of the coupling agent in the metal oxide aqueous sol composition is preferably 0.001 to 5% by weight, more preferably 0.01 to 2% by weight.

Examples of the preservatives that can be used in the present invention include organic nitrogen, sulfur compounds, 1,2-benzisothiazoline compounds and the like.
Species can be used alone or in combination of two or more. The content of the preservative in the metal oxide aqueous sol composition is 0.001.
１1% by weight, more preferably 0.05-0.1% by weight.

The viscosity of the aqueous metal oxide sol composition of the present invention is not limited as long as it is determined by the type and conditions of the coating method, but is 10 to 100,000 m at 25 ° C.
Pa · s is preferable in terms of workability, and 10 mPa · s
If it is less than s, it is not possible to obtain a constant film thickness, and if a metal oxide having a high refractive index such as titanium oxide is used, interference colors are likely to appear, and
If it is more than 000 mPa · s, the viscosity is too high and the handling property is poor. For this reason, 20 to 50,000 mPa
S is preferable, and 50 to 10,000 mPa · s is more preferable. In the case of general screen printing, the viscosity is 50
１００100,000 mPa · s, preferably 100 to 1
000 mPa · s, more preferably 200 to 1,0
About 00 mPa · s, the degree of thixation is 1 to 5, preferably
It is set to about 1.1 to 3.0.

According to the film forming method of the present invention, a part or all of the water-soluble polymer is decomposed and / or burned out by applying the metal oxide aqueous sol composition of the present invention to a substrate and heating it. In this case, a film is formed. By performing this operation, uniform gel transition of the aqueous metal oxide sol becomes possible, and interference colors hardly appear on the coating film surface.

The heating temperature is not limited as long as part or all of the water-soluble polymer is decomposed and / or burned out, but is preferably 200 ° C. or higher, and if it is lower than 200 ° C., the water-soluble polymer is decomposed and / or decomposed. A long time is required for burning out. For this reason, the heating temperature is more preferably 400 ° C. or higher, and further preferably 500 ° C. or higher. The upper limit of the heating temperature is determined by the heat resistance of the substrate on which the metal oxide aqueous sol composition is applied, and is not particularly limited.
° C or lower, more preferably 700 ° C or lower.
In addition, the heating time is not limited because it is completely different depending on the temperature and the base material, but it is necessary to take care that the necessary water-soluble polymer is decomposed and / or burned out, and usually 0.5 minutes to 10 hours. And preferably for 30 to 120 minutes.

The method for applying the aqueous metal oxide sol composition of the present invention includes spraying, roller coating, brush coating,
Manual coating methods such as sponge coating are also possible, but if the work environment is deteriorated due to contamination due to scattering of materials, evaporation of solvents, etc., and productivity is taken into account, screen printing, roll coating, curtain coating, etc. Mechanical coating methods such as flow coating, bar coating, dip coating, spin coating, and ultrasonic coating are preferred. Among them, the screen printing method is particularly advantageous because the roll coating method and the curtain coating method are excellent in continuous coating properties. In the above sense, a film forming method in which the metal oxide aqueous sol composition of the present invention is applied to a substrate by a screen printing method, a roll coating method, or a curtain coating method, and then heated to 200 ° C. or more is preferable.

The coating on the base material thus formed preferably has a thickness of 0.01 to 10 μm.
More preferably, it is 0.1 to 5 μm.

The substrate used for the film forming method of the present invention and the members produced by the method are not limited. For example, polycarbonate resin, acrylic resin, polyester resin, AB
Organic resins such as thermoplastic resins and thermosetting resins such as S resin and polyvinyl chloride, thermosetting resins, ultraviolet curable resins, and electron beam curable resins, glass, ceramics, various metals, and composite materials thereof. Since the film formed by the present invention has no interference color on the surface and is excellent in ultraviolet absorption and transparency, a transparent substrate such as glass, quartz plate, polycarbonate and acrylic resin is particularly suitable. Among these substrates, a glass or quartz plate is more advantageous because it has a high heat resistance, so that the heating temperature can be increased.

As the member of the present invention, the metal oxide aqueous sol composition of the present invention is applied to a substrate and heated,
There is no particular limitation except that the water-soluble polymer is a member manufactured by forming a film by decomposing and / or burning out a part or all of the water-soluble polymer, but the surface of the film formed on the substrate is not limited. Does not show interference colors, further absorbs ultraviolet rays, further purifies water, purifies air, antifouling,
A member having at least one of anti-fogging, dew-proofing, drip-proofing, anti-icing, snow-proofing, antibacterial, mold-proof, algae-proof, odor-proof, and adhesion of foreign substances, or an effect of the present invention, It is preferable in terms of utilizing.

