JP3105340B2 - Method of manufacturing substrate having composite metal oxide film - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The substrate having a composite metal oxide film of the present invention not only has a catalytic action, an electromagnetic wave selecting action, etc., but also has a dye, pigment, chemical,
Can adsorb, sorb, and retain fragrances and metal compounds,
In addition, since it can protect a substrate, a circuit on a substrate, and a design, it is expected to be widely used in many industrial sectors.

[0002]

2. Description of the Related Art Conventionally, a substrate having a composite metal oxide film has been formed by the following method. 1) Mix alkoxides of two metals, dissolve them in alcohol, apply sol hydrolyzed by adding water or acid to a glass plate, dry and heat to form a film (Ceramic Industry Association, 90, 328-333, 1982). 2) A liquid prepared by adding a chelating agent to two or more metal alkoxides is applied to a glass plate and heated to form a film having a maximum thickness of 0.3 μm (see Japanese Patent Publication No. 3-46402). 3) A solution prepared by adding an organic solvent-soluble titanium compound and an organic solvent-soluble compound such as silicon or tin and an organic solvent-soluble phosphorus compound is applied to a glass plate, and heated to a thickness of 0.1 μm. (See JP-A-3-164431).

[0003]

According to the method 1) which has been conventionally used, in order to obtain a film having a thickness of 0.5 μm by one application, a polymer compound such as hydroxypropylcellulose is contained in the sol. , And a roasting treatment at 600 ° C. or more was required for removal. In the conventional methods 1), 2) and 3), only a film having a thickness of 0.1 to 0.3 μm can be obtained in one application, so if the thickness is more than these, application, drying and heating steps are required. It is necessary to repeat the process, which not only complicates the work, but also uniformity of the adhesion at the interface between the film formed in the first step and the film formed in the second step and the composition between the films There was a problem with sex.

[0004]

In order to easily hydrolyze a metal alkoxy compound with water, an acid or an alkali, when a metal alkoxy compound is mixed with an aqueous alumina sol, the metal alkoxy compound is rapidly agitated. The present inventors have a problem of reacting to form a precipitate, and the present inventors have conducted many experiments in order to solve the above-mentioned drawbacks, but have finally completed the present invention. That is,
Organic solvent solution containing an alkoxy-based compound of at least one metal selected from the group consisting of silicon, indium, tin, zinc, germanium, gallium, magnesium, titanium, zirconium, hafnium, scandium, yttrium, and rare earth elements, and an active methylene compound A composite metal oxide film is formed by applying a hybrid sol consisting of water and an aqueous alumina sol to a substrate, followed by drying and heat treatment or / and electromagnetic wave treatment to form a 0.5 to 15 μm thick transparent film on the substrate. Is a method of manufacturing a substrate having:

The present invention will be described in more detail. Silicon,
As the alkoxy compound of at least one metal selected from the group consisting of indium, tin, zinc, germanium, magnesium, titanium, zirconium, hafnium, scandium, yttrium and rare earth elements, the alkoxy group is a methoxy group, an ethoxy group , Isopropoxy, propoxy, n-butoxy, isobutoxy, amylooxy, caprooxy and glycoxy groups. In particular, when an alkoxy-based compound of silicon, indium, tin, zinc, magnesium, titanium and zirconium is used, transparency and film suitability are excellent.

[0006] As active methylene compounds, the main compound names are as follows: acetylacetone, acetoacetic acid and its ester, malonic acid and its ester, cyanoacetic acid and its ester, nitroacetic acid and its ester, benzyl cyanide, phenylacetic acid And at least one compound selected from the group consisting of and esters thereof, trifluoroacetylacetone, trifluoroacetoacetic acid and esters thereof, and hexafluoroacetylacetone are most suitable for the present invention.

The organic solvent includes aromatic hydrocarbons, esters, ketones, chlorinated hydrocarbons, alcohols, amides and the like. Particularly, polar organic solvents such as alcohol solvents and dimethylformamide solvents are available. solvent,
Dimethyl sulfoxide-based solvent, dimethylacetamide-based solvent, ethylene glycol-based solvent, diethylene glycol-based solvent, glycerin-based solvent, tetrahydrofuran-based solvent are suitable for mixing with aqueous alumina sol, alkoxy compounds of the above metals, active methylene compounds and their reactions It is suitable because there is little change with time in the mixture.

