JPH0432802A - Production of color filter - Google Patents

Abstract

PURPOSE:To improve color characteristics and to reduce the cost of production by applying a positive type resist on a substrate constituted by providing a light shielding layer and a layer to be dyed on a light transparent substrate and subjected the resist to imagewise exposing, then developing the resist to remove the exposed parts, forming 1st color picture elements by dyeing and forming 2nd color picture elements similarly at different points. CONSTITUTION:The positive type resist is applied on the substrate 11 constituted by providing the light shielding frame 13 by a photolithographic method or vapor deposition or reduction of a silver salt on the light transparent substrate 11 and further providing the layer to be dyed thereon. After this substrate 11 is subjected to the imagewise exposing, the resist is developed to remove the exposed parts of the resist; thereafter, the 1st color picture elements are formed by dyeing and are subjected to a fixing treatment. The 2nd picture elements are formed by dyeing after the imagewise exposing and the similar developing at the points different from the 1st picture elements and if necessary, the picture elements having the spectral characteristics different from the spectral characteristics of the picture elements of the two colors are similarly formed by as much as the required number of colors. The color filter with which the production process is easy and which is free from the color clouding among the different picture elements and affords good color reproducibility is obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method of manufacturing a color filter, and more particularly to a method of manufacturing a color filter suitable for use in a color liquid crystal display.

[Background of the invention]

As a method for manufacturing color filters,
As described in No. 286, etc., a mordant layer consisting of a natural polymer compound such as gelatin, gryu, or a synthetic polymer compound such as polyvinyl alcohol is provided on a substrate, and after patterning the mordant layer by exposure, treatment, etc. A dyed filter manufacturing method is known in which the relief image is dyed with a dye to form a colored layer.

With this method, there are many dyes that can be used, and it is relatively easy to meet the color characteristics required for filters, but it requires exposure and processing each time the relief of the mordant layer is formed for each color, and in some cases In some cases, a complicated process such as providing an intermediate layer for resist dyeing is required, which causes problems in yield and smoothness and increases costs.

Also, with the same dyed color filter,
As described in No. 76, there is also a method of creating a color filter by dyeing using a patterned resist each time a pixel of each color is formed on the mordant layer without forming a relief of the mordant layer. However, even with this method, there are resist coating, exposure, processing, and peeling steps for each color.
It's hard to say it's an easy method.

[Purpose of the invention]

An object of the present invention is to provide a method for manufacturing a color filter that is easy to manufacture and provides good color reproducibility without color turbidity between different pixels.

[Structure of the Invention] The above-mentioned object of the present invention is to provide a method for manufacturing a color filter having a light-shielding frame and pixels of at least two colors having different spectral characteristics on a light-transmitting substrate. Step of providing a light shielding frame by vapor deposition or reduction of silver salt b) Step of providing a layer to be dyed on the substrate provided with the light shielding frame C) Step of applying a positive resist to the substrate provided with the layer to be dyed d) Step of applying a positive resist to the substrate provided with the layer to be dyed After imagewise exposure of the substrate provided with the mold resist, the exposed part of the resist is removed by development, and then the first resist is dyed.
e) Step of creating a second color pixel by dyeing and fixing it; e) After imagewise exposure to a location different from the pixel, developing in the same manner as above, creating a second color pixel by dyeing, and fixing it; f) This is achieved by a method for manufacturing a color filter, which includes the step of creating, as necessary, pixels having spectral characteristics different from those of the two colors in the same manner as described above for the required number of colors.

The present invention will be explained in more detail below.

In the present invention, the light shielding frame (abbreviated as BM) is created by photolithography, vapor deposition, or reduction of silver salt.

For example, a resist in which a black pigment is dispersed or a resist containing a black dye is applied to a light-transmitting substrate, and then exposed and developed using a mask or the like to create a BM.

Further, after applying the photosensitive layer to be dyed on a light-transmitting substrate, the layer to be dyed is patterned by exposure and development in the same manner. Thereafter, the layer to be dyed is dyed with a black dye to form a BM.

In addition, metals selected from nickel, aluminum, chromium, titanium, copper, iron, silver, gold, etc., or their nitrides, oxides, carbides, etc., are deposited in BM by a vacuum evaporation method, a shuttering method, or an ion blating method. can also be formed.

As a method for forming BM by reduction of silver salt, for example, a silver halide emulsion (for example, a silver bromide emulsion) is deposited on a light-transmitting substrate.
After coating, the portion that will later become BM is exposed using a mask or the like. Then, by developing and fixing, BM
There is a way to leave reduced silver in the area. There is also a method using a silver complex diffusion transfer method.

