JP2865474B2 - Paint for forming antistatic / high refractive index film, transparent material laminate with antistatic / antireflective film, and display device - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paint for forming an antistatic / high-refractive-index film, a transparent material laminate having an antistatic / antireflective film obtained by using the same, and a display device. More specifically, the present invention relates to a display surface of a display device, a surface cover material thereof, a window glass, a glass for a show window, a display surface of a TV cathode-ray tube, a display surface of a liquid crystal device, a cover glass of an instrument, and a cover of a watch. An antistatic / high refractive index film-forming paint useful for coating the surface of a transparent material such as glass and a front image surface of a CRT, which requires prevention of electrostatic charge and prevention of reflection, and is obtained by using the same. The present invention relates to a transparent material laminate having an antistatic / antireflection film and a display device.

[0002]

2. Description of the Related Art Generally, transparent materials for image display, for example, TV
It is known that static electricity tends to be charged on an image display unit of a cathode ray tube, and this static electricity causes dust to adhere to a display surface. Further, there is also known a problem that external light is reflected on the image display surface, or an external image is transmitted, and an image on the display surface is unclear.

In order to solve the above problems, conventionally, a nonaqueous solvent dispersion of antimony-doped tin oxide fine particles and a hydrolysis product of silicon alkoxide is applied to the surface of a transparent substrate, Drying is performed to form an antistatic film layer, and a film layer having a lower refractive index is formed on the antistatic film. This low refractive index film layer
It is usually formed by the hydrolysis product of silicon alkoxide, ie, silica. However, the adhesion between the conventional antistatic film layer and the low refractive index film layer is poor,
There was a problem that delamination easily occurred between these two layers.

The refractive index of the conventional antistatic film layer is about n = 1.50 to 1.54, and as described above, the hydrolysis product of silicon alkoxide (silica)
And the difference between the refractive index of the low refractive index film layer and the low refractive index film layer formed by the conventional method is insufficient. Further, in the conventional antistatic film layer, silicon alkoxide is used as a binder of antimony-doped tin oxide fine powder, and when this silicon alkoxide comes in contact with a large amount of water, hydrolysis and polycondensation are promoted, and insoluble Since silica of the formula (1) is generated and loses its function as a paint at an early stage, it is necessary to use a non-aqueous solvent (generally ethyl alcohol) for the paint for forming an antistatic film layer. However, it is desirable to use water as the paint solvent in order to reduce the cost of the paint, prevent environmental pollution and facilitate handling.

[0005] In order to solve the above-mentioned problems, as described above, charging is carried out from a paint comprising a nonaqueous solvent dispersion containing a mixture of antimony-doped tin oxide fine powder and a hydrolysis product of silicon alkoxide (silica). Forming a barrier layer,
An attempt was made to form a low-refractive-index film layer by applying a coating composed of an aqueous dispersion of a hydrolysis product of silicon alkoxide (silica) thereon, but the resulting adhesion between the two layers was poor. The coatings were sufficient and had an insufficient antireflection effect, had a short life as a paint, and could not be put to practical use.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a transparent material having excellent antistatic properties and a low refractive index film layer.
An antistatic / high refractive index film forming paint useful for easily and inexpensively forming a film layer with good adhesion using water as a solvent, and an antistatic / antireflective film obtained using the same. It is an object of the present invention to provide a transparent material laminate, particularly a transparent material laminate having an antistatic / high-refractive-index film layer and a low-refractive-index film layer formed thereon.

[0007]

SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems by using silicone oil instead of silicon alkoxide as a binder for antimony-doped tin oxide fine powder. The headline was completed based on it.

That is, the coating for forming an antistatic / high-refractive-index film according to the present invention comprises 80 to 99.99 parts by weight of a fine powder of antimony-doped tin oxide and 0.1% by weight of silicone oil.
It is characterized by comprising an aqueous dispersion containing a mixture of 0.01 to ₂₀ parts by weight (in terms of SiO ₂ ).

The paint of the present invention may further contain a colorant having an absorption center wavelength near 600 nm. The content of the colorant in the paint is 3 to 2 with respect to the weight of the solid content of the paint.
Desirably, it is 0%.

