JPH09318810A - Color filter and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain color filters of a high contrast which are inexpensively produced by simplified stages and have smooth surfaces free from light leakage from boundary parts by forming transparent conductive films on a transparent substrate and arranging a black matrix consisting of black inorg. oxide and colored pixel parts thereon. SOLUTION: The transparent conductive film is formed on the transparent substrate and the black matrix consisting of the black inorg. oxide and the colored pixel parts are formed thereon. The colored pixel parts are preferably formed by an electrodeposition method. The transparent conductive film is preferably obtd. by printing and baking the transparent conductive ink consisting of the org. metal compd. expressed by the formula: N(OH)r (R-CO-CH2 -CO-R')S, n=r+s, a solvent and additives. In the formula, N denotes elements, such as indium, tin, antimony, baron, phosphorus, etc.; R, R' denote substd. allyl group or substd. alkyl group; (n) is the valency of N; (r), (s) denote natural numbers.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter for enabling color display when used in various display devices such as liquid crystal display panels and a method for manufacturing the same.

[0002]

2. Description of the Related Art A typical color filter used in the past has been manufactured through two steps, a black matrix forming step and a colored pixel section forming step.

As a method for forming a black matrix, (1) a method of forming a black matrix on a portion to be shielded from light by using an ink or a photosensitizer containing a black pigment, or (2) vapor deposition on a transparent substrate. Metal thin film such as chromium or metal oxide thin film is formed on the entire surface by the sputtering method or the sputtering method, and then a resist is applied on the surface of the light shielding film formed on the entire surface of the transparent substrate and exposed and developed through a mask to correspond to the colored pixel portion. The method of forming the light-shielding film by etching away the light-shielding film is common.

As a method of coloring the colored pixel portion,
(3) A dyeing method of dyeing a dye using a resin such as acrylic, casein or gelatin as a substrate, (4) PVA, acrylic,
There are a pigment dispersion method in which a pigment is dispersed in a resin having photosensitivity such as polyimide to form a colored pixel portion, (5) a transfer method in which a pigment is dispersed in a photosensitive resin to form a film, and (6) a printing method.

Further, as a method of forming the colored pixel portion first and then forming the black matrix, (7) a transparent conductive film is formed on the substrate and the colored pixel portion is formed by electrodeposition, and then a black photosensitive resin is formed. There is an electrodeposition method in which a black matrix is formed by applying and exposing and developing.

[0006]

However, the color filters produced by the above methods have various problems as described below.

In the method (1), it is necessary to increase the film thickness of the black matrix in order to obtain a sufficient light-shielding property. When the film is thickened by using a photosensitizer, the black pigment is finely absorbed by light absorption. It is not possible to obtain a good black matrix. Further, if an optical density of 3.5 or more is to be obtained, the film thickness of the black matrix becomes too thick and smoothness cannot be maintained. That is, the black matrix and the colored pixel portion overlap with each other, the surface smoothness of the color filter is remarkably deteriorated, and this causes uneven alignment of liquid crystals and defective cell gap.

In the method (2), when a metal thin film is used, the black matrix has a metallic luster, so that the black matrix has an extremely high reflectance of 60% or more when observed from the transparent substrate side. That is, the visibility of the panel is significantly reduced. Further, when a metal oxide thin film is used, the number of steps on an expensive vacuum device for forming the oxide film increases, and the etching process of the oxide film is complicated because the oxide film has excellent etching resistance.

Further, in the method of forming the colored pixel portion, the following problems have occurred.

Although the dyeing method (3) has excellent color rendering properties, it requires a large number of manufacturing steps and is complicated.
It was inferior in chemical resistance and heat resistance.

Although the pigment dispersion method (4) is excellent in heat resistance, it is inferior to the other methods in terms of chromaticity and depolarization characteristics. Furthermore, a complicated photolithography process is required.

In the film transfer method of (5), when laminating a transfer film for coloring on a colored pixel portion other than the already formed black matrix, bubbles are generated or the colored pixel portion and the black matrix are combined. There was a problem such as light leakage at the boundary. In particular, in the case of the mosaic pattern, the occurrence rate of light leakage around the colored pixel portion was high because bubbles were likely to occur.

In the printing method of (6), the manufacturing process is simplified, but the product yield is low, and there is a problem in that the smoothness is poor due to the overlap of the black matrix and the colored pixel portion.

The electrodeposition method (7) is a simplified coloring process. However, the transparent conductive film is formed using a large-scale vacuum device, resist is formed thereafter, electrodes are formed into a required pattern shape by a series of photolithography steps, and electrodeposition is performed, which is disadvantageous in terms of cost.

