JPH05107403A - High refractivity conductive film or low reflective anti-static film and manufacture thereof - Google Patents

Abstract

PURPOSE:To provide a highly conductive optical film by coating a substrate thereover with a solution containing conductive microparticles and Ti salt, and thereafter by heating the substrate or irradiating ultraviolet radiation to the substrate. CONSTITUTION:A substrate is coated thereover with a solution containing conductive microparticles and Ti salt, and thereafter, it is heated or irradiated thereto with ultraviolet radiation so as to form a high refractive conductive film. In a method in which a high refractive film and a low refractive film are successively laminated on a substrate so as to produce an anticharge low reflective film, a solution containing conductive micro particles and Ti salt is applied over a substrate, and then is heated or irradiated thereto with ultraviolet radiation so as to form the high refractive film. In this case, SnO2 microparticles doped with Sb or F, conductive titanium oxide microparticles, ITO (In2O3 doped with Sn) micro particles are used as the conductive microparticles. Further, titanium oxide subjected to reduction or titanium oxide doped with pentra-valered metal ions are also usable.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive high refractive index film and an antistatic low reflection film applied to the surface of a substrate such as a cathode ray tube panel, and a method for producing them.

[0002]

2. Description of the Related Art Needless to say, the coating method of a low-reflection film has been used in conventional optical equipment as well as consumer equipment, especially T
V. Many studies have been conducted on cathode ray tubes (CRTs) for computer terminals. A conventional method is disclosed in, for example, JP-A-61-11893.
As described in No. 1, in order to have an antiglare effect on the surface of the cathode ray tube, a method of adhering a SiO ₂ layer having fine irregularities on the surface or etching the surface with hydrofluoric acid to provide irregularities has been used. However, these methods are called non-glare processing that scatters external light, and there is a limit to the reduction of reflectance because it is not a method of essentially providing a low reflection layer, and it is also a cause of lowering resolution in cathode ray tubes. It was

Many studies have been conducted on the provision of an antistatic film, for example, as described in JP-A-63-76247.
A method has been adopted in which the surface of the cathode ray tube panel is heated to about 350 ° C and a conductive oxide layer such as tin oxide or indium oxide is provided by the CVD method.

[0004]

However, in this method, in addition to the high cost of the apparatus, the fluorescent substance in the cathode ray tube may fall off because the cathode ray tube is heated to a high temperature.
There was a problem such as a decrease in dimensional accuracy. In addition, F or Sb-doped tin oxide or Sn-doped indium oxide is the most common material used for the conductive layer. There is a drawback that a low resistance film cannot be obtained.

Further, when an alkoxide is used as a starting material for Ti, a chelating agent is indispensable in order to control the hydrolysis rate. Generally, a chelating agent has a high boiling point (140 ° C. for acetylacetone, methylacetoacetate). (171.7 ℃), and since it is chelated to Ti, the low temperature heating at 120 ℃ left an organic component in the film, which unavoidably reduced the film strength.

It is also known that conductive fine particles are added to the above-mentioned non-glare film to impart antistatic property, but there is a limit to reduction of reflectance, and fine particles are present on the surface. Therefore, there is a defect that the film strength is insufficient.

[0007]

DISCLOSURE OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks of the prior art, that is, a conductive high refractive index film and a film having a high refractive index and high conductivity. It is an object of the present invention to newly provide a high-performance antistatic low-reflection film consisting of two layers in which a film having a low refractive index is disposed on the substrate side on the air side, and a manufacturing method thereof.

That is, the present invention has been made to solve the above-mentioned problems, and after applying a liquid containing conductive fine particles and a Ti salt on a substrate, the conductive material is heated and / or irradiated with ultraviolet rays to make it conductive. A method of manufacturing a conductive high refractive index film, which comprises manufacturing a high refractive index film, and an antistatic low reflection film composed of two layers by sequentially laminating a high refractive index film and a low refractive index film on a substrate. A method for producing a high-refractive-index film, which comprises producing a high-refractive-index film by applying a liquid containing conductive fine particles and a Ti salt onto a substrate, and then heating and / or irradiating with ultraviolet rays. The present invention provides a method for manufacturing an anti-reflective film.

The conductive high refractive index film used in the present invention is obtained by using a solution containing a liquid containing conductive fine particles and TiCl ₄ . The conductive fine particles were doped with Sb or F.
SnO ₂ particles, conductive titanium oxide particles, ITO (Sn
Examples include fine particles of In ₂ O ₃ ). Sb dope
SnO ₂ fine particles (substitution of pentavalent Sb in substitutional solid solution at the Sn lattice position of SnO ₂ ) are low resistance and easy to form ultrafine particles of 100 Å or less, and thus can be used relatively favorably. Fine particles of F-doped SnO ₂ (F ions in which substitutional solid solution of F ions at the 0 lattice position of SnO ₂ ) have low resistance and can be suitably used.