An organic solvent solution containing a metal alkoxy compound and an active methylene compound is generally a uniform transparent or almost transparent solution, and the main component thereof is a metal alkoxide which is a metal-OR (Met-OR). Metal atom, OR is an alkoxy group), active methylene compound is converted to A-CH _2-
B (A and B are methylene group activating atomic groups) are represented as follows (however, in Met-OR, the remaining valences not bonded to the OR of the metal atom are other alkoxy groups, mineral acid anions, organic Bound to an anion.). That is, Me
t-OR and A-CH ₂ -B may form a chelate compound or complex at a specific molar ratio in the solution, or may coexist in the solution. And, these organic solvent solutions are either (a) dissolving Met-OR and A-CH ₂ -B in a solvent,
(B) It can be prepared by either a method of mixing a solution containing Met-OR and a solution containing A-CH ₂ -B, or a combination of both methods.

The organic solvent used in these methods is as described above, and a highly polar and hydrophilic organic solvent is particularly convenient. Of course, among the active methylene compounds, acetylacetone, acetoacetic ester, malonic ester, nitromethane and the like are also excellent as the organic solvent of the present invention.

An aqueous alumina sol (also referred to as a dispersion of alumina hydrate, a sol-like aluminum hydroxide solution, etc.)
For example, aluminum trimethoxide, aluminum triethoxide, aluminum triisopropoxide,
Add aluminum alcoholate such as aluminum tri-n-butoxide to a solvent such as water or alcohol containing water, dissolve, disperse or hydrolyze it, and further add acid such as hydrochloric acid, nitric acid and acetic acid, or ammonia, triethanolamine, It is prepared by adding a base such as triethylamine and hydrolyzing it, or is prepared by hydrolyzing a water-soluble aluminum salt under mild conditions. In particular, those using aluminum alcoholate
Excellent in purity and quality stability. Further, in order to improve the suitability for mixing with the above-mentioned organic solvent solution after the preparation of the aqueous sol, the above-mentioned polar organic solvent may be added. Transparent in the present invention means that, when a film is formed on a transparent glass substrate, the transmittance is 40% or more in a certain wavelength band among wavelengths of 400 to 700 nm with respect to the glass substrate (of course. (This is an expression in a state where dyes and pigments, inorganic pigments, and the like are not adsorbed, sorbed, or mixed in the film).

Examples of the substrate include glass, metal, ceramics, and heat-resistant plastics. In addition, since the purpose of the present invention is to provide a transparent film, the substrate for the purpose of translucency must be transparent, but only a transparent film is required and the translucency is required. If not necessary, an opaque substrate such as a metal substrate can be used.

Drying includes, for example, room temperature to 120 ° C., 5
In about a second to about 180 minutes, the process is performed from the degree of touch-drying due to solvent evaporation to the degree of complete drying at 200 ° C. or less.

The heat treatment includes heating (including baking) with hot air and far-infrared rays, and the heat treatment is carried out under a suitable temperature range from the drying temperature to 1100 ° C. Especially when considering transparency
It is better to select a temperature range up to 600 ° C. Of course, the drying and the heat treatment may be performed continuously or separately. When the heat treatment is performed in an atmosphere of ozone, water vapor, or nitrogen, a film having excellent surface strength and catalytic activity can be obtained.

As the electromagnetic wave treatment, there are treatments (including baking) by ultraviolet irradiation, laser beam irradiation, infrared irradiation, micro electromagnetic wave irradiation and the like. This treatment is effective when using a substrate that cannot be used for a long time at a high temperature. It is more effective to carry out these treatments in an ozone or nitrogen atmosphere. In addition, when heating is used in combination, it is effective for shortening the working time and improving the performance.

The ultraviolet light used for ultraviolet irradiation is 185 n
Those having wavelengths of around m and around 254 nm are effective. Laser light irradiation is performed with a power of 10 to 200 W using a carbon dioxide laser or a YAG laser. A microwave used for microwave irradiation is preferably 2.45 GHz in terms of availability and safety of the device, but is not particularly limited.

