JP2944819B2 - Coating liquid composition for forming glass gel thin film, colored glass gel filter 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 coating 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 an outer surface of a display device to improve contrast. A glass film is usually used as this filter. In order to impart desired filter characteristics to the glass film, a dye having appropriate light absorption characteristics may be contained, and as the dye therefor, there are many types of organic dyes, and thus it is preferable from the viewpoint of obtaining desired filter characteristics. ,
Also, inorganic dyes are possible.

Further, as a method of forming a glass film, a sol-gel method is generally well known. This is a method of obtaining a gel film from a mixed solution of a metal alkoxide, water, an acid, a dye, and an alcohol, that is, a coating liquid composition through hydrolysis and polycondensation. The organic dye is decomposed because it is fired at a temperature. For this reason, JP-A-1-320742 discloses a means for baking at a low temperature to contain a dye therein to form a glass thin film having selective absorption characteristics. In JP-A-1-320742, a dye is used as a coloring matter in order that the body color does not significantly change due to external light and has a desired light absorption filter characteristic.
As a result, desired selective absorption characteristics are obtained.

However, in the sol-gel method, 50
The glass thin film obtained by baking at 0 ° C. or lower has extremely 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, baking is restricted to a maximum of 300 ° C. or less from the viewpoint of heat resistance. As described above, the above-mentioned glass film obtained by low-temperature firing cannot be a sufficiently dense film, and only a so-called glass gel film (hereinafter, referred to as a glass gel film) having a large number of defective pores and being porous can be obtained. Absent.

[0005] As a result, when the dye is a dye, there is a problem of water resistance, that is, a problem that the dye is eluted due to intrusion of water or chemicals from the film surface. In addition, the particle size of the dye is small from the viewpoint of the transparency of the film. There is also a problem that it cannot be prevented. further,
When a defect occurs in the skeleton structure of the glass gel thin film, the strength of the film itself is deteriorated.

For this reason, defects of the glass gel thin film are eliminated by firing at a high temperature using an inorganic dye having good heat resistance,
There is also a means of obtaining sufficient strength by vitrification, but for that purpose, it is necessary to fire at a temperature of at least 500 ° C. for a long time. It is very difficult in the process to perform long-time firing at such a high temperature, and in particular,
It is extremely difficult with an electronic device such as a display device. In addition, the types of inorganic dyes are smaller than those of organic dyes, and it is difficult to obtain desired filter characteristics using only inorganic dyes.

[0007]

As described above, conventionally,
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 thus the porous glass gel film was used. There is a problem, and the particle size of the dye is small from the viewpoint of the transparency of the film, and there is a problem in terms of the ultraviolet light resistance. Further, the film strength of the filter itself was not sufficient.

The present invention provides a coating solution capable of easily forming a dye-containing glass gel thin film having water resistance and ultraviolet light resistance at a low temperature while maintaining 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-mentioned problems, the present invention provides a method comprising the steps of: providing one or both of a metal alkoxide and a condensation polymer of a metal alkoxide;
A glass gel comprising: an alcohol solvent, a dispersant having an adsorbing action on the dye and soluble in alcohol and compatible with a metal alkoxide, wherein the dye has an average particle size of 3 nm to 300 nm. It is 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.
Where B / A = 0.0001 to 2 and 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.

[0011] Further, there is provided a colored glass gel filter formed by applying the coating liquid composition for forming a glass gel thin film on a substrate and baking at a low temperature.

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

[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 the reaction is further advanced to form a gel. By heating the gel, a metal oxide solid is obtained. Things. The best known starting metal compound is an alkoxide. The general process of forming a silica glass film by the sol-gel method is described below. When an alkoxide of Si, for example, tetraethoxysilane, is used as the metal compound, this alkoxide is dissolved in a solvent such as alcohol, and an acid and water are added in small amounts to cause the following reaction in the solution to form a sol.