Further, reduction-treated titanium oxide or titanium oxide doped with pentavalent metal ions can be preferably used. For the reduction treatment, an inert gas, N ₂ gas, H ₂ gas or a mixed gas thereof can be used. or,
It is preferable to use Nb, Sb, Ta or the like as the pentavalent metal ion, and it is possible to dope in a reducing atmosphere.

The dispersion medium and dispersion method of the conductive fine particles are not particularly limited, and various kinds can be used. For example, by adding conductive fine particles to an organic solvent such as water or alcohol,
Adjust pH by adding acid or alkali, colloid mill,
It can be obtained by dispersing with a commercially available pulverizer such as a ball mill, a sand mill, a homomixer or ultrasonic waves.

Further, it is preferable to put the sol liquid in which the conductive fine particles are dispersed in a closed container such as an autoclave and heat and pressurize (hereinafter referred to as hydrothermal treatment) because a film having a lower resistance can be obtained. The treatment temperature is preferably 200 ° C. or higher, more preferably 300 ° C. or higher. The pressure at this time is 200
It is 15 atm at ℃ and 85 atm at 300 ℃. Moreover, it is preferable to treat for 1 hour or more. Also, this dispersion contains alcohol,
It can be optionally diluted with water or the like before use.

Since the sol liquid before the hydrothermal treatment needs to have fluidity so that it can be homogenized, the solid content is preferably about 5%. Since the solid content is too much solvent, the dispersion is taken out after cooling and concentrated using an evaporator or the like to obtain a dispersion of conductive fine particles.

Although the mechanism of lowering the resistance by hydrothermal treatment is not always clear, by conducting hydrothermal treatment on the conductive fine particles, the hydroxyl groups on the surface of the fine particles are firmly attached or the hydrated water molecules are strongly coordinated. It is considered that this is because the interaction with TiCl ₄ introduced as the matrix of the conductive high refractive index film is partially suppressed, and the conductive fine particles are brought into contact with each other during firing.

The average particle size of the conductive fine particles in the dispersion is 300 n
It is preferably m or less. Preferably 40Å
It is preferably about 700 Å, particularly preferably about 40 Å to 200 Å. If it is smaller than 40Å, the contact between the conductive particles becomes insufficient, and it may be difficult to obtain a desired resistance value (10 ¹⁰ Ω / □ or less). If it exceeds 700Å, the film strength will be insufficient. Further, this dispersion can be diluted with alcohol, water or the like.

In order to introduce TiO ₂ into the above-mentioned dispersion liquid of conductive fine particles as a matrix of the conductive high refractive index film.
A solution containing Ti salt is added to obtain a coating solution. In particular,
A chloride represented by TiCl ₄ is dissolved in an organic solvent such as alcohol, and p containing water and / or a counter ion of Cl is added.
It is preferable that the H-adjusting liquid is added and partially hydrolyzed, and then added to the dispersion liquid. At this time, the Ti salt is blocked by Cl, polymerization does not proceed extremely rapidly, and it is not necessary to add a chelating agent for controlling the hydrolysis rate.

Further, in order to improve the adhesion strength and hardness of the conductive high refractive index film, it is preferable to add Si alkoxide to the coating solution. Specifically, Si (OR) _m R _n (m = 1 to 4,
n = 0 to 3, R = C _{1 to} C ₄ alkyl group)
A solution containing Si alkoxide or a partial hydrolyzate is added to the coating solution.

When conductive SnO ₂ fine particles are used as the conductive fine particles, the preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ Ω / □ or less is SnO ₂ : (TiO _{2 in} terms of oxide.
+ SiO ₂ ) = 25: 75 to 90:10. The composition ratio of TiO ₂ and SiO ₂ affects the refractive index and the film strength of the conductive high refractive index layer, and a weight ratio range of TiO ₂ : SiO ₂ = 100: 0 to 10:90 is preferable. When the amount of SiO ₂ is large, the film strength is improved but the refractive index is lowered. Therefore, the composition may be appropriately determined in consideration of these.

In summary, in the present invention, when SnO ₂ fine particles are used, in a conductive high refractive index film, SnO ₂ is contained in the solid content of the film (as oxide) in order to impart conductivity.
In order to obtain a refractive index of at least wt% or 1.60 or more, 5 wt% of TiO ₂ obtained from chloride in the solid content of the film (as oxide)
% Or more is preferable.

As conductive fine particles, TiO _x (x: 1.6 to 1.9
) When using fine particles, a preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ Ω / □ or less is TiO _x (x: 1.6 to 1.9) in terms of oxide, which is introduced as conductive particles. ) :( TiO ₂ + SiO ₂ ) = 20: 80 to 90:10.

