JPH0442102A - Production of color filter - Google Patents

Abstract

PURPOSE:To prevent the generation of film peeling and cracking by forming dye images on a light transparent substrate provided with a gelatin binder, then hardening the films of color filter layers. CONSTITUTION:A coupler-in-developer type color developing method is advantageous for forming dye images by pattern exposing a photosensitive material coated with silver halide emulsions on the light transparent substrate. The development in the coupler-in-developer type color developing method is executed by using a developer contg. one or >=2 kinds of color developing couplers, by which the dyes are fixed or deposited into the emulsion layers. The film hardening of the color filters is then executed. Materials usually known as hardeners in photographic industry are usable for hardening the films of the color filter layers. For example, these materials include an aldehyde system, ethylene imine system, isooxazole system, epoxy system, vinyl sulfone system, acryloyl system, carbodiimide system, cyanuric chloride system, maleimide system, acetylene system, methasulfonate system, etc., which are used slone or in combination.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a color filter and a liquid crystal color display device, and more specifically to a so-called II! II. This invention relates to a liquid crystal color display device that is equipped with a color filter that prevents the occurrence of scratches and cracks, and a substrate with a color filter that has a transparent conductive film with low electrical resistance, and that can realize high-quality images.

[Prior art]

A color filter having a color filter layer on a light-transmitting substrate is, for example, one obtained by dyeing a polymeric material with a dye as described in Japanese Patent Publication No. 53-248, and Japanese Patent Application Laid-open No. 64-1989.
A method of manufacturing a color filter by external development using a silver salt photographic material as described in No. 79701 has been studied.

A dyeing color in which a dyed layer made of a natural polymer compound such as gelatin or gunny is provided on a substrate, and the dyed layer is patterned by exposure, processing, etc., and then the relief image is dyed with a dye to form a colored layer. Filter or known.

Also known is a silver halide photography color filter in which a gelatin layer of a silver halide binder is provided as a photosensitive layer on a substrate, and a color filter is formed by exposing and externally developing the gelatin layer.

The dura of these gelatin layers changes the permeability of the staining solution and affects the coupling speed in external development methods.

However, there has been a need for an appropriately hardened film that will not peel off during the treatment liquid immersion process.

However, when incorporating color filters into liquid crystal cells,
The transparent conductive film formed on the color filter is formed on the color filter due to the heat history of passing through the process of being rapidly cooled from a high temperature of 150°C or higher in the manufacturing process.
! Kura-tsuku was occurring.

In addition, even when a protective layer is provided on the color filter to prevent the permeation of water or gas and to improve the solvent resistance of the color filter, this thermal history can cause cracks in the transparent conductive film on the protective layer and the protective layer as well.・Tsuku was occurring.

[Purpose of the invention]

Therefore, an object of the present invention is to provide a method for manufacturing a color filter that prevents so-called film peeling and cracking caused by the formation of a transparent conductive film.

[Structure of the invention]

The above-mentioned object of the present invention is to produce a color filter in which a dye image is formed by pattern exposure on a light-transmissive substrate provided with a gelatin binder, in which a color filter layer is hardened after the dye image is formed. achieved by.

In the present invention, it is preferable to use a silver 7ide photosensitive material having an emulsion layer formed by coating a light-transmissive substrate with a silver 7ide emulsion.

Examples of the silver halide include silver chloride, silver iodide, silver bromide, silver chloroiodide, silver chlorobromide, and silver iodobromide. These may be used alone or in combination of two or more.

It is preferable to use a silver halide having a small average grain size, and it is particularly preferable to use a so-called Lippmann emulsion having an average grain size of 0.1 μm JJ or less. If the average grain size of silver halide is large, the image quality, especially the graininess, of the resulting color filter may be reduced.

The light transmitting substrate used may be transparent or semitransparent as long as it has light transmittance. Furthermore, since the color filter may be exposed to high temperatures during the vapor deposition process of the transparent electrode, it is preferable that the material for the light-transmitting substrate has good heat resistance.

