JPH0534507A - Antistatic film and production thereof - Google Patents

Abstract

PURPOSE:To provide an antistatic film which can be heat-treated at a low temp. CONSTITUTION:At least one kind of compd. selected among a beta-diketone complex of Ti, salts or alkoxides of the complex and hydrolyzates of them and electric conductive fine particles such as fine particles of SnO2 doped with F or Sb are dispersed or dissolved in a mixed soln. consisting of water and org. solvents. A substrate is coated with the resulting coating liq. to produce an antistatic film.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antistatic film applied on the surface of a glass substrate such as a cathode ray tube panel.

[0002]

2. Description of the Related Art Since a cathode ray tube operates at a high voltage, static electricity is induced on the surface of the cathode ray tube at the time of starting or ending. This static electricity often causes dust to adhere to the surface to cause a reduction in contrast, or causes a discomfort due to a slight electric shock when directly touched.

In the past, many attempts have been made to provide an antistatic film on the surface of a cathode ray tube panel in order to prevent the above-mentioned problems. For example, as described in JP-A-63-76247, the surface of the cathode ray tube panel is heated to about 350 ° C. to perform CV.
A method of providing a conductive oxide layer such as tin oxide and indium oxide by the D method has been adopted. However, in this method, there is a problem in that in addition to the cost of the apparatus, heating of the cathode ray tube at a high temperature causes the fluorescent substance in the cathode ray tube to fall off and the dimensional accuracy to decrease.

[0004]

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks of the prior art, and an object thereof is to provide a novel antistatic film which can be heat-treated at a low temperature. Is.

[0005]

The present invention has been made to solve the above-mentioned problems, and at least one selected from Ti β-diketone complexes, salts or alkoxides thereof, and hydrolyzates thereof. A method for producing an antistatic film, which comprises producing a antistatic film by applying a coating solution in which a seed and conductive particles are dispersed or dissolved in a mixed solution of water and an organic solvent onto a substrate. provide.

The conductive fine particles include SnO ₂ fine particles doped with Sb and F, fine particles of conductive titanium oxide, and ITO (Sn
-Doped In ₂ O ₃ ) fine particles, RuO ₂ fine particles, and SnO ₂
Examples thereof include complex oxide fine particles such as —RuO ₂ and TiO ₂ —RuO ₂ .

It is important that these conductive fine particles are uniformly dispersed in water. When dispersing, it is desirable to stir to facilitate contact between the solution and the powder.
In this case, a commercially available crusher such as a colloid mill, a ball mill, a sand mill or a homomixer can be used. Moreover, when dispersing, it is also possible to heat in the range of 20 to 200 ° C. When stirring above the boiling point of the solution, pressurize to maintain the liquid phase. Thus, an aqueous sol in which the conductive fine particles are dispersed as colloidal particles can be obtained.

In the liquid in which the conductive fine particles are dispersed, in order to prevent the fine particles from aggregating and precipitating and forming a stable sol, Ti (C ₅ H ₇ O ₂ ) ₂ (OR) ₂ is added to the dispersion liquid. It is preferable to add at least one selected from the β-diketone complex of Ti, a salt or alkoxide thereof, and a hydrolyzate thereof. By doing so, the β-diketone covers the fine particles, and the steric hindrance effect, and β
-The electric double layer formed by the outermost surface of the diketone being positively charged repels the fine particles to form a stable sol liquid.

In order to obtain this effect, the addition amount of Ti β-diketone complex, its salt or alkoxide, and their hydrolyzate is SnO ₂ : TiO ₂ = 1: 3 in terms of oxide.
0.1 to 1.0, preferably 1: 0.2 to 0.4. By dispersing this in a sol of conductive fine particles, the sol of conductive fine particles can be stabilized.

The β-diketone used in the present invention includes
Acetylacetone, trifluoroacetylacetone, benzoylacetone, hexafluoroacetone, benzoyltrifluoroacetylacetone, dibenzoylmethane, acetoacetic acid methyl ester, acetoacetic acid ethyl ester, acetoacetic acid butyl ester and the like can be mentioned.

The aqueous sol of the present invention can be used as it is, but it can also be used by dispersing or substituting it in an organic solvent in order to enhance the coating property on the substrate. As the hydrophilic organic solvent, alcohols such as methanol, ethanol, propanol and butanol, and ethers such as ethyl cellosolve can be arbitrarily used.

The liquid used in the present invention contains Si (O 2) as a binder in order to improve the adhesion strength and hardness of the film.
It is also possible to add a silicon compound such as R) _y · R _4-y (y = 3, 4, R: alkyl group). Further, various surfactants can be added to improve the wettability with the substrate. Further, a Ti compound can be further mixed to obtain a film having a high refractive index.

As a method of coating the sol solution synthesized above on the substrate, a conventionally used method, that is, a spin coating method, a dip coating method, a spray coating method or the like can be preferably used. It is also possible to apply spray coating to form irregularities on the surface, and also to provide an antiglare effect. Further, the antistatic film of the present invention may be spray-coated to provide a non-glare coat of silica coating having irregularities on the surface.

Similarly, on the antistatic film of the present invention,
A liquid containing a material having a low refractive index such as MgF ₂ or SiO ₂ may be coated so as to have an appropriate optical film thickness to form a low reflection antistatic film due to a multilayer interference effect.