As conductive titanium oxide fine particles, TiO _x (x:
When 1.6 to 1.9) fine particles are used, the preferable composition range of the conductive high refractive index film is the TiO _x (x: 1.6 to 1.9) fine particles in the solid content (converted to oxide) of the film to impart conductivity. To obtain a refractive index of 20 wt% or more, and 1.60 or more,
TiO ₂ obtained from the alkoxide is preferably 3 wt% or more.

When Nb-doped TiO ₂ fine particles are used as the conductive fine particles, the preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ Ω / □ or less is Nb-doped in terms of oxide.
A weight ratio range of TiO ₂ : (TiO ₂ + SiO ₂ ) = 18: 82 to 90:10 can be mentioned.

Nb-doped Ti as conductive titanium oxide fine particles
When O ₂ fine particles are used, the preferable composition range of the conductive high refractive index film is 18% by weight or more of Nb-doped TiO ₂ fine particles, and 1.60 in the solid content of the film (in terms of oxide) in order to impart conductivity.
Obtained from alkoxide to obtain the above refractive index
It is preferable that TiO ₂ is 3 wt% or more.

When ITO (Sn-doped In ₂ O ₃ ) fine particles are used as the conductive fine particles, a preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ Ω / □ or less is calculated in terms of oxide. ITO: (TiO ₂ + SiO ₂ ) = 15: 85 to 90:10, and the composition ratio of TiO ₂ and SiO ₂ affects the refractive index and film strength of the conductive high refractive index layer and is in a preferable range. Includes a weight ratio range of TiO ₂ : SiO ₂ = 100: 0 to 10:90.

When the conductive ITO fine particles are used, the preferable composition range of the conductive high refractive index film is that the ITO fine particles are 15 in the solid content (as oxide) of the film in order to impart conductivity.
In order to obtain a refractive index of wt% or more and 1.60 or more, it is preferable that the TiO ₂ obtained from the alkoxide be 5 wt% or more.

The coating liquid for forming the conductive high refractive index film is
The total solid content is preferably 0.1 to 30 wt% with respect to the solvent.

In the present invention, the substrate on which the conductive low refractive index film or antistatic low reflection film is formed is not particularly limited, and soda lime silicate glass, aluminosilicate glass, borosilicate glass is used according to the purpose. ,
Glass such as lithium aluminosilicate glass and quartz glass, single crystals such as steel balls, translucent ceramics such as magnesia and sialon, and plastics such as polycarbonate can be used.

There are various possible methods for coating the substrate, such as a spin coating method, a dipping method, a spraying method, a roll coater method and a meniscus coater method. In particular, the spin coater method is excellent in mass productivity and reproducibility and can be preferably used. .. By this method, a film having a thickness of about 100Å to 1 μm can be formed.

In the present invention, the above-mentioned conductive fine particle dispersion liquid is coated with a coating liquid containing TiCl ₄ and preferably Si alkoxide and then heated or exposed to ultraviolet rays, specifically, a wavelength of 180 to 490 nm. The high refractive index film having electroconductivity is formed by irradiating it with ultraviolet light or irradiating with ultraviolet light and heating.

In the present invention, the antistatic low reflection film can be formed by utilizing the interference of light. For example, when the substrate is glass (refractive index n = 1.52), n (conductive high refractive index film) /
The reflectance can be reduced most by forming a low refractive index film having a ratio of n (low refractive index film) of about 1.23.

The outermost low refractive index film of the antistatic low reflection film consisting of two layers is formed by using at least one solution selected from a solution containing MgF ₂ sol and a solution containing Si alkoxide. To do. In terms of the refractive index, MgF ₂ is the lowest among the materials, and it is preferable to use a solution containing MgF ₂ sol to reduce the reflectance, but SiO ₂ is mainly used in terms of film hardness and scratch resistance. Membranes of component are preferred.

Various liquids can be adopted as the liquid containing the Si alkoxide for forming the low refractive index film.
R) _m R _n (m = 1 to 4, n = 0 to 3, R = C _{1 to} C ₄ alkyl group), a liquid containing a Si alkoxide or a partial hydrolyzate. For example, a monomer or polymer of silicon ethoxide, silicon methoxide, silicon isopropoxide or silicon butoxide can be preferably used.

Si alkoxides are alcohols, esters,
It can be used by dissolving it in ether or the like, or can be used by adding hydrochloric acid, nitric acid, acetic acid or an aqueous ammonia solution to the solution to hydrolyze it. The Si alkoxide is preferably contained in the solvent in an amount of 1 to 30 wt%.

In addition to the above-mentioned solutions, the solution for forming such a low refractive index film may further include, as a binder, alkoxides such as Zr, Ti and Al, or a portion thereof in order to improve the strength of the film. If a hydrolyzate is added and one of ZrO ₂ , TiO _{2, and} Al ₂ O ₃ , or a mixture of at least two of these, or a composite is precipitated simultaneously with MgF ₂ , SiO ₂ , MgF ₂ and SiO _2. good. Alternatively, various surfactants may be added to improve the wettability with the substrate. For example, as the surfactant to be added, linear sodium alkylbenzene sulfonate, alkyl ether sulfate, etc. may be mentioned.

