JP2003217346A - Method for manufacturing colored transparent conductive film forming composition and glass with colored transparent conductive film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a colored transparent conductive film forming composition capable of simply coloring a glass base plate without impairing conductivity; and glass with colored transparent conductive film. <P>SOLUTION: The colored transparent conductive film forming composition comprises a treating liquid obtained by mixing a conductive fine particle dispersion liquid and at least one colloid dispersion liquid selected from a gold colloid dispersion liquid and a silver colloid dispersion liquid. The weight ratio (A/B) of a solid content (A) of the colloid dispersion liquid and a solid content (B) of the conductive fine particle dispersion liquid is 0.01-0.8. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a composition for forming a colored transparent conductive film and a method for producing a glass with a colored transparent conductive film. More specifically, a glass substrate can be colored easily without impairing the conductivity of the transparent conductive film. And a method for producing a heat-resistant colored conductive film having excellent heat resistance.

[0002]

2. Description of the Related Art Conventionally, as a method for forming a colored transparent conductive film, (1) colloidal metal fine particles, a dispersion stabilizer adsorbed on the surface of the colloidal metal fine particles, and an aggregation attractant for aggregating the colloidal metal fine particles. , And a treatment solution containing water, tetraethoxysilane, ethanol, nitric acid, etc. are alternately applied and laminated on a glass substrate to form a slightly colored colored transparent conductive film. No. 10-110123) (2) Black or chromatic inorganic pigments and metal compounds (indium, tin, zinc,
A method of forming a colored transparent conductive film by coating and baking a treatment liquid composed of an antimony compound) and a binder (a heat decomposable resin, a photodegradable resin or a photopolymerizable resin) on a glass substrate (JP-A-09-237518). (Japanese Patent Laid-Open No. 2001-58851), and (3) a method of forming a colored transparent conductive film by a spray method or a CVD method.

[0003]

However, a treatment liquid containing an organic silver compound, a dispersion stabilizer, a flocculation attractant, water and a treatment liquid containing tetraethoxysilane, ethanol, nitric acid, etc. are coated and laminated on a glass substrate. The method for forming a slightly colored colored transparent conductive film is
Since it was necessary to apply twice, there was a problem that productivity was poor.

Further, a treatment liquid comprising a black or chromatic color inorganic pigment, a metal compound (a compound of indium, tin, zinc, antimony) and a binder (a heat decomposable resin, a photodegradable resin or a photopolymerizable resin) is treated with glass. The method of forming a colored transparent conductive film by coating and baking on a substrate has a problem that heat resistance is poor because a resin is contained in the composition.

Further, the method of forming a colored transparent conductive film by the spray method or the CVD method has a drawback that productivity is deteriorated because large-scale production equipment is required.

The present invention solves such a problem, and provides a composition for forming a colored transparent conductive film and a method for producing a glass with a colored transparent conductive film, which can be easily colored without impairing the conductivity of the glass substrate. The purpose is to provide.

[0007]

That is, the invention according to claim 1 of the present application is to mix a conductive fine particle dispersion with at least one colloidal dispersion selected from a gold colloidal dispersion and a silver colloidal dispersion. In the composition for forming a colored transparent conductive film comprising the treated liquid, the fixed conductive fine particles carry conductivity, while gold and / or silver are colloidally dispersed in a state surrounded by the conductive fine particles. In addition, it is transparent and can be colored from red to yellow.

The invention according to claim 2 of the present application comprises the solid content (A) of at least one colloidal dispersion selected from the gold colloidal dispersion and the silver colloidal dispersion, and the solid content (B) of the conductive fine particle dispersion. Has a weight ratio (A / B) of 0.01 to
The composition for forming a colored transparent conductive film having a concentration of 0.8.

According to a third aspect of the present invention, the weight ratio (A / B) of the solid content (A) of the colloidal dispersion and the solid content (B) of the conductive fine particle dispersion is 0.01 to 0. No. 4, which is the composition for forming a colored transparent conductive film.

The invention according to claim 4 of the present application includes claims 1 to 1.
In the method for producing a glass with a colored transparent conductive film, which comprises coating the composition for forming a colored transparent conductive film according to any one of 3 above on a glass substrate and firing the conductive fine particles fixed on the glass substrate. On the other hand, since gold and / or silver are colloidally dispersed in a state of being surrounded by conductive fine particles, transparent and red or yellow coloring is possible.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The conductive fine particle dispersion liquid used in the present invention comprises zinc oxide, tin oxide, antimony-doped tin oxide, which are fine particles having a primary particle diameter of several nm to several tens nm.
Add tin-doped indium oxide to ethanol or propanol
10 to 30% by weight is dispersed in a dispersion medium such as alcohols such as ethylene glycol, glycols such as ethylene glycol and hexylene glycol, aromatic hydrocarbons such as toluene and xylene. If the primary particle diameter of the fine particles is larger than several tens of nm, packing at the time of film formation is deteriorated and the electric resistance value is not lowered.

