JPH05173009A - Antistatic low reflection film and method for manufacturing the same - Google Patents

Abstract

PURPOSE:To produce an antistatic low reflection film having high hardness and high adhesion strength with good productivity without heating at high temp. CONSTITUTION:An aq. soln. in which conductive fine particles are dispersed is treated at high temp. under high pressure, to which a liquid containing Ti salt and/or Ti alkoxide and a liquid containing Si alkoxide are added. The obtd. liquid is applied and heated to form a conductive film. Then a liquid containing an isocyanate compd. of Si is applied to form a low refractive index film.

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, a coating method for a low-reflection film has been used in conventional optical equipment, and in particular, 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
As described in JP-A-118931, 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 lower resolution in cathode ray tubes. It was

Many studies have also been made on the provision of an antistatic film, for example, Japanese Patent Laid-Open No. 63-76247.
As described in the above item, a method of heating the surface of the cathode ray tube panel to about 350 ° C. and providing a conductive oxide layer such as tin oxide or indium oxide by the CVD method has been adopted.

[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. Further, as the material used for the conductive layer, F or Sb-doped tin oxide and Sn-doped indium oxide are the most common. In this case, CVD is used.
The method and the wet method (pyrolysis method) have a drawback that a sufficiently low resistance film cannot be obtained by heating at a low temperature of about 200 ° C.

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.

Further, when a multi-layer film is formed on the glass surface by the wet method and low reflection antistatic property is exhibited by low temperature curing, there is a problem that the interface strength between the films is lowered. In particular, in a film containing conductive fine particles, the amount of surface hydroxyl groups, which influences the interfacial bond strength, is reduced, which may cause remarkable deterioration of the film strength.

[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 a solution containing a conductive fine particle at a high temperature and a high pressure and a liquid containing a Ti salt and / or a Ti alkoxide is coated on a substrate. After that, it is heated or irradiated with ultraviolet rays to form a high refractive index conductive film, and a solution containing a Si isocyanate compound such as an alkylsilyl isocyanate compound, an alkoxysilane isocyanate compound, or a tetraisocyanate compound is applied onto the conductive film to reduce the refractive index. A method for producing a low-reflection antistatic film comprising two layers by forming a rate film.

Generally, the optical performance of a thin film is determined by the refractive index and the film thickness of the film. Where the constant refractive index n
_When a thin film having a refractive index n is attached to a substrate having _S and light having a wavelength λ is incident from a medium having a refractive index n _O , the energy reflectance R is the phase difference of the difference of the light passing through the film. Δ
Then Δ = 4πnd / λ (d: film thickness)

[0010] Δ = (2m + 1) π , i.e. when the phase difference delta is a half wavelength of an odd multiple, takes a minimum value, this time _{^{R = ((n 2 -n O}} n S) / (n 2 + n O n _S )) ² <Equation (1)>.

[0011] nonreflective condition is satisfied, the equation (1), R = 0 Distant _{n = (n O n S)} 1/2 <(2) expression> is required. When the formula (2) is expanded to a two-layer structure, n _S n ₁ ² = n ₂ ² n _O <(3) formula>. (N ₁ : medium side layer, n ₂ : substrate side layer)

Here, n _O = 1 (air), n _S = 1.52
When (glass) is applied to the equation (3), n ₂ / n ₁ = 1.
23, and in this case, the maximum low reflectivity of the two-layer constitution film is obtained. Of course, even if n ₂ / n ₁ = 1.23 is not satisfied, low reflectivity is exhibited when the refractive index of the two-layer film takes a value close to this. Therefore, it is desirable that the high refractive index layer provided on the substrate side and the low refractive index layer provided on the medium side have a refractive index ratio of both as close to 1.23 as possible.

In the present invention, the high refractive index layer provided on the substrate side has a refractive index of 1.60 or more, and the low refractive index layer formed thereon is composed of a silicon compound having a lower refractive index.
The above object is achieved. In the present invention,
The thickness of the multilayer film and the single layer film can be optically determined by a conventionally known method.