The dyeable polymer compound that can be used as the mordant layer used in the present invention is usually used in the dyeing process with water or a hydrophilic solvent (e.g. alcohol such as methanol or ethanol, cellosolub such as methyl cellosolve or ethyl cellosolve). In consideration of the fact that glycols such as ethylene glycol, propylene glycol, etc. (hereinafter the same) are used, resins having swelling properties are preferred.

Among such dyeable polymer compounds, examples of natural polymer compounds include natural polymer proteins such as gelatin, casein, and gris. Also, polyvinyl alcohol,
Synthetic polymer compounds such as acrylic synthetic resins and water-soluble nylon/poval/stilbazole resins containing dyeable functional groups are also preferably used.

In the present invention, it is preferable that the layer to be dyed contains a mordant, and it is more preferable that the mordant contains a weight ratio of 1/10 to 10 to the dyeable polymer compound.

Preferred types of mordants include the following general formulas (I) to (
Examples include, but are not limited to, those shown in m.

General formula (1) In the formula, A is a monomer unit containing at least two ethylenically unsaturated groups, B is an α,β-ethylenically unsaturated monomer unit, and R is a hydrogen atom, a methyl group or an ethyl group. represent. x, y, z indicate molar ratio, X is 0 to 5 mol%
, y is 0 to 90 mol%, and 2 is 10 to 100 mol%.

General formula (II) In the formula, A and B have the same meanings as A and B in general formula (1), R1 is a hydrogen atom or a methyl group, R1 and R3 are each a lower alkyl group, R1 is an alkyl group, Aralkyl group, cycloalkyl group or cycloalkylalkyl group, xe represents an anion, X is 0.5-B, 0,
y is O~79.5.2 is 20~99.5.

General formula (I [I) ÷ A + RI,
R! and R1 each represent a group selected from the group consisting of a carbocyclic group and an alkyl group.

Mo represents an anion, X is about 0.25 to about 5 mol%,
y is about 0 to about 90 mol%, 2 is about 0 to about 99 mol%, and is represented by the general formula (IV)! where the unit A is derived from one or more α,β-ethylenically unsaturated monomers, and R is a hydrogen atom or a carbon atom
6, a substituted or unsubstituted alkyl group, Q is a substituted or unsubstituted alkylene group, an arylene group, an arylene alkylene group, or a -〇〇R''- or -CONHR''- group (wherein R1 is a substituted or unsubstituted alkylene group) , arylene group or arylene alkylene group). R1 is a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, or together with Q, each X is a leaving group capable of being removed by a nucleophile, each Y
is a hydrogen atom, an inert (non-leaving) group or -(NH) p-
The bonds bonded to Q-, E and F, each represent a single bond or an atomic group necessary to combine to complete a 5- to 7-membered heterocycle, n is 0.1 or 2, m is 1.2 or 3, n
The sum of +m is 3 or less, and p is O or 1. X is 0 to 90% by weight of the polymer, and y is 10 to 100% by weight of the polymer.

General Formula (V) ■X R' In the formula, Q represents a nitrogen or phosphorus atom, R1, R2 and Rs each represent a carbocyclic group or an alkyl group, and R' represents hydrogen or an alkyl group. X@ represents an anion; ■ represents a residue of a monomer containing at least two polymerizable ethylenically unsaturated residues; M represents a residue of a monomer containing a polymerizable ethylenically unsaturated residue;

y and 2 are numbers characterizing the respective proportions of individual fumonomers in the polymer; X represents 10-99 mol%, y 0-90 mol%, 2 0-5 mol%.

In addition, the water-soluble dyes used in the present invention include acid dyes, direct dyes, reactive dyes, and cationic dyes that are soluble in water, hydrophilic solvents, or a mixture of both. Alternatively, it is preferably used after being purified. Among these, acid dyes are particularly preferred.

Specifically, Suminol Fast Red G (C, 1, Ac1d Redl18, manufactured by Sumitomo Chemical Co., Ltd.) and Kayanol Milling Red R3 (CI
, 80id Redl14, manufactured by Nippon Daiyosha), Diazid Fast Red 3BL (C, 1, Ac1d
Red15B, manufactured by Mitsubishi Chemical Industries, Ltd.), Kayanol Yellow NGS (C.