Further, the transparent material laminate with an antistatic / antireflection film according to the present invention comprises a transparent substrate and a coating for forming the antistatic / high refractive index film of the present invention on the surface of the transparent substrate. An antistatic / high-refractive-index film layer formed by applying and drying, and formed on the antistatic / high-refractive-index film layer, and having a refractive index lower than the refractive index by 0.1 or more, And a low-refractive-index film layer.

The display device of the present invention is the display device of the present invention.
An antistatic / high-refractive-index film layer formed by applying and drying a coating material for forming a high-refractive-index film, and formed on the antistatic / high-refractive-index film layer and having a refractive index of 0.1 or more. The low refractive index film layer having a low refractive index is formed at least on a display surface.

[0012]

The coating composition for forming an antistatic / high-refractive-index film of the present invention
In the used antimony-doped tin oxide fine powder / silicone oil mixture, the ratio of the content of antimony-doped tin oxide fine powder to the content of silicone oil (in terms of SiO ₂ ) is 80 to 99.99: 20 to 0.01. It is. When the ratio of the content of the antimony-doped tin oxide fine powder to the total weight of the mixture (the amount of the silicone oil is converted to SiO ₂ ) is less than 80/20, the content of the silicone oil becomes excessive, and the mechanical properties of the resulting film layer are reduced. The target strength becomes insufficient. On the other hand, if it exceeds 99.99 / 0.01, the content of silicone oil will be too low, and the resulting antistatic / high refractive index film layer will have another material, ie, a transparent substrate or low refractive index. Adhesion with the rate film layer becomes insufficient.

In a conventional antistatic film-forming paint containing a silicon alkoxide, the content of the antimony-doped tin oxide fine powder is determined by the content of the fine powder and the silicon alkoxide (SiO 2).
_(In terms of ₂ ) was generally less than 80% by weight. This means that the content of the antimony-doped tin oxide fine powder, and that of the silicon alkoxide (SiO
_{If the} content is 80% by weight or more based on the total weight of the mixture of ( ₂ ), the degree of dispersion of the fine powder of antimony-doped tin oxide decreases, and a uniform coating layer cannot be formed.

However, in the present invention, the use of silicone oil makes it possible to contain antimony-doped tin oxide fine powder at a content of 80% by weight or more in the paint. For this reason, the antistatic and high refractive index film layer obtained by using the paint of the present invention not only exhibits an extremely excellent antistatic effect, and an electromagnetic wave shielding effect,
It became possible to have a high refractive index of n = 1.55 to 2.0. Therefore, the refractive index of the low refractive index film layer formed thereon (generally, n = 1.45 or less) and
The difference from the refractive index of the antistatic / high refractive index film layer can be 0.1 or more, preferably 0.15 or more,
For this reason, the combination of the antistatic / high-refractive-index film layer and the low-refractive-index film layer obtained by the present invention exhibits excellent antireflection properties.

That is, the reflected light from the surface of the low refractive index film layer can be canceled by the interference of the reflected light from the interface between the antistatic / high refractive index film layer having a high refractive index and the low refractive index film layer. Therefore, the antireflection effect can be enhanced more than before. In the antimony-doped tin oxide fine powder used in the present invention, tin oxide is produced by a gas phase method,
, Hydrothermal method and carbonate method. The shape of the fine particles is not particularly limited, and may be any of a spherical shape, a needle shape, a plate shape, and a chain shape.

The method of doping antimony with respect to tin oxide and the amount of doped antimony are not particularly limited, but are generally 1 to 5 with respect to the weight of tin oxide.
%. Thereby, the tin oxide fine powder can further enhance its antistatic effect, electromagnetic wave shielding effect, and the like. The antimony-doped tin oxide fine powder used in the present invention preferably has an average particle size of 1 to 100 nm. When the average particle size is less than 1 nm, the electric conductivity is reduced, and the particles are easily aggregated, and it is difficult to uniformly disperse the particles in the paint,
The viscosity of the paint increases, and it is necessary to add a large amount of a dispersing solvent in order to reduce the viscosity, and therefore, the concentration of the antimony-doped tin oxide fine powder in the paint may be excessively low.

