JP2000212514A - Composition for forming spray membrane and transparent electroconductive membrane having spray membrane formed by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in durability and stain resistance by including a specific silicon alkoxide oligomer. SOLUTION: This composition for forming a spray membrane contains one or more kinds of compounds selected from the group consisting of a metal alkoxide having a 1-4C alkoxy (the metal is Si, Ti, Sn or Zr) and a silicon alkoxide oligomer represented by the formula (SiO)n(OR1)4-2n (n is 0-1; R1 is a 1-4C alkyl group), a fluoroalkylsilane, an acid catalyst and a solvent in (4:1) to (6:1) weight ratio of the compound to the fluoroalkylsilane. The spray membrane from the above composition can be formed in the outermost corner layer to realize the water repellency and thereby prevent a reduction in membrane strength of a transparent electroconductive membrane and an increase in membrane staining thereof caused by water permeation in use or storage under high-temperature and high-humidity conditions.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for forming a spray film used in the production of a transparent conductive film for an image display device such as a cathode ray tube, and more particularly to a composition having improved durability and contamination resistance. The present invention relates to an excellent composition for forming a spray film, and to a transparent conductive film having a spray film formed using the composition.

[0002]

2. Description of the Related Art A transparent conductive film is a thin conductive thin film formed on the surface of an insulating material having a high light transmittance. The transparent conductive film is an antistatic film of an electric appliance, an electromagnetic wave shielding film, a flat panel liquid crystal display device, or an electric field. It is widely used for transparent electrodes for applying power to light emitting elements.

In some cases, the present invention provides an antistatic and antireflection function mounted on the outer surface of a panel of a cathode ray tube. The present invention particularly relates to this field.

As one method of forming a transparent conductive film on the outer surface of a glass panel of a cathode ray tube, there is a wet coating method. This method comprises: a metal oxide, a metal alkoxide,
Alternatively, it is a method of spraying a mixed dispersion comprising a silicon alkoxide and a solvent on the surface of a cathode ray tube and then thermally curing the mixture.

As an improved method, a composition for forming a conductive film containing a high-refractive-index conductive material having a high purity and a solvent is coated on a glass panel, dried, and then cooled to form a conductive film. Form. A composition containing a silicon alkoxide or a metal alkoxide, a hydrolysis catalyst, and a solvent is applied over the conductive film, and then dried and cooled to form a protective film. Then, there is a method in which silica is sprayed on the protective film to scatter light incident from the outside to form an uneven spray film that can prevent reflection.

However, when the transparent conductive film absorbs moisture from the outside, the surface of the film may be stained. Such stains on the surface of the film frequently occur not only during long-term transport and storage, but also during manufacture and use, and are difficult to remove, resulting in deterioration of product quality. In addition, there is a problem that the film strength is rapidly lowered due to the absorbed water, and the film is peeled off or dropped off.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is therefore an object of the present invention to provide a composition for forming a spray film having durability and stain resistance. .

Another object of the present invention is to provide a spray film formed by using the above-mentioned composition, so that its characteristics can be maintained even when stored or used for a long time in a poor external environment, particularly in a high-temperature and high-humidity environment. An object of the present invention is to provide a transparent conductive film which is not deteriorated and hardly contaminated by an external contamination source.

[0009]

An object of the present invention is to provide a metal alkoxide having an alkoxy having 1 to 4 carbon atoms, wherein the metal is Si, Ti, Sn or Zr.
And chemical formula 1:

[0010]

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(Wherein n is a real number from 0 to ¹ and R ¹ is an alkyl group having 1 to 4 carbon atoms) selected from the group consisting of silicon alkoxide oligomers represented by the formula:
At least one compound, a fluoroalkylsilane, an acid catalyst, and a solvent, wherein the weight ratio of the compound to the fluoroalkylsilane is from 4: 1 to 6: 1. Is done.