On the other hand, a transparent conductive film is formed on the entire surface, a black mask is formed by an electrodeposition method, and then colored pixel portions are sequentially formed. Alternatively, contrary to the above, first, the colored pixel portions are electrodeposited and then exposed. Although a method of forming a desired black matrix by applying a protective black and exposing it from the back surface of the substrate is disclosed, both of them do not have sufficient light-shielding properties to obtain high contrast. More specifically, in order to provide a black matrix having an insulating property and a low reflectance,
When the photosensitive resin of (1) is used, when the black matrix is formed by applying the photosensitive resin on the entire surface after the coloring step and exposing the entire surface from the back surface, a residue is generated on the surface of each color of RGB and the hue is deteriorated. The harmful effect such as doing occurred. In addition, due to the light absorption of the black pigment, the film thickness of the photosensitive resin became a thin film and the desired optical density could not be obtained. Further, the optical density can be increased by increasing the carbon content or increasing the film thickness, but increasing the film thickness makes it extremely difficult to adjust the sensitivity in the case of the black photosensitive resin. . Further, in the electrodeposition method, it is necessary to use an insulating black matrix in the process, which is inconvenient for a conductive black matrix.

Further, when the black matrix of (2) is used and the metal thin film is used, there is the above-mentioned problem that the visibility of the liquid crystal display panel is remarkably lowered due to the metallic luster. Further, the use of the metal oxide film has a problem that it takes time to perform an expensive vacuum apparatus and etching.

Further, as a problem of the electrodeposition method, in the color filter for TFT, in order to achieve high contrast, the black matrix is mainly formed in a lattice shape, and in the electrodeposition method, the lattice-shaped black matrix is formed. Although it can be produced, it requires a complicated process, which is a factor of lowering the yield.

Therefore, the present invention solves the above problems, can be manufactured at a low cost through a simplified process, has a smooth surface, and has no light leakage from the boundary portion between the black matrix and the colored pixel portion. An object of the present invention is to provide a contrast color filter and a manufacturing method thereof.

[0019]

In order to achieve the above object, a color filter and a method for producing the same according to the present invention include:
It was configured as follows.

That is, the color filter of the present invention is
A transparent conductive film was formed on a transparent substrate, and a black matrix made of a black inorganic oxide and a colored pixel portion were arranged on the transparent conductive film.

Further, in the above invention, the colored pixel portion may be formed by an electrodeposition method.

Further, in the above invention, the transparent conductive film, the general formula _{N (OH) r (R-} CO-CH 2 -CO-R ') s, n
Alternatively, the transparent conductive ink composed of an organic metal compound represented by the formula: = r + s, a solvent, and an additive may be obtained by printing and baking. However, N represents an element which is at least one selected from the group consisting of indium, tin, antimony, boron, phosphorus, aluminum, bismuth, silicon, titanium, selenium, tellurium, hafnium, and zinc. R, R '
Represents a substituted allyl group or a substituted alkyl group. n is the valence of N, and r and s are natural numbers.

In the above invention, the black matrix is a transparent active film obtained by coating and firing an organometallic compound represented by the general formula M (OR ₁ ) ₁ (OR ₂ ) _m X _p Y _q. The inside of the layer may be blackened by a redox reaction of a metal.

In the above invention, the metal used in the redox reaction is tin, nickel, cobalt, copper,
It may be configured to be either silver or gold.

Further, in the above invention, the black matrix and the colored pixel portion may be arranged so as not to overlap with each other.

In the above invention, the black matrix may have a volume resistivity of 1 × 10 ⁷ Ω · cm or more.

Further, in the above invention, there is no light leakage from the boundary portion between the black matrix and the colored pixel portion, the total reflectance from the glass surface is 6.0% or less, and the optical density of the black matrix is It may be configured to be 3.5 or higher.

Further, the method of manufacturing a color filter of the present invention is such that an organic metal represented by the general formula M (OR ₁ ) _l (OR ₂ ) _m X _p Y _q is formed on a transparent substrate on which a transparent conductive film is formed. The compound is coated and baked to form a transparent active film layer, the inside of the active film layer is blackened by a redox reaction of a metal, and the blackened active film layer other than the black matrix is removed and exposed. A colored pixel portion was formed on the transparent conductive film by an electrodeposition method. However,
M represents at least one element selected from the group consisting of magnesium, calcium, zirconium, titanium, hafnium, germanium, yttrium, indium, aluminum, gallium, tin and silicon. R ₁ and R _{2 each} represent a hydrogen atom, an alkyl group or an acyl group. X and Y each represent a hydrogen atom, a chlorine atom or a hydroxyl group. l, m, p, and q are integers of 0 to 8, and l + m + p + q is equal to the valence of M.

In the above invention, the type of metal of the black matrix formed by the redox reaction is
It may be constituted by any one of tin, nickel, cobalt, copper, silver and gold.

Further, in the above invention, in the electrodeposition method, the exposure of the electrodeposition photosensitive resist is performed at different exposure times each time the mask for colored pixel portion is moved by one pixel pitch.
The exposure may be performed twice.