Examples of materials that make up such a light-transmissive substrate include:
Examples include polymeric compounds such as polyethylene terephthalate, polybutylene terephthalate, polystyrene, polycarbonate, polyether sulfone, polyvinyl alcohol and cellulose acetate, glasses such as soda glass, borosilicate glass, and inorganic substances such as quartz and sapphire. I can do it.

The light-transmitting substrate can be used in the form of a plate, a notebook, a film, or the like using the above-mentioned materials.

The thickness of the light-transmitting substrate can be set appropriately depending on the purpose and material, and is usually 0.5 μm to 10 mm.
is within the range of In particular, when glass is used as a light-transmissive substrate for a liquid crystal color display, for example, the thickness is preferably within the range of 03 to 2IIIa.

In addition, there are no particular restrictions on the surface of the light-transmitting substrate forming the emulsion layer as long as it has the same surface precision as the light-transmitting substrate conventionally used for color filters. In order to achieve high image quality, it is desirable that the surface precision of the light-transmitting substrate be ±01 μm.

External color development is advantageous in forming a dye image by exposing a light-sensitive material coated with a silver halide emulsion onto a light-transmitting substrate in a pattern as described above.

In the external color development method, development is performed using a developer containing one or more color couplers.
This is a method of dyeing or precipitating a dye into an emulsion layer.

The developer used contains at least a color forming coupler and a developing agent.

As developing agents, N.E.K. Mees, T.H. Noemes (C, E, Ni, Mees and
TH, 4atses) [The Theory]
) Otographic Process 3rd Edition (The The
ory of thePhotographic Pr
3rd Edition)”, 293-2
The compounds described on page 98 can be mentioned, and specific examples include (1) 4-amino-3-methyl-N-(2-hydroquinethyl)aniline sulfate (2) N-ethyl- N-methoxyethyl-3-methyl-
p-phenylenediamine p-)luenesulfonate (3
) 4-Amino-3-methyl-N-ethyl-N-(2-methylsulfonamidoethyl)aniline sulfate hydrate (4) N,N-diethyl-p-phenylenediamine sulfate (5) N , N-diethyl-3-methyl-p-phenylenediamine sulfate, and the like.

In the developer, it is preferable to select and use one type of developing agent from among the developing agents listed above. The selection of the developing agent is usually made in consideration of the type and combination of color forming couplers.

Unlike the internal coupler (ballast type coupler) used in ordinary color photography, the color-forming coupler is added to the developer to form a small amount (partially dissolved in the developer). The external coupler used is a known external coupler.

Yellow couplers include anruacetanilide,
In particular, pivaloylacetanilide couplers, 5-pyrazolone and pyrazoloazole couplers are preferably used as magenta couplers, and phenol and naphthol couplers are preferably used as cyan couplers.

To harden the color filter layer, those commonly known as hardeners in the photographic industry can be used. Examples include aldehyde-based, ethyleneimine-based, isoxazole-based, epoxy-based, vinylsulfone-based, acryloyl-based, carbodiimide-based, cyanuric chloride-based, maleimide-based, acetylene-based, methanesulfonic acid ester, etc., and these may be used alone or in combination. use.

The amount of hardening agent used varies depending on the type of hardening agent, the amount of gelatin, etc., but generally the degree of swelling measured by the following method is 20.
It may be determined to be 0% or less, preferably 150% or less.

Measurement of swelling degree> After leaving the filter sample at 23° C. and 55% RH for 12 hours, the weight A is measured, and then immersed in a color developer (any color) at 25° C. for 6 minutes. Immediately after this, after quickly measuring the weight B, the paint film was washed away with bleach, etc. After drying, the sample was left at 23°C and 55% RH for more than 12 hours.
Measure weight C. The degree of swelling is calculated using the following formula.