Further, the present invention is characterized in that the solvent is a mixed solvent containing at least one selected from the group consisting of methanol, ethanol, isopropyl alcohol, N-methylpyrrolidone, dimethylformamide, and water. The composition for forming a spray film.

Still another object of the present invention is a transparent conductive film in which a conductive film and a spray film are sequentially formed on a glass panel, wherein the spray film has 1 to 4 carbon atoms.
(Wherein the metal is Si, Ti, Sn or Zr), and a chemical formula 1:

[0014]

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(Wherein n is a real number of 0 to ¹ and R ¹ is an alkyl group having 1 to 4 carbon atoms) at least one compound selected from the group consisting of silicon alkoxide oligomers And a hydrolyzate of fluoroalkylsilane in a weight ratio of 4: 1 to 6: 1.

Further, according to the present invention, the conductive film contains at least one conductive substance selected from the group consisting of indium tin oxide, indium titanium oxide, tin oxide, titanium oxide, antimony tin oxide, and antimony zinc oxide. The transparent conductive film described above.

Further, the present invention provides a metal alkoxide having an alkoxy having 1 to 4 carbon atoms (wherein the metal is Si, Ti, Sn or Zr) between the conductive film and the spray film. :

[0018]

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(Wherein n is a real number from 0 to ¹ and R ¹ is an alkyl group having 1 to 4 carbon atoms) An oligomer of at least one compound selected from the group consisting of silicon alkoxides The transparent conductive film according to claim 1, further comprising a protective film comprising:

Further, according to the present invention, the spray film formation area is preferably 30 to 7 with respect to the total area of the glass panel.
0% of the transparent conductive film.

[0021]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The composition for forming a spray film of the present invention comprises a metal alkoxide having an alkoxy having 1 to 4 carbon atoms (wherein the metal is Si, Ti, Sn or Zr);
And chemical formula 1:

[0023]

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(Wherein n is a real number from 0 to 1 and R is an alkyl group having 1 to 4 carbon atoms) at least one compound selected from the group consisting of silicon alkoxide oligomers , A fluoroalkylsilane, an acid catalyst, and a solvent.

Examples of the fluoroalkylsilane include fluoromethoxysilane, fluoroethoxysilane, and fluoroisopropoxysilane.
The content is from 4: 1 to 6: 1 by weight of the compound and the fluoroalkylsilane. When the content is less than this range, the water repellency is not sufficient. On the other hand, when the content exceeds this range, the film strength is rather increased. It is not desirable because it may lead to a decrease in

As the acid catalyst, any acid catalyst which can be generally used in the field of the present invention can be used. For example, nitric acid or hydrochloric acid is used.

The solvent may be at least one mixed solvent selected from the group consisting of alcohols such as methanol, ethanol and isopropyl alcohol, N-methyl-2-pyrrolidone (NMP), dimethylformamide and water. desirable.

Further, the transparent conductive film of the present invention is one in which a conductive film and a spray film are sequentially formed on a glass panel. The spray film may include a hydrolyzate of one or more compounds selected from the group consisting of the metal alkoxide and the silicon alkoxide oligomer represented by Formula 1 and a hydrolyzate of fluoroalkylsilane in a ratio of 4: 1. When it is contained in a weight ratio of 6: 1 and is less than this range, the water repellency is not sufficient. On the other hand, when it exceeds this range, the film strength may be reduced, which is not desirable. Examples of the fluoroalkylsilane are the same as those described above.

In the transparent conductive film of the present invention, the conductive layer contains a conductive material such as indium tin oxide, indium titanium oxide, tin oxide, titanium oxide, antimony tin oxide, and antimony zinc oxide.

If necessary, a hydrolyzate of at least one compound selected from the group consisting of the metal alkoxide and the silicon alkoxide oligomer represented by the chemical formula 1 may be provided between the conductive film and the spray film. May further include a protective film.