The gold colloidal dispersion liquid and the silver colloidal dispersion liquid used in the present invention are 1) protected by a pigment dispersant and dispersible in a solvent such as alcohol, ketone, ether or toluene, and have a particle size of 1 to 100 nm. Preferably 1 to 50 nm
Gold fine particles, silver fine particles produced by reducing the gold ion of, or 2) produced by a vapor deposition method in a gas,
Gold particles or silver particles having a particle size of 1 to 100 nm, preferably 1 to 50 nm are independently dispersed in a solvent such as α-terpineol, toluene, or 3) the particle size is 1 to 1
Examples thereof include gold fine particles and silver fine particles having a thickness of 100 nm, preferably 1 to 50 nm, which are dispersed in a polymer or oligomer soluble in a solvent such as alcohol, ketone, ether, and toluene.

As the above-mentioned polymer or oligomer,
Terminal or side chain cyano group of a molecule (-CN), amino group (-NH _2), and are those having at least one functional group selected from a thiol group (-SH), the functional group is particularly fine It is easy to form a covalent bond or a coordinate bond with the gold atom on the surface of the, the grain growth is suppressed, and the dispersibility of fine particles is enhanced. The skeleton of the above polymer or oligomer is made of polyethylene oxide, polyethylene glycol, polyvinyl alcohol, nylon 11, nylon 6, nylon 66, nylon 6.10, polyethylene terephthalate, polystyrene, etc., and its melting point or softening point is 40 to 100 ° C. Is. The average molecular weight of the oligomer is not particularly limited, but is about 500 to 6,000.

In the gold colloidal dispersion liquid and the silver colloidal dispersion liquid, it is desirable that the particles have a particle diameter of several nm to several tens nm. If particles of 100 nm or more are present, the color developability deteriorates and sufficient coloring cannot be achieved.

The weight ratio (A / B) between the solid content (A) of at least one colloidal dispersion selected from the gold colloidal dispersion and the silver colloidal dispersion and the solid content (B) of the conductive fine particle dispersion is It is preferably 0.01 to 0.8, and more preferably 0.01 to 0.4. When the weight ratio exceeds 0.8, the amounts of the gold colloid dispersion liquid and the silver colloid dispersion liquid are large. When it is excessively baked, a gold film or a silver film is formed on the glass surface and the transparency is impaired. On the other hand, 0.01
If the amount is less than the above, the solid content of the gold colloid dispersion liquid and the silver colloid dispersion liquid is too small, and the coloring effect is lost.

The method for producing a glass with a colored transparent conductive film which can be easily colored without impairing the conductivity of the glass substrate is as follows:
Spray, dip, roll coat on a glass substrate made of soda lime glass, quartz glass, or alkali-free glass.
After being applied by a method such as coating and spin coating and drying the solvent, it is baked in a furnace at 500 to 800 ° C. for 10 to 50 minutes, and cooled to obtain glass with a colored transparent conductive film.

If the firing temperature is less than 500 ° C., a sufficient electric resistance value of the film cannot be obtained. On the other hand, when the temperature exceeds 800 ° C., the coloring of the gold fine particles and the silver fine particles becomes insufficient, and the function as the heat resistant colored transparent conductive film cannot be achieved.

[0018]

Next, the present invention will be described in more detail with reference to specific examples. The evaluation method of the glass with a colored transparent conductive film is as follows.

1. Optical characteristics In order to determine the transparency of the glass with a transparent conductive film, the Hz ratio, the transmittance and the transmitted color tone were measured using a color difference meter and a turbidimeter.

2. After the glass with a heat-resistant colored transparent conductive film was left in an oven at 700 ° C. for 0.5 hour, the state of the coating film before and before that was visually confirmed.

3. Electrical Properties Coloring To measure the electrical properties of the glass with a transparent conductive film, Loresta FP was used, and the electrical properties were measured by the four-point probe method.

Examples 1 to 6 and Comparative Examples 3 to 4 Examples 1 to 6 and Comparative Examples 3 to 4 have the composition shown in Table 1 and are conductive fine particle dispersions prepared by dispersing tin-doped indium oxide fine particles in ethanol. A silver colloid dispersion liquid was prepared by mixing a gold colloid dispersion liquid in which gold colloid was dispersed in terpineol and a dispersion liquid in which silver colloid was dispersed in ethanol. A spin coating method (3,000 rpm × 20 s) on a soda lime glass substrate having a thickness of 3.5 mm using the treatment liquid.
The coated substrate was dried at 100 ° C. for 5 minutes and then baked in a muffle furnace at 600 ° C. for 10 minutes to prepare a glass with a colored transparent conductive film having a thickness of about 1 μm. Table 1 shows the results of the heat resistance test and the electrical property evaluation of the obtained glass with a colored transparent conductive film.