A method for producing a hybrid sol from an organic solvent solution containing the metal alkoxide compound and the active methylene compound and an aqueous alumina sol includes mechanical stirring, shaking mixing, ultrasonic mixing, homogenizer stirring, roll mill mixing, and the like. And at room temperature to 100 ° C. If necessary, it may be kept at 0 to 80 ° C. for aging. When or after preparing this hybrid sol, dyes and pigments, inorganic pigments, inorganic spheres, metal salts, resins, defoamers, dispersants, leveling agents,
You may add a silane coupling agent, a titanium coupling agent, etc. By adjusting the ratio of aluminum in the metal atoms of this hybrid sol to be 10% or more, the strength of the film,
The film-forming properties are particularly good.

As a method of applying the hybrid sol to the substrate,
There are a coating method such as a gravure coater, a reverse coater and a roll coater, a printing method such as a gravure printing method and a screen printing method, and a coating method such as a spray method, a dipping method and an electrodeposition method. Since the transparent composite metal oxide film is transparent but porous, it can adsorb and sorb various substances. This film may be colorless or colored, or may be subjected to coating, drying or repeating coating, drying, heat treatment and / or electromagnetic wave treatment a plurality of times.

[0018]

The metal alkoxy compound easily reacts abruptly with water, acid or alkali contained in the aqueous alumina sol, so that it precipitates or becomes cloudy before forming a mixed sol with the aqueous alumina sol. By adding an aqueous alumina sol to an organic solvent solution containing a metal alkoxy compound and an active methylene compound, a uniform hybrid sol can be formed, and this problem can be solved.

[0019]

【Example】

Example 1 After mixing 100 g of tetraethyl orthosilicate and 100 g of ethanol, adding 250 g of ethyl acetoacetate and stirring at 30 ° C., adding 980 g of aluminum isopropoxide to 4 kg of an aqueous hydrochloric acid solution and reacting at 80 ° C. The mixed sol was obtained by adding ultrasonic wave to the alumina sol and mixing the mixture. Furthermore, it was left at room temperature for 12 hours. This hybrid sol is coated on a glass plate with a roll coater, dried at 80 ° C and heat-treated at 450 ° C for 4 hours to obtain a composite metal oxide having a thickness of 1 µm and an atomic ratio of silicon to aluminum of 1:10. A glass plate having an object film was obtained. This film had a transmittance of 92% or more in the wavelength range of 400 to 700 nm, was porous, had a high surface strength, and was excellent in chemical resistance.

Example 2 An aqueous alumina sol prepared by adding 110 g of aluminum sec-butoxide to 10 kg of an aqueous acetic acid solution and reacting at 90 ° C., and further adding 7 kg of isopropyl alcohol, was mixed with di-n-butoxybis (triethanolaminato). ) 50% of titanium
4.03 kg of the n-butanol solution and 10 g of a silicon-based antifoaming agent were mixed and mechanically stirred to obtain a mixed sol. It was kept at 40 ° C. for 3 hours. Next, after coating this hybrid sol on a polyethylene terephthalate film by a spray method,
Polyethylene terephthalate having a composite metal oxide film with a thickness of 0.5 μm and a titanium to aluminum ratio of 9: 1 by drying at ℃ and irradiating ultraviolet rays having a wavelength of 185 nm while heating to 150 ° C. A film was obtained. This film had a transmittance of 90% in the wavelength range of 400 to 700 nm, was excellent in friction resistance, and was excellent in optical characteristics.

Example 3 100 g of magnesium acetylacetonate was added to 2 kg of acetone.
Then, 3.1 kg of aluminum nitrate was dissolved in an aqueous nitric acid solution, and the mixture was mixed with an aqueous alumina sol obtained by reacting at 50 ° C. and 10 g of a fluorine-based leveling agent, followed by stirring to obtain a mixed sol. Then, after standing at room temperature for 2 hours, this mixed sol was coated on an alumina substrate by dipping, dried at 60 ° C., and heat-treated at 500 ° C. for 4 hours, to a thickness of 15 μm.
m and the atomic ratio of magnesium to aluminum is 3:97
An alumina plate having a composite metal oxide film was obtained. This film had a transmittance of 95% or more in the wavelength range of 400 to 700 nm, was porous, and was excellent in chemical resistance.

