JPH05178623A - Coating liquid composition for forming thin glass gel film, colored glass gel filter and display device - Google Patents

Abstract

PURPOSE:To improve the water and light resistance of a thin glass gel film while maintaining the strength. CONSTITUTION:This coating liq. compsn. for forming a thin glass gel film contains Si(OC2H5)4 as metal alkoxide, an org. pigment as coloring matter, isopropanol as an alcoholic solvent and ethylcellulose as a dispersant and a colored glass gel filter formed from this compsn. The particle diameter of the coloring matter is 3-300nm and the dispersant has adsorbing action to the coloring matter and a great affinity for the metal alkoxide and its hydrolyzate.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating solution composition for forming a glass gel thin film comprising a metal alkoxide and a dye, a colored glass gel filter and a display device using the same.

[0002]

2. Description of the Related Art Conventionally, a filter is provided on the outer surface of a display device to improve the contrast. A glass film is usually used as this filter. In order to provide the glass film with desired filter characteristics, a dye having an appropriate light absorption property may be contained, and since there are many kinds of organic dyes as dyes therefor, it is preferable in terms of obtaining desired filter properties. ,
Inorganic dyes are also possible.

Further, as a method of forming a glass film, the sol-gel method is generally well known. This is a method for obtaining a gel film from a mixed solution of a metal alkoxide, water, an acid, a dye and an alcohol, that is, a coating solution composition through hydrolysis and polycondensation, but a usual sol-gel method is about 1000 ° C. Since it is fired at a temperature, the organic dye is decomposed. Therefore, a means for forming a glass thin film having a selective absorption property by baking at a low temperature to contain a dye therein is disclosed in JP-A-1-320742. In JP-A-1-320742, a dye is used as a pigment so that the body color does not largely change due to external light and has desired light absorption filter characteristics.
As a result, the desired selective absorption characteristic is obtained.

However, in the sol-gel method, 50
The glass thin film obtained by firing at 0 ° C. or lower has many pores and is porous. In particular, when a dye or an organic pigment capable of obtaining a sharp color is used as a coloring matter, firing is restricted to a maximum of 300 ° C. or less from the viewpoint of heat resistance, so that the tendency to become porous becomes large. As described above, the above-mentioned glass film obtained by low-temperature firing cannot be made into a sufficiently dense film, and only a so-called glass gel-like (hereinafter referred to as glass gel film) porous with a large number of defective pores is obtained. Absent.

As a result, particularly when the dye is a dye, there is a problem of water resistance, that is, the dye elutes when water, chemicals or the like penetrates from the film surface. Although the particle size of the dye is small from the viewpoint of transparency of the film, this glass gel thin film is also permeable to oxygen and the like, so that it is sufficiently resistant to ultraviolet rays, that is, oxidation fading of the dye due to ultraviolet rays and the like is small because the particle size is small. There is also a problem that it cannot be prevented. further,
When the skeleton structure of the glass gel thin film has a defect, the strength of the film itself is deteriorated.

Therefore, an inorganic dye having good heat resistance is used to eliminate defects in the glass gel thin film by high temperature firing,
There is also a means of obtaining sufficient strength by vitrification, but for that purpose, it must be fired at a temperature of at least 500 ° C. or longer for a long time. Performing firing at such a high temperature for a long time is extremely difficult in the process, and in particular,
It is extremely difficult for electronic devices such as display devices. Inorganic dyes are smaller in type than organic dyes, and it is difficult to obtain desired filter characteristics only with inorganic dyes.

[0007]

SUMMARY OF THE INVENTION As described above,
Although a glass film having filter characteristics was formed by the sol-gel method, the firing temperature was set low from the viewpoint of the heat resistance of the dye, and therefore a porous glass gel film was formed, so that in terms of water resistance. There is a problem, and the particle size of the dye is small in view of the transparency of the film, which is a problem in terms of ultraviolet resistance. Also, the film strength of the filter itself was not sufficient.

The present invention provides a coating liquid which allows a dye-containing glass gel thin film having water resistance and ultraviolet resistance to be easily formed at low temperature while maintaining the excellent optical properties of the dye-containing glass gel film. An object of the present invention is to provide a display device having a dye-containing glass gel thin film and having excellent contrast and color purity characteristics.

[0009]

In order to solve the above problems, the present invention provides either or both of a metal alkoxide and a condensation polymer of a metal alkoxide, a dye, and
A glass gel comprising an alcohol solvent and a dispersant which has an adsorbing effect on the dye, is soluble in alcohol and is compatible with metal alkoxide, and the dye has an average particle diameter of 3 nm to 300 nm. A coating liquid composition for forming a thin film.

The total weight of the metal alkoxide or the condensation polymer of the metal alkoxide is A, the total weight of the dye is B, the total weight of the dispersant is C, and the total weight of the coating liquid is D.
, B / A = 0.0001 to 2, C / A = 0.
0001-2, (A + B + C) /D=0.001-0.
5 is the coating liquid composition for forming a glass gel thin film.

Further, it is a colored glass gel filter formed by applying the above-mentioned coating solution composition for forming a glass gel thin film onto a substrate and baking at a low temperature.

Further, on the outer surface of the light transmitting display substrate,
The display device is provided with the colored glass gel filter set so as to selectively absorb at least a wavelength region other than a wavelength at which emission energy is large.