Comparative Example 1 In Comparative Example 1, an organic paint in which conductive fine particles were dispersed in an epoxy resin was applied on a soda lime glass substrate having a thickness of 3.5 mm by a bar coater and baked at 180 ° C. for 30 minutes. I used the one. Table 1 shows the results of the heat resistance test and the electrical property evaluation of the obtained glass with a colored transparent conductive film.

Comparative Example 2 In Comparative Example 2, only the conductive fine particle dispersion liquid has a thickness of 3.5 mm.
It was applied on a soda lime glass substrate of, dried at 100 ° C. for 5 minutes, and baked at 600 ° C. for 10 minutes. Table 1 shows the results of the heat resistance test and the electrical property evaluation of the obtained glass with a colored transparent conductive film.

Comparative Examples 5-6 In Comparative Examples 5-6, the conductive fine particles of Example 1 and Example 3 were applied onto a soda lime glass substrate having a thickness of 3.5 mm by spin coating (3,000 rpm × 20 s). The coated glass substrate is dried at 100 ° C. for 5 minutes, and then the gold colloid dispersion liquid and the silver colloid dispersion liquid are coated by the spin coating method (3,000 rpm × 20 s), and the coated glass substrate is heated at 100 ° C. for 5 minutes. After being dried for a minute, it was baked in a muffle furnace at 600 ° C. for 10 minutes to prepare a glass with a colored transparent conductive film having a thickness of about 1 μm. Table 1 shows the results of the heat resistance test and the electrical property evaluation of the obtained glass with a colored transparent conductive film.

[0026]

[Table 1]

As shown in Table 1, with respect to heat resistance, it was confirmed that Comparative Example 1 cannot be used under the condition that heat resistance is required because the coating film disappears after heating at 700 ° C. for 0.5 hours. It was On the other hand, Examples 1 to 6 and Comparative Example 2
In No. 6, it was confirmed that the coating film remained even after heating at 700 ° C. for 0.5 hours, and that it had sufficient heat resistance.

Table 1 shows Hz of Examples 1-6 and Comparative Examples 1-6.
The ratio, the transmittance, and the transmission color tone are shown. In Comparative Example 1, it can be confirmed that there is no coloring, as indicated by the transmitted color tone. On the other hand, in Examples 1 to 2 and 5 to 6, the transmission color tone is red, and in Examples 3 to 4, the transmission color tone is yellow.
It is shown that the silver colloid is dispersed and fixed in the transparent conductive film made of conductive fine particles without significantly impairing the electrical characteristics.

It was also confirmed that the shade of coloring can be adjusted by changing the ratio of the solid content of the conductive fine particle dispersion to the gold colloid dispersion solid content and the silver colloid dispersion solid content. In Comparative Examples 3 to 6, the gold colloid and the silver colloid are not fixed to the transparent conductive fine particles and are deposited on the surface to form a gold film or a silver film on the film surface, resulting in impaired transparency and a transparent conductive film. Will no longer function.

Table 1 shows Examples 1 to 6 and Comparative Examples 1 to 1.
6 shows the results of evaluation of electrical characteristics of Example 6, Examples 1 to 6 have a smaller amount of change in electric resistance value as compared with Comparative Example 1, and the ratio of the conductive fine particles to the gold fine particles or the silver fine particles according to claim 1. It was confirmed that there was little change in the electric resistance value due to coloring inside.

[0031]

As described above, according to the invention described in the claims of the present application, a colored transparent mixture of a conductive fine particle dispersion liquid, a gold colloid dispersion liquid and at least one colloid dispersion liquid selected from a silver colloid dispersion liquid is mixed. A method for producing a glass with a colored transparent conductive film, which comprises coating a composition for forming a conductive film and the composition on a glass substrate and baking the composition, which has excellent heat resistance and does not impair the electrical properties of the transparent conductive film. Glass with a conductive film can be manufactured.

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Claims (4)

[Claims] 1. A colored transparent conductive film forming method comprising a treatment liquid in which a conductive fine particle dispersion liquid and at least one colloidal dispersion liquid selected from a gold colloid dispersion liquid and a silver colloid dispersion liquid are mixed. Composition. 2. A weight ratio (A / B) of the solid content (A) of at least one colloidal dispersion selected from the gold colloidal dispersion and the silver colloidal dispersion and the solid content (B) of the conductive fine particle dispersion. Is 0.01 to 0.8, The composition for forming a colored transparent conductive film according to claim 1. 3. The weight ratio (A / B) between the solid content (A) of the colloidal dispersion and the solid content (B) of the conductive fine particle dispersion is 0.01 to 0.4. A composition for forming a colored transparent conductive film. 4. A method for producing a glass with a colored transparent conductive film, which comprises applying the composition for forming a colored transparent conductive film according to any one of claims 1 to 3 onto a glass substrate and baking the composition.