1, Ac1d YellowllO1 manufactured by Nippon Kayaku Co., Ltd.)
, Nippon Kayo Co., Ltd.'s First Eye o-G (C, 1, Ac
1d Yellow61, manufactured by Sumitomo Chemical Co., Ltd.), Alzarine Green (C,1, Ac 1dGreen9, manufactured by Tokyo Chemical Industry Co., Ltd.), Brilliant India Blue 5C (
C, 1, Ac1d Blue103, manufactured by Hetost),
Kayanor Cyanine 6B (CAcid BIue8
3. Made by Nippon Daiyosha), Ant Noah = 77BFH (
C, i, Ac1d BlueOO1 manufactured by Hodogaya Chemical Industry Co., Ltd.), Red 136P, Red 137P, Blue 5P
, Blue 43P1, Green CFG-111, PC Cyan 2, PSPC N'an 16 (all manufactured by Nippon Daiyo Co., Ltd.), Black 008P, Black 1BIP, etc. Also, as reactive dyes, Prosyn Brilliant Yellow-H -5G(
C, 1, Reactive Yellow 2, manufactured by Nippon Daiyosha), Dia Mira Bu
Reliant
GD (C, 1, Reac mouth ve
Red63, manufactured by Mitsubishi Chemical Industries, Ltd.), Mikasion Green 2BS (Jin 1.Reactive Green7, manufactured by Nippon Daiyo Co., Ltd.), Sumifix Navy Blue R (C,
1, ReacLive Blue20, produced by Sumitomo Chemical Co., Ltd.);
Yellow GN (C, 1, Direct Yellow
w85, manufactured by Nippon Daiyosha), Sumilight Red 4B (
C,1,Direct Red81, manufactured by Sumitomo Chemical Co., Ltd.), Kayaras Supra Blue BWL (C,1,Dir
ectBlue237, made by Nippon Daiyosha), crampons
Green GX (C, 1, DirecL Green8
, manufactured by Sumitomo Chemical Industries, Ltd.) or two or more thereof can be applied.

As a dyeing method, the above-mentioned dye is mixed with water in a ratio of 001 to 5.
%, preferably 0.05 to 2%, the substrate on which the layer to be dyed and the resist pattern are provided may be immersed for 1 to 30 minutes at 40 to 90°C.

As a positive resist according to the present invention, FBM120
FBM-110, FPM (all manufactured by Daikin), 0
EBR-1013, CF2 (Tokyo Ohka Gen), E
BR-1, EBR-9 (all manufactured by Toshi), FMRE10
2C Fuji Pharmaceutical), MCP-1400, ll5-1
9 (hereinafter referred to as Nopley far yeast), etc.

The light-transmitting substrate used in the present invention may be transparent or semi-transparent as long as it has light-transmitting properties. Furthermore, since the color filter may be exposed to high temperatures during the vapor deposition process of the transparent electrode, it is preferable to use a material with good viscosity resistance as the material for the substrate.

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

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

The thickness of the light-transmitting substrate can be set appropriately depending on the purpose and material, but it is usually 0.5 μm to 1.5 μm. O
It is within the range of mm. In particular, when glass is used as a light-transmissive substrate for a liquid crystal color display,
It is preferable that the thickness is within the range of 0.3 to 2 mm.

(Example) Next, an example will be shown to further specifically explain the present invention. Note that % in the examples represents weight % unless otherwise specified.

Example 1 A transparent borosilicate glass substrate (I Oc m
A resist material containing black pigment (hereinafter abbreviated as black resist, Color Mosaic K manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was applied to a resist material (hereinafter referred to as "black resist", Color Mosaic K, manufactured by Fuji Hunt Electronics Technology Co., Ltd.) to a thickness of approximately 1 μm on a 10 cm x 10 cm film, and dried on a hot plate. . Thereafter, a chromium mask for a color filter was placed so that the exposed area was the BM area shown in FIG. 1, and exposure was performed using a mercury lamp. Next, the film was developed with a 1% aqueous sodium carbonate solution, washed with pure water, and then heated and cured in an oven to obtain a BM portion on the substrate.

Add 1 portion of ammonium dichromate to the sample on which the BM part has been formed.
% gelatin aqueous solution (contains 7% low molecular weight gelatin)
was applied so that the dry film thickness was approximately 1 μm. 60℃,
After baking for 1 hour, the glass substrate was exposed to light from the back side using a mercury lamp and developed to provide a layer to be dyed in the gaps between the BMs.