When the average particle size of the antimony-doped tin oxide fine powder is larger than 100 nm, light is remarkably irregularly reflected due to Rayleigh scattering in the obtained antistatic / high refractive index film layer, so that it appears white and the transparency is increased. descend. The silicone oil used in the present invention is not particularly limited, but includes an amino group, a carboxyl group,
It is desirable to select an organosiloxane compound having at least one hydrophilic group selected from an epoxy group, a hydroxyl group, a polyether group, an ester group, an alkoxy group and the like, and which is not hydrolyzed by an aqueous solvent. Examples of such an organosiloxane compound include amino-modified silicone oil, carboxy-modified silicone oil, epoxy-modified silicone oil, hydroxyl-based silicone oil, polyether-modified silicone oil, ester-modified silicone oil, and alkoxy-modified silicone oil. .

As the solvent, it is preferable to use water, but the solvent compatible with water is 6% based on the total weight of the solvent.
It may be mixed with water in an amount of 0 weight or less.

In the laminate of the present invention, the thickness or weight of the antistatic / high-refractive-index film layer formed on the transparent substrate is not particularly limited, but is generally 0.05 to 0.2 μm. It is preferred to have. On the antistatic / high-refractive-index film layer formed by using the paint of the present invention, a low-refractive-index film layer is formed. The low-refractive-index film layer is effective for filling voids on the surface of the antistatic / high-refractive-index film layer, suppressing irregular reflection, and improving its friction resistance.

The low-refractive-index film layer can be formed by applying a coating composed of a non-aqueous solvent solution containing silicon alkoxide on the antistatic / high-refractive-index film layer, drying it, and subjecting it to a baking treatment. Silicon alkoxide used in the coating material for forming the low refractive index film layer can be selected from tetraalkoxysilane-based compounds, alkyltrialkoxysilane-based compounds, dialkyldialkoxysilane-based compounds, and the like. It can be selected from compounds, glycol ether compounds, ester compounds, ketone compounds and the like. These may be used alone or as a mixture of two or more.

When the above coating material is applied to the antistatic / high-refractive-index film layer, dried and baked, the silicon alkoxide hydrolysis product becomes silica. The refractive index of silica is n = 1.46, which is lower than the refractive index of antimony-doped tin oxide. However, in order to increase the refractive index difference between the antistatic / high refractive index film layer and the low refractive index film layer. Is preferably a combination of a substance having a lower refractive index and a higher transparency than silica.

In the present invention, it is preferable that the silicon alkoxide-containing coating material further contains magnesium fluoride (n = 1.38) fine powder. The content of the magnesium fluoride fine powder in the low-refractive-index film layer is not particularly limited, and can be appropriately adjusted according to the composition of the corresponding antistatic / high-refractive-index film layer. 0.01 to the weight of silicon alkoxide (in terms of SiO ₂ )
Preferably it is within the range of 50%.

The magnesium fluoride fine powder used for forming the low refractive index film layer preferably has an average particle size of 1 to 100 nm. When the average particle size is larger than 100 nm, light is irregularly reflected due to Rayleigh number disorder in the obtained low refractive index film layer, and the low refractive index film layer looks whitish, and its transparency may be reduced. Is 1
If it is less than nm, the fine particles are likely to agglomerate, which makes it difficult to uniformly disperse the fine particles in the paint, and causes problems such as an excessive increase in the viscosity of the paint. Further, when the amount of the solvent used is increased in order to lower the viscosity of the paint, there arises a problem that the concentrations of the magnesium fluoride fine powder and the silicon alkoxide in the paint are reduced.

The magnesium fluoride fine powder used in the present invention can be obtained by a gas phase method (gasification of the compound, cooling and solidification of the compound in the gas phase), a CVD method (gasification of the component elements, And the product is cooled and solidified), and the carbonate (or oxalate) method (transformation from the carbonate or oxalate of the metal element in the gas phase and cooling and solidification) is performed. Can be manufactured. An acid-alkali method for producing an ultrafine sol of the target compound by mixing and reacting an aqueous solution of a fluoride of a component element and an aqueous solution of a basic compound, or a hydrothermal method for removing a solvent therefrom, etc. It can be used for producing powder. In the above hydrothermal method, the growth of fine particles, spheroidization,
Alternatively, the surface can be modified. Further, the shape of the fine particles may be any of spherical, needle-like, plate-like, and chain-like.