As specific examples, for example, various road members such as road wall panels, reflectors, and information display boards, interior and exterior materials for buildings, interior and exterior materials for vehicles, ships, aircrafts, etc., air conditioners, cleaning machines Household appliances such as refrigerators and washing machines, water treatment facilities such as water purifiers and water treatment plants, various types of glass such as plate glass, glass fiber, and glass powder, mirrors, lighting fixtures, tiles, and quartz plates. Further, since a coating having no interference color is provided, a window member of a vehicle, a ship, an aircraft, or a building requiring visibility, or a vehicle or interior / exterior of a building requiring design is preferable.

[0075]

Next, the present invention will be described in detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In addition,% indicates weight% unless otherwise specified.

Synthesis Example 1 (Synthesis of Titanium Oxide) 3 ml of titanium tetrachloride TiCl ₄ was placed in a 1000 ml separable flask equipped with a stirrer, thermometer and nitrogen inlet tube.
A 0% solution (manufactured by Sumitomo Citix Co., Ltd.) was charged, cooled to 15 ° C. in a reaction bath equipped with a condenser, and 207 ml of distilled water was gradually added with stirring. Meanwhile, 3ml in a 50ml beaker
Of ammonium hydroxide (NH ₄ OH) (manufactured by Takasugi Pharmaceutical Co., Ltd.), and further diluted with 27 ml of distilled water. This ammonium hydroxide solution was put into a dropping funnel, dropped into a separable flask, and a neutralization reaction was performed with stirring. At that time, nitrogen was flowed into the gas phase at 20 ml / min, and the temperature in the reaction bath was kept at 15 ° C. During the reaction, a white gel-like suspended substance was formed. After the neutralization reaction, the pH was adjusted to 6.5 to 6.8 with hydrochloric acid or aqueous ammonia, stirring was stopped, and after allowing the mixture to stand for a while, the supernatant was discarded. Thereby, titanium hydroxide Ti (O
H) ₄ was obtained. Further, about 4 times the amount of distilled water of the gel was added to the gel, and the gel was sufficiently stirred and left.

A portion of the supernatant was taken, a drop of 1% silver nitrate solution was added dropwise to the solution, and water washing was repeated until turbidity did not occur (until chloride ions in the supernatant disappeared). The liquid was discarded to obtain a purified titanium hydroxide gel. At this time, in some cases, dehydration treatment could be performed by centrifugation.

This pale blue white titanium hydroxide gel 360
The mixture was charged into a 1000 ml separable flask and cooled to 5 ° C., and then 21 ml of 35% hydrogen peroxide solution was added every 30 minutes for 2 minutes.
It was added in portions and stirred overnight. The titanium hydroxide gel was gradually dissolved to obtain about 250 ml of a yellow transparent amorphous titanium peroxide aqueous sol. In the above steps,
When sufficient cooling was not performed, it was found that substances insoluble in water, such as metatitanic acid, were deposited. This amorphous titanium peroxide aqueous sol was heated at 100 ° C. for 6 hours to obtain an anatase-type titanium oxide aqueous sol, which was adjusted so that the anatase-type titanium oxide content was 1.7% by weight.
TS-1. This anatase-type titanium oxide aqueous sol has a pH of 6.0 to 7.0 and an average particle size of anatase-type titanium oxide of 8 to 20 nm.
It was stable without gelling.

Preparation Example 1 (Dissolution of Water-Soluble Polymer) Hydroxypropylcellulose HPC manufactured by Nippon Soda Co., Ltd.
-H (trade name, viscosity at 20 ° C., 2% by weight aqueous solution: about 2,500 mPa · s, weight average molecular weight: about 105,0
(00) was adjusted to 5% by weight in distilled water to obtain a water-soluble polymer aqueous solution HP-1. In addition, the following, respectively, manufactured by Nippon Soda Co., Ltd., hydroxypropylcellulose HPC-
L (trade name: 20 ° C., viscosity in 2% by weight aqueous solution: about 8.0)
mPa · s, weight average molecular weight: about 360,000)
The water-soluble polymer aqueous solution HP-2 was dissolved in distilled water so as to have a weight%, and polyethylene glycol PEG # 600 (number of repeating units of oxyethylene: about 14, weight average molecular weight: about 700) manufactured by Lion Corporation was used. A water-soluble polymer aqueous solution HP-3 was dissolved in distilled water so as to be 5% by weight,
Shin-Etsu Chemical Co., Ltd., Metros 60SH-4000
(Trade name, hydroxypropyl methylcellulose, 20
C, viscosity in 2% by weight aqueous solution: about 4,550 mPa ·
s, weight-average molecular weight: about 350,000) in distilled water so as to be 5% by weight.
I got