After forming the layer to be dyed, apply a positive resist MCP- to the entire surface of the sample.
1400 (manufactured by Shipley Far East) using a spinner to a thickness of approximately 1.5 μm to form a positive resist layer. Then, in Figure 1,
A chrome mask for a color filter was arranged so that the exposed area was part B, and exposure was performed using a mercury lamp.

After resist development and patterning of the exposed substrate (referred to as A), 0.25% blue dye Blu
e 5P (manufactured by Nippon Daiyo Co., Ltd.), and was immersed for 8 minutes in a blue dye aqueous solution at 40°C whose pH was adjusted to 5 with a 56% acetic acid aqueous solution, and then immersed in a 1% aqueous solution each of tannic acid and tartarite for 5 minutes.
A fixation process was performed by dipping at 0° C. for 1 minute to create a blue light transmitting pixel.

Next, another chromium mask for color filter is placed on the substrate A after the above processing so that the exposed part becomes part G in FIG.
After 4 minutes of immersion in a 40°C green dye aqueous solution containing 0.5% green dye CFG-111 (manufactured by Nippon Daiyo Co., Ltd.) and adjusted to pH 5 with a 56% acetic acid aqueous solution, fixation treatment was performed in the same manner. A green light transmitting pixel was created.

Next, the entire surface of the substrate A after the above treatment was exposed to light 7, and after a resist phenomenon, a 56% acetic acid aqueous solution containing 0.3% red dye Red137P (manufactured by Nippon Daiyo Co., Ltd.) was added to +1)1.
Figure 1 Procedural amendment (method) 1. Indication of the case 1990 Patent Application No. 139141 2 Name of the invention Method for manufacturing color filters 3 Person making the amendment Relationship to the case Patent applicant address Nishi-Shinjuku, Shinjuku-ku, Tokyo 1-26-2 Contact information 1-1 Sakura-cho, Hino-shi, Tokyo 191 Konica Co., Ltd. (Telephone: 0425-83-1521) Patent
Part 4: Date of the amendment order 5, the "Detailed Description of the Invention" column and the "Brief Description of Drawings" column of the specification to be amended.

Contents of correction The amendment is made by adding pages 17 and 18 of the specification.

A red light transmitting pixel was created by immersing it in a 60° C. red dye aqueous solution with a temperature of 5 for 20 minutes. The color filter thus produced was designated as sample CF-1.

Comparative Example 1 Referring to the example of Japanese Patent Publication No. 52-17376, first, a BM is formed by dyeing using a method of patterning the resist, and then the resist is patterned in the same way for each color pixel each time it is dyed. A color filter was prepared using the method and designated as sample CF-2.

Color filter sample CF-1 thus obtained
For each color pixel of 2 and 2, SR-
When the spectral transmittance was measured using CF-1 and the maximum transmittance was determined for each, the maximum transmittance value of CF-1 was 3 to 8% higher for each color pixel than CF-2, indicating good spectral characteristics. showed that.

〔Effect of the invention〕

The color filter based on the manufacturing method of the present invention has good color properties. In addition, compared to the manufacturing method of the CF-2 color filter, there are fewer steps of resist coating and patterning, and compared to the dyeing method in which patterning of the layer to be dyed is performed for each color pixel disclosed in Japanese Patent Publication No. 61-51286. ,
Since there are fewer steps for coating and patterning the layer to be dyed, manufacturing costs are also reduced.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing an example of a color filter obtained by the manufacturing method of the present invention, and FIG. 2 is a cross-sectional view showing an example of a liquid crystal color display using the color filter obtained by the manufacturing method of the present invention. It is a diagram. 11...Light-transparent substrate 12...Colored part 13...
Light-shielding frame 24, color filters 25a, 25b, polarizing plate 26, liquid crystal 27a,
27b・ Electrode

Claims (1)

[Scope of Claims] A method for manufacturing a color filter having a light-transmitting substrate and a light-shielding frame and at least two color pixels having different spectral characteristics, comprising: a) photolithography, vapor deposition, or silver salt reduction on the light-transmitting substrate; b) providing a layer to be dyed on the substrate provided with the light blocking frame; c) applying a positive resist to the substrate provided with the layer to be dyed; d) substrate provided with the positive resist. After imagewise exposure, development and removal of the exposed area of the resist, the first
e) Step of creating a second color pixel by dyeing and fixing it; e) After imagewise exposure to a location different from the pixel, developing in the same manner as above, creating a second color pixel by dyeing, and fixing it; f) A method for manufacturing a color filter, comprising the step of creating pixels having spectral characteristics different from the pixels of the two colors as many as necessary in the same manner as described above, if necessary.