Further, in the above invention, the transparent conductive film general formula _{N (OH) r (R-} CO-CH 2 -CO-R ') s, n
Alternatively, the transparent conductive ink composed of an organic metal compound represented by the formula: = r + s, a solvent, and an additive may be obtained by printing and firing. However, N represents an element which is at least one selected from the group consisting of indium, tin, antimony, boron, phosphorus, aluminum, bismuth, silicon, titanium, selenium, tellurium, hafnium, and zinc. R and R'represent a substituted allyl group or a substituted alkyl group. n is the valence of N, and r and s are natural numbers.

Further, in the above invention, the solvent of the transparent conductive ink is 5 to 60% by weight of at least one organic solvent selected from alcohols, ketones, esters and ethers having a boiling point of 40 to 140 ° C. It may be composed of a mixture of 40 to 95% by weight of at least one organic solvent selected from carbitols, glycols and cellosolves at 150 to 280 ° C.

In the above invention, the conductivity of the black matrix may be 1 × 10 ⁷ Ω · cm or more in terms of volume resistance.

[0034]

BEST MODE FOR CARRYING OUT THE INVENTION A method of manufacturing a color filter according to the present invention comprises a transparent substrate on which a transparent conductive film is formed, and a general formula M (OR ₁ ) ₁ (OR 2) _m X _p Y _q (where M is Magnesium, calcium, zirconium, titanium, hafnium, germanium, yttrium, indium,
At least one element selected from the group consisting of aluminum, gallium, tin, and silicon is shown. R ₁ and R _{2 each} represent a hydrogen atom, an alkyl group or an acyl group. X
And Y represent any one of a hydrogen atom, a chlorine atom and a hydroxyl group. l, m, p, and q are integers of 0 to 8, and 1 + m +
p + q is equal to the valence of M. ) Is applied and baked to form a transparent active film layer, and the inside of the active film layer is blackened by a redox reaction of the metal, and the blackened active film of the portion other than the black matrix is formed. The layer is removed, and the colored pixel portion is formed on the exposed transparent conductive film by the electrodeposition method.

As the transparent substrate, those used for ordinary liquid crystal display panels may be used. For example, non-alkali glass, borosilicate glass as a typical low expansion glass, soda lime glass coated with silicon dioxide, etc. can be used. As the transparent conductive film, ITO, ATO, F
It is effective to use a transparent oxide-based conductive film that is a transparent n-type semiconductor represented by TO, FATO, CTO, ZO, SnO2, or the like. It is particularly effective that the resistance value is 200Ω / sq or less, the transmittance is at least 85% or more, and the light absorption at a specific wavelength is not performed. Further, in consideration of the manufacturing process of the present invention, SnO ₂ and AT which have chemical stability when the black active oxide film is removed by etching are taken into consideration.
O, SnO ₂ , ATO, FTO, FATO and the like are effective as the transparent conductive film. As a method for forming the transparent conductive film, PVD represented by EB vapor deposition method and sputtering method is used.
Method, a chemical vapor deposition method (CVD method) or a sol-gel method may be used.

To form the transparent conductive film, it may be formed on the entire surface of the substrate, or may be formed only on the entire colored pixel portion and the routing circuit portion. It is effective to pattern the transparent conductive film with the increase in the area of the transparent substrate to prevent the voltage drop in the electrodeposition method. Usually, the transparent conductive film is patterned by forming a transparent conductive film on the entire surface, applying a resist, exposing and developing, and then patterning by removing by etching, or patterning by a mask vapor deposition method or a mask sputtering method. However, a large-scale device is required and the manufacturing process is complicated. However, the metal hydrate obtained from the metal alkoxide by the sol-gel method,
Alternatively, a high-quality transparent conductive film can be formed at low cost by coating or printing a transparent conductive ink obtained by mixing a metal chelate with a solvent and an additive as appropriate and then baking. In particular, the general formula _{N (OH) r (R-} CO-CH 2 -CO-R ') s, n =
A transparent conductive ink composed of an organic metal compound represented by r + s, a solvent, and an additive is formed by patterning by printing, and by firing in an atmosphere at 400 to 550 ° C., a transparent conductive film having a high transparency and a low resistance value is obtained. Obtainable.
In the general formula, N is indium, tin, antimony, boron, phosphorus, aluminum, bismuth, silicon, titanium,
An element which is at least one selected from the group consisting of selenium, tellurium, hafnium, and zinc is shown. R and R'represent a substituted allyl group or a substituted alkyl group. n is the valence of N,
r and s are natural numbers.

