JPH0194301A - Color mosaic filter - Google Patents

Abstract

PURPOSE:To improve spectral characteristics by incorporating at least one of specific cyan couplers into a color developing soln. CONSTITUTION:This color filter is obtd. by exposing light patterns to the emulsion layer of a photosensitive material, which is provided with at least one layer of the silver halide emulsion layers on a light transmittable base, then forming the dye image corresponding to the patterns by external type color development, thereafter repeating the similar stages to form at least two colors of the patterns and subjecting the emulsion layers to a desilvering processing after the final color development. At least one of the cyan couplers expressed by the formulas I and II are incorporated into the color developing soln. In the formulas I, II, R1 and R2 respectively denote the groups which can be substd. to a benzene ring; m and n respectively denote 0-5 integer; there is no case in which m and n are simultaneously 0; R1 may be respectively the same or different from each other when m is >=2; R2 may be respectively the same or different from each other when n is >=2. The respective groups expressed by R1, R2 include the groups having substituents as well. The performance as the green filter and blue filter is thereby improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color filter, and particularly to a color mosaic filter suitable for use in color displays and image pickup tubes.

[Background of the invention]

Conventionally known color filters include those described in Japanese Patent Publication No. 53-248, in which polymeric materials are dyed with dyes. There are complicated manufacturing steps such as resist coating, image exposure, development, coloring, and resist removal, and the resulting color filters are extremely expensive.

In order to eliminate these drawbacks, methods for manufacturing color filters using color silver salt photographic materials using internal development methods and external development methods have been investigated.

For example, the applicant has studied a method for producing a color filter using an internal development method, and as a result, the applicant has found that, in general, a three-layer silver halide film having two different couplers among a yellow coupler, a magenta coupler, and a cyan coupler is used. He proposed a material for color filters having layers and an invention for color filters (Japanese Unexamined Patent Publication No. 1986-14).
No. 8952). This color filter was manufactured by an internal development method and had very good spectral characteristics.

However, although the color filter itself according to the above proposal has good characteristics, the manufacturing method of color filters using this internal development method, including the color filter according to the above proposal, is generally not suitable for color filters. Preparation of photosensitive materials is very complicated.

On the other hand, a method for manufacturing a color filter using an external development method is described in JP-A-55-6342.

In this manufacturing method, pattern exposure is performed on the emulsion layer of a photographic material having a black and white silver halide emulsion layer provided on a support,
This is a method in which patterns of two or more colors are formed on a support by repeating development operations using an external color development method. The external developer used in this method contains any one of a magenta coupler, a yellow coupler, and a cyan coupler. A pattern consisting of magenta, yellow, and cyan is formed on a color filter obtained by sequentially developing using such an external developer.

Furthermore, this patent states that an external developer containing a magenta coupler and an external developer containing a yellow coupler are mixed at a ratio of 3:1.
Mix the external mixed developer, the external developer containing the cyan coupler, and the external developer containing the yellow coupler.
: Exposure and development using an external mixed developer mixed in 1:2 and an external mixed developer in which a cyan coupler-containing external developer and a magenta coupler-containing external developer were mixed in a ratio of 1:2. A specific example of manufacturing red, green, and yellow striped filters by repeating the above steps is also shown.

However, although a color filter having a pattern of magenta, yellow, and cyan colors is suitable for an image pickup tube or a solid-state image sensor, it cannot be used as a color filter for a color display.

Furthermore, due to subtle changes in the conditions during the production of color filters, the spectral properties of the resulting color filters change significantly, making it extremely difficult to produce color filters with the same spectral properties. .

In general, color filters for color displays are
It is required to have excellent color reproducibility so that the difference between the reproduced color and the actual color is reduced, and it is also required to have excellent spectral characteristics.

[Purpose of the invention]

The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a color filter with good spectral characteristics using external color development in photographic technology. A second object of the present invention is to provide a color filter with excellent color reproducibility and stable quality.

[Structure of the invention]

The above object of the present invention is to provide at least one
After exposing a light pattern to the emulsion layer of the light-sensitive material provided with the silver halide emulsion layer of the layer, a dye image corresponding to the pattern is formed by external color development, and the same process is repeated to form at least two In a color mosaic filter obtained by forming a color pattern and performing desilvering treatment after final color development, the following general formula [I
] and CI+).

General formula [I] General formula [■] In the formula, RI and R2 each represent a group that can be substituted on the benzene ring. m and n each represent an integer from 0 to 5,
m and n cannot be O at the same time, and when m is 2 or more, R1 may be the same or different, and when n is 2 or more, R2 may be the same or different. You can leave it there.

The polygroups represented by RI and Rz include those having substituents.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent.

The present invention will be explained in more detail below.

The present inventor investigated the above-mentioned problems of color filters obtained by a development method using an external mixed developer obtained by mixing known external developers, and found that these problems were found. It has been found that the above problem occurs because the external mixed developer contains two types of developing agents. That is,
In the external development method, exposed silver halide converts a color developing agent (hereinafter referred to as developing agent) in a developing solution into an oxidized form, and this oxidized developing agent reacts with a coupler in the developing solution. Since this is a developing method that utilizes a mechanism that generates a dye, the developing agent is generally used in accordance with the type of coupler, reactivity, etc. Therefore, when using two types of couplers, it is recommended to mix a external type developer containing the optimal developing agent for the coupler, or use a external type developer containing two types of developing agent to correspond to the two types of couplers. A developer is used.

However, developing agents do not selectively react only with specific couplers, and furthermore, the reaction rate differs depending on the type of developing agent.

Such differences in reaction conditions such as selectivity of developing agents or reaction rates are very noticeable as spectral characteristics in color filters such as liquid crystal displays that visually sense images based on transmitted light.

Furthermore, in external mixed developers, there are a wide variety of variable factors in the condition settings, such as coupler combinations, developing agent combinations, and coupler and developing agent combinations, so slight differences in each variable factor may occur. has a very large effect on the characteristics of color filters, making it extremely difficult to manufacture color filters with stable characteristics.

The color filter developer of the present invention is different from the conventional external developer containing two types of developing agents, and contains one type of developing agent and two or more types of couplers having different hues.

The developing agent used in the present invention is not particularly limited as long as it can be dispersed or dissolved in the developer.

As the developing agent that can be used in the present invention, C.
E.K. Meese, J.T. James (C
, E., Mees and J., T., James)
Author: The Theory of the Photographic Process, 3rd Edition
PhotographicProcess 3rd,
Edition) J, pages 293 to 298, and specific examples include (1) 4-amino-3-methyl-N-ethyl-N-(2
-hydroxyethyl)aniline sulfate (2) 4-amino-3-methyl-N=ethyl-N-(2
-methoxyethyl)aniline p-toluenesulfonate (3) 4-amino-3-methyl-N-ethyl-N-(2
-methanesulfonamidoethyl) aniline sulfate hydrate (4) 4-amino-N,N-diethylaniline sulfate (5) 4-amino-3-methyl-N,N-diethylaniline sulfate etc. can be mentioned.

In the color filter developer used in the present invention, one type of developing agent is selected and used from among the developing agents listed above.

The selection of a developing agent is usually made in consideration of the type and combination of couplers, etc.

The developing agent in the developer is usually 0% in the developer.
．． It is contained in the range of 1-10g. If the content is less than 0.1g, effective development may not be possible, and even if more than 10g is used, not only will there be no significant improvement in developability, but depending on the type of developing agent, it may not be sufficient. may not dissolve.

It is preferable to use 0.5 to 7 g of developing agent per 1Q of developer solution, and particularly preferably 1 to 5 g of developing agent.

By setting the amount of the developing agent within this range, the development time at normal temperatures can be kept within an appropriate range (for example, within the range of 1 to 10 minutes), regardless of the type of coupler used. This results in very good workability. Furthermore, by keeping it within this range, coloring properties tend to be particularly good.

The developer contains two or more couplers that provide different hues. That is, couplers can be classified into magenta couplers, cyan couplers, and yellow couplers, depending on the wavelength at which they develop color. In the present invention, two or three of these couplers having different hues are used in combination.

With the combination of these couplers, the color that appears in the colored part of the color filter is developed through subtractive color mixing, so the combination of magenta coupler and cyan coupler produces a blue color developer, and the combination of yellow coupler and cyan coupler produces a green color developer. The magenta coupler and yellow coupler are combined to form a red color developer. Then, a black color developing solution is obtained by combining three types of couplers having different hues: a magenta coupler, a cyan coupler, and a yellow coupler.

The coupler used in the present invention is different from the internal coupler (ballast type coupler) used in ordinary color photography, and is used in a state where it is added to the developer and is at least partially dissolved in the developer. In the present invention, a known external coupler can be used.

Next, the cyan couplers represented by the general formulas (1) and [II] used in the present invention will be explained.

General formula (I) Below is a blank space General formula (n) In the formula, R1 and R2 each represent a group that can be substituted on the benzene ring. m and n each represent an integer from 0 to 5,
m and n are never 0 at the same time, and when m is 2 or more, R1 may be the same or different, and when n is 2 or more, R8 may be the same or different. You can leave it there.

The polygroups represented by R1 and R2 include those having substituents.

X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent.

In general formulas [I] and (n), the groups that can be substituted on the benzene ring represented by R and R2, respectively, are:
Halogen atoms, alkyl groups, alkoxy groups, carbamoyl groups (e.g. alkylcarbamoyl groups, arylcarbamoyl groups, etc.), sulfamoyl groups (e.g. alkylsulfamoyl groups, arylsulfamoyl groups, etc.), alkoxycarbonyl groups, ureido groups (e.g. alkylcarbamoyl groups, arylsulfamoyl groups, etc.) ureido group, aryl ureido group, etc.), carboxyl group, cyano group, nitro group, hydroxyl group, -NHCOR.

-Nl (COOR1 group, -NHR, group (R, and R1
each represents 1, a hydrogen atom, an alkyl group or an aryl group. ) etc.

m and n each represent an integer of O to 5, but m and n are never 0 at the same time. Also m.

When each n is 2 or more, R,, R, may be the same or different.

Furthermore, at least one of R1 and R2 is -NHC
ORs, -NHCONR3, -NHRl, -OH,
-NHCOOR3゜R3 -NH302R3 and -NHSOJRs are preferred, and in particular -NHCOOR! which directly bonds to the benzene ring of the mother nucleus! , -NORs, -OH,
-NHCONRs.

-N11SOzNR,, -NHCOOR3 or -N
Preferably, it has an IISO2R group.

Furthermore, it is more preferable that one or more of these groups is located at the 0-position with respect to the position bonded to the imidazole ring.

Further, the polygroups represented by R,, R, include those having substituents.

Examples include a cup with an oxidized color developing agent represented by X, but a halogen atom is preferred, and a chlorine atom is particularly preferred. R6 represents an alkyl group, an aryl group or a heterocyclic group.

May form an elementary ring.

Typical specific examples of cyan couplers represented by general formula [I] or (I[) are shown below.

The following margin [Effects of the invention] The pigment obtained from the present invention + the cyan pigment used is 60
It has an absorption in the red region of 0 to 700 n+s, but has a molar absorption coefficient 2 to 3 times that of the phenol or 7 toll type cyan couplers commonly used in the photographic industry, and the absorption is sharp (half-width (approximately 273) and the green part has good sharpness. In addition, the absorption of the chromosomal part is also small. Therefore, by using the cyan coupler of the present invention, the performance as a green filter and a blue filter is improved.

In addition, since a color developing solution containing one type of developing agent for two or more types of couplers is used, the color reaction does not become complicated and a colored area without color turbidity can be formed, and the resulting color filter has a spectral spectral profile. The characteristics are very good. Therefore, by using this color filter as a color filter for, for example, a liquid crystal display, the color reproducibility of the liquid crystal display can be greatly improved.

Furthermore, since the color development reaction can be controlled by the relationship between one type of developing agent and the coupler, it is easy to control the reaction, set reaction conditions, etc. Further, since mutual reactions between the plurality of developing agents and the plurality of couplers cannot occur, the color filter obtained by the present invention has stable quality.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Example 1 (Preparation of color developer) In the following blue color developer composition, a methanol solution of the coupler was mixed with developing agent aqueous solution B, water was added to bring the total volume to 14, and the pH was adjusted to 11 with sodium hydroxide. ，
5 (25°C).

methanol l 1 ・ ・ ・ ・ ・ ・ 115
0ffi11 Next, in the following green color developer composition, after adding the coupler methanol solution A to the developing agent aqueous solution B, the total volume was made up to 1Q with water, and the solution was diluted with sodium hydroxide.
The temperature was adjusted to fl 10.5 (25°C).

The following red color developing solution composition was prepared in exactly the same manner, and the total amount was reduced to 1 liter.
Q and pH 11.5 (25℃) with sodium hydroxide.
Adjusted to.

(Preparation of silver halide photosensitive material) A silver nitrate aqueous solution and an aqueous solution containing potassium bromide and potassium iodide were simultaneously added to a 10% aqueous solution of gelatin to prepare a silver iodobromide emulsion (containing 3 mol% silver iodide). Gelatin concentration 9
%)made. Precipitation conditions were regulated to obtain a Lippmann emulsion with an average grain size of 0.05 μm.

The above silver iodobromide emulsion was deposited on a 1.1 mm thick transparent borosilicate glass substrate (30 cm x 30 cm) to a dry film thickness of 3 μm.
A silver halide photosensitive material was produced by coating the film in an amount of m.m.

(Exposure and Development) A chromium mask for a color filter having a square opening of 150 μm on a side was placed on top of this silver halide photosensitive material, and a first exposure was performed using a tungsten lamp.

The photosensitive material subjected to the first exposure was immersed in the blue color developing solution at 25°C for 3 minutes, and then the stop solution (11
28% acetic acid 32ta (l) and sodium sulfate 45g
A blue portion was formed on the substrate by immersing the substrate in a solution containing (containing) for 30 seconds, washing with water for 5 minutes, and drying.

Next, another chrome mask for color filter is placed immediately next to the formed blue part, and a second chrome mask is placed in the same manner as above.
The second exposure was made.

The photosensitive material subjected to the second exposure was developed, stopped, washed with water, and dried to form a green area on the substrate in the same manner as the first exposure, except that the green developer was used.

Furthermore, a third color filter chrome mask was placed on the right side of the formed green area (that is, on the left side of the blue area), and a third exposure was performed in the same manner as above.

The photosensitive material subjected to this third exposure was treated in the same manner as the first and second exposures, except that the red color developing solution was used.
After developing and stopping, it was immersed in a bleaching solution of the following composition for 5 minutes and a fixing solution for 5 minutes at 25°C (desilvering treatment) to form a red area on the support, which was designated as sample 1 (comparison). .

Bleach solution composition Ammonium bromide 160.0g Ammonia water (28%) 25.0m (2
Ethylenediaminetetraacetic acid iron sodium salt...
・・・・・・・・・130.0g Glacial acetic acid・・・・・・
・・・・・・・・・14. Add OmQ water to bring the total volume to 2.

Fixer composition Sodium tetrapolyphosphate 2.0g Anhydrous sodium sulfite 4.0g Ammonium thiosulfate (70% aqueous solution) 175. OmQ Sodium Bisulfite... Add 4.0g water and make the total amount IQ.

Next, color filter samples 2 and 3 were prepared using the same photosensitive material as Sample 1 and performing the same operations except that the cyan coupler in the blue color developing solution was replaced with the cyan coupler according to the present invention as shown in Table 1. Obtained.

In each of the color filters obtained in this way, the blue, green, and red parts of a square with sides of 150 IJm are uniformly formed over the entire borosilicate glass substrate, and no color turbidity is observed in each color. There wasn't.

450 am of the blue filter part of samples 1.2 and 3.

Table 1 shows the results of measuring the spectral transmittance at 550 nm and 650 na+.

As is clear from Table 1, the color filter of the present invention increased the transmittance of blue light. This is because the cyan coupler of the present invention has less absorption in the blue region than the comparative cyan coupler.

Example 2 Using the same photosensitive material as Sample 1 in Example 1, the magenta coupler in the blue developer was replaced with 7-chloro-3,6-
Cymethyl-IH-pyrazolo[5,1-cl-1,2,4
- Sample 1.2 in the same manner except that triazole was used.
Samples 4.5 and 6 corresponding to and 3 were obtained.

Samples 4.5 and 6 blue filters, 45-on spatula,
Table 2 shows the results of measuring the spectral transmittance at 550 nm and 650 nm.

As is clear from Table 2, the transmittance of blue light was further increased by using the magenta coupler with low absorption near 440 nm in combination with the cyan coupler of the present invention.

Example 3 Samples 7 to 11 were obtained in the same manner as in Example 1, using the same photosensitive material as Sample 1, except that the cyan coupler in the green developer was replaced with the cyan coupler of the present invention shown in Table 3. .

450 nm, 550 nm of part of the green filter of sample 7-11
The spectral transmittance at nm and 650 nm was measured.

The results are shown in Table 3.

Table 3 As is clear from Table 3, the green light transmittance of the sample using the cyan coupler of the present invention also increased.

Example 4 In Example 1, during exposure to form a blue part, a green part, and a red part, a convergence of 20
Exposure is performed using a chrome mask for color filters that can form unexposed areas of μm to form blue, green, and red areas, and then the unexposed areas are exposed using a black stripe mask. did.

Next, a color filter was prepared in the same manner as in Example 1, except that development was performed using a black color developing solution (preparation method is the same as in Example 1) containing the following three types of cyan coupler, magenta coupler, and yellow coupler. Created.

Black stripes (light-opaque sections) are located between the blue, green, and red parts of the resulting color filter.
was formed, and the blue, green, and red areas were clearly divided by these black stripes.

Black color developer composition j tp y 9 fi″″−°°°°°°°°°0・
After mixing 86g of liquid A with liquid B, add water to bring the total amount to 1a.
and adjusted to pH 11-5 with sodium hydroxide.

[Brief explanation of the drawing]

FIG. 1 is a conceptual diagram of a liquid crystal color display for boat fishing. FIG. 2 is a cross-sectional view showing an example of pattern exposure in the method of implementing the present invention. FIG. 3 is a sectional view showing an example of a color filter obtained by the present invention. FIG. 4 is a sectional view showing another example of a color filter obtained by the present invention. 1... Luminous body, 2... Polarizing plate, 3... Liquid crystal layer,
4... Color filter, 21... Light-transmitting support, 22... Emulsion layer, 23... Silver halide photosensitive material, 24... Photomask, 25... Opening, 26...
・・Exposure scheduled portion, 31.41 ・・Light transparent support 3
2.42...Colored Section Applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Scope of Claims] After exposing a light pattern to the emulsion layer of a light-sensitive material having at least one silver halide emulsion layer provided on a light-transmitting support, the above-mentioned pattern is formed by external color development. In a color mosaic filter obtained by forming a dye image, repeating the same steps to form a pattern of at least two colors, and performing desilvering treatment after final color development,
A color mosaic filter characterized in that the color developing solution contains at least one cyan coupler represented by the following general formulas [I] and [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1 and R_2 each represent a group that can be substituted on the benzene ring. m and n each represent an integer from 0 to 5, m and n are never 0 at the same time, and when m is 2 or more, R_1 may be the same or different, and n is When 2 or more, R_2 may be the same or different. Each group represented by R_1 and R_2 includes those having a substituent. X represents a hydrogen atom or a group that can be separated by a coupling reaction with an oxidized product of a color developing agent. ]