Example 1 To 50 parts by weight of ATS-1 obtained in Synthesis Example 1 above, 16 parts by weight of HP-1 obtained in Preparation Example 1 and 20 parts by weight of HP-2 and 20
Parts by weight were added and dispersed until uniform. Then, γ-
Butyrolactone, 10 parts by weight, and further 4 parts by weight of distilled water were added, and dispersed until uniform to obtain a composition J-1.

Example 2 The ATS-1 obtained in Synthesis Example 1 was added to 50 parts by weight of the HP-1 obtained in Preparation Example 1, 16 parts by weight, and HP-3, 10 parts by weight.
Parts by weight were added and dispersed until uniform. Then, γ-
Butyrolactone, 10 parts by weight, and further 14 parts by weight of distilled water were added, and the mixture was dispersed until it became uniform to obtain a composition J-2.

Example 3 To 50 parts by weight of ATS-1 obtained in Synthesis Example 1, 1 part by weight of HP-4 obtained in Preparation Example 1 was added and dispersed until uniform. Thereafter, 10 parts by weight of γ-butyrolactone and 39 parts by weight of distilled water were added and dispersed until the mixture became uniform to obtain a composition J-3.

Comparative Example 1 50 parts by weight of ATS-1 obtained in Synthesis Example 1 was added to γ
-Butyrolactone, 10 parts by weight, and 40 parts by weight of distilled water were added, and dispersed until uniform to obtain a composition H-1.

Comparative Example 2 10 parts by weight of γ-butyrolactone and 89 parts by weight of distilled water were added to 1 part by weight of HP-4 obtained in the above Preparation Example 1 and dispersed until it became uniform. 2 was obtained.

Evaluation (1) Viscosity, thixotropic degree The compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 2
According to IS K 6901, the viscosity was measured with a rotor # 2 (60 rpm) using a BM-type rotational viscometer, and the viscosity measured at 6 rpm was divided by the viscosity measured at 60 rpm to determine the degree of fluctuation. Calculated and the results are shown in Table 1.

Evaluation (2) Composition stability The compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were treated with 100 c
c was placed in a glass sample bottle, and left standing at room temperature in a dark place for one month to observe the presence or absence of gelation.
It was shown to.

Evaluation (3) Screen Printing Coating and Coatability The compositions obtained in Examples 1 to 3 and Comparative Examples 1 and 2 were screen printed under the following conditions, and dripping from the mesh and coating were performed. Immediately after, the coating property was evaluated as good, indicating that the coating could be performed without problems such as insufficient adhesion to the base material, such as a film thickness of 40 μm or less, and the coating properties were evaluated. -Apparatus: LS-34GX printing machine manufactured by NEW LONG Co., Ltd.-Plate: 70 mesh, emulsion film thickness: 50 µm-Gap between substrate and screen: 2 mm-Pushing amount: 0.4 mm-Substrate: acetone 1.7 mm thick glass plate heat-treated at 600 ° C. for 30 minutes after washing well ・ Squeegee: silicon square type, speed: 3 mm / s, ・ Environment: temperature: 20 ° C., humidity: 66%

[0088]

[Table 1] The test pieces coated by screen printing under the above conditions were pre-dried at 80 ° C. for 30 minutes, baked at 550 ° C. for 30 minutes, and cooled to room temperature, and subjected to the following experiment.

Evaluation (4) Coating interference color The coating state of the test piece was visually evaluated for the presence or absence of glare and the state. The results are shown in Table 2.

Evaluation (5) Ultraviolet transmittance The ultraviolet transmittance of the test piece was measured using a U-2000 type Hitachi double beam spectrophotometer manufactured by Hitachi, Ltd. at a wavelength of 300 nm, and the results were tabulated. 2 is shown.

Evaluation (6) Visible Light Transmittance The visible light transmittance of the test piece was measured using a U-2000 type Hitachi double beam spectrophotometer manufactured by Hitachi, Ltd., and the light transmittance at a wavelength of 650 nm was measured. Are shown in Table 2.

Evaluation (8) The adhesion test piece was subjected to JIS K5
The adhesion to the substrate was evaluated according to a 400 crosscut test method, and the results are shown in Table 2.