In the present invention, the thickness of the low refractive index film layer is not particularly limited, but preferably has a thickness of 0.05 to 0.2 nm. Since the low refractive index film layer having a thickness in the above range is relatively thin, even if it covers the antistatic / high refractive index film layer, the conductive property of the antistatic / high refractive index film layer can be reduced. Depending on the properties, practically sufficient antistatic properties and electromagnetic wave shielding properties can be exhibited.

The transparent substrate used in the present invention can be selected from glass materials, plastic materials and the like. Further, the coloring agent used in the present invention can be appropriately selected from those conventionally used for the material and the paint.

[0027]

The present invention will be further described with reference to the following examples.

Example 1 (1) A coating (A) for forming an antistatic / high-refractive-index film layer was prepared as follows. That is, 2.8 g of antimony-doped tin oxide fine powder (manufactured by Sumitomo Cement Co., particle size: 5 to 5 g)
10 nm) and 0.3 g (in terms of SiO ₂ ) of a polyether-modified silicone oil (silicone surfactant, trademark:
L-77, manufactured by Nippon Unicar Co., Ltd.) in 196.4 g of water, and the mixture was stirred to form a uniform dispersion.

(2) A coating material (a) for forming a low refractive index film layer was prepared by the following operation. That is, 0.8 g of tetraethoxysilane, 0.8 g of 0.1 N hydrochloric acid, 9 g
9.2 g of ethyl alcohol was mixed to obtain a uniform solution. (3) Production of Laminate The coating material (A) was applied on one surface of a glass substrate at a temperature of 40 ° C. by a spin coating method, and dried with warm air of 50 ° C. for 3 minutes. An antistatic / high refractive index film layer having a thickness of 0.1 μm was formed. Next, the coating material (a) is applied on the antistatic / high-refractive-index film layer of this glass substrate at a temperature of 40 ° C. by a spin coating method.
And baked at 150 ° C. for 20 minutes to form a 0.1 μm-thick low-refractive-index film layer.

(4) Test The surface resistivity (by a surface resistance meter) and the surface reflectance (wavelength by a spectrophotometer using a regular reflection jig of an incident angle of 5 °) of the transparent material laminate obtained as described above. The single-sided value of the light reflectance at 550 nm was measured.) And the adhesion between the antistatic / high-refractive-index film layer and the low-refractive-index film layer (eraser test, load 1 kg, 50 reciprocations) was measured. Table 1 shows the test results.

Example 2 The same operation as in Example 1 was performed. However, the paint (b) prepared as described below was used instead of the paint (a) for forming a low refractive index film layer. That is, 0.4 g of magnesium fluoride fine powder (manufactured by Sumitomo Cement Co., particle size: 10 to 20 nm) was added to 0.6 g of tetraethoxysilane, 10 g of water, 0.6 g of
g of 0.1N hydrochloric acid and 89 g of ethyl alcohol, and uniformly dispersed. Table 1 shows the test results.

Example 3 The same operation as in Example 1 was performed. However, instead of the coating material (a) for forming a low refractive index film, a coating material (c) prepared as follows was used. That is, the coating (c) for forming a specific wavelength selective absorption / low refractive index film layer was prepared as follows. 0.
After mixing 8 g of tetraethoxysilane and 0.8 g of 0.1 N hydrochloric acid with 98.9 g of ethyl alcohol, a colorant (Chugano Violet3BN 33%, manufactured by Chugai Chemical Co., Ltd., Acid)
Green V conc. 5%, Kayanol Millin, manufactured by Nippon Kayaku
g 52% Red 6BW and Neo Super Bl manufactured by Chuo Gosei Kagaku Co., Ltd.
0.3 g of a mixture with 10% of ue C-551) was added thereto, followed by stirring to obtain a uniform solution. Table 1 shows test results
Shown in

Comparative Example 1 The same operation as in Example 1 was performed. However, the antistatic
A coating material (B) prepared as follows was used instead of the coating material (A) for forming a high refractive index film layer. That is, 1 g of antimony-doped tin oxide (particle size: 5 to 10 nm) was mixed with 1.68 g of tetraethoxysilane, 4.1 g of 0.1 N hydrochloric acid, and 143 g of ethyl alcohol, and uniformly dispersed. Table 1 shows the test results.