[0013]

The sol-gel method is well known as a method for obtaining an amorphous metal oxide such as glass at a low temperature. In this sol-gel method, a solution of a metal organic or inorganic compound is hydrolyzed and polycondensed to form a sol, and a sol is formed by further advancing the reaction to obtain a solid metal oxide by heating the gel. It is a thing. The most well-known metal compound as a starting material is an alkoxide. A general process for forming a silica glass film by the sol-gel method will be described below. When Si alkoxide such as tetraethoxysilane is used as the metal compound, the alkoxide is dissolved in a solvent such as alcohol and a small amount of acid and water are added to cause the following reaction in the solution to form a sol.

Hydrolysis reaction: Si (OR) ₄ + 2H ₂
O → Si (OH) ₄ +4 ROH dehydration condensation reaction: nSi (OH) ₄ → [SiO ₂ ] _n +
2nH ₂ O During the process of coating and drying this sol solution on a substrate, the sol coated on the substrate changes into a gel. At this time,
The sol particles form a siloxane bond, and the sol particles combine to form a skeleton structure of the gel body. Further, by firing the obtained glass gel film, the number of siloxane bonds between particles can be increased and a glass gel thin film having high strength can be obtained. In order to eliminate the pores of this glass gel thin film and form a complete glass film,
For example, in the case of silica, at least 500 ° C. or higher, usually 1000 ° C. or higher is required.

The glass gel thin film according to the present invention is a glass gel thin film obtained by firing at a temperature not higher than the decomposition temperature of the dye contained in the sol-gel method, and the glass in this case is an amorphous metal oxide. Point

The reason why such a glass gel thin film is used to obtain an optical thin film having a specific spectral transmittance characteristic is that the heat resistance of the dye is a problem as well as the pursuit of process simplicity. That is, most pigments, especially dyes and organic pigments, decompose at a high temperature of 300 ° C. or higher. In addition, many inorganic materials, such as molybdenum orange and ultramarine, have a problem in heat resistance. Therefore, it suffices to perform firing at a decomposition temperature that is determined for each dye or less, but when formed at a temperature of 300 ° C or less, a considerable amount of dyes can be used regardless of organic or inorganic, and the spectral transmittance This is preferable because the characteristics and hue can be freely selected.

However, when such a glass gel thin film is provided with a desired spectral transmittance by using a dye, there are problems such as water resistance and light resistance. Hereinafter, this problem will be described.

For example, in order to form a glass gel thin film into which a dye has been introduced, it is sufficient to mix the dye with the starting solution, form a sol, then coat and dry the dye. However, most of the dyes are incorporated in the gel during application and drying, that is, in the form of being sandwiched between sol particles during gel formation. In other words, most of the dye is present in the pores of the gel formed. This is the same when the siloxane bond between the sol particles is developed by firing.
By the way, since the surface of the pores of this gel has hydroxyl groups generated by the hydrolysis reaction of metal alkoxide or the like, it has a high affinity for water, and therefore water easily penetrates into the pores. Therefore, there is a problem of water resistance, that is, the water permeated into the pores elutes the dye existing in the pores, so that the glass gel thin film cannot maintain desired spectral transmittance characteristics.

Also, when a pigment or the like is used, it is incorporated into the gel so as to be sandwiched between sol particles at the time of gel formation as in the above case. If the particle size of the pigment is too small, the elution phenomenon is caused as in the case of the dye, and if it is large, the pigment particles cause light scattering and impair the transparency.

Further, even if the particle size is such that transparency is not impaired, the strength deteriorates for the following reasons. That is, the pigment particles form a gel skeleton structure together with the metal oxide particles obtained by hydrolysis and polycondensation of a metal alkoxide or the like. However, the structure of the gel itself becomes weak because the bond between the pigment particles and the metal oxide particles does not occur,
The obtained glass gel thin film cannot obtain sufficient strength. This is because the bond between the metal oxide particles obtained by the sol-gel method is a state in which the particle surface is bound to a hydroxyl group due to a hydrolysis reaction during sol formation, and the particles are dehydrated and condensed. .. Such a bond cannot be expected between the pigment and the fine particles of the metal oxide.

In order to increase the hardness of the glass gel thin film containing such pigment particles, the porosity of the glass gel is reduced by raising the firing temperature to bring the pigment into a complete glass membrane or a state close to it, and the pigment is skeleton-structured. It must be wrapped in. The firing temperature for this purpose must be at least 500 ° C. or higher, which greatly limits the dye used.

Therefore, the inventors, through various experiments,
It was confirmed that if the particle size of the dye is controlled to 3 nm or more, the above-mentioned problem, that is, the problem of water resistance does not occur in the glass gel thin film obtained by low temperature firing. At that time, it was also found that it is possible to prevent the deterioration of the hardness of the glass gel film due to the pigment particles by adding a substance having an adsorbing action to the pigment and having a strong affinity with the metal alkoxide and its hydrolyzate.

The effect of the particle size of the dye in the present invention will be described in detail below.

First, the relationship between the particle size of the dye and the above-mentioned water resistance and light resistance will be described.

(Evaluation of Water Resistance) For the evaluation of water resistance, thin films containing dyes of various particle sizes were each wetted with water and detergent on a white cloth, and a rubbing test was repeated 500 times. The presence or absence of peeling was confirmed. Table 1 shows the test results.