Hydrolysis reaction: Si (OR) ₄ + 2H ₂
O → Si (OH) ₄ + 4ROH Dehydration condensation reaction: nSi (OH) ₄ → [SiO ₂ ] _n +
2nH ₂ O In the process of applying and drying this sol solution on the substrate, the sol applied on the substrate changes to a gel. At this time,
The sol particles form a siloxane bond, and the sol particles bond with each other to form a skeleton structure of a gel body. Further, by firing the obtained glass gel film, the number of siloxane bonds between the particles is increased, and a strong glass gel thin film 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 above-mentioned sol-gel method. In this case, the glass is an amorphous metal oxide. Point out.

The reason for using such a glass gel thin film in order to obtain an optical thin film having a specific spectral transmittance characteristic is that, in addition to the simplicity of the process, the problem of the heat resistance of the dye is great. That is, most of pigments, especially dyes and organic pigments, are decomposed at a high temperature of 300 ° C. or higher. In addition, many inorganic materials have a problem with heat resistance, such as molybdenum orange and ultramarine blue. Therefore, firing may be performed at a decomposition temperature or lower determined for each dye, but when formed at a temperature of 300 ° C. or lower, a considerable variety of dyes can be used regardless of whether organic or inorganic, and the spectral transmittance is high. It is preferable because 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, the dye may be mixed with the starting solution, and the sol may be formed, then coated and dried. Most of the dye is incorporated into 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 formed gel. This is the same when the siloxane bond between the sol particles is developed by firing.
By the way, since the surface of the pore portion of this gel has a hydroxyl group generated by a hydrolysis reaction of a metal alkoxide or the like, the gel has a high affinity for water, so that water easily penetrates into the pores. Accordingly, there is a problem of water resistance, that is, water penetrating into the pores elutes the dye present 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 taken into the gel so as to be sandwiched between the sol particles at the time of gel formation in the same manner as described above. If the particle size of the pigment is too small, an elution phenomenon is caused as in the case of the dye, and if the particle size is too large, the pigment particles cause light scattering and impair transparency.

Further, even if the particle size is such that the transparency is not impaired, the strength is deteriorated for the following reason. In other words, the pigment particles form a gel skeleton structure together with the metal oxide particles obtained by hydrolysis and polycondensation of metal alkoxide and the like. However, since the bonding between the pigment particles and the metal oxide particles does not occur, the structure of the gel itself is weakened,
The obtained glass gel thin film cannot obtain sufficient strength. This is because the bonding between the metal oxide particles obtained by the sol-gel method is caused by a hydrolysis reaction at the time of forming the sol, the surface of the particles is in a state of hydroxyl groups, 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 dye particles, the porosity of the glass gel is reduced by raising the firing temperature, and the dye is brought into a state of a perfect glass film or almost the same as that of the glass gel. It must be wrapped in. The firing temperature for this must be at least 500 ° C. or higher, and the dyes used are greatly restricted.

Therefore, the present inventors have conducted various experiments,
It was confirmed that if the particle size of the dye was controlled to 3 nm or more, the above-mentioned problem, that is, the problem of water resistance did not occur even in a glass gel thin film obtained by firing at a low temperature. At that time, it was also found that the addition of a substance having an adsorbing effect on the dye and having a high 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.

Hereinafter, the function of the particle size of the dye in the present invention will be described in detail.

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) In order to evaluate water resistance, a thin film containing dyes having various particle diameters was immersed in water and a detergent on a white cloth and subjected to a 500 reciprocating rubbing test. The presence or absence of peeling was checked. Table 1 shows the test results.

The glass gel film used was composed of 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 (Hosta Palm Pink E)… 0.25 Parts by weight Dispersant: 0.06 parts by weight Isopropyl alcohol: 89.89 parts by weight A coating liquid composition was applied on a glass substrate and baked at about 150 ° C. for 20 minutes. The average particle size of the pigment was measured using an elastic light scattering method. This method is a method of irradiating a pigment dispersion with light and quantifying fluctuations of scattered light by a photon correlation method, and was performed using a scatterometer manufactured by Union.