Comparative Example 2 The same operation as in Example 1 was performed. However, instead of the antistatic / high-refractive-index film-forming coating (A), a coating (C) prepared as follows was used. That is, 2 g of antimony-doped tin oxide (particle size 5 to 10 nm) was added to 1.1 g
g (SiO ₂ equivalent) of silicone oil and 196.
It was mixed with 4 g of water and dispersed uniformly. Table 1 shows test results
Shown in

[0035]

[Table 1]

[0036]

The coating material for forming an antistatic / high-refractive-index film according to the present invention is a film having excellent antistatic properties, a high refractive index, and excellent adhesion to a low-refractive-index film layer on a transparent substrate. The layer can be easily and inexpensively formed by using water as a solvent. In particular, a low-refractive-index film is formed on an antistatic / high-refractive-index film layer obtained by using the same. By combining the layers, it has become possible to provide a transparent material laminate with an antistatic / antireflection film having excellent practical performance and a display device.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C09D 1/00 C09D 1/00 5/24 5/24 183/04 183/04 H04N 5/72 H04N 5/72 A // G02B 1/11 G02B 1/10 A (58) Field surveyed (Int. Cl. ⁶ , DB name) C09D 5/00 C09D 5/24 C09D 1/00

Claims (10)

(57) [Claims] 1. Fine powder of tin oxide doped with antimony
80 to 99.99 parts by weight and silicone oil 0.01 to
A coating for forming an antistatic / high-refractive-index film, comprising an aqueous dispersion containing a mixture with 20 parts by weight (in terms of SiO ₂ ) . 2. The antimony-doped tin oxide fine powder is 1
2. The coating for forming an antistatic / high-refractive-index film according to claim 1, having an average particle diameter of from about 100 nm to about 100 nm. 3. The method according to claim 1, wherein the silicone oil comprises an amino group, a carboxyl group, an epoxy group, a hydroxyl group, a polyether group,
Selected from organosiloxane compounds having at least one selected from an ester group and an alkoxy group
The coating for forming an antistatic / high-refractive-index film according to claim 1, wherein: 4. The coating for forming an antistatic / high-refractive-index film according to claim 1, further comprising a colorant having an absorption center wavelength near 600 nm. 5. A transparent substrate, and on the surface of the transparent substrate,
An antistatic / high-refractive-index film layer formed by applying and drying the antistatic / high-refractive-index film-forming coating according to claim 1, and formed on the antistatic / high-refractive-index film layer, And a low-refractive-index film layer having a refractive index lower than the refractive index by 0.1 or more. 6. The low-refractive-index film layer is formed by applying and drying a paint containing a silicon alkoxide and a non-aqueous solvent on the antistatic / high-refractive-index film layer, and subjecting the coating to a baking treatment. 6. The antistatic / antistatic device according to claim 5, wherein
A transparent material laminate with an anti-radiation film . 7. The antistatic / reflective material according to claim 6, wherein the silicon alkoxide-non-aqueous solvent-containing paint further contains a magnesium fluoride fine powder dispersed therein.
A transparent material laminate with a protective film . 8. The method according to claim 1, wherein the magnesium fluoride fine powder is 1 to 1
The transparent material laminate with an antistatic / antireflection film according to claim 7, having an average particle diameter of 00 nm. 9. The antistatic / antistatic material according to claim 5, wherein the colorant is colored by a colorant having an absorption center wavelength near 600 nm, thereby having a filter function.
A transparent material laminate with an anti-radiation film . 10. The antistatic and high refractive index according to claim 1.
Antistatic and high formed by coating and drying the film-forming paint
Formed on the refractive index film layer and this antistatic / high refractive index film layer
And has a refractive index lower by 0.1 or more than that
Low refractive index film layer is formed at least on the display surface
A display device.