The glass gel film used was Si (OC ₂ H ₅ ) ₄ ... 7.0 parts by weight nitric acid ... 1.3 parts by weight water ... 1.5 parts by weight Pigment (Hostaperm Pink E) ... 0.25 Parts by weight Dispersant: 0.06 parts by weight Isopropyl alcohol: 89.89 parts by weight A coating solution composition is applied onto a glass substrate and baked at about 150 ° C. for 20 minutes. The average particle size of the pigment was measured using the elastic light scattering method. This method is a method in which the pigment dispersion is irradiated with light and the fluctuation of scattered light is quantified by the photon correlation method, and it was performed using a scatterometer manufactured by Union Corporation.

[0027]

[Table 1] Further, FIG. 1 is a diagram for explaining the difference in the effect of Table 1 above, and (a) shows (b) when the particle diameter of the dye is 3 nm.
FIG. 3 is a schematic cross-sectional view showing a case where the particle diameter of the dye is several angstroms. Further, FIG. 2 shows a further enlarged view of the bonding state of the metal oxide 2 and the dye 3 of the glass gel thin film 1 of FIG.

FIG. 1 is a schematic diagram for explaining the difference in the above effects when the particle size is several angstroms and when the particle size is 3 nm. FIGS. 2A and 2B are enlarged views of the bonding portion between the metal oxide and the pigment particles of the glass gel thin film formed of the metal oxide shown in FIG. The glass gel thin film 1 formed of a metal alkoxide and containing the dye 3 therein has a network structure of about several angstroms, and pores 4 which are defects are present in some places. The average size of the pores is several angstroms to several hundred angstroms.

As can be seen from FIG. 1, the dye 3 is liberated by the invasion of water into the pores 4 in a concentrated manner. When the contact area is large and is firmly fixed by the metal oxide 2 constituting the glass gel thin film 1, elution is unlikely to occur and strength deterioration does not occur. It is considered that this strength deterioration is due to the following reasons. That is, FIG. 2B
As shown in Fig. 3, the pigment particles form a part of the skeleton structure of the glass gel thin film, so when the bond between the pigment and the metal oxide or hydroxide fine particles is weak, the strength of the skeleton structure in that portion is weak. Since it deteriorates, the strength of the film is reduced.
However, as shown in FIG. 2B, the dye and the metal oxide,
When the hydroxide fine particles are strongly bonded to each other, the skeleton structure of the glass gel film containing the pigment particles also retains sufficient strength, so that the strength of the film does not deteriorate. this is,
This can be achieved by adding a substance that has an adsorbing action on the dye and has a strong affinity with the metal alkoxide and its hydrolyzate.

The pencil strength (pencil hardness test JIS K5400) of the glass gel thin film used in the rubbing test was 7H or more regardless of the particle size. Further, in the rubbing test, the glass gel film on the surface is damaged by friction and causes the dye to elute in the same manner, but also in this case, if the particle size of the dye is large, decolorization does not occur for the same reason as above. .. For the above reasons, it is speculated that the results in Table 1 were obtained.

(Ultraviolet resistance) Further, by increasing the particle size of the dye, the ultraviolet resistance is improved as well as the above-mentioned water resistance. Table 2 shows the results of measuring the fading of the dyes by encapsulating the dyes of various particle sizes in a glass gel thin film for the evaluation of the ultraviolet resistance property.

The glass gel film used is the same as that used in the above water resistance evaluation.

[0033]

[Table 2] At this time, using Hosta Perm Pink E as a dye and metal halide as a light source, ultraviolet rays of 100 mW / cm ² were irradiated for 4 hours to compare the residual absorption rate of the main absorption peak of the dye. The absorption residual rate is the initial main peak transmittance T ₀ ,
When the main peak transmittance after 4 hours is T _n , it is given by the following equation.

D = {(1-T _n ) / (1-T ₀ )} × 100 (%) It can be seen from Table 2 that the larger the particle size of the dye, the better the tendency. It is considered that this is because the larger the particle size of the dye is, the more the penetration of ultraviolet rays into the dye is suppressed and the dye molecules inside are protected. From Table 2, the particle size of the dye is preferably 3 nm or more.

As described above, if the particle size of the dye is increased, the water resistance is improved.
It was found that the characteristics were improved in terms of light resistance.

When the particle size of the dye exceeds 300 nm, light scattering occurs and the transparency is impaired. Table 3 shows the relationship between particle size and transparency. Here, the transparency was evaluated by the following method. That is, a glass coated with a film not added with a dye is placed on a blackened table made of graphite, and the reflectance is set to 100%, and the glass coated with a film added with a dye having various particle diameters is placed on the same table. When the reflectivity is measured by mounting it and the increase in the reflectivity is clearly observed, it is considered that the transparency is impaired.

The glass gel film used is the same as that used in the above water resistance evaluation.

[0038]

[Table 3] The maximum diameter of light that passes through the particles is λ / 2 or less, where λ is the wavelength of light.
Considering the case of (00 to 700 nm), when the particle size exceeds 200 nm, light scattering occurs and transparency is impaired, which is not preferable in terms of optical characteristics, and it is considered that the particle size is preferably 200 nm or less. However, in the present invention, 3
Does not impair transparency up to 00 nm. This is because the dye particles are incorporated in the glass gel thin film, so by reducing the difference between the refractive index of the dye and the refractive index of the medium, it is possible to reduce the surface reflectance of the dye particles themselves. It is considered that it is possible to extend the particle shape of the dye to a particle size of about 300 nm, which is more advantageous in terms of light resistance and water resistance, beyond the above limit.