[0027]

[Table 1] FIGS. 1A and 1B are diagrams for explaining the difference between the effects shown in Table 1 above. FIG. 1A shows the case where the particle diameter of the dye is 3 nm, and FIG.
FIG. 3 is a schematic cross-sectional view showing a case where the particle diameter of a dye is several angstroms. FIG. 2 shows a further enlarged view of the bonding state between 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 between the above-described effects in the case of a few angstrom particles and 3 nm. FIGS. 2A and 2B further show the bonding portion between the metal oxide and the dye particles of the glass gel thin film composed of the metal oxide of FIG. 1 in a further enlarged manner. 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 has pores 4 which are defective parts in some places. The size of the pores is several Å to several hundred Å on average.

As can be seen from FIG. 1, the dye 3 is liberated by intensively penetrating water into the pores 4. At this time, the particle size of the dye 3 is large, When the contact area is large and firmly fixed by the metal oxide 2 constituting the glass gel thin film 1, elution hardly occurs and the strength does not deteriorate. This strength deterioration is considered to be for the following reason. That is, FIG.
As shown in the figure, since the pigment particles form a part of the skeleton structure of the glass gel thin film, if the bond between the pigment and the metal oxide or hydroxide fine particles is weak, the strength of the skeleton structure in that part is low. Because of the deterioration, the strength of the film is reduced.
However, as shown in FIG.
When the bonding between the hydroxide fine particles is strong, the skeleton structure of the glass gel film containing the pigment particles also maintains a sufficient strength, so that the strength of the film does not deteriorate. this is,
This can be achieved by adding a substance which has an adsorbing effect on the dye and has a high affinity for 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. Also, in the above rubbing test, the glass gel film on the surface is damaged by friction and causes the dissolution of the dye in the same manner, but in this case, if the particle size of the dye is large, decolorization does not occur for the same reason as described above . For the above reasons, it is inferred that the results in Table 1 were obtained.

(Ultraviolet resistance) By increasing the particle size of the dye, the ultraviolet resistance as well as the water resistance described above is improved. Table 2 shows the results obtained by enclosing dyes having various particle diameters in a glass gel thin film and measuring the fading of the dyes in order to evaluate the UV resistance.

The glass gel film used was the same as the one used in the above-mentioned water resistance evaluation.

[0033]

[Table 2] At this time, Hostaperm Pink E was used as the dye, and metal halide was used as the light source. Irradiation with ultraviolet light of 100 mW / cm ² was performed for 4 hours, and the residual ratio of absorption at the main absorption peak of the dye was compared. The residual absorption ratio is obtained by calculating the initial main peak transmittance as T ₀ ,
If the main peak transmittance after 4 hours is _Tn , it is given by the following equation.

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

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

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

The glass gel film used was the same as that used in the above-mentioned water resistance evaluation.

[0038]

[Table 3] The maximum diameter at which light passes through the particles is assumed to be λ / 2 or less, where λ is the wavelength of the light.
Considering the case of (00 to 700 nm), if the particle size exceeds 200 nm, light scattering occurs and transparency is impaired, which is not preferable in terms of optical characteristics. Simply, it is considered that the particle size is preferably 200 nm or less. However, in the present invention, 3
It does not impair the transparency up to 00 nm. This is because the pigment particles are incorporated in the glass gel thin film, and by reducing the difference between the refractive index of the pigment and the refractive index of the medium, the surface reflectivity of the pigment particles themselves can be reduced. It is thought that beyond the limits, the particle type of the dye can be expanded to a particle size of about 300 nm, which is more advantageous in terms of light resistance and water resistance.

Therefore, as described above, from the viewpoint of water resistance, a particle size larger than the size of the defect of the glass gel thin film, that is, 1 nm or more is preferable, and from the viewpoint of light resistance, a particle size of 3 nm or more. However, when the particle size is too large, there is a problem that transparency is impaired. Thus, the theoretical upper limit of the particle size has been determined to some extent, but according to the present invention, a particle size exceeding this upper limit can be used. That is, the particle diameter of the dye is 3 nm to 300 nm.
By setting the thickness to nm, water resistance and light resistance can be improved without impairing the transparency of the glass gel thin film. Preferably, it is 5-200 nm.