In particular, when printing is performed by using a thin film forming apparatus as disclosed in Japanese Examined Patent Publication No. 3-11630, the transparent conductive ink includes alcohols, ketones, esters having a boiling point of 40 to 140 ° C. Consists of a mixture of 5-60% by weight of at least one organic solvent among ethers and 40-95% by weight of at least one organic solvent among carbitols, glycols and cellosolves having a boiling point of 150-280 ° C. By such adjustment, a good transparent conductive film having excellent continuous printability can be obtained. This thin film forming apparatus is rotatably supported by a supporting frame of a base and has an intaglio roll having a large number of ink cells with a depth of 1.0 to several tens of μm on the surface, and a low viscosity of 1.0 to 10,000 Cp on the surface of the intaglio roll. A doctor that is provided at a predetermined location around the intaglio roll supported by a support frame and an ink feeder that supplies ink, and spreads the ink supplied to the intaglio roll onto the surface of the intaglio roll to hold a certain amount of ink in the ink cells. A printing roll that has a convex portion that is rotatably supported below the intaglio roll of the support frame and that contacts the intaglio roll, and that transfers the ink in the ink cells to the convex portion on the surface of the intaglio roll, and is supported by the support frame. A drive device for synchronously rotating the printing roll and the intaglio roll, a printing position A on which the printing medium is placed and in contact with the printing roll on the base, and retreat positions B and C separated from the printing roll. A movable platen, a printing medium drive device that moves the platen between the above two positions, rotation of the printing roll, and movement of the platen from the retracted positions B and C to the printing position A. And a control device for printing the ink transferred to the convex portion of the printing roll on the printing medium.

When only the low boiling point solvent is used instead of the above solvent composition, it is dried when the transparent conductive ink is supplied to the intaglio roll of the thin film forming apparatus, and the transparent conductive ink is applied to the substrate. It cannot be transferred. Also,
As disclosed in JP-A-63-9018, the boiling point is
80 to 97% by weight of low boiling point solvent of 30 to 100 ℃, and boiling point of 130 to 25
Even when a mixed solvent with a high boiling point solvent of 3 to 20% by weight at 0 ° C. is used, drying starts when the transparent conductive ink is supplied to the intaglio roll, and the transparent conductive ink can be transferred to the substrate. However, if printing is continuously performed, the viscosity of the transparent conductive ink on the intaglio roll gradually increases, the film thickness of the printing material gradually increases, and finally printing cannot be performed.

On the transparent substrate on which the transparent conductive film thus formed is partially or entirely formed, the general formula M (O
R ₁ ) _l (OR ₂ ) _m X _p Y _q A sol obtained by hydrolyzing a simple substance or a mixture of an organometallic compound is applied, dried and baked to form a transparent active film layer. Obtainable. In the general formula, M is magnesium, calcium, zirconium, titanium, hafnium, germanium, yttrium, indium, aluminum,
At least one element selected from the group consisting of gallium, tin, and silicon is shown. R ₁ and R ₂ represent a hydrogen atom, an alkyl group or an acyl group, and they may be the same or different. X and Y are hydrogen atom, chlorine atom,
It represents a hydroxyl group, which may be the same or different. l, m, p, and q are integers of 0 to 8, and 1 + m +
p + q is equal to the valence of M. Examples of the organometallic compound represented by the general formula include tetraethyl silicate, aluminum triisopropoxide, titanium tetrabutoxide, zirconium tetrabutoxide, and partial hydrolysates thereof. Here, the sol means metal alkoxide, water, hydrochloric acid serving as a catalyst for hydrolysis, sulfuric acid, nitric acid,
Consists of acetic acid and alcohol. Examples of the method for forming the coating film include bar coating, roll coating, spin coating, dip coating, and printing methods. The firing temperature may be appropriately selected within the range of 300 to 600 ° C. The coating thickness is 0.5-10 μm, preferably 0.8
-5 μm is optimal. If it is less than 0.5 μm, the desired light-shielding property cannot be obtained. The film thus formed is transparent and has fine pores with a diameter of about several nm to 100 nm, and becomes an active film.

Further, a sol liquid which becomes a transparent active film layer by baking is applied onto a substrate on which a transparent conductive film is formed by printing and dried at a low temperature, and the transparent conductive film and the active film are formed by baking once. It is also possible to form layers.

The transparent substrate having the active film layer thus obtained is immersed in a solution in which a reducing agent is dissolved. As the reducing agent, stannous chloride, stannous chloride-palladium chloride, sodium potassium tartrate, borohydride compound, sodium hypophosphite, hydrazine, formaldehyde and the like are used.

After the reducing agent is sufficiently adsorbed in the fine pores of the active film layer, the transparent substrate is immersed in a solution in which metal ions to be deposited as colloid are dissolved. The pH of the solution in which the reducing agent and the metal ion are dissolved depends on the metal used. The type of metal used may be selected from tin, nickel, cobalt, copper, silver, gold and the like. When the transparent substrate on which the reducing agent is adsorbed is dipped in a solution in which metal ions are dissolved, the following reaction occurs in the fine pores of the active film layer, and the metal is deposited in the fine pores. The deposited metal becomes colloidal particles, not a general bulk metal, and has a black color without metallic luster.