〔Effect of the invention〕

According to the present invention, a color filter can be obtained in which no cracks occur during the manufacturing process of a transparent conductive film formed on the color filter.

〔Example〕

Next, examples of the present invention will be shown and the present invention will be explained in more detail.

(Example 1) ■ Formation of color filter layer By simultaneously adding a silver nitrate solution and a solution containing potassium bromide and potassium iodide to a 10% by weight gelatin aqueous solution, an iodine solution containing 3 mol% silver iodide was formed. 9% by weight) is the so-called photosensitizer! I did 2. The precipitation conditions during this preparation were 0.
．． It was regulated to obtain a lip-mano emulsion having an average particle size of 0.05 μm.

Next, the thickness is 1. Iwm borosilicate glass substrate (80i ×
90 mm) to form a photosensitive agent layer by applying the above photosensitive agent to a dry thickness of 3 μm.

Next, on this silver halide photosensitive material, a side of 150
A chromium mask for a color filter having a square opening of t1 m was loaded, and a first exposure was performed using a light/Gesten wrap.

The silver halide photosensitive material subjected to this first exposure is
1Iff for 3 minutes in a blue color developing solution adjusted to a solution temperature of 25°C.
Soaked.

A blue color developing solution was obtained by dissolving the composition described below in 800 ml of water, and then adding water to make the total amount 11.

Blue color developer composition Cyan coupler......121gN-(2
-acetamidophenethyl)-1-hydroquino-2-naphthoamidide silver emulsion (average particle size 0.05μ■, gelatin-concentrated magenta coupler...054g6-[-butyl-7-chloro-3-( 3-Methylbutyl)IH-pyrazolo[3,2-C]-1,2,4-triazole developing agent 2.0g 4-amino-
3-Methyl-N-ethyl-N-β methanesulfonamide ethylaniline 11/2 sulfate monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3. OOd Anhydrous sodium sulfate...20.0 g Sodium bromide...1.0 g Sodium sulfite...
・・・・・・ 10.00g ethylene glycol・・・・
... 10.0m/polyethylene glycol...
・ Add 20g water 11
Incidentally, sodium hydroxide was added to the above blue color developer to adjust the pH value to 120 at 25°C.

Next, the substrate coated with the silver halide photosensitive material was immersed for 30 seconds in a stop solution containing 28% acetic acid (32%) and sodium sulfate (45 g), and then washed with water for 5 minutes and dried. The blue part was formed.

Next, another chrome mask for a color filter was placed immediately adjacent to the blue area, and a second exposure was performed in the same manner as above.

The silver halide photosensitive material subjected to this second exposure was
A green portion was formed on the substrate by immersing it in a green color developing solution adjusted to a liquid temperature of 25° C. for 3 minutes, further immersing it in a stop solution for 30 seconds, washing with water for 5 minutes, and drying.

A green color developing solution was obtained by dissolving the composition described below in 800 ml of water, and then adding water to make the total amount 11.

Green color developer composition Noan coupler...1.26 gN
-(2-acetamidophenethyl)-1hydroxy-2
−Naphthamide yellow coupler・・・・・・・・157g α−(
4-Carnaquinophenoquino)-α-pivaloyl-24-
Dichloroacetanilide developing agent・・・・・・・・・
...2.0g4-amino-3-methyl-N-ethyl-N-β methanesulfonamidoethylaniline・11/
Disulfate monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 300 - Anhydrous sodium sulfate 200g Sodium bromide...
・・・・・・・・・30g Sodium sulfite・・・・・・
... 10.00 g ethylene glycol...
... 100-Polyethylene glycol...
・Add 20g water II"
Incidentally, sodium hydroxide was added to the above green color developer to adjust the pH value at 25°C to 12.0.

Next, the right neighbor of the front 2 green part (i.e. the left neighbor of the blue part)
Place the third color filter chrome mask on
A third exposure was performed in the same manner as above.