The conductive high refractive index film used in the present invention can be obtained by using a solution obtained by treating conductive particles at high temperature and high pressure and a solution containing a liquid containing a Ti salt. As the conductive fine particles, S
Examples thereof include SnO ₂ particles doped with b or F, fine particles of conductive titanium oxide, ITO (In ₂ O ₃ doped with Sn), and fine particles of ruthenium oxide.

Sb-doped SnO ₂ fine particles (pentavalent Sb is a substitutional solid solution at the Sn lattice position of SnO ₂ )
Since it is easy to form ultrafine particles having a low resistance and a particle size of 100Å or less, it can be used relatively favorably. F-doped SnO ₂ fine particles (F ions having substitutional solid solution at the 0 lattice position of SnO ₂ ) have low resistance and can be suitably used.

Also, reduction-treated titanium oxide or titanium oxide doped with pentavalent metal ions can be preferably used. For reduction treatment, inert gas, N ₂ gas, H ₂
Gas or a mixed gas thereof can be used.
Further, 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.

Ruthenium oxide is one of the most conductive materials among the conductive oxides, and is SnO ₂ or In ₂
It is not necessary to develop conductivity by doping with another element such as O ₃ , and it can be suitably used.

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,
It can be obtained by adding an acid or an alkali to adjust the pH, and dispersing with a commercially available pulverizer such as a colloid mill, a ball mill, a sand mill, a homomixer or ultrasonic waves.

The sol solution in which the conductive fine particles are dispersed is placed in a closed container such as an autoclave and heated and pressurized (hereinafter referred to as hydrothermal treatment) to firmly attach the hydration water molecules to the surface of the conductive fine particles. Alternatively, the amount of surface hydroxyl groups can be increased. When the solution containing the hydrothermally-treated conductive fine particles is applied to form a coating film, the surface of the conductive particles appears on a part of the outermost surface of the film, but it is presumed that more hydroxyl groups are present than in the case without hydrothermal treatment. This is preferable because it contributes to the improvement of the film strength (in particular, the strength of the interface between the films).

The treatment temperature is preferably 200 ° C. or higher, more preferably 300 ° C. or higher. The pressure at this time is 20
It is 15 atm at 0 ° C. and 85 atm at 300 ° C. Further, it is preferable that the treatment is performed for 1 hour or more. Further, this dispersion can be used after being arbitrarily diluted with alcohol, water or the like.

Since the sol liquid before the hydrothermal treatment needs to have fluidity enough to make it uniform, the solid content is preferably about 5%. Since the amount of the solid content is too much of the solvent, after cooling, the dispersion is taken out and concentrated using an evaporator or the like to obtain a dispersion of conductive fine particles. It is also preferable to reduce the resistance by hydrothermal treatment.

Although the mechanism of lowering the resistance by hydrothermal treatment is not always clear, by conducting hydrothermal treatment on conductive fine particles, hydroxyl groups on the surface of the fine particles are firmly attached or hydrated water molecules are strongly coordinated. It is considered that this is because the interaction with the Ti salt 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 30.
It is preferably 0 nm or less. Preferably 4
It is preferably from 0 to 700Å, particularly preferably from 40 to 200Å. If it is smaller than 40Å, the contact between the conductive particles becomes insufficient and the desired resistance value (10 ¹⁰ Ω / □
The following) may be difficult to obtain. If it exceeds 700Å, the film strength becomes insufficient. Further, this dispersion can be diluted with alcohol, water or the like.

A solution containing a Ti salt or Ti alkoxide for introducing TiO ₂ as a matrix of the conductive high refractive index film is added to the above dispersion liquid of the conductive fine particles to prepare a coating liquid. Specifically, a chloride represented by TiCl ₄ is dissolved in an organic solvent such as alcohol, and a pH adjusting solution containing water and / or Cl counter ions is added for partial hydrolysis, and then the above dispersion is performed. It is preferably added to the liquid. At this time, the Ti salt is blocked by Cl, and the polymerization does not proceed extremely rapidly.