Therefore, as described above, from the viewpoint of water resistance, it is preferable that the particle size is equal to or larger than the size of defects of the glass gel thin film, that is, 1 nm or more, and from the viewpoint of light resistance, the particle size is 3 nm or more. The larger the value, the better the characteristics. However, if the particle size is too large, there is a problem that the transparency is impaired. Therefore, although the theoretical upper limit of the particle size has been determined to some extent, according to the present invention, particle sizes exceeding this upper limit can be used. That is, the particle size of the dye is 3 nm to 300
By setting the thickness to nm, water resistance and light resistance can be improved without impairing the transparency of the glass gel thin film. It is preferably 5 to 200 nm.

In the above description, the particle size of the dye means the average particle size.

(Description of Coating Liquid) The particle diameter of the dye has been described above. Next, a coating liquid for forming the glass gel thin film will be described.

As described above, in order to form a colored glass gel filter by the sol-gel method, a coating liquid in which a dye is dispersed in an alcohol solution in which a metal alkoxide is dissolved is required.

Therefore, for the dye used in the present invention,
As a result of further research on a dispersant that uniformly disperses a dye in a metal alkoxide solution, even if the resin is soluble in alcohol, it is not adsorbed by the dye, and if the so-called dispersant is not present, the dye aggregates. As a result, a uniform dispersion liquid cannot be obtained, and the formed gel film becomes opaque and semi-clear. Rosin resin, ketone resin, and shellac showed such behavior. Further, even if the resin is soluble in alcohol and has a dispersive power for the dye, if it is not compatible with the alcohol solution containing the metal alkoxide, the gel film will be opaque and semi-sharp. The vinylpyrrolidone resin showed such behavior.

That is, by using a dispersant satisfying the following conditions, it is possible to greatly improve the dispersibility of the dye and also the strength of the formed film. In other words, as a result of further research on substances that have an adsorbing action on the dye and have a strong affinity with the metal alkoxide and its hydrolyzate, when these substances are alcohol-soluble, the dye added to the glass gel coating solution It was found that the dispersibility was significantly improved. As described above, as a result of earnest studies, the present inventors have found that as a means for dispersing a pigment as a dye, it is soluble in alcohol, is compatible with metal alkoxide, and has an adsorption action (dispersing power) on the pigment. It has been found that excellent dispersions can be obtained with the substances. In addition, it was also discovered that the addition of a substance having an adsorbing action to the dye and having a strong affinity for the metal alkoxide and its hydrolyzate can prevent the deterioration of the hardness of the glass gel film due to the dye particles. This is presumed to be due to the following reasons.

That is, as can be seen from FIG. 2 described above,
The pigment particles form a part of the skeleton structure of the glass gel thin film. When the bond between the dye and the metal oxide or hydroxide fine particles is weak, the strength of the skeleton structure in that portion is deteriorated, and the strength of the film is reduced. As described above, when the dye has an adsorptive action and has a high affinity for the metal alkoxide or its hydrolyzate, the bond between the dye and the metal oxide or hydroxide fine particles is strengthened, and the glass gel thin film containing the dye particles. Since the skeletal structure of the film retains sufficient strength, it does not cause deterioration of the strength of the film.

The following are effective as such a dispersion.

(1) Polyvinyl butyral resin. For example, S-REC BLS, S-REC BL-1 (trade name)
etc. (2) Polyvinyl alcohol resin. For example, Gocelan L-0301 (trade name) and the like. (3) Acrylic resin. For example, Hitech 532 (trade name). (4) Ethyl cellulose. For example, Ethocel (trade name)
etc. (5) Unsaturated polycarboxylic acid. For example, Big 104S
(Product name) etc. (6) Phosphate ester activator. For example, Death Call A
-200 (trade name), etc. (7) Polyester resin. For example, Polyester WR-
901 (trade name) etc.

(8) Silane coupling agent. For example, K
BM-502, BBM-902 (trade name) and the like. (9) Titanium coupling agent. For example, B-1 (TB
T) (brand name) etc. (10) Aluminum coupling agent. For example, aluminum chelate M (trade name).

The amount of these substances added is 5 w with respect to the dye.
t% to 100 wt% is preferable.

By the way, some dyes react with a metal alkoxide to cause a change with time in a solution. The inventors have also found that such a dye can be stabilized by protecting it with the dispersant. In order for these dispersants to exhibit such effects, the amount of the dispersant to the metal alkoxide is about 0.01.
It is necessary to have wt% or more. On the other hand, if the amount of the dispersant is too large, the effect of retaining the strength is reduced, and the strength is deteriorated. This is because the action of the dispersant itself has an auxiliary role of promoting the binding between the dye and the metal oxide particles, and does not itself form a film structure. Therefore, the amount of dispersant is 20 with respect to the amount of metal alkoxide.
It is preferably 0 wt% or less.

The metal alkoxide is generally M
(OR) _n . Here, M is a metal element, OR
Is an alkoxyl group, and n is the oxidation number of the metal. Si (OR) ₄ is typically used as the metal alkoxide, but Zn, Zr, Ti, Al, Fe, C may be used in addition to Si.
O, Ni and the like can be used alone or in combination according to the purpose. For example, when it is desired to increase the reflectance, it is useful to mix Ti or Zn, when it is necessary to improve strength and alkali resistance, Zr, and when it is desired to further improve light resistance, Ni or the like is mixed. is there. In these cases, the dye can be dispersed by almost the same method. And SiO, which is a decomposition product of Si (OR) _4.
2 also serves as a binder because it enters the gap between the substrate and the dye. Moreover, as R of M (OR) _n , an alkyl group having 1 to 5 carbon atoms is generally preferable.