Further, as described above, the solution containing various Zr, Ti, Al, and Sn compounds may be added to the solution for the low refractive index film used in the present invention, but especially Zr acetylacetone alkoxide Zr (C _{The use of 5} H ₇ O ₂ ) _n (OR) _m is preferable because the stability of the coating solution is improved.

Zr (C ₅ H ₇ O ₂ ) _n (OR) _m (where n + m =
4, n = 1 to 3, m = 1 to 3, R = C _{1 to} C ₄ alkyl group) can be added as they are to the MgF ₂ sol or the Si alkoxide solution, or an alcohol, ether, ester, It can also be used by dissolving it in an aromatic hydrocarbon or the like.
When the MgF ₂ sol or Si alkoxide liquid and the liquid containing Zr acetylacetone alkoxide are mixed, the final total solid content is preferably in the range of 0.1 to 5.0 wt% in terms of oxide. Further, the weight ratio of MgF ₂ and SiO ₂ can be arbitrarily changed,
The amount of ZrO ₂ added is preferably in the range of 0.05 to 0.2 weight ratio with respect to SiO ₂ .

As the coating method of the liquid for forming the low refractive index film on the conductive high refractive index film, various methods such as the spin coater method are preferable as in the coating method of the conductive high refractive index film. Can be adopted.

After applying the liquid for forming the low-refractive index film, the low-refractive index film is formed by irradiating ultraviolet rays or heating, or irradiating ultraviolet rays and heating sequentially.

The conductive high refractive index film in the present invention is made of TiCl ₄
It has a high refractive index because it contains TiO ₂ formed from
For example, when applied to a λ / 2-λ / 4 or λ / 4-λ / 4 film having a two-layer structure, a preferable combination is a substrate / SnO ₂ —TiO ₂
-SiO ₂ / MgF ₂ -SiO _2, the substrate _{/ SnO 2 -TiO 2 -SiO 2 /} SiO 2 and the like.

The method for producing a conductive high refractive index film and a low reflection antistatic film of the present invention can be applied to the production of a multilayer conductive low reflection film. As the structure of the multilayer low-reflection film having the antireflection property, the wavelength to be antireflection is set to λ, and the high refractive index layer-low refractive index layer is formed with an optical thickness of λ / 2-λ / 4 from the substrate side. Low-reflecting film of three layers, a medium-refractive index layer-high refractive index layer-low refractive index layer formed from the substrate side with an optical thickness of λ / 4-λ / 2-λ / 4. Refractive Index Layer-Medium Refractive Index Layer-
High Refractive Index Layer-Low Refractive Index Layer Optical Thickness λ / 4-λ / 4-λ / 2-
A four-layer low reflection film or the like formed with λ / 4 is known as a typical example, and various conductive multilayer films are produced by using the conductive high refractive index film of the present invention as a high refractive index film. It is also possible to do so.

[0041]

In the high refractive index antistatic film of the present invention, TiCl
_{Since 4} is used, it is considered that TiO ₂ is partially deposited after heating the film and / or irradiating it with ultraviolet rays to increase the refractive index. Ti
When the source is introduced with Ti alkoxide, acetylacetone (β-diketones), methyl acetoacetate and ethyl acetoacetate (ketoesters) are indispensable for controlling the hydrolysis rate. These chelating agents have high boiling points (140 ° C for methyl acetoacetate and 180 ° C for ethyl acetoacetate), and as a heat treatment of 120 ° C, they remain in the film when only extremely low temperature treatment is performed. Strength is reduced. In addition, organic components derived from Ti alkoxide also cause a decrease in film strength.

The present invention has succeeded in synthesizing a stable solution without using a chelating agent by utilizing the inhibition of Ti polymerization by Cl to stabilize the Ti salt.

Taking Ti alkoxide as an example, Ti (OPr) ₄ is dissolved in ethanol so as to be 3 wt% in terms of TiO ₂ , and no water is added for hydrolysis without adding a chelating agent.
If H ₂ O / TiO ₂ = 2 molar ratio is added, hydrolysis will proceed rapidly and TiO ₂ will be produced and precipitate. However, if TiCl _{4 according} to the present invention is used as a Ti starting material, no particular hydrolysis is required, and even if water is added, the blocking of Ti by Cl occurs, so the liquid state is stable. Is.

However, crystallization may not be completely progressed only by these, and particularly with respect to TiO ₂ , a nonstoichiometric compound is also easily formed, and as the strength of the film, it is not sufficient to sinter at a low temperature of about 120 ° C. Because there is a possibility
Si (OR) _m R _n (m + n = 4, m = 1 to 4, n = 0 to 3, R
= C ₁ -C ₄ alkyl group) monomer or polymer was introduced as the matrix of the membrane.