Ti alkoxide can also be preferably used. When using Ti alkoxide, it is necessary to control the hydrolysis of Ti alkoxide by adding and chelating β-diketone such as acetylacetone or ketoester such as methyl acetoacetate.

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 liquid. Specifically, Si (OR) _m R _n
A solution containing a Si alkoxide represented by (m = 1 to 4, n = 0 to 3, R = C _{1 to} C ₄ alkyl group) or a partial hydrolyzate is added to the coating liquid.

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 S in terms of oxide.
nO ₂ : (TiO ₂ + SiO ₂ ) = 25: 75 to 90:
It is 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, Sn is added in the solid content of the film (as oxide) in order to impart conductivity.
In order to obtain a refractive index of O ₂ of 25 wt% or more and 1.60 or more, it is preferable that TiO ₂ obtained from chloride or alkoxide is 5 wt% or more in the solid content (as oxide) of the film. ..

As conductive fine particles, TiO _x (x: 1.6
˜1.9) When using fine particles, a preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ or less is TiO _x (x: 1.6 to 1.9) as oxide. (Introduced as particles): (TiO ₂ + SiO ₂ ) = 2
A weight ratio range of 0:80 to 90:10 can be mentioned.

TiO _x as conductive titanium oxide fine particles
When (x: 1.6 to 1.9) fine particles are used, the preferable composition range of the conductive high refractive index film is such that the TiO _x (as oxide) in the solid content (converted to oxide) of the film in order to impart conductivity. x:
1.6-1.9) 20 wt% or more of fine particles, and 1.6
In order to obtain a refractive index of 0 or more, TiO ₂ obtained from alkoxide or chloride is preferably 3 wt% or more.

When Nb-doped TiO ₂ fine particles are used as the conductive fine particles, a preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ or less is Nb-doped TiO ₂ : (TiO ₂ + SiO _{2 in} terms of oxide. ) = 18: 82-
A weight ratio range of 90:10 is included.

When Nb-doped TiO ₂ fine particles are used as the conductive titanium oxide fine particles, the preferable composition range of the conductive high refractive index film is Nb-doped in the solid content (oxide conversion) of the film in order to impart conductivity. 18w of TiO ₂ particles
To obtain a refractive index of t% or more and 1.60 or more, 3 wt% of TiO ₂ obtained from alkoxide or chloride is used.
% Or more is preferable.

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 or less is as follows.
In terms of oxide, ITO: (TiO ₂ + SiO ₂ ) = 15:
85 to 90:10, TiO ₂ and SiO.
The composition ratio of ₂ affects the refractive index and the film strength of the conductive high refractive index layer, and a preferable range is TiO ₂ : SiO _2.
The weight ratio range is 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 1 in the solid content (oxide conversion) of the film in order to impart conductivity.
In order to obtain a refractive index of 5 wt% or more and 1.60 or more, it is preferable that TiO ₂ obtained from an alkoxide or chloride is 5 wt% or more.

When RuO ₂ fine particles are used as the conductive fine particles, the preferable film composition ratio for imparting conductivity of 1 × 10 ¹⁰ or less is RuO ₂ : (Ti
O ₂ + SiO ₂ ) = 10: 90 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 a preferable range is as follows. TiO ₂ : SiO ₂ = 100: 0 to 10: 9
A weight ratio range of 0 may be mentioned.

In the case of using RuO ₂ fine particles, the preferable composition range of the conductive high refractive index film is that the RuO ₂ fine particles are 1 in the solid content of the film (as oxide) in order to impart conductivity.
In order to obtain a refractive index of 0 wt% or more and 1.60 or more, TiO ₂ obtained from alkoxide or chloride is preferably 5 wt% or more.