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

(Explanation of Coating Solution) The particle diameter of the dye has been described above. Next, a coating solution for forming a 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 solution 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 the dye in the metal alkoxide solution, even if the resin is soluble in alcohol, it is not adsorbed by the dye, and if there is no dispersing power, the dye will aggregate. As a result, a uniform dispersion cannot be obtained, and the formed gel film becomes opaque and semi-clear. Rosin resin, ketone resin and shellac showed such behavior. In addition, even if a resin is soluble in alcohol and has a dispersing power of a dye, if the resin is not compatible with an alcohol solution containing a metal alkoxide, the gel film will be opaque and semi-clear. Vinylpyrrolidone resin showed such behavior.

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

That is, as can be seen from FIG.
The pigment particles form part of the skeleton structure of the glass gel thin film. If the bond between the dye and the metal oxide or hydroxide fine particles is weak, the strength of the skeleton structure at that portion is deteriorated, and the strength of the film is reduced. As described above, if it has an action of adsorbing the dye 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 is used. The skeletal structure also has a sufficient strength, so that the strength of the film does not deteriorate.

The following are effective as such a dispersion.

(1) Polyvinyl butyral resin. For example, Eslec BLS, Eslec BL-1 (product name)
etc. (2) Polyvinyl alcohol resin. For example, Gohselan L-0301 (product name) and the like. (3) Acrylic resin. For example, Hitec 532 (product name) and the like. (4) Ethyl cellulose. For example, Ethocel (product name)
etc. (5) unsaturated polycarboxylic acids. For example, Big 104S
(Product name) etc. (6) Phosphate ester activators. For example, desk call A
-200 (product name) and the like. (7) Polyester resin. For example, Polyester WR-
901 (product name) and the like.

(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) (product name) and the like. (10) Aluminum coupling agent. For example, aluminum chelate M (product name) and the like.

The addition amount of these substances is 5 w
t% to 100 wt% is preferred.

By the way, the dye reacts with the metal alkoxide depending on the kind, and changes with time in the 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 an effect, the amount of the dispersant relative to the metal alkoxide should be about 0.01%.
wt% or more is required. On the other hand, if the amount of the dispersant is too large, the effect of maintaining the strength is reduced, and the strength is deteriorated. This is because the function 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. For this reason, the amount of the dispersant is 20 to the amount of the metal alkoxide.
The content is preferably 0% by weight 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. As the metal alkoxide, Si (OR) ₄ is typical, but other than Si, Zn, Zr, Ti, Al, Fe, C
Those of o, Ni, etc. can be used alone or in combination depending on the purpose. For example, it is useful to mix Ti and Zn when it is desired to increase the reflectance, Zr when it is necessary to improve the strength and alkali resistance, and Ni when it is necessary to further improve the light resistance. is there. In these cases, it is possible to disperse the dye by almost the same method. And SiO (decomposition product of Si (OR) ₄ )
₂ also functions 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 the viscosity of the M (OR) _n alcohol solution with the increase in the number of carbon atoms, and may be appropriately selected in consideration of this point. 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, it is possible to prepare the coating liquid composition of the present invention by using almost all organic pigments and laked and powdered dyes, for example, azo yellow, such as benzidine yellow and carmine FB. , Red pigments, perylene, perinone, dioxazine, thioindigo, isoindolinone, quinophthalone, condensed pigments such as quinacridone, phthalocyanine pigments, titanium white,
There are inorganic pigments such as red iron, graphite and cobalt blue, and inorganic pigments such as carbon black. It is necessary to select a dye from these in consideration of the emission spectrum of a filter. For example, it is possible to make the filter absorption characteristic large in a spectrum region where the energy is small. Further, the coloring power of the pigment differs depending on the pigment. When the transmittance of the maximum absorption portion was measured using an organic pigment having relatively large coloring power (Heliogen Blue E-7S), the results were as shown in Table 4.

The glass gel film used was as follows: 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 ... 0.00007 to 0.7 parts by weight Part Pigment (Heliogen Blue E-7S): 0.00007 to 0.7 parts by weight Isopropyl alcohol: A coating liquid composition consisting of the remainder was applied on a glass substrate and baked at about 150 ° C. for 20 minutes. Things.

[0055]

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

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

The glass gel film used was composed of 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 to 3.7 parts by weight Part: Pigment (Heliogen Blue E-7S): 7.0 to 15.4 parts by weight Isopropyl alcohol: A coating liquid composition consisting of the remainder was applied on a glass substrate and baked at about 150 ° C. for 20 minutes. Things.