Further, the alcohol for dissolving the alkyl group increases in viscosity of the alcohol solution of M (OR) _{n as} the number of carbon atoms increases, and therefore it may be appropriately selected in consideration of this point. Examples of generally usable alcohols include alcohols having 1 to 5 carbon atoms. Specific examples include isopropyl alcohol, ethanol,
Methanol, butanol, pentanol, methoxyethanol, ethoxyethanol, propoxyethanol,
Almost all alcohols such as butoxyethanol can be used.

As the coloring matter, almost all organic pigments and laked and powdered dyes can be used to prepare the coating liquid composition of the present invention. For example, azo yellow such as benzidine yellow and carmine FB can be used. , Red pigments, perylene, perinone, dioxazine, thioindigo, isoindolinone, quinophthalone, condensation pigments such as quinacridone, phthalocyanine pigments, titanium white,
There are inorganic pigments such as red iron oxide, yellow lead, cobalt blue, and inorganic pigments such as carbon black. It is necessary to select the dye from these in consideration of the emission spectrum of the substance forming the filter. For example, the filter absorption characteristics can be large in the low energy spectral range. Furthermore, the coloring power of the pigment differs depending on the pigment. The transmittance of the maximum absorption portion was measured using an organic pigment (Heliogen Blue E-7S) having a relatively large coloring power.

[0054] Incidentally, glass gel _{film, Si (OC 2 H 5)} 4 ... 7.0 parts by weight of nitric acid ... 1.3 parts by weight water --- 1.5 parts by weight dispersing agent ... 0.00007 to 0.7 weight used Parts Pigment (Heliogen Blue E-7S) ... 0.00007-0.7 parts by weight Isopropyl alcohol ... obtained by coating a glass substrate with a coating liquid composition and baking at about 150 ° C. for 20 minutes. It is a thing.

[0055]

[Table 4] As a result, the addition amount of the dye is preferably at least 0.01 wt% or more.

Table 5 shows the relationship between the amount of dye added and the film strength.
Shown in.

The glass gel film used was: Si (OC ₂ H ₅ ) ₄ 7.0 parts by weight nitric acid 1.3 parts by weight water 1.5 parts by weight Dispersant 1.7-3.7 parts by weight Parts Pigment (Heliogen Blue E-7S) ... 7.0 to 15.4 parts by weight Isopropyl alcohol ... Obtained by coating a glass substrate with a coating liquid composition consisting of the rest and baking at about 150 ° C. for 20 minutes. It is a thing.

[0058]

[Table 5] As a practical level, a pencil hardness of at least 6H or more is required, and therefore the amount of the dye added is preferably 200 wt% or less.

From the above, in consideration of coloring and film strength, the weight ratio of the dye to the binder is 0.01 wt.
% -200 wt% is preferable, and if it is too small, it does not serve as a filter and does not make sense of the filter.

Further, the ratio of the total amount of solids (the total amount of metal alkoxide, the condensation polymer of metal alkoxide, the dye and the dispersant) to the total amount of the coating liquid is not more than 50 wt% from the viewpoint of the stability of the liquid. I won't. 5
If it is 0 wt% or more, it will be about 1 after preparing the coating solution.
The liquid itself gels like agar in about a day. further,
Even before gelation, the liquid properties such as viscosity change every moment, and they are not applied under the same conditions. Further, in order to obtain a practical film thickness of 0.1 μm or more, the total solid content is preferably 0.1 wt% or more.

Since the particle size of the dye is increased,
By making it less susceptible to the acid that is a catalyst in the coating liquid, it becomes possible to use dyes that have some problems with acid resistance, and the storage stability as a coating liquid is also improved.

When the amount of the dispersant is 0.01 part by weight or less based on 100 parts by weight of the metal alkoxide, the dye may react with the metal alkoxide to cause a change with time. Further, if the amount is 200 parts by weight or more, the film strength will deteriorate. More preferably, the amount of the dispersant is preferably 5 to 100 parts by weight based on the weight of the dye.

Therefore, in the coating liquid composition of the present invention, when the total weight of the metal alkoxide is A, the total weight of the dye is B, and the total weight of the dispersant is C, the total weight of the coating liquid is D. When B / A = 0.0001 to 2,
C / A = 0.0001 to 2, (A + B + C) / D = 0.
It is preferably set to 001 to 0.5. Further, more preferably, C / B = 0.05-1. B / A is 0.
When it is 0001 or less, coloring is insufficient, and when B / A is 2 or more, the film strength is deteriorated. C / A is 0.0001
When it is less than the above range, stability is deteriorated depending on the pigment, and when C / A is 2 or more, the film strength is deteriorated. further,
If (A + B + C) / D is 0.001 or less, a practical film thickness cannot be obtained, and (A + B + C) / D is 0.5.
When it is above, there arises a problem in the stability of the coating liquid.

The disperser required to prepare the dispersion liquid was a two-roll, three-roll, Banbury mixer,
Examples include SG mills and attritors.