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

The low refractive index film used in the present invention is formed by applying a solution containing an isocyanate compound of Si such as an alkylsilyl isocyanate compound, an alkoxysilane isocyanate compound and a tetraisocyanate compound.

The isocyanate compound has a Si--NCO bond and reacts with an active hydrogen compound to form a SiO ₂ film. In the present invention, the conductivity of the high refractive index conductive film formed under the low refractive index film is reduced. -OH groups are formed on the surface of the conductive fine particles by hydrothermal treatment of the conductive fine particles, the cleavage reaction of the silyl isocyanate proceeds on the surface of the high refractive index conductive film, and the film strength (especially the interface between the films is increased). (Strength) is improved, which is preferable.

In the invention, the substrate for forming the antistatic low reflection film is not particularly limited, and soda lime silicate glass, aluminosilicate glass, borosilicate glass, lithium aluminosilicate glass, quartz glass is used according to the purpose. And the like, single crystals such as steel balls, translucent ceramics such as magnesia and sialon, and plastics such as polycarbonate can be used.

Various methods such as a spin coating method, a dipping method, a spraying method, a roll coater method and a meniscus coater method can be considered as the coating method on the substrate, but the spin coater method is particularly preferable because it is excellent in mass productivity and reproducibility. .. By this method, a film having a thickness of about 100Å to 1 μm can be formed.

In the present invention, TiCl ₄ and / or Ti alkoxide,
And preferably, after applying a coating solution containing Si alkoxide, it is heated or ultraviolet rays, specifically 180 to 4
Irradiation with ultraviolet rays having a wavelength of 90 nm, or irradiation with ultraviolet rays and heating is performed to form a high refractive index film having conductivity.

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) / n (low refractive index) on the conductive high refractive index film (n ≧ 1.60). The reflectance can be reduced most by forming a low refractive index film such that the ratio value of the film is about 1.23.

The conductive high refractive index film in the invention is TiCl
T formed from ₄ and / or Ti alkoxide
Since it contains iO ₂ , it has a high refractive index. 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 / SiO ₂ , substrate / ITO-TiO
₂ -SiO ₂ / SiO _2, the substrate / RuO ₂ -TiO ₂ -
SiO ₂ / SiO _2, the substrate / TiO _2-x -TiO ₂ -S
Examples include iO ₂ / SiO ₂ .

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. The structure of the multilayer low-reflection film having antireflection performance is as follows. The wavelength to be antireflection is set to λ, and the high refractive index layer-the low refractive index layer has an optical thickness of λ / 2-λ / 4 from the substrate side.
The two-layer low-reflectivity film formed in step (1) has a medium-refractive-index layer-high-refractive-index layer-low-refractive-index layer with an optical thickness of λ / 4-λ / 2-λ /
The three-layer low-reflectivity film formed in 4, the low refractive index layer-medium refractive index layer-high refractive index layer-low refractive index layer from the substrate has an optical thickness λ / 4-
A four-layer low-reflection film formed by λ / 4-λ / 2-λ / 4 is known as a typical example, and the conductive high refractive index film of the present invention is used as a high refractive index film. It is also possible to manufacture various conductive multilayer films.

[0046]

The conductive fine particles used in the high-refractive-index antistatic film of the present invention can be hydrothermally treated in advance to firmly attach hydrated water molecules to the surface of the conductive fine particles or increase surface hydroxyl groups. It will be possible. This partially suppresses the reaction with the Ti salt and causes the particles to come into contact with each other, so that the conductivity of the film can be improved. In addition, the amount of hydroxyl groups on the film surface can be increased by partially exposing the conductive particles to the film surface, which leads to improvement in interfacial strength between the films.

Further, by including an isocyanate silane compound in the solution used for the low refractive index film of the present invention and combining it with the above high refractive index conductive film having increased surface hydroxyl groups, the film strength is further improved. Planned.