[0058]

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

As described above, in consideration of coloring and film strength, the weight ratio of the dye to the binder is 0.01 wt.
% To 200% by weight is preferred. When the amount is too small, the coloring becomes insufficient and the filter does not make sense. On the contrary, when the amount is too large, the strength of the film itself becomes weak, and even if a dye having a particle size suitable for the present invention is used, decolorization occurs.

Further, the ratio of the total amount of the solid content (the total amount of the metal alkoxide, the condensation polymer of the metal alkoxide, the coloring matter and the dispersant) to the total amount of the coating liquid must be 50 wt% or less from the viewpoint of the stability of the liquid. No. 5
When the content becomes 0 wt% or more, about 1
The liquid itself gels to agar in about a day. further,
Even before gelation, liquid properties such as viscosity change every moment, and they are not applied under the same conditions. In order to obtain a practical film thickness of 0.1 μm or more, the total solid content is preferably 0.1% by weight or more.

Also, since the particle diameter of the pigment is increased,
It is less susceptible to the acid as a catalyst in the coating solution, so that it is possible to use even a dye having a problem with acid resistance, and the storage stability of the coating solution is improved.

If the amount of the dispersing agent is 0.01 part by weight or less based on 100 parts by weight of the metal alkoxide, there is a possibility that the dye reacts with the metal alkoxide to cause a change with time. If the amount is more than 200 parts by weight, the film strength will be deteriorated. More preferably, the amount of the dispersant is preferably 5 to 100 parts by weight based on the weight of the dye.

Accordingly, 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 = 0.0001-2,
C / A = 0.0001-2, (A + B + C) / D = 0.
It is preferably set to 001 to 0.5. Further, more preferably, C / B = 0.05 to 1. B / A is 0.
When it is less than 0001, the coloring becomes insufficient, and when B / A is 2 or more, the film strength is deteriorated. C / A is 0.0001
If it is less than the above, the stability of some pigments deteriorates. If C / A is 2 or more, the film strength deteriorates. further,
When (A + B + C) / D is 0.001 or less, a practical film thickness cannot be obtained, and (A + B + C) / D is 0.5
If it is more than the above, a problem occurs in the stability of the coating liquid.

The dispersing machine required for preparing the dispersion liquid includes two rolls, three rolls, a Banbury mixer,
SG mill, attritor, and the like.

(Colored Glass Gel Filter) The colored glass gel filter according to the present invention can be formed by applying the above-mentioned coating liquid composition on a substrate and baking it at 100 ° C. to 300 ° C. The formed colored glass gel filter contains a pigment having a desired spectral transmittance characteristic in an inorganic glass gel thin film containing SiO ₂ as a main component, and the pigment has an average particle diameter of 3 nm or more.
It is set to 300 nm. At this time, since a substance having an adsorbing effect on the dye and having a high affinity for the metal alkoxide and its hydrolyzate is added, the deterioration of the hardness of the glass gel film due to the dye particles can be prevented as described above. That is, 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 at a sufficient strength, so that the strength of the film is not deteriorated.

The thickness is practically 0.1 μm to 3 μm. 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) By forming the colored glass gel filter on the light-transmitting display portion base of the display, the contrast and the color purity can be improved.

Display devices include 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. Normally, a filter film is formed by coating on a screen glass substrate which is a light-transmitting display portion base. In the case of a projection type display device, a filter film may be formed on a projection screen.

It is necessary to select a dye in consideration of the emission spectrum of each display device. For example, it is possible to make the filter absorption characteristic large in a spectrum region where the energy is small.

Further, 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 color light emitted from a fluorescent lamp or the like. In this case, a dye that cuts a specific wavelength may be selected.

Further, the present invention can be applied to a magnetic disk, an optical disk and the like.