On the other hand, it is desirable that the spray film is formed in about 30 to 70% of the area of the glass panel, but if it is less than 30%, environmental resistance and stain resistance are not as expected. If the ratio exceeds the% range, there is a problem that the resolution of an image display device employing the ratio is hindered, which is not desirable.

The transparent conductive film of the present invention is characterized in that the transparent conductive film is provided with water repellency by a hydrolyzate of fluoroalkylsilane contained in the spray film of the outermost corner layer. FIG. 1 schematically shows a water-repellent state of a normal transparent conductive film, and FIG. 2 schematically shows a water-repellent state of the transparent conductive film of the present invention.

After dropping water drops on each transparent conductive film,
As a result of measuring the contact angle, in the case of a normal transparent conductive film,
The angle is about 40 to 42 ° (α in FIG. 1), whereas in the case of the transparent conductive film of the present invention, it is about 84 to 85 ° (90 ° −β in FIG. 2). From these test results, it can be seen that the transparent conductive film provided with the spray film containing the hydrolyzate of fluoroalkylsilane exhibits extremely excellent water repellency. Therefore, even if such a transparent conductive film is used or stored for a long time under conditions of high temperature and high humidity, the film strength does not decrease and is hardly contaminated by an external contamination source.

A method for manufacturing a transparent conductive film according to one embodiment of the present invention will be schematically described. First, indium tin oxide,
A metal oxide having a high refractive index, such as indium titanium oxide, tin oxide, titanium oxide, antimony tin oxide, and antimony zinc oxide, is mixed with a mixed organic solvent containing alcohol, N-methyl-2-pyrrolidone, dimethylformamide, or water. Disperse. This dispersion is spin-coated on a glass panel and cured to form a conductive film having a high refractive index.

Next, a silicon oxide having a low refractive index is dissolved in a mixed organic solvent, and an acid catalyst such as hydrochloric acid or nitric acid is added thereto and reacted at about 50 ° C. for about 1 hour. Next, this composition is spin-coated on the conductive film and cured to form a protective film.

Next, the silicon alkoxide and the fluoroalkylsilane are dissolved in an organic solvent mixture, an acid catalyst is added thereto, and the mixture is reacted at about 50 ° C. for about 24 hours. After spraying the obtained composition on the protective film, it is dried to form a spray film. At this time, the area of the formed spray film is preferably in the range of 30 to 70% of the area of the glass panel. The transparent conductive film thus formed has excellent durability and stain resistance.

Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention is not limited to this.

[0038]

<Example 1> 2 g of indium tin oxide was added to 1
Dispersion prepared by dispersing in
After spin coating on a glass panel of a cathode ray tube at a speed of 50 rpm, it was dried to form a conductive film.

Next, after dissolving 0.8 g of tetraethyl orthosilicate in 100 ml of ethanol, 0.3 ml of hydrochloric acid was added thereto and reacted. The obtained composition was spin-coated on the conductive layer at a speed of 150 rpm and dried to form a protective film.

Finally, a mixture of 1.2 g of tetraethylorthosilicate and 0.25 g of heptadecafluorodecyltrimethoxysilane was dissolved in 100 ml of ethanol, and 0.25 ml of nitric acid was added thereto for reaction. The obtained composition was spray-coated on the protective layer using a spray gun and dried to form a spray layer, and the resultant was fired at 200 ° C. for 2 hours to obtain a transparent conductive film.

The obtained transparent conductive film was subjected to severe conditions (temperature:
After standing at 45 ° C. and a relative humidity of 95 RH for 24 hours, the surface resistance and the film strength were measured, and the occurrence of stains was visually observed. The results are shown in Table 1 below.

Example 2 The same method as in Example 1 except that the same amount of heptadecafluorodecyltriisopropoxysilane was used instead of heptadecafluorodecyltrimethoxysilane to form a spray film. Thus, a transparent conductive film was formed. The surface resistance and the film hardness of the transparent conductive film were measured in the same manner as in Example 1, and the presence or absence of stains was observed. The results are shown in Table 1.