(Colored glass gel filter) The colored glass gel filter according to the present invention can be formed by applying the coating liquid composition on a substrate and baking at 100 ° C to 300 ° C. The formed colored glass gel filter contains a pigment having desired spectral transmittance characteristics in an inorganic glass gel thin film containing SiO ₂ as a main component, and the average particle diameter of the pigment is 3 nm to 3 nm.
It is set to 300 nm. At this time, since a substance having an adsorptive action to the dye and having a strong affinity with the metal alkoxide and its hydrolyzate is added, as described above, the hardness deterioration of the glass gel film due to the dye particles can be prevented. That is, since the bond between the dye and the metal oxide or hydroxide fine particles is strengthened and the skeleton structure of the glass gel film containing the dye particles can be maintained with sufficient strength, the strength of the film is not deteriorated.

The film thickness of 0.1 μm to 3 μm is practical. If it is less than 0.1 μm, the coloring power is insufficient, and if it is 3 μm or more, cracks and cloudiness occur, which is not practical.

(Display Device) By forming the above-mentioned colored glass gel filter on the light-transmitting display substrate of the display device, the contrast, color purity, etc. can be improved.

As the display device, there are a color picture tube, a black and white picture tube, a projection type color TV set, a liquid crystal display, a projection type liquid crystal display, a plasma display and the like. Usually, a filter film is formed by coating on a screen glass substrate which is a light-transmitting display substrate, but in the case of a projection type display device, the filter film may be formed on the projection screen.

It is necessary to select the dye in consideration of the emission spectrum of each display device. For example, the filter absorption characteristics can be large in the low energy spectral range.

As another application, it is also possible to form a coating on the outside or inside of the lamp for the purpose of changing the colored light of a fluorescent lamp or the like. In this case, a dye that cuts a specific wavelength may be selected.

Furthermore, the present invention can be applied to magnetic disks, optical disks and the like.

[0072]

Embodiments of the present invention will be described below with reference to the drawings.

(Example 1) Hosta Palm Pink E (pigment) 2.5 wt% TSL8311 (silane coupling agent, manufactured by Toshiba Silicon) 0.1 wt% Etocel 7CP (ethyl cellulose) 0.5 wt% Isopropyl alcohol 96.9 wt% Then, the above materials are dispersed for 12 hours using an SG mill (disperser) using 0.5 mm zircon beads to prepare a pigment dispersion liquid (pigment dispersion liquid 1). Then, the following composition was mixed with a propeller-type stirrer to obtain a coating liquid composition having a dye having an average particle diameter of about 20 nm.

Si (OC ₂ H ₅ ) ₄ (metal alkoxide) 7.0 wt% Nitric acid 1.3 wt% Water 1.5 wt% Pigment dispersion 1 10.0 wt% Isopropyl alcohol 80.2 wt% Composition of the above coating liquid composition The ratio was Si (OC ₂ H ₅ ) ₄ (metal alkoxide) 7.0 wt% nitric acid 1.3 wt% water 1.5 wt% pigment 0.25 wt% dispersant 0.06 wt% alcohol 89.89 wt%. ing. That is, when the total weight of the metal alkoxide is A, the total weight of the dye is B, the total weight of the dispersant is C, and the total weight of the coating liquid is D, B / A = 0.036,
C / A = 0.0086, (A + B + C) /D=0.07
3 and C / B = 0.24.

After coating this composition on a glass substrate,
Firing was carried out at 150 ° C. for 20 minutes to form a colored glass gel filter having a film thickness of 0.2 μm.

The light transmission characteristics of the colored glass gel filter formed from the coating liquid composition of this example are as shown in 6A of FIG. The colored glass gel filter was subjected to a rubbing test with a detergent for water resistance evaluation. As a result, no discoloration occurred and the UV resistance was 92%, which was a good characteristic. The strength of the film is 8H in pencil hardness, which is practically sufficient. The pencil hardness was measured according to JIS K5400. In addition, the pot life of the coating liquid was extended to about one month as compared with the conventional one week, and good characteristics were obtained.

(Example 2) A description will be given below of the case where the colored glass gel filter shown in Example 1 is formed on the outer surface of the screen of a color picture tube.

FIG. 4 is a partially cutaway side view showing a color picture tube manufactured according to the present invention. This color picture tube
Reference numeral 10 has an airtight glass envelope 11 whose inside is exhausted. The envelope 11 has a neck 12 and a cone 13 continuous from the neck 12. Further, the envelope 11 has a cone 13 and a face plate 14 sealed with frit glass. A metal tension band 15 is wound around the side wall of the face plate 14 to prevent explosion. This neck 12 has an electron gun 16 that emits an electron beam.
Are arranged. Inside the face plate 12, excited by the electron beam from the electron gun 16, red, green,
A phosphor screen 17 including a stripe-shaped phosphor layer that emits blue light and a stripe-shaped black light absorption layer that is arranged between the phosphor layers is provided. Further, a shadow mask (not shown) having through-holes provided on the entire surface is arranged close to the phosphor screen 17. Cone 13
A deflecting device (not shown) for deflecting the electron beam so as to scan the phosphor screen 17 is attached to the outside of the.

On the outer surface of the face plate 17 of the color picture tube 10, a colored glass gel filter 18 having a selective absorption property is formed by a spin coating method. The firing temperature and film thickness are the same as in Example 1 above.