However, when only the Ti salt is introduced as the matrix of the film, crystallization may not be completely progressed, and particularly with respect to TiO ₂ , a nonstoichiometric compound is likely to be formed, and the film strength is about 200 ° C. Since firing at low temperature may not be sufficient, Si (O
R) _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 irradiating with ultraviolet rays 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 ultraviolet 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, the high-refractive-index film on the substrate side contains conductive fine particles, so that the film is treated at a low temperature of 200 ° C. or lower (baking and / or baking).
(Or ultraviolet irradiation) can give a sufficiently low specific resistance, and at the same time, TiO 2 can serve as a matrix.
_A high refractive index can be imparted by introducing ₂ .

Therefore, it becomes unnecessary to introduce conductive fine particles into the outermost low refractive index film of the antistatic low reflection film, and Si
It becomes possible to use a low refractive index film made of O ₂ . Further, since the high refractive index film does not have a sufficiently high hardness because it contains conductive fine particles, the conductive particles are subjected to hydrothermal treatment, and a low refractive index film formed on the conductive particles is formed of Si. By adopting a high hardness film containing SiO ₂ formed from an isocyanate compound, at the same time as antireflection property,
An antistatic low reflection film having high hardness as the entire two layers is realized.

[0052]

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 Relative humidity 3 with a Hiresta resistance measuring instrument (manufactured by Mitsubishi Yuka)
Measure the surface resistance of the film surface in an atmosphere of 0% or less.

2) Scratch resistance Under a load of 1 kg, an eraser (50-50, manufactured by LION) was used to reciprocate the membrane surface 50 times, and the scratches on the surface were visually evaluated. The evaluation criteria are as follows. ○: No scratches at all △: Some scratches are found ×: Many scratches or film peeling

3) Pencil Hardness Under a load of 1 kg, the surface of the film was scanned with a pencil, and then the hardness of the pencil at which scratches on the surface began to occur was judged to be the pencil hardness of the film. 4) Luminous reflectance (at the time of forming two layers) 400 of the film by GAMMA spectroscopic reflection spectrum measuring device
The luminous reflectance at -700 nm was measured.

[Example 1] 30 g of SnO ₂ ultrafine particle powder (average particle size 6 nm) doped with 16 mol% of Sb was added to 70 g of an aqueous solution, and the mixture was stirred and dispersed in a mill for 4 hours to prepare a sol. This sol was diluted with water to a solid content of 5 wt% and placed in an autoclave at 350 ° C. and 170 atm.
After holding for a time, it was cooled and the antimony-doped tin oxide sol was taken out.

The solid content of this was adjusted to 20 with an evaporator.
It was concentrated to wt% and further diluted with ethanol to adjust the concentration to 3 wt% (solution A).

Example 2 To an ethanol solution of Ti (OC ₄ H ₉ ) ₄ (solid content of TiO ₂ 20 wt%), acetylacetone was added at a ratio of 2 mol with respect to Ti (OC ₄ H ₉ ) _{4 and} stirred for 1 hour. .. After that, H ₂ O is replaced with Ti (OC ₄ H
₉ ) 2 mol ratio was added to ₄ , and the mixture was further stirred for 1 hour (solution B).

An ethanol solution of Si (OC ₂ H ₅ ) ₄ (solid content of SiO _{2 of} 28.9 wt%) was added to Si (OC 2
_A 9 mol ratio of an aqueous solution adjusted to pH 2.0 with hydrochloric acid was added to ₂ H ₅ ) _{4 and} stirred for 2 hours (solution C).

Liquid B and liquid C are each 3 wt% in terms of oxide.
After being diluted with ethanol so that
It mixed so that it might become 2: 3 weight ratio (D liquid).

Further, liquid D: liquid A was mixed in a weight ratio of 1: 1 and coated on the surface of the cathode ray tube panel at a rotation speed of 1200 rpm for 5 seconds, and then heated at 200 ° C. for 30 minutes to have a refractive index of 1. A film with a thickness of 70 and a thickness of about 100 nm was obtained.