Comparative Example 1 1.5 g of tetraethylorthosilicate was dissolved in a mixed solvent of 40 ml of methanol, 40 ml of isopropyl alcohol and 20 ml of normal butyl alcohol, and 0.25 ml of nitric acid was added thereto.
A transparent conductive film was formed in the same manner as in Example 1, except that a spray film was formed using the composition obtained by adding and reacting the compound. The surface resistance and the film hardness of the transparent conductive film were measured in the same manner as in Example 1, and the presence or absence of stains was observed. The results are shown in Table 1.

[0044]

[Table 1]

From the results shown in Table 1, the transparent conductive film of the present invention was
It can be seen that the film strength can still be maintained even when stored for a long time under severe conditions. Further, since no stain is generated on the surface, it can be seen that the stain resistance is excellent and the surface resistance is maintained at the same level as the conventional transparent conductive film.

[0046]

As described above, the transparent conductive film according to the present invention has a water-repellent spray film in the outermost corner layer. Problems such as a decrease in membrane strength caused by permeation and an increase in membrane contamination can be prevented.

[Brief description of the drawings]

FIG. 1 is a schematic view of an electron micrograph showing the form of a water drop dropped on the surface of a conventional transparent conductive film.

FIG. 2 is a schematic view of an electron micrograph showing a form of a water drop dropped on a surface of a transparent conductive film according to the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme court ゛ (Reference) H01J 9/20 H01J 9/20 A 29/88 29/88 (72) Inventor Kim Jun-hime Seoul Special City of Korea 245 -31 245 Yaa-dong, Gangbuk-gu

Claims (6)

[Claims] 1. A metal alkoxide having an alkoxy having 1 to 4 carbon atoms (wherein the metal is Si, Ti, Sn or Zr), and a chemical formula 1: (In the above formula, n is a real number of 0 to ¹ , and R ¹ has 1 to 4 carbon atoms.
Is an alkyl group. ) Comprising at least one compound selected from the group consisting of silicon alkoxide oligomers, a fluoroalkylsilane, an acid catalyst, and a solvent, wherein the weight ratio of the compound to the fluoroalkylsilane is
A composition for forming a spray film, wherein the composition is from 4: 1 to 6: 1. 2. The method according to claim 1, wherein the solvent is methanol, ethanol,
1 selected from the group consisting of isopropyl alcohol, N-methylpyrrolidone, dimethylformamide, and water
2. A mixed solvent containing at least one species.
The composition for forming a spray film according to item 1. 3. A transparent conductive film in which a conductive film and a spray film are sequentially formed on a glass panel, wherein the spray film is a metal alkoxide having an alkoxy having 1 to 4 carbon atoms (wherein Metals are Si, Ti, S
n or Zr), and Formula 1: Wherein n is a real number of 0 to ¹ and R ¹ is an alkyl group having 1 to 4 carbon atoms. Hydrolysis of one or more compounds selected from the group consisting of silicon alkoxide oligomers And a hydrolyzate of a fluoroalkylsilane in a weight ratio of 4: 1 to 6: 1. 4. The conductive film includes at least one conductive material selected from the group consisting of indium tin oxide, indium titanium oxide, tin oxide, titanium oxide, antimony tin oxide, and antimony zinc oxide. The transparent conductive film according to claim 3. 5. A metal alkoxide having an alkoxy having 1 to 4 carbon atoms (where the metal is Si, Ti, Sn or Zr) between the conductive film and the spray film;
And chemical formula 1: (Wherein, n is a real number of 0 to ¹ and R ¹ is an alkyl group having 1 to 4 carbon atoms.) An oligomer of one or more compounds selected from the group consisting of silicon alkoxides represented by The transparent conductive film according to claim 3, further comprising a protective film. 6. The transparent conductive film according to claim 3, wherein a formation area of the spray film is 30 to 70% based on a total area of the glass panel.