[0093]

[Table 2] Evaluation (9) Dye decomposability A red ink (manufactured by Pilot Co., Ltd.) diluted 20-fold with distilled water was spray-coated on the test piece, dried at room temperature, and then dried.
A 20 W black light (FL20S SL-B manufactured by Matsushita Electric Works, Ltd.) was irradiated from a distance of cm to observe the degree of disappearance of the color of the red ink. Table 3 shows the results.

[0094]

[Table 3] Evaluation (10) Antibacterial activity The test specimen was subjected to an antibacterial activity test according to the method of the revised edition of the Anti-Technical Association of 1998. That is, 1 diluted with phosphate buffer
/ 500NB medium in Escherichia coli IFO3
972) is evenly planted per sample, and irradiated with 20 W black light (FL20S SL-B manufactured by Matsushita Electric Works, Ltd.) from a distance of 20 cm from the sample, and the bacteria on the sample at 25 ° C. The number was measured over time. In addition, a blank glass plate having no coating film was also used as a blank. The results are shown in Table 4.

[0095]

[Table 4] As described above, the metal oxide aqueous sol composition of the present invention has a viscosity and a thixotropic degree that can be adjusted, has no problem in storage stability of the metal oxide sol, and can be screen-printed. is there. The formed film has little interference color and is excellent in ultraviolet absorption. In addition, it is transparent and has excellent adhesion and contamination prevention properties. Furthermore, it has a function of decomposing dirt and an antibacterial property by the photocatalytic ability.

[0096]

The metal oxide aqueous sol composition of the present invention comprises:
When a low-viscosity aqueous sol is applied by screen printing, roll coating, or curtain coating, which has excellent continuous coating properties, it is not possible to achieve a uniform film thickness and oxidize metal with a high refractive index, such as titanium oxide. The problem is that interference color tends to appear when using a substance, and when a polymer compound or filler is added to increase the viscosity of an aqueous sol, the added substance hinders uniform gel transition of the sol and easily causes interference color. When a molecular compound is added, the stability of the metal oxide aqueous sol is impaired, and in some cases, the problem of gelling of the composition can be solved at the same time.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C01G 23/04 C01G 23/04 C 4G047 23/047 23/047 4G059 C02F 1/00 C02F 1/00 U 4G069 1/32 ZAB 1/32 ZAB 4H020 1/72 101 1/72 101 4J038 C03C 17/27 C03C 17/27 C09D 101/26 C09D 101/26 171/02 171/02 C09K 3/00 112 C09K 3/00 112Z 3/18 3/18 (72) Inventor Masayoshi Kazuki, Kashima-gun, Ibaraki Pref., In the Kashima Office, Hitachi Chemical Co., Ltd. (72) Inventor Yasushi Kojima, Yazaki in Hasaki-cho, Ibaraki, Japan Hitachi Chemical Co., Ltd., Kashima Plant (72) Inventor Kazuo Aizu, Ozaki, Hazaki-cho, Kashima-gun, Ibaraki Prefecture Kashima Plant Co., Ltd. (72) Inventor Shiro Ogata 3-1-1-409, Kami Aso, Aso-ku, Kawasaki City, Kanagawa Prefecture F-term (reference) 4C080 AA05 BB01 CC01 HH06 JJ06 KK08 LL03 MM02 NN24 NN27 4D037 AA01 BA18 CA11 4D050 AA01 BC06 BC09 4D075 CA45 DA06 DB13 EA02 EA12 EB07 EB52 EC02 EC30 EC35 EC52 EC02 4DC03 DC02 4DC03 4G03A02 AB01 AB09 AC21 AC22 AC30 EA04 EB07 4G069 AA03 AA08 AA09 BA04A BA04B BA04C BA48A BA48C BB08C CA00 CA07 CA10 CA17 DA06 EA08 FA02 FB23 FB36 4H020 AA01 DA01 DA02 BA09 DA01 DA01 BA02 DA091 DD002 DF011 DF012 DG001 DG002 DJ021 DJ022 DL031 DL032 HA161 HA162 JA18 JA25 JA33 JC32 JC38 KA06 KA09 MA08 MA10 NA05 NA06 PA19 PC02 PC03 PC08

Claims (33)