[0043] _{R + H 2 O → O X} + H + + e Mn + + n e → M 0 or _{^{2H + + 2e → H 2 (}} R is a reducing agent, M indicates a metal.)

The transparent substrate, which is observed as black due to the metal colloid particles in the active film layer, has a black coating with a total reflectance of 6.0% or less as seen through the glass surface and an optical density of 3.5 or more. Becomes A film with a total reflectance of 6.0% or less and an optical density of 3.5 or more is formed by light scattering / absorption of metal colloidal particles deposited in the micropores of the active film layer whose pore size is several hundred Å or less. , Because it exhibits a black color.

It is desirable that the conductivity of the black matrix is 1 × 10 ⁷ Ω · cm or more in terms of volume resistance. The reason is that when the colored image areas are sequentially formed by the electrodeposition method, the transparent conductive film serving as the underlying electrode is evenly provided at least over the entire surface of the colored pixel area, and when the black matrix has conductivity. The formation of the colored pixel portion is also started from the peripheral portion, and it is difficult to form a smooth surface.
The conductivity of the black matrix is 1 × 10 ⁷ Ω in terms of volume resistance.
In order to achieve cm or more, it is preferable to stop the formation of the metal colloid in the porous body up to the surface of the substrate so that the bulk metal is not formed on the surface of the substrate and has electrical conductivity.

Next, a positive type photoresist is applied on the blackened active film layer, and exposed and developed through a mask to form a resist on the portion to be shielded from light, and an unnecessary active film layer is etched. Are removed to pattern the black active film layer to form a black matrix. As the etching agent, phosphoric acid or the like that does not corrode the transparent conductive film is optimal.

Next, a photoresist is applied on a transparent substrate with a black matrix and dried, and then exposed and developed through a mask for colored pixel portion to expose the colored pixel portion of the first color (red pixel). At this time, it is necessary to remove the photoresist on the extraction electrode portion for electrodeposition. First, the patterned transparent substrate is immersed in the first color electrodeposition liquid for about several seconds to 30 minutes to form a colored pixel portion. As the electrodeposition liquid, a generally used cation type or anion type may be used. Acrylic, polyester, epoxy, or urethane resin materials are used as the binder of the electrodeposition liquid, and dyes and pigments such as phthalocyanine green and anthraquinone blue are preferably used as colorants. The energization conditions are appropriately adjusted depending on the area of the colored pixel portion and the resistance value of the transparent conductive film. Usually, electrodeposition is performed in the range of 10 to 300V. Further, in order to make the thickness of the colored pixel portion and the thickness of the black matrix uniform, the concentration of the electrodeposition liquid and the electrodeposition time are adjusted.

Next, using the already formed positive type photoresist, the colored pixel portion of the second color (green pixel) is exposed and developed through the mask for the colored pixel portion to expose the transparent conductive film. A colored pixel portion for the second color is formed in the same manner as for the first color.

Further, the colored pixel portion of the third color (blue pixel) is exposed and developed through the mask for the colored pixel portion using the already formed photoresist to expose the transparent conductive film and similarly the third pixel is formed. A colored pixel portion of a color is formed. In addition,
When forming the colored pixel portion of the third color, the transparent conductive film can be exposed by exposing and developing the entire surface from the back surface of the substrate.

In addition to the method in which the exposure and the development are repeated three times in order to form each of the RGB colored pixel portions as described above, there is the following method. In the exposure of the first color, the exposure is performed for a certain period of time, then the mask for the colored pixel portion is shifted by one pixel pitch, the exposure of the second color is made longer (or shorter) than that of the first color, and further colored by one pixel pitch. The pixel portion mask is shifted, and the exposure of the third color is performed longer (or shorter) than that of the second color. Thereafter, the electrodeposited transparent electrode for the first color is exposed and electrodeposition is performed under predetermined developing conditions. Subsequently, the second color development and electrodeposition are performed. Thereafter, the third color is similarly developed and electrodeposited. By doing so, it is possible to reduce the number of passes of the exposure device and shorten the process. That is, in order to expose the transparent electrode of the pixel to be colored, in the step of exposing and developing the positive resist, the exposure of each color of RGB is performed by parallel translation by one pixel pitch using one colored pixel portion mask, By providing a step for the exposure amount, exposure for three colors can be performed in one exposure process.

Alternatively, predetermined exposure for the first color is performed using a mask dedicated to each color, exposure is then performed using a mask pattern for the second color while changing the exposure amount, and a mask pattern for the third color is further formed. Exposure is performed with an exposure amount different from that of the first and second colors. After that, predetermined development is performed as described above to form each color by the electrodeposition method.

A protective film may be applied on the black matrix and the colored pixel portion. By applying the protective film, the smoothness of the color filter surface is improved. The protective film may be either an inorganic film or an organic film. The inorganic film may be formed by a sol-gel method of silicon oxide, zirconium oxide, or the like having an autocatalytic property, or a general sputtering method. The organic film may be formed of acrylic resin, silicon resin, epoxy resin, or the like.