Tetraisocyanate silane Si (NC
O) ₄ was dissolved in butyl acetate so as to be 3 wt% in terms of SiO ₂ (solution E). Solution E is applied on the film formed by solution D for 5 seconds at a rotation speed of 1500 rpm,
Let stand for a minute.

[Embodiment 2] Sb in Embodiment 1 is 16
Mol% -doped SnO ₂ ultrafine powder was added to TiO _x.
The same procedure as in Example 1 was carried out except that the fine particles (x: 1.6 to 1.9) were used.

[Example 3] The same operation as in Example 1 was carried out except that the Sb-doped SnO ₂ ultrafine particles in Example 1 were changed to Nb-doped TiO ₂ particles.

[Example 4] The same procedure as in Example 1 was carried out except that the Sb-doped SnO ₂ ultrafine particles in Example 1 were changed to ITO particles.

Example 5 The same procedure as in Example 1 was carried out except that the Sb-doped SnO ₂ ultrafine particles in Example 1 were changed to RuO ₂ particles.

[Example 6] 200 ° C in Example 1 3
Example 1 was repeated except that the heating for 0 minutes was changed to the irradiation for 30 minutes with ultraviolet rays having a main wavelength of 254 nm.

[Embodiment 7] Heating at 200 ° C. for 30 minutes in Embodiment 5 is carried out with 10 times of ultraviolet rays having a main wavelength of 365 nm.
The same procedure as in Example 5 was performed except that the irradiation was changed to minutes.

[Example 8] The same procedure as in Example 1 was carried out except that the application of the E liquid in Example 1 was changed to the standing for 30 minutes at 120 ° C for 10 minutes.

[Comparative Example 1] The same procedure as in Example 1 was carried out except that the solution E was changed to the solution C in Example 1.

[Comparative Example 2] The same procedure as in Example 1 was carried out except that the solution E was changed to the solution C in Example 8. The results are shown in Table 1.
Shown in.

[0072]

[Table 1]

[0073]

According to the present invention, it is possible to manufacture a low-reflection antistatic film which is strong and has excellent long-term storage stability without heating the substrate to a high temperature. Since the present invention is excellent in productivity and does not require a vacuum, the device can be relatively simple. In particular, it can be sufficiently applied to a large-area substrate such as the face surface of a CRT and mass production is possible, and its industrial value is very high.

 ─────────────────────────────────────────────────── ─── 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 Laboratory (72) Inventor Ken Kawari 1150 Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture Asahi Glass Co., Ltd. Central Research Laboratory

Claims (5)

[Claims] 1. A coating solution containing a solution of a conductive fine particle dispersed at high temperature and high pressure and a Ti salt and / or Ti alkoxide is coated on a substrate and then heated and / or heated.
Alternatively, ultraviolet irradiation is performed to form a high-refractive-index conductive film, and a low-refractive-index film having a refractive index smaller than that of the conductive film is formed on the high-refractive-index conductive film to manufacture a low-reflection antistatic film composed of two layers. Method for producing low-reflection antistatic film. 2. A method for producing a low-reflection antistatic film comprising a multi-layer containing at least one conductive film, the conductive film being a high-temperature high-pressure solution of an aqueous solution in which conductive fine particles are dispersed, and a Ti salt. And / or a coating liquid containing Ti alkoxide is applied, followed by heating and / or irradiation with ultraviolet rays to form a low refractive index film having a smaller refractive index than the conductive film. A method for producing a multilayer low reflection antistatic film. 3. The method for producing a multilayer antireflection antistatic film as claimed in claim 1, wherein the low refractive index film is formed by applying a solution containing an isocyanate compound of Si. 4. A glass article on which the low-reflection antistatic film according to claim 1, 2 or 3 is formed. 5. A Braun tube on which the low-reflection antistatic film according to claim 1, 2 or 3 is formed.