EXAMPLE 4 500 g of zinc bisacetylacetonate was added to 3 k of acetylacetone.
Then, 288 g of aluminum ethoxide was added to 3 kg of an aqueous nitric acid solution and reacted at 80 ° C., and the mixture was stirred with a sol obtained by adding 5 kg of ethanol to an aqueous alumina sol to obtain a mixed sol. This hybrid sol is coated on a glass plate on which a pattern is installed with an organic pigment by a spray method, dried at 80 ° C., and heat-treated at 250 ° C. for 2 hours to have a thickness of 2
A glass plate with a design having a composite metal oxide film with a ratio of zinc and aluminum of 1: 1 in terms of atomic ratio in μm was obtained. This film had a transmittance of 60% or more in a wavelength range of 400 to 700 nm, a high surface strength, and an effect of blocking ultraviolet rays.

Example 5 After mixing 100 g of triisopropoxy indium and 31 g of tetraisopropoxy tin with 500 g of acetylacetone and stirring, 87 g of aluminum isopropoxide was added to an aqueous solution of nitric acid 1
The resulting mixture was mixed and stirred with an aqueous alumina sol obtained by adding 1 kg of isopropyl alcohol to an aqueous alumina sol obtained by reacting at 90 ° C. to obtain a mixed sol. After coating this hybrid sol on a glass plate by dipping method, microwave (2.
Processed by 45GHz microwave) method, 0.7μm thick
The ratio of indium, tin and aluminum in atomic ratio is
A glass plate having a 8: 2: 10 composite metal oxide film was obtained. This film has a transmittance of 65% in the wavelength range of 550 to 700 nm.
It had the above transparency, had an antistatic effect, and was excellent in surface strength.

Example 6 4 kg of isopropyl alcohol was added to an aqueous alumina sol obtained by adding 500 g of aluminum isopropoxide to 6 kg of an aqueous nitric acid solution and reacting at 90 ° C., and then adding diisopropoxy.
2.38 kg of a 75% isopropyl alcohol solution of bis (acetylacetonato) titanium was added and stirred to obtain a mixed sol. Next, 1 kg of a red pigment was added and mixed with a roll mill to prepare a red ink. After a floral pattern was printed on a glass plate by screen printing using this ink, it was dried and heat-treated at 250 ° C. for 1 hour to obtain a glass plate having a red floral composite metal oxide film. This film was beautiful and had excellent surface strength.

[0025]

According to the present invention, the composition state of the film was uneven and unstable because a film thickness of 0.5 μm or more could not be obtained unless a number of treatments such as coating, drying and heating were performed. Can obtain a transparent film having a thickness of 0.5 to 15 μm at one time, so that the composition state of the film becomes uniform and a substrate having a composite metal oxide film stably expressing desired physical properties can be obtained. In addition, since the number of times of processing may be a small number of times, it is very economical, space saving and energy saving of the working space can be achieved, and the working environment is less polluted. Furthermore, if the characteristics are further mentioned, by using such a hybrid sol, the conditions such as heating required for forming a film can be significantly reduced as compared with the case of the aqueous alumina sol, and the processing operation can be performed. Because it is easy, it can be developed for various uses. Further, by changing the type and amount of the metal alkoxy compound used, it is also easy to exert an electromagnetic wave selecting action of selectively transmitting only electromagnetic waves having a specific wavelength.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C09D 1/00 C09D 1/00 183/04 183/04 185/00 185/00 // C01F 7/16 C01F 7/16 (58 ) Fields investigated (Int.Cl. ⁷ , DB name) C23C 18/00-18/54 C01B 13/32 C01G 1/00 C03C 17/02 C08J 7/04 C09D 1 / 00,183 / 04,185 / 00

Claims (1)

(57) [Claims] 1. An alkoxy compound and an active methylene compound of at least one metal selected from the group consisting of silicon, indium, tin, zinc, germanium, gallium, magnesium, titanium, zirconium, hafnium, scandium, yttrium, and rare earth elements. A hybrid sol consisting of an organic solvent solution containing water and an aqueous alumina sol is applied to a substrate, dried, and then subjected to heat treatment or / and electromagnetic wave treatment to form a 0.5 to 15 μm thick transparent film on the substrate. A method for producing a substrate having a composite metal oxide film.