In the present invention, after applying the coating solution having the above composition, by performing ultraviolet irradiation as the curing condition of the film, it is possible to achieve high film strength which could not be achieved by conventional heating or IR baking alone. You can It is considered that this is because the UV irradiation further promoted the conversion of the film into TiO ₂ and further improved the refractive index of the film.

In the antistatic low-reflection film having a two-layer structure of the present invention, by incorporating conductive fine particles in the high refractive index film on the substrate side, a low-temperature treatment at 200 ° C. or lower (baking and / or UV irradiation) is performed. It is possible to impart a sufficiently low specific resistance, and at the same time, it is possible to impart a high refractive index by introducing TiO ₂ as a matrix.

Therefore, it is not necessary to introduce conductive fine particles into the outermost low refractive index film of the antistatic low reflection film, and SiO ₂
It is possible to use a film having a sufficiently low refractive index such as MgF ₂ or MgF ₂ . The high-refractive index film does not have sufficiently high hardness because it contains conductive fine particles, but a high-hardness film containing SiO ₂ is used as the low-refractive index film formed thereon. By doing so, at the same time as the antireflection property, an antistatic low reflection film having high hardness as the entire two layers is realized.

[0048]

EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the following examples and comparative examples, the evaluation methods of the obtained films are as follows.

1) Conductivity evaluation A relative humidity of 30 was measured by a Hiresta resistance measuring instrument (manufactured by Mitsubishi Yuka).
The surface resistance of the film surface is measured in an atmosphere of less than 100%. 2) Refractive index For the refractive index of a single layer of a conductive high refractive index film, an ellipsometer (L-116 manufactured by GAERTNER SCINETIFIC CORPORATION
Measured according to A).

3) Scratch resistance After reciprocating the membrane surface under a load of 1 kg (50-50 manufactured by LION), scratches on the surface were visually judged. The evaluation criteria are as follows. ○: No scratches were found △: Some scratches were found ×: Film peeling occurred in part

4) Pencil Hardness Under a load of 1 kg, the surface of the film was scanned with a pencil, and the pencil hardness at which scratches on the surface began to be visually observed was judged to be the pencil hardness of the film. 5) Luminous reflectance GAMMA Spectral reflectance
The luminous reflectance at 400 to 700 nm was measured.

Example 1 SnO ₂ powder doped with Sb in an amount of 10 mol% (average particle size 0.5 μm)
15 g was added to water, kept at 30 ° C., and stirred for 1 hour with a homomixer to prepare a sol (solution A). TiCl ₄ was dissolved in ethanol and adjusted so that the solid content in terms of TiO _{2 was} 10 wt% (liquid B).

Liquid A and liquid B were diluted with ethanol so that each of them would be 3 wt% in terms of oxide, and then mixed so that the ratio of liquid A: liquid B was 2: 1 by weight, and 1200 rp was formed on the surface of the cathode ray tube panel.
It was applied at a rotation speed of m 2 for 5 seconds and then heated at 120 ° C. for 5 minutes to obtain a conductive high refractive index film having a thickness of about 100 nm.

Example 2 Example 1 was repeated except that SnO ₂ : TiO ₂ was mixed at a weight ratio of 1: 1.

Comparative Example 1 Solution A was diluted with ethanol to a solid content of 3 wt% and used as a coating solution to obtain a 100 nm film. The evaluation was performed in the same manner as in Example 1.

Comparative Example 2 Ti (OC ₄ H ₉ ) ₄ ethanol solution (TiO ₂ conversion solid content 20.0 wt
%) Acetylacetone with respect to Ti (OC ₄ H ₉ ) ₄ 2.0 mol
After specific addition, the mixture was refluxed at 85 ° C. for 4 hours and chelated with acetylacetone. After that, H ₂ O is replaced with Ti (OC ₄
2 mol ratio was added to H ₉ ) _{4 and the} mixture was further stirred for 1 hour (C
liquid). Liquid A and liquid C were diluted with ethanol so that each would be 3.0 wt% in terms of oxide, and then mixed so that the ratio of liquid A: liquid C = 2: 1 by weight, and 1200 rp on the surface of the cathode ray tube panel.
The coating was carried out at a rotation speed of m 2 for 5 seconds and then heated at 120 ° C. for 5 minutes to obtain a film having a thickness of about 100 nm.

Table 1 shows the evaluation results of Examples 1 and 2 and Comparative Examples 1 and 2.