The colored pixel portion thus obtained is surrounded by the black matrix and is deposited, and there is no gap that causes light leakage at the boundary between the black matrix and the colored pixel portion. Further, the black matrix and the colored pixel portion do not overlap with each other and are smooth. Further, by controlling the thickness of the black matrix and the thickness of the colored pixel portion, it is possible to obtain a uniform color filter having almost no unevenness on the color filter surface. Furthermore, the photoresist coating process is performed twice, and the black matrix and RGB3 are used.
Coloring is possible, the manufacturing process is simplified, and the yield and cost can be improved.

[0054]

【Example】

Example 1 6.6% by weight of indium nitrate trihydrate was completely dissolved in 90% by weight of ethanol, and 1.8% by weight of 2,4-pentanedione (chelating agent) and 1.6% by weight of lactic acid (stabilizer) were added, A uniform transparent liquid was created. This was passed through a column packed with 20% by weight of ion-exchange resin (Amberlist A-15 manufactured by Organo Corporation) dried after activation, and a pale yellow liquid was added to this effluent with 30% by weight of acetic acid (stabilizer) and acetylacetone. 17% by weight of a 50% tin (divalent) 2-propanol solution was added and concentrated by removing the solvent at 20 mmHg and 60 ° C., and 20% by weight of acetic acid (stabilizer) and hexylene glycol 34
A transparent conductive ink was obtained by adding 0% by weight and stirring uniformly.

The transparent conductive ink was printed on a 300 × 300 × 1.1 mm non-alkali glass substrate using a thin film forming apparatus (Angstromer (registered trademark) in-line type manufactured by Nissha Printing Co., Ltd.). The glass substrate was pre-dried, fired at 500 ° C. in a conveyor-type atmosphere furnace, redox-oxidized and then cooled to room temperature to obtain a transparent conductive film. The transparent conductive film had a volume resistance of (1.1 ± 0.1) × 10 ⁻³ Ω · cm and was excellent in uniformity of film thickness and resistance value distribution.

Next, a transparent sol liquid obtained by hydrolyzing and polycondensing aluminum isopropoxide was applied onto a substrate with a transparent conductive film by using a bar coater. This was dried at 70 ° C. and then baked at 450 ° C. for 1 hour to obtain an inorganic transparent film having a thickness of 1.2 μm.

Next, this glass was immersed in a solution in which a reducing agent having the following formulation was dissolved for 5 minutes.

Stannous chloride 5% by weight 36% Hydrochloric acid 20% by weight Pure water 75% by weight

Then, it was washed with water and dried, and immersed in a silver plating bath having the following composition at 60 ° C. for 10 minutes.

Silver nitrate 3% by weight Ammonia water Appropriate amount N-methylolamine 10% by weight Water balance (total 100% by weight)

The glass substrate was pulled up from the plating solution, washed with water and dried to obtain a glass substrate having a black coating on the entire surface. The optical density of the black film is 4.0 or higher, and the integrated sphere reflectance (400 ~
(700 nm) was 3% or less. Ordinary chrome substrate (optical density 3.0, integrated sphere reflectance (400-700 nm) 59%)
And a resin film obtained by dispersing a black pigment in a photosensitizer (optical density: 2.8, integrated sphere reflectance (400 to 700 nm): 5%), which was far superior.

A positive resist (OFPR-800 manufactured by Tokyo Ohka Kogyo Co., Ltd.) was applied on a black-coated glass substrate, dried, and exposed and developed using a mask which shields a portion to be left as a black mask.

Next, the transparent conductive film corresponding to the colored pixel portion other than the black matrix is exposed by immersing it in phosphoric acid at 40 ° C. for 15 minutes to remove the black film by etching, and then the resist on the black matrix is removed. Peeled off.

Next, a resist was applied again on the entire surface of the substrate and dried, and the portion where the R pixel was formed was exposed by exposure and development. After that, the substrate was immersed in the electrodeposition liquid shown below, and a direct current voltage of 70 V was applied between the transparent electrode on the substrate and the positive electrode. The bath temperature was set at 60 ° C., after immersion for 10 minutes, it was pulled up, washed with water, and thermally cured at 100 ° C. to form an R pixel with a thickness of 1.2 μm.

Electrodeposition liquid composition for red 8% by weight of electrodeposition polyester-melamine resin (ED-3000 manufactured by Shinto Paint Co., Ltd.) Red pigment (Chromoftal Red A2B manufactured by Ciba-Geigy) 2% by weight Water 90% by weight

In the same manner, G and B colors were exposed and developed in the same manner, and the pigment component was immersed in an electrodeposition solution having the composition shown below and electrodeposited to prepare a color filter.