[0072]

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

Example 1 Hostaperm Pink E (pigment) 2.5 wt% TSL8311 (silane coupling agent, manufactured by Toshiba Silicon) 0.1 wt% Ethocel 7CP (ethyl cellulose) 0.5 wt% Isopropyl alcohol 96.9 wt% The above-mentioned materials are dispersed for 12 hours using 0.5 mm zircon beads in an SG mill (dispersing machine) to prepare a pigment dispersion (pigment dispersion 1). Then, the mixture was mixed with a propeller type stirrer according to the following formulation to obtain a coating liquid composition having an average particle diameter of the dye 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 liquid 1 10.0 wt% Isopropyl alcohol 80.2 wt% Composition of the above coating liquid composition The ratio was as follows: 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, C / B = 0.24.

After applying this composition on a glass substrate,
Baking was performed at 150 ° C. for 20 minutes to form a colored glass gel filter having a thickness of 0.2 μm.

The light transmission characteristics of the colored glass gel filter formed by the coating liquid composition of this example are as shown in FIG. 3A. The colored glass gel filter was subjected to a rubbing test with a detergent to evaluate water resistance. As a result, no decolorization occurred, and the UV resistance exhibited excellent characteristics of 92%. Further, the strength of the film is 8H in pencil hardness, which is a sufficient strength for practical use. The pencil hardness was measured according to JIS K5400. In addition, the pot life of the coating solution was increased to about one month as compared with the conventional one week, and good characteristics were obtained.

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

FIG. 4 is a partially cutaway side view showing a color picture tube manufactured according to the present invention. This color picture tube
10 has an airtight glass envelope 11 whose inside is evacuated. The envelope 11 has a neck 12 and a cone 13 continuing from the neck 12. Furthermore, 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 outer periphery of the side wall of the face plate 14 for explosion protection. The neck 12 has an electron gun 16 for emitting an electron beam.
Is arranged. The inside of the face plate 12 is excited by an electron beam from the electron gun 16 to generate red, green,
A phosphor screen 17 is provided which includes a striped phosphor layer that emits blue light and a striped black light absorbing layer disposed between the phosphor layers. In addition, a shadow mask (not shown) having a through hole 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 on the phosphor screen 17 is mounted on the outside.

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

The filter characteristics are 400 to 650 nm
Has a maximum absorption wavelength in a wavelength range of 575 ± 20 nm in the range of 575 ± 20 nm, and has a wavelength of 450 nm, 530 nm, 550 nm,
Assuming that the transmittance for light having a wavelength of 30 nm and the maximum absorption wavelength is T ₄₅₀ , T ₅₃₀ , T ₅₅₀ T ₆₃₀ , and T _min , 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
.Ltoreq.1.43, specifically, as shown in FIG. 3A. In FIG. 3, reference numeral 6 denotes a light transmission characteristic of the colored glass gel filter, and reference numeral 7 denotes an emission spectrum of the color picture tube. Also, the effect of improving the contrast is
The ratio of the luminance reduction rate ΔB to the external light reflectance reduction rate ΔR _f , that is, BCP (Brightness Contrast Performance)
) = ΔB / (ΔR _f ) ^1/2 . As a result, in this example, the BCP was 1.07. water resistant,
The UV resistance and the film strength are the same as in the first embodiment.

Accordingly, 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% by weight Gohselan L-0301 (polyvinyl alcohol resin) 0.5% by weight Isopropyl alcohol 97.5% by weight The above materials were used in the same manner as in Example 1. To prepare a pigment dispersion (pigment dispersion 2).

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

Heliogen Blue EP-7S (pigment) 2.5 wt% Prenact 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-type stirrer to obtain a coating liquid composition having an average particle size 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 liquid 28 0.0 wt% Pigment dispersion 3 2.0 wt% Isopropyl alcohol 82.0 wt% The composition ratio of the 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 and 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 applying this on a glass substrate, 150
C. for 20 minutes to form a colored glass gel filter having a thickness of 0.2 .mu.m.

The light transmission characteristics of this colored glass gel filter are the same as those shown in FIG. 3B. In addition, when a rubbing test with a detergent was performed to evaluate the water resistance, no decolorization occurred, and the UV resistance exhibited excellent characteristics of 90%. 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 sintering temperature and the film thickness are the same as those in the second embodiment.

The filter characteristics are as shown in FIG. 3B. In this example, the BCP was 1.08. The water resistance, ultraviolet light resistance and film strength are the same as in Example 3 above.