[0058]

[Table 1]

Example 3 3 g of H ₂ O was added to 100 g of ethanol, and 0.05 mg of MgCl ₂ was added.
mol and BF ₃ .C ₂ H ₅ OH (0.033 mol) were added, and the completely mixed and dissolved solution was placed in a flask equipped with a reflux condenser and reacted at 85 ° C. for 1 hour to obtain MgF ₂ sol. An ethanol solution of silicon ethoxide was mixed with this solution so that the total solid content in terms of oxide and fluoride was 3 wt% and MgF ₂ : SiO ₂ = 4: 6 weight ratio. Further, an ethanol solution of Zr (C ₅ H ₇ O ₂ ) ₂ (OC ₄ H ₉ ) ₂ was added to and mixed with this solution so as to be 10 wt% of SiO ₂ in terms of ZrO ₂ . (D liquid)

Liquid D was applied on the conductive high refractive index film prepared in the same manner as in Example 1 at a rotation speed of 2000 rpm for 5 seconds, and then heated at 120 ° C. for 5 minutes to form a 100 nm low refractive index film. As a whole, an antistatic low reflection film consisting of two layers of (substrate /) conductive high refractive index / low refractive index film was obtained.

Example 4 The procedure of Example 3 was repeated, except that after applying the liquid D in Example 3, heating was performed at 200 ° C. for 30 minutes.

Example 5 The procedure of Example 3 was repeated, except that after applying the liquid D in Example 3, heating was carried out at 450 ° C. for 30 minutes.

Example 6 The same procedure as in Example 3 was carried out except that a solution of MgF ₂ : SiO ₂ = 5: 5 was used in the preparation of solution D in Example 3 and the solution was applied and heated at 450 ° C. for 30 minutes. It was

Example 7 The same procedure as in Example 3 was carried out except that a partial hydrolyzate of ethyl silicate (3 wt% in terms of SiO ₂ solid content) was used instead of the liquid D in Example 3.

Comparative Example 3 The procedure of Example 3 was repeated, except that the partial hydrolyzate of ethyl silicate was coated on the film obtained in Comparative Example 1 as in Example 7.

Comparative Example 4 The procedure of Example 3 was repeated, except that the partial hydrolyzate of ethyl silicate was coated on the film obtained in Comparative Example 2 as in Example 7.

In addition, Examples 3 to 7 and Comparative Examples 3 and 4 were also evaluated for low reflectivity. The results are shown in Table 2. The luminous reflectance is the one-sided luminous reflectance of the film measured by a GAMMA spectroscopic reflectance spectrophotometer.

[0068]

[Table 2]

An example in which a conductive high refractive index film is formed by irradiating ultraviolet rays will be shown below.

Example 8 Sb 16 mol% doped SnO ₂ ultrafine powder (average particle size 6
(30 nm) in 70 g of water, stirred and dispersed in a sand mill for 4 hours, and further diluted with ethanol to a concentration of 3 wt.
% (Solution E). Solid content of TiCl ₄ converted to TiO ₂ 20.0 wt
It was dissolved in ethanol and adjusted so that
liquid).

In an ethanol solution of Si (OC ₂ H ₅ ) ₄ (solid content of SiO _{2 of} 28.9 wt%), pH of Si (OC ₂ H ₅ ) _{4 was} adjusted with NH ₄ Cl.
An aqueous solution adjusted to 5.0 was added in an amount of 8 mol and stirred for 30 minutes (solution G). To an ethanol solution of Si (OC ₂ H ₅ ) ₄ (solid content of SiO _{2 of} 28.9 wt%), add 9 mol of an aqueous solution of Si (OC ₂ H ₅ ) ₄ adjusted to pH 1.6 with HCl and stir for 2 hours. Did (H
liquid).

The liquids F and G were diluted to 3.0 wt% in terms of oxide, and then mixed so that the ratio of liquid F: liquid G was 2: 3 (liquid I). Further, solution I: solution E = 1: 1
Mix so that the weight ratio becomes, and further dilute to 1.0wt%,
After spin coating the surface of a cathode ray tube panel with a surface temperature of 60 ° C for 60 seconds at a rotation speed of 100 rpm, it is irradiated with ultraviolet rays having a wavelength of 365 nm for 30 minutes to obtain a conductive high refractive index with a refractive index of 1.70 and a thickness of about 100 nm. A film (first layer) was obtained. H on this film
The solution was diluted with ethanol and adjusted to be 0.75 wt% in terms of oxide. Similarly, spin coating was performed at a surface temperature of 60 ° C at a rotation speed of 100 rpm for 60 seconds, and then heated at 120 ° C for 5 minutes to prepare a substrate-side coating. A silicon compound film having a refractive index of 1.46 and a film thickness of about 90 nm was formed as two layers.

Example 9 The mixing ratio of the liquid F and the liquid G shown in the embodiment 8 was F liquid: G liquid =
Example 8 was repeated except that the weight ratio was 3: 2.

Example 10 The mixing ratio of solution I and solution E shown in Example 8 was changed to solution I: solution E =
Example 8 was repeated except that the weight ratio was 4: 3.

Example 11 Except that TiCl ₄ was partly replaced by Ti (OPr) ₄ in the F liquid preparation process shown in Example 8 so that the molar ratio was TiCl ₄ / Ti (OPr) ₄ = 1. Was performed in the same manner as in Example 8.