Electrodepositing composition for green Electrodepositable polyester-melamine resin 8.0% by weight (ED-3000 manufactured by Shinto Paint Co., Ltd.) Green pigment 1.0% by weight (Fastgen Super Yellow manufactured by Dainippon Ink and Chemicals, Inc.) ) Green pigment 0.5 wt% (Ciba Green Co., Ltd. Cross Green 2YS) Water 90.5 wt%

Electrodeposition liquid composition for blue Electrodepositable polyester-melamine resin 8.0% by weight (ED-3000 manufactured by Shinto Paint Co., Ltd.) Blue pigment 1.0% by weight (Fast Violet BLB manufactured by Sanyo Dye Co., Ltd.) Blue Pigment 0.5% by weight (Ciba-Geigi Co., Ltd. Lionol Blue ES) Water 90.5% by weight

The color filter thus obtained has a surface roughness R _{max of} 0.3 μm or less, is smooth, has no light leakage, and has a black matrix with an optical density of 5.0 or more and an integrating sphere reflectance of 2.8% or less. It was excellent in high contrast.

Example 2 A transparent conductive pattern was formed by printing with the transparent conductive ink and the thin film forming apparatus described in Example 1, and after irradiation with ultraviolet rays 500
A transparent conductive substrate with a drawing circuit was formed by firing in an atmosphere at ℃ for 1 hour.

Next, a transparent sol solution obtained by hydrolyzing and polycondensing aluminum isopropoxide was applied onto a substrate with a transparent conductive film by using a bar coater. After drying this at 80 ℃, calcination at 430 ℃ for 1 hour,
A transparent active film layer with a thickness of 1.0 μm was obtained.

Then, in the same manner as in Example 1, after forming a black film, a black matrix having a width of 20 μm was formed by etching.

After stripping the resist, a resist is again formed by coating. At the time of exposure, first, the exposure is performed at 100 mj, then the mask for the colored pixel portion is moved by one pixel pitch, and the exposure is performed at 200 mj.
Furthermore, the mask for the colored pixel portion is moved by one pixel pitch,
It was exposed at 350 mj.

Next, the portion corresponding to the R pixel was developed under predetermined developing conditions, and then the R pixel was formed by electrodeposition.

Thereafter, G and B pixels were formed in the same manner to prepare a color filter.

The color filter thus obtained is
The optical density of the black matrix was 4.5 or more, the integrated sphere reflectance (400 to 700 nm) was 3.0% or less, and it was excellent with high contrast and high transmittance.

Example 3 An effluent obtained by subjecting 5.6% by weight of indium chloride, 90% by weight of 2-propanol, 2.9% by weight of ethyl acetoacetate and 1.5% by weight of acetic acid (stabilizer) to ion exchange treatment was obtained as in Example 1. The same treatment was carried out to obtain a transparent conductive ink.

A transparent conductive pattern is formed by printing a transparent conductive ink on a thin film forming apparatus (Angstromer (registered trademark) in-line type manufactured by Nissha Printing Co., Ltd.), and then fired to obtain a volume resistance of 0.9 × 10 ⁻⁴ Ω · cm. To obtain a substrate with a transparent conductive film.

Thereafter, a color filter was prepared in the same manner as in Example 1.

The color filter thus obtained was excellent in surface smoothness and had no light leakage.

[0081]

Since the present invention has the above-described structure, it has the following effects.

The color filter of the present invention has a structure in which a transparent conductive film is formed on a transparent substrate, and a black matrix made of a black inorganic oxide and a colored pixel portion are arranged on the transparent conductive film.

Therefore, the color filter of the present invention has a high contrast.

The method of manufacturing a color filter according to the present invention is characterized in that a transparent substrate on which a transparent conductive film is formed has the general formula M (OR ₁ ) _l (OR ₂ ) _m X _p Y _q (where M is magnesium). , At least one element selected from the group consisting of calcium, zirconium, titanium, hafnium, germanium, yttrium, indium, aluminum, gallium, tin and silicon, wherein R ₁ and R ₂ are a hydrogen atom, an alkyl group or an acyl group. X and Y each represent a hydrogen atom, a chlorine atom, or a hydroxyl group, l, m, p, and q are integers of 0 to 8 and l + m + p.
+ Q is equal to the valence of M. ) Is applied and baked to form a transparent active film layer, and the inside of the active film layer is blackened by a redox reaction of the metal, and the blackened active film of the portion other than the black matrix is formed. Remove the layers,
A colored pixel portion is formed on the exposed transparent conductive film by an electrodeposition method.

Therefore, in the method of manufacturing a color filter according to the present invention, the colored pixel portion is formed in the so-called frame of the black matrix formed in advance by the electrodeposition method, so that the boundary surface between the black matrix and the colored pixel portion is formed. There is no gap and no light leakage occurs.

Since the thickness of the black matrix can be adjusted according to the thickness of the colored pixel portion, the surface of the color filter can be made smooth.

Further, in order to obtain a color filter of RGB three colors, normally four complicated photo process steps are required, but in the present invention, the color filter can be obtained by two photoresist coating steps. The yield can be improved and the cost can be reduced.