This filter characteristic is 400 to 650 nm.
Has a maximum absorption wavelength in the wavelength region of 575 ± 20 nm, and the wavelength is 450 nm, 530 nm, 550 nm, 6
Letting T ₄₅₀ , T ₅₃₀ , T ₅₅₀ T ₆₃₀ and T _min be the transmittances for light of 30 nm and the maximum absorption wavelength, respectively, T _min ≦ T ₅₅₀ <T ₅₃₀ , 1 ≦ T ₄₅₀ / T ₆₃₀ ≦
2, 1 ≦ T ₆₃₀ / T ₅₃₀ ≦ 2, 0.7 ≦ T ₄₅₀ / T ₅₃₀
The relation is ≦ 1.43, and specifically, it is as shown in 6A of FIG. In FIG. 3, 6 is the light transmission characteristic of the colored glass gel filter, and 7 is the emission spectrum of the color picture tube. Also, the effect of improving the contrast is
The ratio of the brightness decrease rate ΔB and the outside light reflectance decrease rate ΔR _f , that is, BCP (Brightness Contrast Performance)
) = ΔB / (ΔR _f ) ^1/2 . As a result, in this example, BCP was 1.07. water resistant,
The ultraviolet resistance and the film strength are the same as in Example 1 above.

Therefore, the water resistance and the ultraviolet resistance can be improved without deteriorating the film strength of the colored glass gel filter for improving the contrast and the color purity.

(Example 3) Permanent carmine FBB-02 (pigment) 2.5 wt% Gocelan L-0301 (polyvinyl alcohol resin) 0.5 wt% Isopropyl alcohol 97.5 wt% The same materials as in Example 1 were used. And dispersed to prepare a pigment dispersion liquid (Pigment dispersion liquid 2).

The following materials are dispersed by the same means,
A pigment dispersion liquid (Pigment dispersion liquid 3) was prepared.

Heliogen Blue EP-7S (pigment) 2.5 wt% Planeact KR44 (titanium coupling agent) 0.1 wt% Hitec 532 (acrylic resin) 0.5 wt% n-butyl alcohol 96.9 wt% The mixture was mixed with a propeller stirrer to obtain a coating liquid composition having an average particle diameter of the dye of about 5 nm.

Si (OC ₂ H ₅ ) ₄ (Metal alkoxide) 5.0 wt% Zr (OC ₂ H ₅ ) ₄ (Metal alkoxide) 2.0 wt% Nitric acid 0.5 wt% Water 0.5 wt% Pigment dispersion 2 8 0.0 wt% Pigment Dispersion Liquid 3 2.0 wt% Isopropyl Alcohol 82.0 wt% Composition ratio of the above coating liquid composition is metal alkoxide 7.0 wt% nitric acid 0.5 wt% water 0.5 wt% pigment 0.25 wt% dispersant It is 0.052 wt% alcohol 91.608 wt%. That is, when the total weight of the metal alkoxide is A, the total weight of the dye is B, the total weight of the dispersant is C, and the total weight of the coating liquid is D, B / A = 0.036,
C / A = 0.0074, (A + B + C) /D=0.07
3, C / B = 0.208.

After coating this on a glass substrate, 150
Firing was carried out at 20 ° C. for 20 minutes to form a colored glass gel filter having a film thickness of 0.2 μm.

The light transmission characteristics of this colored glass gel filter are the same as those shown in 6B of FIG. In addition, a rubbing test with a detergent was carried out to evaluate the water resistance. As a result, no discoloration occurred and the UV resistance was 90%, which was a good property. Further, the film strength is 8H, which is practically sufficient.

(Example 4) The colored glass gel filter shown in Example 2 was formed on the outer surface of the screen of a color picture tube by spin coating. The firing temperature and the film thickness are the same as in Example 2 above.

This filter characteristic is as shown in 6B of FIG. Further, BCP was 1.08 in this example. The water resistance, ultraviolet resistance, and film strength are the same as in Example 3 above.

(Example 5) Red iron oxide (pigment) 2.5 wt% S-REC BLS 0.5 wt% Silane coupling agent 0.1 wt% Isopropyl alcohol 96.9 wt% The above materials are dispersed by the same means as in Example 1, A pigment dispersion liquid (pigment dispersion liquid 4) is prepared.

Then, the following composition was mixed with a propeller-type stirrer to obtain a coating liquid composition having an average particle diameter of the dye of about 50 nm.

Si (OC ₂ H ₅ ) ₄ (Metal alkoxide) 7.0 wt% Nitric acid 1.3 wt% Water 1.5 wt% Pigment dispersion 4 10.0 wt% Isopropyl alcohol 80.2 wt% Composition of the above coating liquid composition The ratio is metal alkoxide 7.0 wt% nitric acid 1.3 wt% water 1.5 wt% pigment 0.25 wt% dispersant 0.06 wt% alcohol 89.89 wt%. That is, when the total weight of the metal alkoxide is A, the total weight of the dye is B, the total weight of the dispersant is C, and the total weight of the coating liquid is D, B / A = 0.036,
C / A = 0.0086, (A + B + C) /D=0.07
3 and C / B = 0.24.

This was applied onto a glass substrate and baked at 150 ° C. for 20 minutes to give a film thickness of 0.2 μm and 8 in FIG.
A colored glass gel filter having the following properties was formed.

Regarding this colored glass gel filter,
A rubbing test with a detergent was conducted to evaluate the water resistance. No discoloration occurred and the UV resistance was 100%.
And showed good characteristics. Further, the film strength is 8H which is practically sufficient.

(Example 6) The colored glass gel filter shown in Example 5 was formed on the outer surface of the screen of the plasma display. The firing temperature and the film thickness are the same as in Example 2 above.