Example 12 In the process of forming the silicon compound film of the second layer on the substrate side of Example 8, the heating step at 120 ° C. for 5 minutes was followed by irradiation with ultraviolet rays (365 nm) for 5 minutes, and then at 120 ° C. for 5 minutes. The same procedure as in Example 8 was performed except that the heating step was changed.

Example 13 The procedure of Example 12 was repeated except that the wavelength of ultraviolet rays shown in Example 12 was 254 nm.

Comparative Example 5 The procedure of Example 8 was repeated, except that the ultraviolet irradiation shown in Example 8 was changed to heating at 100 ° C. for 30 minutes. The average particle size of the SnO ₂ particles is TEM (JEM-
It was measured using 100 CX). The results are shown in Table 3.

[0079]

[Table 3]

The following is an example of hydrothermal treatment of a sol in which conductive particles are dispersed.

Example 14 SnO ₂ ultrafine particle powder (average particle size 6
(30 nm) was added to 70 g of water, and the mixture was stirred and dispersed in a sand mill for 4 hours to prepare a sol. Solid content of this sol is 5 wt%
% Diluted and put in an autoclave at 350 ° C, 170 atm 2
After holding for a time, it was cooled and the antimony-doped tin oxide sol was taken out. The solid content of this is 20 wt.
%, And further diluted with ethanol to adjust the concentration to 3 wt% (solution J).

Solution I and solution J were mixed so that solution I: solution J = 1: 1 weight ratio, further diluted with ethanol to 1.0 wt%, and rotated at 100 rpm on the surface of a cathode ray tube panel having a surface temperature of 60 ° C. The coating was spin-coated at a speed of 60 seconds and then heated at 120 ° C. for 5 minutes to obtain a conductive high refractive index film (first layer) having a refractive index of 1.69 and a thickness of about 100 nm. Solution H was diluted with ethanol on this film to adjust it to 0.75 wt% in terms of oxide, and spin coating was performed at a surface temperature of 60 ° C for 60 seconds at a rotation speed of 100 rpm, and then at 120 ° C for 5 minutes. By heating, a silicon compound film having a refractive index of 1.46 and a film thickness of about 90 nm was formed as the second layer on the substrate side.

Example 15 The mixing ratio of the F liquid and the G liquid shown in the embodiment 14 was F liquid: G liquid =
Example 14 was repeated except that the weight ratio was 3: 2.

Example 16 The mixing ratio of liquid I and liquid J shown in Example 14 was I liquid: J liquid =
Example 14 was repeated except that the weight ratio was 4: 3.

Comparative Example 6 30 g of SnO ₂ ultrafine particle powder doped with 16 mol% of Sb shown in Example 14 was changed to have an average particle size of 50 nm, and this was mixed with water.
The same procedure as in Example 14 was carried out except that the solution was added to 70 g and stirred and dispersed in a sand mill for 4 hours, and then diluted with ethanol to prepare a sol having a solid content of 3 wt% and used as the solution J.

Comparative Example 7 The same procedure as in Comparative Example 6 was carried out except that the SnO ₂ ultrafine particles doped with 16 mol% of Sb shown in Comparative Example 6 were changed to have an average particle size of 3 nm. The average particle size of SnO ₂ particles was measured using a TEM (JEM-100CX) manufactured by JEOL Ltd. The results are shown in Table 4.

[0087]

[Table 4]

Next, an example in which conductive titanium oxide, ITO, or F-doped SnO ₂ is used as the conductive fine particles will be described.

Example 17 15 g of conductive titanium oxide TiO _x (x = 1.6 to 1.9) was added to 85 g of water, pulverized with a sand mill for 4 hours, and peptized by heating at 90 ° C. for 1 hour, and then the concentration was 10 weight. % To prepare a sol. Furthermore, dilute it with ethanol to obtain 3.0 wt.
It adjusted so that it might become% (K liquid). Solution I and solution K:
Mix K solution = 1: 1 weight ratio, further dilute to 1.0 wt% with ethanol and spin coat the surface of a cathode ray tube panel with a surface temperature of 60 ° C at a rotation speed of 100 rpm for 60 seconds, and then at 120 ° C. After heating for 5 minutes, a conductive high refractive index film (first layer) having a thickness of about 100 nm was obtained.

Liquid H was diluted with ethanol on this film and adjusted to be 0.75 wt% in terms of oxide.
Spin coating at 60 ° C for 60 seconds at 100 rpm,
Thereafter, the substrate was heated at 120 ° C. for 5 minutes to form a silicon compound film having a refractive index of 1.46 and a film thickness of about 90 nm as the second layer on the substrate side.

Example 18 The mixing ratio of the F liquid and the G liquid shown in Example 17 was F liquid: G liquid =
Example 17 was repeated except that the weight ratio was 3: 2.