The silver halide photosensitive material subjected to this third exposure was
A red color was formed on the substrate by immersing it in a red color developing solution adjusted to a solution temperature of 25°C for 3 minutes, further immersing it in a stop solution for 30 seconds, washing with water for 5 minutes, and drying it.

A red color developing solution was prepared by dissolving the composition described below in 8001 water, and then adding water to make the total amount 11.

Red color developer composition Magenta coupler...028g6-t
-butyl-7-chloro-3-(3-methylbutyl)-1
H pyrazolo[3,2-c]-1,2,4-triazole yellow coupler 15gα-(4
-Carnakinophenoki/)-α-pivaloyl-2,4-
Dichloroacetanilide developing agent・・・・・・・・・
...2.0g 4-amino-3-methyl-N-ethyl-N-β methanesulfonamide ethylaniline 11
/2 sulfate monohydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3. OOJ anhydrous sodium sulfate... 20.0g sodium bromide.
・・・・・・・・・ 3.0g sodium sulfite...
・・・・・・ 10.00g ethylene glycol...
... 10, OOJ polyethylene glycol...
・・・ Add 2.0g water
11 Note that sodium hydroxide was added to the above red color developing solution to adjust the pH value at 25°C to 12.0.

Next, it was immersed in a fixing solution whose temperature was adjusted to 30° C. for 1 minute, and then washed with water for 5 minutes.

Fixer composition Ammonium thiosulfate...175.0g Sodium sulfite...8.5g Sodium metasulfite...23g Add water...
・・・・・・・・・ 11 (pH=6. using acetic acid)
o+: m adjustment. ) The thus obtained color filter layer has a square blue part, green part and red part each side of which is 150μ square, which are uniformly formed over the entire borosilicate glass substrate. No color turbidity was observed in the red part.

(2) Hardening of the color filter layer The color filter layer formed in step (2) above was immersed for 3 minutes in a hardening bath whose temperature was adjusted to 30°C.

For the hardening bath, the composition described below was dissolved in 8,001 liters of water, and then water was added to make the total amount 11.

Hardening fluid composition Sodium p-toluenesulfonate 1g sulfur # (18N) 5.4
111 Succinaldehyde sodium bisulfite 8.5g
Sodium sulfate 147g Sodium bromide (anhydrous) 2g Sodium acetate (anhydrous) 20g
Formalin (37%) 27m 27℃ pH 4.8+0.1 27℃ Specific gravity 1.136+0
．． 003 Next, the color filter layer on the substrate was hardened by immersing it in the neutralization bath described below for 30 seconds, washing with water for 5 minutes, and drying.

Neutralization bath Hydroxylamine sulfate 18 g Sodium bromide 17 g Glacial acetic acid 10 g Sodium hydroxide 6.8 g Sodium sulfate 50 g After dissolving in 8,001 g of water, add more water to bring the total volume to 1! And so.

pH27℃ 5
When the degree of hardness of the gelatin layer was determined for the color filters formed as in Example 1 or above, the degree of swelling was 150%.

■ Formation of a protective layer A coating solution consisting of a heat-resistant silicone modified resin (product name: JHR-3000, manufactured by Japan Synthetic Rubber ■) was dropped onto the color filter layer formed in step (1) above, and coated at 3000 rpm using a spin coater. / After applying in 30 seconds,
Baked for 60 minutes at 150″C to obtain a film thickness of 1.0μ■
A protective layer was provided.

■Formation of transparent conductive tIM When a transparent conductive film was formed on the color filter formed in the above step (■) by a reactive vapor deposition method using a high frequency discharge device (manufactured by ANELVA ■), the transparent conductive film on the color filter cracked. (A good film was obtained.)

Claims (1)

[Claims] A method for producing a color filter, which comprises forming a dye image by pattern exposure on a light-transmitting substrate provided with a gelatin binder, which comprises hardening the color filter layer after forming the dye image.