Example 5 Bengala (pigment) 2.5 wt% ESREC BLS 0.5 wt% Silane coupling agent 0.1 wt% Isopropyl alcohol 96.9 wt% The above materials were dispersed by the same means as in Example 1, A pigment dispersion (pigment dispersion 4) is prepared.

Then, the mixture was mixed with a propeller-type stirrer in the following composition 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 as follows: 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, C / B = 0.24.

This was applied on a glass substrate, and baked at 150 ° C. for 20 minutes.
A colored glass gel filter having the following characteristics was formed.

The colored glass gel filter is as follows:
A rubbing test with a detergent was performed to evaluate the water resistance. No decolorization occurred, and the UV resistance was 100%.
And 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 a plasma display. The sintering temperature and the film thickness are the same as those in the second embodiment.

The filter characteristics are as shown 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. In this embodiment, BCP is 1.
It was 10. The water resistance, ultraviolet light resistance and film strength are the same as in Example 3 above. In the case of a plasma display, it is preferable to absorb a wavelength region of 400 nm to 600 nm.

(Embodiment 7) A 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 will be described below.

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 each opposing surface of the substrates 21 and 22, respectively.
Electrode of predetermined pattern consisting of TO (Indium Tin Oxide)
23, 24, alignment films 25, 26 formed on the opposing surfaces of the pair of substrates 21, 22 so as to cover the electrodes 23, 24, and alignment films 25, 26 disposed between the substrates 21, 22. 26, a spacer 27 made of a thermosetting resin that 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. A colored glass gel filter 30 is provided on the outer surface of one of the substrates 21 forming the display base.

This colored glass gel filter 30 is formed by sealing the portion other than the portion where the colored glass gel filter 30 is formed, and applying the glass gel thin film forming coating solution of Example 1 so that the film thickness becomes 0.1 μm. , And then fired.

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

(Embodiment 8) In Embodiment 7, the transmission type liquid crystal display device has been described. However, 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 to a screen of a rear projection type liquid crystal display device using the composition shown in Example 1 above.

The filter characteristics are the same as those of the first embodiment, and the BCP is 1.10. The water resistance, ultraviolet light resistance and film strength are the same as in the first embodiment.

Although the above embodiments have been described with respect to a display device such as a color picture tube, a liquid crystal display device, or the like, the present invention is not limited to the display device, but is intended to change the emission color of a fluorescent lamp or the like. Can be applied to 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 or the like using a laser is also possible.

[0105]

As described above, according to the present invention, a thin film having extremely high degree of freedom of coloring, having excellent water resistance and ultraviolet resistance, and having sufficient strength can be subjected to low-temperature sintering by the sol-gel method. Thus, a coating liquid composition and a colored glass gel filter which can be formed can be obtained.

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

[Brief description of the 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 bonding 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 light transmission characteristics 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 illustrating a configuration of a liquid crystal display 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. ⁶ Identification symbol FI H01J 29/88 H01J 29/88 29/89 29/89 (72) Inventor Kazuo Sakai 2-23-2 Obana, Kawanishi-shi, Hyogo Prefecture Fuji Stock Company In-company (58) Field surveyed (Int.Cl. ⁶ , DB name) C03B 8/02 C03B 19/12

Claims (4)

(57) [Claims] 1. A metal alkoxide and / or a condensation polymer of a metal alkoxide, and a dye,
A glass gel comprising: an alcohol solvent, a dispersant having an adsorbing effect on the dye and being soluble in alcohol and compatible with a metal alkoxide, wherein the dye has an average particle size of 3 nm to 300 nm. A coating liquid composition for forming a thin film. 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 5. The coating liquid composition for forming a glass gel thin film according to claim 1, wherein 3. A colored glass gel filter, wherein the coating liquid composition for forming a glass gel thin film according to claim 1 is applied on a substrate and formed by firing at a low temperature. 4. The colored glass gel filter according to claim 3, wherein the colored glass gel filter is set on the outer surface of the light-transmitting display portion base so as to selectively absorb at least a wavelength region other than a wavelength having a large emission energy. A display device characterized by the above-mentioned.