──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location G02F 1/1343 G02F 1/1343

Claims (14)

[Claims] 1. A color filter characterized in that a transparent conductive film is formed on a transparent substrate, and a black matrix made of a black inorganic oxide and a colored pixel portion are arranged on the transparent conductive film. 2. The color filter according to claim 1, wherein the colored pixel portion is formed by an electrodeposition method. 3. A transparent conductive film, the general formula _{N (OH) r (R-} CO-CH 2 -CO-R ') s, n
The color filter according to claim 1, which is obtained by printing and baking a transparent conductive ink comprising an organic metal compound represented by the formula: = r + s, a solvent, and an additive. (However, N represents at least one element selected from the group consisting of indium, tin, antimony, boron, phosphorus, aluminum, bismuth, silicon, titanium, selenium, tellurium, hafnium, and zinc. R and R ′ are substituted. Represents an allyl group or a substituted alkyl group, n is the valence of N, and r,
s represents a natural number. ) 4. A transparent active film layer obtained by coating and baking an organometallic compound represented by the general formula: M (OR ₁ ) ₁ (OR ₂ ) _m X _p Y _q , wherein the black matrix is metal. The color filter according to any one of claims 1 to 3, which is blackened by the redox reaction of. (However, M is magnesium, calcium, zirconium, titanium, hafnium, germanium,
Yttrium, indium, aluminum, gallium,
At least one element selected from the group consisting of tin and silicon is shown. R ₁ and R _{2 each} represent a hydrogen atom, an alkyl group or an acyl group. X and Y each represent a hydrogen atom, a chlorine atom or a hydroxyl group. l, m, p and q are 0
Is an integer from ˜8 and l + m + p + q is equal to the valence of M. ) 5. The metal used in the redox reaction is tin,
The color filter according to claim 4, which is one of nickel, cobalt, copper, silver, and gold. 6. The color filter according to claim 1, wherein the black matrix and the colored pixel portion are arranged so as not to overlap with each other. 7. The black matrix has a volume resistance of 1
The color filter according to claim 1, which has a conductivity of × 10 ⁷ Ω · cm or more. 8. The light leakage does not occur from the boundary between the black matrix and the colored pixel portion, the total reflectance from the glass surface is 6.0% or less, and the optical density of the black matrix is 3.5 or more. Item 8. A color filter according to any one of items 1 to 7. 9. A transparent substrate on which a transparent conductive film is formed,
An organic metal compound represented by the general formula M (OR ₁ ) _l (OR ₂ ) _m X _p Y _q is applied and baked to form a transparent active film layer, and the inside of the active film layer is subjected to a redox reaction of metal. Blackening, the blackened active film layer other than the black matrix is removed, and a colored pixel portion is formed on the exposed transparent conductive film by an electrodeposition method. (However, M represents at least one element selected from the group consisting of magnesium, calcium, zirconium, titanium, hafnium, germanium, yttrium, indium, aluminum, gallium, tin, and silicon. R ₁ and R ₂ are hydrogen atoms. ,
Indicates either an alkyl group or an acyl group. X and Y
Represents one of a hydrogen atom, a chlorine atom and a hydroxyl group.
l, m, p, and q are integers of 0 to 8 and l + m + p + q
Is equal to the valence of M. ) 10. The method for producing a color filter according to claim 9, wherein the kind of metal of the black matrix formed by the redox reaction is any one of tin, nickel, cobalt, copper, silver and gold. 11. The electrodeposition method according to claim 9, wherein the photosensitive resist for electrodeposition is exposed three times at different exposure times each time the mask for colored pixel portion is moved by one pixel pitch.
0. The method for producing a color filter according to any one of 0. 12. The transparent conductive film general formula _{N (OH) r (R-} CO-CH 2 -CO-R ') s, n
The method for producing a color filter according to any one of claims 9 to 11, which is obtained by printing and firing a transparent conductive ink comprising an organic metal compound represented by = r + s, a solvent, and an additive. (However, N represents an element which is at least one selected from the group consisting of indium, tin, antimony, boron, phosphorus, aluminum, bismuth, silicon, titanium, selenium, tellurium, hafnium, and zinc. R and R'are substituted. Represents an allyl group or a substituted alkyl group, n is the valence of N, and r,
s represents a natural number. ) 13. The transparent conductive ink solvent has a boiling point of 40 to 14
5 to 60% by weight of at least one organic solvent among alcohols, ketones, esters and ethers at 0 ° C. and at least one of carbitols, glycols and cellosolves having a boiling point of 150 to 280 ° C. The method for producing a color filter according to any one of claims 9 to 12, which comprises a mixture with 40 to 95% by weight of an organic solvent. 14. The method for producing a color filter according to claim 9, wherein the conductivity of the black matrix is 1 × 10 ⁷ Ω · cm or more in terms of volume resistance.