This filter characteristic is as shown by 8 in FIG. In FIG. 5, 8 is the light transmission characteristic of the colored glass gel filter, and 9 is the emission spectrum of the plasma display. Further, in this embodiment, the BCP is 1.
It was 10. The water resistance, ultraviolet resistance, and film strength are the same as in Example 3 above. In the case of a plasma display, it is preferable to absorb in the wavelength region of 400 nm to 600 nm.

(Embodiment 7) A description will be given below of the case where the colored glass gel filter shown in the above Embodiment 1 is formed on the outer surface of a color liquid crystal display device.

FIG. 6 shows a liquid crystal display device. This liquid crystal display device includes substrates 21 and 22 made of a pair of glass facing each other.
And I formed on the facing surfaces of the substrates 21 and 22, respectively.
Predetermined pattern electrode made of TO (Indium Tin Oxide)
23 and 24, the alignment films 25 and 26 formed on the facing surfaces of the pair of substrates 21 and 22 so as to cover the electrodes 23 and 24, and the alignment films 25 and 26 disposed between the substrates 21 and 22. A spacer 27 made of a thermosetting resin that is fixed to the substrate 26 and regulates the distance between the pair of substrates 21 and 22, and a liquid crystal 28 filled between the substrates 21 and 22.
And a sealant 29 for sealing the peripheral edges of the substrates 21 and 22 filled with the liquid crystal 28. The colored glass gel filter 30 is provided on the outer surface of the one substrate 21 that forms the display base.

The colored glass gel filter 30 was sealed except for the portion where the colored glass gel filter 30 was formed, and the coating solution for forming a glass gel thin film of Example 1 was applied to a film thickness of 0.1 μm. After that, it is formed by firing.

As a result, a good glass gel filter having a film strength of 8H can be formed on the outer surface of the substrate. This filter characteristic is as shown in 6A of FIG. 3, and the BCP was 1.06. Further, the water resistance, the ultraviolet resistance, and the film strength are the same as those in Example 1 above. In the case of a liquid crystal display device, it is preferable to absorb the wavelength region of 550 nm to 600 nm.

(Embodiment 8) Although the above-mentioned Embodiment 7 describes the transmission type liquid crystal display device, the present invention is not limited to this and can be applied to a projection type liquid crystal display device. That is,
A selective absorption filter was formed by applying a colored glass gel filter on the screen of a rear projection type liquid crystal display device using the composition shown in Example 1 above.

This filter characteristic is the same as that of the first embodiment, and the BCP is 1.10. Further, the water resistance, the ultraviolet resistance, and the film strength are the same as those in Example 1 above.

Although the above embodiments have been described as applied to display devices such as color picture tubes and liquid crystal display devices, the present invention is not limited to the display devices, and is intended to change the emission color of fluorescent lamps and the like. It is also possible to form by coating on the inside or outside of the lamp. In this case, a dye that cuts a specific wavelength may be selected.

Further, application to a recording member using a laser is also possible.

[0105]

As described above, according to the present invention, a thin film having an extremely large degree of freedom in coloring, excellent water resistance and ultraviolet resistance, and having sufficient strength can be used for low temperature baking in the sol-gel method. It is possible to obtain a coating liquid composition and a colored glass gel filter which can be formed by

Further, a display device having high contrast and high color purity can be provided by selecting an appropriate dye.

[Brief description of drawings]

FIG. 1 is a schematic diagram for explaining the effect of the particle size of a dye.

FIG. 2 is a schematic diagram for explaining a binding state between a dye and a glass gel film in FIG.

FIG. 3 is a diagram showing light transmission characteristics of a colored glass gel filter and an emission spectrum of a color picture tube according to an embodiment of the present invention.

FIG. 4 is a partially cutaway plan view showing a configuration of a color picture tube according to the present invention.

FIG. 5 is a diagram showing a light transmission characteristic of a colored glass gel filter and an emission spectrum of a plasma display according to another embodiment of the present invention.

FIG. 6 is a cross-sectional view showing a configuration of a liquid crystal display device according to an embodiment of the present invention.

[Explanation of symbols]

 1 ... Glass gel film 2 ... Metal oxide 3 ... Dye 4 ... Pore

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical indication location H01J 29/89 9057-5E (72) Inventor Kazuo Sakai 2-23-2 Obana, Kawanishi-shi, Hyogo Fuji Dye Co., Ltd.

Claims (4)

[Claims] 1. A metal alkoxide and / or a condensation polymer of a metal alkoxide, and a dye;
A glass gel comprising an alcohol solvent and a dispersant which has an adsorbing effect on the dye, is soluble in alcohol and is compatible with metal alkoxide, and the dye has an average particle diameter of 3 nm to 300 nm. Coating liquid composition for thin film formation. 2. The total weight of the metal alkoxide or the condensation polymer of the metal alkoxide is A, the total weight of the dye is B,
When the total weight of the dispersant is C and the total weight of the coating liquid is D, B / A = 0.0001 to 2, C / A = 0.0001 to 2, (A + B + C) /D=0.001 to 0 The coating liquid composition for forming a glass gel thin film according to claim 1, wherein the coating liquid composition is 5. 3. A colored glass gel filter characterized by being formed by applying the coating liquid composition for forming a glass gel thin film according to claim 1 on a substrate and baking it at a low temperature. 4. The colored glass gel filter according to claim 3, which is set to selectively absorb at least a wavelength region other than a wavelength at which emission energy is large, on the outer surface of the light-transmitting display substrate. A display device characterized by the above.