As the substrate for forming the antistatic film of the present invention, various glass such as cathode ray tube panel, glass plate for copying machine, computer panel, clean room glass, front plate of display device such as CRT or LCD, and plastic. A substrate can be used.

The coating solution of the present invention can obtain a uniform film by drying at room temperature when a solvent having a low boiling point is used, but when a solvent having a high boiling point is used or when the strength of the film is desired to be improved, the coating solution is applied. The formed substrate is heated and / or irradiated with UV (ultraviolet).
The upper limit of the heating temperature is determined by the softening point of glass, plastic, etc. used for the substrate. Considering this point, the preferable temperature range is 100 to 500 ° C.

[0017]

The present invention will be further described below with reference to examples of the present invention, but the present invention is not limited thereto. The films obtained in the following Examples and Comparative Examples were evaluated for surface resistance of the film surface, haze, and pencil hardness under a load of 1 kg.

[Example 1] Sb-doped Sn having an average particle size of 60Å
A SnO ₂ sol liquid obtained by grinding O ₂ with a sand mill was diluted to 3 wt% with ethanol. (Liquid A) Add an aqueous hydrochloric acid solution to an ethanol solution of Ti (C ₅ H ₇ O ₂ ) ₂ (OC ₃ H ₇ ) _2.
8 mol ratio was added to Ti (C ₅ H ₇ O ₂ ) ₂ (OC ₃ H ₇ ) _{2 and the} mixture was stirred for 1 hour, and prepared so that the solid content concentration in terms of TiO ₂ was 3 wt%. (Liquid B)

The liquid A and the liquid B were mixed so that the ratio of the liquid A to the liquid B was 25: 9. A (C _{solution) Si (OC 2 H 5)} 4 in ethanol, hydrochloric acid aqueous solution was added 9mol ratio relative to _{Si (OC 2 H 5) 4} , is in terms of SiO ₂ solid content concentration 3w
It was adjusted to be t%. (Solution D) Solution C and Solution D were mixed in a ratio of Solution C: Solution D: 17: 8 by weight, and this solution was applied onto a 70 mmφ glass plate surface by a spin coating method at a rotation speed of 750 rpm for 5 seconds, and 200
Heat at 30 ° C. for 30 minutes.

[Example 2] Liquid A and liquid B were liquid A: liquid B =
The mixture was mixed at a 5: 1 weight ratio. (Solution E) The same operation as in Example 1 was carried out except that instead of the solution C, the solution E was used and mixed so that the solution E: solution D = 3: 2 weight ratio was obtained.

[0021] 1mol [Example 3] Ti (OC ₃ H _{7) 4} methyl acetoacetate in ethanol solution with respect to Ti (OC ₃ H _{7) 4}
After a specific addition and stirring for 1 hour, an aqueous hydrochloric acid solution was added at a ratio of 2 mol with respect to Ti (OC ₃ H ₇ ) ₄ and further stirred for 1 hour. (F
Liquid) Liquid D and liquid F were mixed at a ratio of D liquid: F liquid = 4: 1 by weight. (Solution G) The same operation as in Example 2 was carried out except that instead of the solution D, the solution G was used and mixed so that the solution E: solution G = 3: 2.

[Comparative Example] The same procedure as in Example 1 was carried out except that the solution A was used instead of the solution C.

Table 1 shows the evaluation results of the films obtained in Examples 1 to 3 and Comparative Example.

[0024]

[Table 1]

[0025]

According to the present invention, an excellent antistatic film can be efficiently provided by a simple method such as spraying, spin coating or immersing a substrate in a solution. Since the present invention is excellent in productivity and does not require a vacuum, the apparatus may be relatively inexpensive. In particular, it can be applied to a large-area substrate such as a panel face surface of a CRT and can be mass-produced, so that its industrial value is very high.

By adding at least one selected from β-diketone complexes of Ti, salts or alkoxides thereof, and hydrolysates thereof, conductive particles such as SnO ₂ are stably dispersed in the coating solution and are highly dispersed. A high-performance film is obtained.

Continued front page    (72) Inventor Keisuke Abe             1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa             Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Keiko Kubota             1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa             Asahi Glass Co., Ltd. Central Research Laboratory (72) Inventor Ken Kawari             1150 Hazawa-machi, Kanagawa-ku, Yokohama-shi, Kanagawa             Asahi Glass Co., Ltd. Central Research Laboratory

Claims (5)

[Claims] 1. A β-diketone complex of Ti, at least one selected from a salt or alkoxide thereof, and a hydrolyzate thereof, and conductive fine particles are dispersed or dissolved in a mixed solution of water and an organic solvent. A method for producing an antistatic film, which comprises applying the coating liquid to a substrate to produce the antistatic film. 2. The method for producing an antistatic film according to claim 1, wherein the coating liquid contains a silicon compound. 3. An antistatic film obtained by the method for producing an antistatic film according to claim 1. 4. A glass article having an antistatic film formed on a glass substrate by the method for producing an antistatic film according to claim 1. 5. A Braun tube having an antistatic film formed on the surface of the Braun tube by the method for producing an antistatic film according to claim 1.