JPH05323102A - Antireflection-antistatic film and its production - Google Patents

Abstract

PURPOSE:To obtain a film which can be formed in a large area in any shape and both of reflection and electrification of the coated body can be prevented by dispersing metal fine particles and/or oxide semiconductor fine particles in a porous glass. CONSTITUTION:Metal fine particles and/or oxide semiconductor fine particles are dispersed in a porous glass. Therefore, scattering of light due to the porous glass and reflection from the glass surface, especially when the glass has the higher refractive index, can be prevented, and electrification can be prevented by the conducting property of metal fine particles and/or oxide semiconductor fine particles dispersed in the porous glass. More preferably, by making a porous glass and porous oxide semiconductor in one body, reflection is prevented by scattering property of pores. The porous glass is SiO2, Al2O3, SiO2-Al2O3, which is transparent in a visible region and the reflectance can be decreased.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film for preventing light reflection and electrification and a method for producing the same. By applying it to a surface of a display, a solar cell, etc. The present invention relates to a coating capable of preventing reflection of light from the surface and a method for producing the coating.

[0002]

2. Description of the Related Art Reflection of light from the surface of a display such as a window glass of a metal, a cathode ray tube, a liquid crystal, or electroluminescence (EL) causes eye fatigue, and the surface is charged with dust and dust. A technique for preventing reflection and charging of light from the display surface has attracted attention because it causes adhesion.

As a conventional technique in this field, there is one in which a transparent conductive film is formed on the surface of the glass or plastics in order to prevent them from being charged. In this method, (1) a very thin film such as Au or Pd is formed on the surface by sputtering, (2) a semiconductor thin film such as In ₂ O ₃ is formed on the surface by sputtering, or chemical vapor deposition. Further, there are (3) various conductive polymers formed on the surface by a coating method.

[0004]

The method of manufacturing the antistatic film according to the above method has the following problems. (1) In the case of a metal thin film: A vacuum device is required to produce a thin film, and it is difficult to form a coating film having a large area. Further, it is difficult to coat a substance having a complicated shape such as a curve. That is, a large vacuum device and a large metal target are required, but it is extremely difficult to make the diameter 10 cm or more in consideration of the uniformity of the formed film, and the sputtering method forms the film only on a flat surface. Because you cannot do it.

(2) In the case of a semiconductor thin film: A vacuum device is required to produce a thin film as in the case of a metal thin film, and it is difficult to form a large-area coating film for the same reason as above. Also, it is difficult to coat a substance having a complicated shape such as a curved shape. Further, in such a sputtering method, it is not easy to control the composition of the semiconductor because there is a difference in the sputter evaporation rate of the elements constituting the semiconductor.

(3) In case of conductive polymer: A coating film can be easily formed by a coating method or a dip coating method. However, since it has poor moisture resistance, it lacks long-term stability and the film gradually devitrifies over time.

According to the present invention, it is possible to easily form a coating film composed of porous glass and fine metal particles or an oxide semiconductor on a large area without taking a shape, and to reflect light from the coated material. An object of the present invention is to provide a coating film capable of simultaneously preventing the electrostatic charge and a method for producing the same.

[0008]

In order to solve the above problems, the reflection-antistatic film of the present invention is a reflection-antistatic film in which metal fine particles and / or oxide semiconductor fine particles are dispersed in porous glass. Consists of.

Further, the reflection-antistatic film of the second invention.
Is a mixture of porous glass and a porous oxide semiconductor?
It consists of an integrated object. Reflection of any of the above inventions
-In the antistatic film, the porous glass is SiO 2. ₂, A
l₂O₃, SiO₂-Al₂O₃Or SiO₂-Ti
O₂It is preferably a porous glass selected from

In the reflection-antistatic film of the first invention, the fine metal particles are Au, Pd, Pt and Cu.
It is preferably at least one kind of metal fine particles selected from the following.

Further, the reflection of the first or second invention-
In the antistatic film, the oxide semiconductor is SnO ₂ , In
₂ O ₃ , V ₂ O ₅ , Sb doped SnO ₂ , Sn doped I
It is preferably at least one oxide semiconductor selected from n ₂ O ₃ and TiO ₂ .

Next, the invention of a method for producing a reflection-antistatic film in which fine metal particles are dispersed in a first porous glass is
It consists of hydrolyzing and heat-treating a mixed solution of a metal alkoxide, which is a raw material of porous glass, and a metal salt which precipitates metal fine particles when reduced.

The invention of a method for producing a reflection-antistatic film comprising a second mixture of a porous glass and a porous oxide semiconductor is a metal alkoxide, which is a raw material for the porous glass, and a porous material. A mixed solution of a metal alkoxide, which is a raw material of another oxide semiconductor, is hydrolyzed and heat-treated.

The invention of a method for producing a reflection-antistatic film comprising oxide semiconductor fine particles dispersed in a third porous glass is a metal alkoxide which is a raw material of the porous glass, and is heated and oxidized. It consists of hydrolyzing and heat-treating a mixed solution with a metal salt solution to be an oxide semiconductor.

[0015]

In the reflection-antistatic film of the present invention, since the metal fine particles and / or the oxide semiconductor fine particles are dispersed in the porous glass, light scattering by the porous glass and
In particular, the larger the refractive index of the glass is, the more it is possible to prevent the reflection of light from the glass surface, and the electrical conductivity of the metal fine particles and / or the oxide semiconductor dispersed and carried in the porous glass material makes it possible to prevent the charging. ..

Further, the reflection-antistatic film of the second aspect of the present invention is an integrated product composed of a mixture of porous glass and a porous oxide semiconductor, so that the porous glass and the porous oxide semiconductor are formed. Due to the scattering of light by the porosity of
It is possible to prevent the reflection of light and prevent the electrification due to the conductivity of the oxide semiconductor component.

In the above structure, the porous glass may be SiO ₂ , Al ₂ O ₃ , SiO ₂ -Al ₂ O ₃ or S.
By using a porous glass selected from iO ₂ —TiO ₂ , these glass components are substances that are transparent in the visible region, and have a larger refractive index than ordinary borosilicate glass, and thus have a higher reflectance due to the difference in refractive index. It is preferable because it can be made small.

In the above structure, the metal fine particles are A
By using at least one kind of metal fine particles selected from u, Pd, Pt, and Cu, these metals can be easily made into fine particles and have high electrical conductivity, and therefore, the antireflection property can be achieved without significantly lowering the transparency. It is preferable because the antistatic property can be achieved.

Further, the oxide semiconductor having the above structure is SnO.
_{2, In 2 O 3, V} 2 O 5, Sb de - flop SnO _2, Sn
By using at least one oxide semiconductor selected from doped In ₂ O ₃ and TiO _2, since these oxide semiconductors are transparent in the visible region and have electrical conductivity, the transparency is improved. It is preferable because the antireflection property and the antistatic property can be achieved without lowering.

Next, the first method for producing a reflection-antistatic film of the present invention is that the porous glass is prepared by hydrolyzing and heat-treating a metal alkoxide as a raw material of the porous glass and a metal salt as fine metal particles. Metal particles can be dispersed uniformly in the material, there is no agglomeration of metal particles even in the raw material preparation stage, and it is possible to disperse the metal particles uniformly at low temperature. The prevention film can be easily obtained.

In the second method for producing a reflection-antistatic film of the present invention, a mixed solution of a metal alkoxide as a raw material for porous glass and a metal alkoxide as a porous oxide semiconductor is hydrolyzed and heat treated. By doing so, it is possible to form an integral mixture of porous glass and a porous oxide semiconductor, and since both raw materials are metal alkoxides, it is possible to mix the raw materials uniformly, and the reflectance is low and the conductivity is low. The provided antistatic film can be easily obtained.

Further, in the third method for producing a reflection-antistatic film of the present invention, a mixed solution of a metal alkoxide which becomes porous glass and a metal salt solution which becomes heated and oxidized to become oxide semiconductor fine particles is hydrolyzed. By decomposing and heat-treating, oxide semiconductor fine particles can be configured to be dispersed in porous glass, and even in this case, there is no aggregation of metal salt in the raw material preparation stage, and the oxide semiconductor is uniform at low temperature. Can be dispersed, and an antistatic film having a low reflectance and conductivity can be easily obtained.

[0023]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the present invention, the porous glass produced by the gel method of metal alkoxide is chemically stable, optically transparent in a wide wavelength range, and has a larger refractive index than conventional borosilicate glass, SiO ₂ , Al. ₂ O ₃ ,
SiO ₂ -Al ₂ O ₃ or glass such as SiO ₂ -TiO ₂ are preferred.

Typical examples of metal alkoxides used as raw materials for porous glass include lower alkoxides of silicon such as tetramethoxysilane and tetraethoxysilane, and lower alkoxides of aluminum such as trimethoxyaluminum and trisecondary butoxyaluminum. Alkoxides, lower alkoxides of tin such as tetramethoxytin and tetraisopropoxide tin, lower alkoxides of titanium such as tetramethoxytitanium and tetrapropoxytitanium, lower alkoxides of zinc such as dimethoxyzinc and diethoxyzinc, trimethoxy Examples thereof include lower alkoxides of indium such as indium and triethoxyindium. As a dispersion medium of such alkoxide, water and / or lower alcohol such as methanol and ethanol or ethylene glycol is used, and as a hydrolysis catalyst, an acid such as hydrochloric acid or ammonia, an alkali is usually used. To use. The dispersion medium solution of the alkoxide is not particularly limited, but usually a solution of 0.1 to 5 mol% is preferably used, and the hydrolysis catalyst is usually 0.01 to 0.5 mol with respect to the metal alkoxide. % Is preferably used.

In the present invention, when the metal alkoxide sol is gelled, it is effective to add a catalyst for hydrolysis usually at room temperature to 70 ° C. .. The metal fine particles dispersed in the present invention are Au, P
d, Pt, Cu, etc. are preferable, and the average radius of the metal fine particles used here is preferably 10-100 nm from the viewpoint of less coloring and uniform dispersion. Further, it is preferable to use the metal fine particles in an amount of about 0.01 to 5 wt% with respect to the porous glass from the viewpoint of transparency and antistatic property.

Examples of the raw material of the metal fine particles include chloroauric acid, palladium chloride, which has a relatively high solubility in water,
Chloroplatinic acid and cupric nitrate are preferred. These metal salts are usually used in the form of an aqueous solution. The concentration of the metal salt in the aqueous solution is not particularly limited, but is usually 0.1-5 mo.
About 1% is preferable.

Further, as an oxide semiconductor used in the present invention
For example, SnO₂, In₂O ₃, V₂O_Five, Sb
Dope SnO₂, Sn Dope In₂O₃And TiO₂
Etc. are preferred, and the raw materials are stannic chloride and indium nitrate.
, Ammonium metavanadate, antimony pentachloride,
Titanium tetrachloride is preferred. Also used in the form of alkoxide
If it is present, for example, Sn (OCH₃)_Four, In (O
CH₃)₃, Sb (OCH₃)₃, VO (OCH₃)₃
Are easily available, but are not always limited to these
It is not something that will be done. The dispersion medium depends on the compound used.
Water and / or methanol, ethanol
Such as lower alcohol or ethylene glycol
It is used and is not particularly limited, but usually 0.1 to
A 5 mol% solution is preferably used.

When the oxide semiconductor is used as fine particles deposited in porous glass and used, the average radius is 10 −.
100 nm is preferred. This can be controlled by adjusting the heat treatment temperature and heat treatment time of the formed film. Further, it is preferable that the oxide semiconductor fine particles are used in an amount of about 0.1 to 50 wt% with respect to the porous glass from the viewpoint of transparency and antistatic property.

Next, the coating film of the present invention in which the metal fine particles are dispersed in the porous glass is hydrolyzed by mixing the metal alkoxide, which is the raw material of the porous glass, and the metal salt to be the metal fine particles. It is produced by heat treatment. Gelation can be promoted by heating after adding the hydrolysis catalyst.

Further, the coating film composed of an integrated product made of a mixture of the above-mentioned porous glass and a porous oxide semiconductor is obtained by hydrolyzing and heat-treating the above-mentioned respective metal alkoxide mixed solutions as raw materials. It can be made. In this case, the amount of the produced porous oxide semiconductor is 0.1 to 50 relative to the produced porous glass.
It is preferable to adjust the mixing ratio of the raw materials so as to be about wt%. Furthermore, the reflection-antistatic film formed by dispersing oxide semiconductor fine particles in the porous glass is a metal that is the raw material of the porous glass described above. It is prepared by mixing an alkoxide and a metal salt which is a raw material of oxide semiconductor fine particles, and then hydrolyzing and heat treating the mixture. Gelation can be promoted by heating after adding the hydrolysis catalyst. The average radius of the produced oxide semiconductor fine particles is preferably 10-100 nm, and this can be controlled by adjusting the heat treatment temperature and the heat treatment time of the produced film.

The film thickness of the reflection-antistatic film of the present invention is
From the viewpoint of having a high antireflection effect and strengthening the adhesive force with the base material, it is preferably about 0.1 to 0.3 μm. Specific examples of the present invention will be described below. Example 1 Gold colloid prepared by the following method was added to a sol having the composition shown in Table 1 so as to be 0.2% by volume, and the surface of the cathode ray tube was immersed in this solution and dried at room temperature. A film was formed on the film, and the film was dried at a temperature of 60 ° C. for 5 hours and then gelled. The gold colloid was prepared by adding an aqueous solution of chloroauric acid (1 g-Au / l) to distilled water and boiling, then adding an aqueous solution of sodium citrate (1 wt%) and boiling.
Further polyvinyl alcohol was added. In addition to sodium citrate, hydrogen, hydrazine, sodium borohydride, etc. could be used for the reduction of metal ions to metals. Further, it was possible to stabilize the colloid by protecting the gold colloid using polyvinylpyrrolidone in addition to polyvinyl alcohol. The average radius of the gold colloid was 30 nm. The electrical resistance value of the gold fine particle-dispersed SiO ₂ glass produced in this way is 10 ⁴ to 10 ⁵
It was Ω / □. The thickness of the formed film is 200 nm
And the translucency was 88%.

The cathode ray tube according to this example had a reflectance of 80% or more smaller than that of a conventional cathode ray tube having no coating film, and the adhesion of dust was extremely small.
Even if platinum, palladium, or copper was used instead of gold in the above process, a porous SiO ₂ glass in which the respective metal fine particles were dispersed could be produced, and the same effect as that of gold could be obtained. Further, even if porous Al ₂ O ₃ was used instead of porous SiO ₂ glass, almost the same effect as that of SiO ₂ was obtained.

[0033]

[Table 1]

Example 2 A sol having the composition shown in Table 2 was prepared, and the surface of the cathode ray tube was dipped in this solution and dried at room temperature to form a film on the surface of the cathode ray tube, which was further dried at a temperature of 60 ° C. for 5 hours. It gelated afterwards. SnO ₂ -Si produced in this way
The electric resistance value of the O ₂ —TiO ₂ porous film is 10 ⁵ to 1
It was 0 ⁶ Ω / □. The thickness of the formed film is 200
nm, and the light transmittance was 90%.

The cathode ray tube according to this example had a reflectance of 82% or more smaller than that of a conventional cathode ray tube having no coating film, and the adhesion of dust was extremely small.

[0036]

[Table 2]

Example 3 A sol having the composition shown in Table 3 was prepared and the surface of the cathode ray tube was cleaned.
Of the cathode ray tube by immersing it in the solution of
Form a film on the surface and dry at 60 ℃ for 5 hours
It gelated afterwards. Sn doped In produced in this way
₂O₃-SiO ₂-TiO₂Electric resistance of porous film
Is 10^Five-10⁶It was Ω / □. Also, the formed film
Had a thickness of 300 nm and a translucency of 90%.

The cathode ray tube according to this example had a reflectance of 78% or more smaller than that of a conventional cathode ray tube having no coating, and the adhesion of dust was extremely small.

[0039]

[Table 3]

Example 4 A sol having the composition shown in Table 4 was prepared, and the surface of the cathode ray tube was immersed in this solution and dried at room temperature to form a film on the surface of the cathode ray tube, which was further dried at a temperature of 60 ° C. for 5 hours. It gelated afterwards. SnO ₂ -Si produced in this way
The electric resistance value of the O ₂ —TiO ₂ porous film is 10 ⁴ to 1
It was 0 ⁵ Ω / □. The thickness of the formed film is 200
nm, and the light transmittance was 90%. The average particle size of the SnO ₂ fine particles was 60 nm.

The cathode ray tube according to this example had a reflectance of 69% or more smaller than that of a conventional cathode ray tube having no coating film, and the adhesion of dust was extremely small.

[0042]

[Table 4]

Example 5 A sol having the composition shown in Table 5 was prepared, and the surface of the cathode ray tube was dipped in this solution and dried at room temperature to form a film on the surface of the cathode ray tube, and further dried at a temperature of 60 ° C. for 5 hours. It gelated afterwards. The electrical resistance value of the SiO ₂ —TiO ₂ porous coating in which the V ₂ O ₅ fine particles thus prepared were dispersed was 10 ⁵ to 10 ⁶ Ω / □. The thickness of the formed film was 200 nm, and the translucency was 90%.
The average particle size of the V ₂ O ₅ fine particles was 50 nm.

The cathode ray tube according to this example had a reflectance of 81% or more smaller than that of a conventional cathode ray tube having no coating film, and the adhesion of dust was extremely small.

[0045]

[Table 5]

Example 6 A coating film was formed on the surface of a solar cell module for photovoltaic power generation by the same method using the same sol solution as in Examples 1 and 3, and the solar cell without this coating film was formed. Compared to the module, the reflected light was small and the adhesion of dust was extremely small, so that the conversion efficiency of the solar cell could be improved by 0.8%.

[0047]

INDUSTRIAL APPLICABILITY The reflection-antistatic film in which metal fine particles and / or oxide semiconductor fine particles are dispersed in the porous glass of the present invention can be a reflection-antistatic film excellent in long-term stability. In addition, it is possible to easily form a coating on the surface of a substance having a complicated shape, and it is possible to provide a reflection-antistatic film capable of easily coating a large-area surface.

Further, a reflection formed of an integrated product of a mixture of the porous glass of the present invention and a porous oxide semiconductor.
The antistatic film is excellent in transparency and can be a reflection-antistatic film having excellent long-term stability, and can easily form a coating on the surface of a substance having a complicated shape. It is possible to provide a reflection-antistatic film capable of easily covering a large area surface.

The porous glass is made of SiO ₂ , Al ₂ O.
_A preferred embodiment of the porous glass selected from ₃ , SiO ₂ —Al ₂ O ₃ or SiO ₂ —TiO ₂ can provide a reflection-antistatic film having good transparency and a smaller reflectance.

The dispersed metal fine particles are Au, Pd,
By using at least one kind of metal fine particles selected from Pt and Cu as a preferable mode, the antireflection property and the antistatic property can be achieved without significantly lowering the transparency, which is preferable.

Further, the above oxide semiconductor is replaced with SnO ₂ , I
By adopting a preferred embodiment of at least one oxide semiconductor selected from n ₂ O ₃ , V ₂ O ₅ , Sb doped SnO ₂ , Sn doped In ₂ O ₃ and TiO ₂ ,
It is preferable because the antireflection property and the antistatic property can be achieved without lowering the transparency.

Next, according to the first method for producing a reflection-antistatic film of the present invention, the metal fine particles can be uniformly dispersed in the porous glass, and the metal fine particles do not aggregate even in the raw material preparation stage. Further, it is possible to disperse the metal fine particles uniformly at a low temperature, it is possible to form a reflection-antistatic film having excellent transparency and excellent long-term stability, and the surface of a substance having a complicated shape can be easily obtained. It is also possible to form a coating on the surface, and it is possible to easily coat a large area surface.

Further, according to the second method for producing a reflection-antistatic film of the present invention, since both the raw materials of the porous glass and the porous oxide semiconductor are metal alkoxides, they are uniform. It is possible to mix the raw materials, it is possible to obtain a reflection-antistatic film having excellent transparency and excellent long-term stability, and it is possible to easily form a coating on the surface of a substance having a complicated shape. Moreover, a large-area surface can be easily coated, and an antistatic film having low reflectance and conductivity can be easily obtained.

Further, the third reflection-antistatic film of the present invention is prepared by hydrolyzing and heat-treating a mixed solution of a metal alkoxide which becomes porous glass and a metal salt solution which is heated and oxidized to become oxide semiconductor fine particles. The manufacturing method is a reflection-antistatic film which has no aggregation of metal salts in the raw material preparation stage, can disperse the oxide semiconductor uniformly at low temperature, has excellent transparency, and has excellent long-term stability. It is possible to easily form a coating on the surface of a substance having a complicated shape, and also it is possible to easily coat a large-area surface, which has low reflectance and conductivity, and which is antistatic. The membrane can be easily obtained.

Claims (8)

[Claims] 1. A reflection-antistatic film comprising metal fine particles and / or oxide semiconductor fine particles dispersed in a porous glass. 2. A reflection-antistatic film which is an integrated product composed of a mixture of porous glass and a porous oxide semiconductor. 3. The porous glass is SiO 2.₂, Al₂O₃,
SiO₂-Al₂O ₃Or SiO₂-TiO₂Select from
Either of claim 1 or 2 which is a porous glass that has been exposed.
The antireflection-antistatic film described in 1. 4. The fine metal particles are Au, Pd, Pt and C.
The reflection-antistatic film according to claim 1, which is at least one kind of metal fine particles selected from u. 5. The oxide semiconductor is SnO ₂ , In ₂ O ₃ ,
V ₂ O _5, Sb de - flop SnO _2, Sn-de - flop In ₂ O _3
3. The reflection according to claim 1, which is at least one kind of oxide semiconductor selected from TiO ₂ and TiO _2.
Antistatic film. 6. A method of hydrolyzing and heat treating a mixed solution of a metal alkoxide, which is a raw material for porous glass, and a metal salt, which precipitates fine metal particles when reduced, and the fine metal particles are dispersed in the porous glass. And a method for producing a reflection-antistatic film. 7. A porous glass and a porous glass obtained by hydrolyzing and heat-treating a mixed solution of a metal alkoxide as a raw material for porous glass and a metal alkoxide as a raw material for a porous oxide semiconductor. The method for producing a reflection-antistatic film according to claim 2, wherein the reflection-antistatic film is composed of an integrated product of a mixture with an oxide semiconductor. 8. Oxidation in a porous glass by hydrolyzing and heat-treating a mixed solution of a metal alkoxide, which is a raw material of the porous glass, and a metal salt solution, which is heated and oxidized to be an oxide semiconductor. A method for producing a reflection-antistatic film in which fine semiconductor particles are dispersed.