Example 19 The mixing ratio of solution I and solution K shown in Example 17 was as follows: solution I: solution K =
Example 17 was repeated except that the weight ratio was 4: 3.

Example 20 Instead of the oxygen deficient type (TiO _x : x = 1.6 to 1.9) as the conductive titanium oxide shown in Example 17, NbCl ₅ was changed to TiO ₂ powder.
Example 17 was repeated except that the Nb-TiO ₂ powder obtained by doping Nb in TiO ₂ by impregnating with 0.05 mol ratio and heating at 900 ° C. in a N ₂ gas atmosphere for 2 hours was used. ..

Example 21 The same procedure as in Example 17 was carried out except that the conductive titanium oxide shown in Example 17 was changed to ultrafine particles of ITO (Sn-doped In ₂ O ₃ ) (average particle size 20 nm). It was

Example 22 The same procedure as in Example 19 was carried out except that the conductive titanium oxide shown in Example 19 was replaced with ultrafine particles of ITO (Sn-doped In ₂ O ₃ ) (average particle size 20 nm). It was

Example 23 Example 23 was repeated, except that the step of heating at 120 ° C. for 5 minutes after coating the substrate-side first layer shown in Example 17 was changed to irradiation with ultraviolet rays mainly having a wavelength of 365 nm for 5 minutes. Same as 17

Example 24 Example 24 was repeated except that the step of heating at 120 ° C. for 5 minutes after coating the substrate-side first layer shown in Example 20 was changed to irradiation with ultraviolet rays having a wavelength of 254 nm for 5 minutes. Same as 20.

Example 25 Except that the step of heating at 120 ° C. for 5 minutes after coating the substrate-side first layer shown in Example 21 was changed to the step of irradiating with ultraviolet rays mainly at a wavelength of 365 nm for 5 minutes, The same procedure as in Example 21 was performed. The results are shown in Table 5.

[0099]

[Table 5]

[0100]

According to the present invention, a strong and highly conductive high refractive index film can be provided without heating to a high temperature.
Further, by providing a low reflection film made of MgF ₂ , SiO ₂ or the like on the conductive high refractive index film, it is possible to provide an antistatic low reflection film excellent in low reflectivity and hardness.

The conductive high-refractive index film and the antistatic low-reflection film of the present invention are excellent in productivity, can manufacture high-quality films at low temperatures, and require no vacuum, so the apparatus is relatively simple. good. In particular, it has a large area such as the face surface of a CRT, is sufficiently applicable to substrates that are difficult to be heated at high temperatures, and can be mass-produced, and thus has an extremely high industrial value.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Satoshi Takemiya 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Asahi Glass Co., Ltd. Central Research Laboratory (72) Keiko Kubota 1150, Hazawa-machi, Kanagawa-ku, Yokohama Asahi Glass Co., Ltd. Central research institute

Claims (11)

[Claims] 1. A conductive high refractive index film, characterized in that a conductive high refractive index film is produced by applying a liquid containing conductive fine particles and a Ti salt onto a substrate and then heating and / or irradiating with ultraviolet rays. Membrane manufacturing method. 2. A liquid containing a liquid in which conductive particles are dispersed at a high temperature and high pressure and a liquid containing a Ti salt is used as a liquid for coating on a substrate. A method for producing a conductive high refractive index film. 3. A method for producing an antistatic low reflection film consisting of two layers by sequentially laminating a high refractive index film and a low refractive index film on a substrate, wherein the high refractive index film is made of conductive fine particles. A method for producing an antistatic low-reflection film, which comprises applying a liquid containing a Ti salt on a substrate and then heating and / or irradiating with ultraviolet rays. 4. The method for producing a conductive high refractive index film according to claim 1 or 2, or the method for producing an antistatic low reflection film according to claim 3, wherein the Ti salt is TiCl ₄ . 5. A liquid containing conductive fine particles and a Ti salt. 6. A device manufactured by the manufacturing method according to claim 1.
A conductive high refractive index film comprising TiO ₂ and conductive fine particles and having a refractive index of 1.60 or more. Comprises SnO ₂ as 7. conductive fine particles, in terms of oxide, SnO ₂ is 25 wt% or more, TiO ₂ is 5 wt% or more, the conductivity of claim 6, characterized in that it contains high Refractive index film. 8. A conductive multilayer film having at least one conductive high refractive index film according to claim 6 or 7. 9. An antistatic low-reflection film consisting of two layers in which a high-refractive index film and a low-refractive index film are sequentially laminated on a substrate, wherein the high-refractive index film has high conductivity. An antistatic low reflection film, which is a refractive index film. 10. A glass article on which the conductive high refractive index film according to claim 6 or 7, the conductive multilayer film according to claim 8, or the antistatic low reflection film according to claim 9 is formed. 11. A cathode ray tube having the electroconductive high refractive index film according to claim 6 or 7, the electroconductive multilayer film according to claim 8 or the antistatic low reflection film according to claim 9.