[Claims] 1. A composition for forming a metal oxide film by applying it to a base material and heating it, comprising a metal oxide aqueous sol and a water-soluble polymer. Composition. 2. Two kinds of raw materials comprising a metal oxide aqueous sol and a water-soluble polymer or an aqueous solution thereof, or a metal oxide aqueous sol, a water-soluble polymer or an aqueous solution thereof, and water and / or an organic solvent. The aqueous metal oxide sol composition according to claim 1, which is obtained by mixing three or four kinds of raw materials consisting of: 3. The metal oxide aqueous sol composition according to claim 1, comprising 0.005 to 4% by weight of a metal oxide and 0.001 to 10% by weight of a water-soluble polymer. 4. The metal oxide aqueous sol composition according to claim 1, 2 or 3, wherein the viscosity at 25 ° C. of the metal oxide aqueous sol composition is 10 to 100,000 mPa · s. 5. The metal oxide aqueous sol composition according to claim 1, wherein the average particle diameter of the metal oxide in the metal oxide aqueous sol is 100 nm or less. 6. The metal oxide aqueous sol composition according to claim 1, wherein the metal oxide contains titanium oxide. 7. The aqueous metal oxide sol composition according to claim 1, wherein the metal oxide is an anatase type titanium oxide. 8. The aqueous metal oxide sol composition according to claim 1, wherein the water-soluble polymer contains a cellulose derivative. 9. The aqueous metal oxide sol composition according to claim 8, wherein the cellulose derivative is an etherified product and / or an esterified product of a hydroxyl group of a cellulose skeleton. 10. The metal oxide aqueous sol composition according to claim 9, wherein the cellulose derivative is a derivative of hydroxypropyl cellulose. 11. The viscosity at 20 ° C. of a 2% by weight aqueous solution of a water-soluble polymer is from 1 to 200,000 m
The aqueous metal oxide sol composition according to any one of claims 1 to 10, which is Pa · s. 12. The aqueous metal oxide sol composition according to claim 1, wherein the water-soluble polymer contains a polyoxyalkylene. 13. The metal oxide aqueous sol composition according to claim 12, wherein the polyoxyalkylene is polyethylene glycol. 14. The metal oxide aqueous sol composition according to claim 13, wherein the polyoxyalkylene has 1 to 200 oxyalkylene repeating units. 15. The metal oxide aqueous sol composition according to claim 1, wherein the organic solvent is an alcohol. 16. The method according to claim 1, wherein the organic solvent is ethanol.
6. The metal oxide aqueous sol composition according to 5. 17. The method according to claim 1, wherein the organic solvent is a lactone.
17. The metal oxide aqueous sol composition according to any one of items 16 to 16. 18. The metal oxide aqueous sol composition according to claim 17, wherein the organic solvent is γ-butyrolactone. 19. The metal oxide aqueous sol composition according to claim 1, wherein the organic solvent is a cellosolve. 20. The metal oxide aqueous sol composition according to claim 19, wherein the organic solvent is butyl cellosolve. 21. The aqueous metal oxide sol composition according to claim 1, wherein the content of the organic solvent in the aqueous metal oxide sol composition is 3 to 95% by weight. 22. An aqueous metal oxide sol of 0.2 to 99.9.
98% by weight, 0.002 to 99.
8% by weight, water 0 to 99.798% by weight and organic solvent 0
The aqueous metal oxide sol composition according to any one of claims 1 to 21, which is obtained by mixing two, three, or four kinds of raw materials consisting of 95% by weight. 23. A surfactant, a leveling agent, an antifoaming agent,
The aqueous metal oxide sol composition according to any one of claims 1 to 22, further comprising at least one additive selected from the group consisting of a coupling agent and a preservative. 24. After applying the aqueous metal oxide sol composition according to any one of claims 1 to 23 to a substrate,
A film-forming method, characterized in that a film is formed by decomposing and / or eliminating part or all of the water-soluble polymer by heating as described above. 25. The film forming method according to claim 24, wherein the heating is performed at a temperature of 400 ° C. or higher. 26. The film forming method according to claim 25, wherein the heating is performed at a temperature of 400 to 1000 ° C. 27. The film forming method according to claim 24, wherein the application of the metal oxide aqueous sol composition to the substrate is performed by a screen printing method, a roll coating method, or a curtain coating method. 28. A member obtained by forming a film on a substrate by the film forming method according to claim 24. 29. The member according to claim 28, wherein the substrate is a transparent substrate. 30. The member according to claim 28, wherein the substrate is a glass or quartz plate. 31. The member according to claim 28, wherein the surface of the coating does not show an interference color. 32. The member according to claim 28, wherein the surface of the coating absorbs ultraviolet light. 33. The coating has a function of purifying water, purifying air, antifouling, antifogging, dewproofing, dripproofing, icing, snowproofing, antibacterial, antifungal, antialgal, deodorizing and foreign matter adhesion preventing. 33. The member according to claim 28, having at least one function of: