JPH01172802A - Color mosaic filter - Google Patents

Abstract

PURPOSE:To obtain a color filter having good spectral characteristics by incorporating pyrazoloazole type cyan couplers having electron-withdrawing groups and/or hydrogen bondable groups in substitutable positions except at active points into a color developing soln. CONSTITUTION:>=2 Kinds of the couplers which impart different hues are incorporated into the color developing soln. At least one of the pyrazoloazole compds. having at least one electron-withdrawing groups and/or hydrogen bondable groups in the substitutable positions except at the active points are used as the cyan couplers. Since the dye obtainable from such cyan coupler has less absorption of the blue part and green part and, therefore, the color filter which is increased in the transmittance of the blue part and green part is obtainable. Since the color developing soln. contg. one kind of developing agent is used for >=2 kinds of the couplers, the chromatic part having no color clouding is formed without complicating the color forming reaction. The spectral characteristics of the resulted color filter are thus 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 present applicant has studied a method for manufacturing a color filter using an internal development method, and as a result, the applicant has found that, roughly speaking, a three-layer halogenated layer having two different types of couplers among a yellow coupler, a magenta coupler, and a cyan coupler is used. He proposed the invention of a color filter material and a color filter having a silver layer (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.
An external mixed developer, an external developer containing a cyan coupler, and an external developer containing a yellow coupler mixed in 1:
Exposure and development are carried out using the external mixed developer mixed in step 2 and the external mixed developer prepared by mixing an external developer containing a cyan coupler and an external developer containing a magenta coupler at a ratio of 1:2. A specific example of producing red, green and blue striped filters by repeating 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, at least one electron-withdrawing group and a substitutable position other than the active site are added to the color developer. This was achieved by containing at least one pyrazoloazole cyan coupler having a hydrogen-bonding group.

The effects of the present invention can be more effectively achieved by containing at least one coupler having a different hue from the coloring dye in the color developing solution.

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
), “The Theory of the Photographic
The Theory of the Process 3rd Edition
Photographic Process 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-t)reninsulfonate (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 contained in the developer 112 in an amount of 0.1 to 10 g. Content is 0.1
If it is less than g, effective development may not be possible.
Furthermore, even if more than the log amount is used, not only is there no significant improvement in developability, but depending on the type of developing agent,
It may not dissolve sufficiently.

It is preferable to use 0.5 to 7 g of developer per 11 developer solutions, 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 the yellow and low couplers are combined to form a red color developing solution. 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. However, as the cyan coupler, at least one pyrazoloazole compound having at least one electron-withdrawing group and/or hydrogen-bonding group at a substitutable position other than the active site is used.

In the present invention, the electron-withdrawing group is preferably Ham
A substituent whose substituent constant 6p defined by Mett is +0.2 or more, specifically sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl,
Examples include polygroups such as carbamoylsyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogenated alkoxy, 10genated aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.

Examples of the sulfonyl group include groups such as alkylsulfonyl, arylsulfonyl, halogenated alkylsulfonyl, and halogenated arylsulfonyl.

Examples of the sulfinyl group include groups such as alkylsulfinyl and arylsulfinyl.

Examples of the sulfonyloxy group include groups such as alkylsulfonyloxy and arylsulfonyloxy.

Examples of the sulfamoyl group include groups such as N,N-dialkylsulfamoyl, N,N-diarylsulfamoyl, and N-alkyl-N-arylsulfamoyl.

Examples of the phosphoryl group include groups such as alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoolol, and arylphosphoryl.

Examples of the carbamoyl group include groups such as N,N-dialkylcarbamoyl, N,N-diarylcarno(moyl), and N-alkylN-arylcarbamoyl.

Examples of the acyl group include groups such as alkylcarbonyl and arylcarbonyl.

As the acyloxy group, alkylcarbonyloxy and the like are preferred.

As the oxycarbonyl group, alkoxycarbonyl,
Examples include groups such as aryloxycarbonyl.

As the halogenated alkoxy group, an α-)10genated alkoxy group is preferable.

As the halogenated aryloxy group, polygroups such as tetrafluoroaryloxy and pentafluoroaryloxy are preferred.

Examples of the pyrrolyl group include groups such as l-pyrrolyl.

Examples of the tetrazolyl group include groups such as l-tetrazolyl.

In addition to the above substituents, trifluoromethyl groups, heptafluoroisopropyl groups, tetrafluoroaryl groups, pentafluoroaryl groups, and the like are also preferably used.

In the present invention, a hydrogen-bonding group refers to a substituent having an active hydrogen atom that forms a hydrogen bond with the nitrogen atom forming the pyrazoloazole ring.

Representative examples of hydrogen-bonding groups include Rb Ktl
KO here, Ra, Rb,,R
c, Rd, Re and Rf each represent a hydrogen atom or a substituent, α represents 0 or 1, m represents 1 or 2, and n represents an integer from θ to 4. When n is 2 or more, the plurality of Rfs may be the same or different.

Ra, Rh and Rd each represent a hydrogen atom, an alkyl group,
Represents an aryl group, a heterocyclic residue, etc.

Rc and Re each represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic residue, a sulfonyl group, a sulfinyl group, or a carbonyl group which may be substituted with an alkyl group, an aryl group, or the like.

Re is preferably a sulfonyl group, a sulfinyl group, or a carbonyl group.

There are no particular limitations on the substituent represented by Rf.

Preferred hydrogen-bonding groups in the present invention are -SO, NHRc, -5ONHRc, -CON
HRc and these hydrogen-bonding groups may further contain a substituent such as a hydrocarbon group.

A pyrazoloazole cyan coupler is one in which an azole ring is fused to a pyrazole ring, and can be specifically represented by the following general formula CI).

General formula CI) In the formula, 2 represents a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle, and R2 represents a substituent bonded to the carbon blue atom of the heterocycle. At least one of R and R1 represents an electron-absorbing group or a hydrogen-bonding group. X represents a hydrogen atom or a group that can be separated by reaction with an oxidized product of a color developing agent. n represents an integer from θ to 2. In "general formula CI), when R8 or R8 is not an electron-withdrawing group or a hydrogen-bonding group, R1 and R2 each represent a hydrogen atom or a substituent, and this substituent is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, and other groups, but also halogen atoms, cycloalkenyl, alkynyl, heterocycle, hydroxyl, mercapto, alkoxy, Aryloxy, heterocyclicoxy, siloxy,
Amino, alkylamino, imide, ureido, thioureido, sul7amoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio polygroups, spiro compound residues, bridged hydrocarbon compound residues Also mentioned are groups.

The alkyl group represented by R or R1 preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the alkyl group and aryl group represented by R1 or R2 above.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.

The ureido group includes an alkylureido group, an arylureido group, etc.; the sulfamoylamino group includes an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; the heterocyclic group is preferably a 5- to 7-membered one; Examples include 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc. The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, such as 3.
4.5.6-tetrahydropyranyl-2-oxy group, l
-Phenyltetrazole-5-oxy group, etc.; The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-penzothiazolylthio group, 2.4-diphenoxy- 1,3,5-1-riazole-6 monothio group, etc.; siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group, etc.; imide groups include succinimide group, 3-heptadecylsuccinimide group, phthalimide group, glutarimide group, etc.; spiro compound residues include spiro [3,3]hebutan-1-yl; and bridged hydrocarbon compound residues include bicyclo [2゜2.
1] Hebutan-1-yl, tricyclo [3゜3゜1.
Examples thereof include M decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

Groups that can be separated by reaction with the oxidized product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxyaryloxycarbonylsithio, arylthio, heterocyclicthio, alkyloxythiocarbonylthio, acylamino, sulfonamide, Ny
Nitrogen-containing heterocycle bonded with a K atom, alkyloxycarbonylamino, aryloxycarbonylamino, carboxyl ,' and R
,' represents a hydrogen π molecule, an aryl group, an alkyl group, or a heterocyclic group. ), preferably a halogen atom. Particularly preferred among these groups represented by X are hydrogen atoms and chlorine atoms.

Examples of the nitrogen-containing heterocycle formed by Z or Z' include a pyrazole ring, imidazole ring, triazole ring, and tetrazole ring.

-fi Among the compounds represented by the formula (I), compounds in which at least one of R1 and R2 is an electron-withdrawing group are more specifically described. In (na), at least Ra, or Ra, HCDI
a) at least Ra, or Ra3; (IVa) at least Ra, , Ra, or Ra; (V a)
At least Ra, , Ra, or Ra7; (VIa
) in at least Ra, or Ra; in [■a] R
In [■a], at least Ral or Rag; represents an electron-withdrawing group, X has the same meaning as X in the general formula (1), and p represents an integer of O to 4.

Y represents a hydrogen atom or a substituent, and the preferable substituent represented by Y is, for example, one that separates from the compound of the present invention after the compound of the present invention reacts with the oxidized developing agent. The substituent represented is JP-A No. 61-228444.
Groups that can be separated under alkaline conditions, such as those described in JP-A-56-133734, and substitutions that couple off by reaction with oxidized developing agents, as described in JP-A-56-133734, etc. Examples include groups. Y is preferably a hydrogen atom.

In addition, in the general formula CTI a] to [■a], Rag
In -Rag, a group that is not an electron-withdrawing group represents a hydrogen atom or a substituent, and there are no particular restrictions on this substituent. Specifically, in general formula CI), R, or R7
When is other than an electron-withdrawing group or a hydrogen-bonding group, the substituents represented by R1 or R2 or those mentioned above as hydrogen-bonding groups can be mentioned.

The pyrazoloazole type cyan coupler having an electron-withdrawing group according to the present invention is disclosed in Japanese Patent Application No. 62-47323 and No. 62-47323;
-48895, 62-53417, 62-53
No. 418, No. 62-62162, No. 62-62163
No. 62-99950, No. 62-184552,
It can be easily synthesized according to the methods described in various specifications such as No. 62-184553.

Among the compounds represented by the general formula CI), compounds in which at least one of R8 and R2 is a hydrogen-bonding group are more specifically described as follows: General formula % Formula % General formula (■b) N-N -N-Y In the above general formula, general formula (m b), (v b),
Rh in (Vl b) and [■b] is the above-mentioned hydrogen bonding group, and at least Rh in (m b), or Rh, 1(
rvb), or Rh; [■
b] at least Rh, or Rh in [b].

represents a hydrogen-bonding group, X has the same meaning as X in the general formula CI), and Y represents the general formula (II a), (m a
), (It/a), (VTa), [■a] and [■a
] has the same meaning as Y in ]. q represents an integer from θ to 3.

In addition, Rb in general formula (n b) ~ [■ b], ~R
In b r o, a group that is not a hydrogen-bonding group represents a hydrogen atom or a substituent, and the substituent is not particularly limited. Specifically, in the general formula [I], those mentioned as the substituent represented by R or R3, or those mentioned above as the electron-withdrawing group can be mentioned.

The pyrazoloazole cyan coupler having a hydrogen-bonding group according to the present invention is disclosed in Japanese Patent Application No. 62-85510 and No. 62-85510.
No. 2-85511, No. 62-114838, No. 62-
It can be easily synthesized according to the methods described in specifications such as No. 115946 and No. 62-184554.

Among the cyan couplers represented by general formula (I) below, yellow couplers include open-chain ketomethylene compounds (for example, ff-(4-carboxyphenoxy)-σ-pivaloyl-2,4-dichloroacetanilide, etc.). acylacetanilide), and furthermore, U.S. Pat. Nos. 3,510,306 and 3,6
No. 19.189, Special Publication No. 40-33775, No. 44-
Those described in No. 3664 and the like can be used.

In addition, as a magenta coupler, an active methylene compound (for example, 1-(2,4,6-drichlorophenyl)-3
-(4-nitroanilino)-5-pyrazolone, acylacetonitrile);
No. 52,896, No. 3,615,502, Special Publication No. 1977
-133111 etc. can be used.

Typical specific examples of magenta couplers and yellow couplers that can be used in the present invention are shown below (magenta coupler) (yellow coupler) In addition to the above-mentioned couplers, rThe Theory of
he Photographic Process
3rd EditionJ (mentioned above), Chapter 17, 38
Those described on pages 2 to 395 can also be used.

The total amount of couplers in the color filter developer IQ used in the present invention is usually preferably 0.5 to 20 g. If it is less than 0.5 g, the color may not develop sufficiently, while if it is more than 20 g, so-called fog may occur. In particular, in the present invention, by setting the total amount of coupler in the developer 112 to 1 to 10 g, a color filter with less color turbidity and good spectral characteristics can be manufactured.

In addition, the compounding ratio of couplers with different hues in the developer is
It can be appropriately set in consideration of the coloring property of the coupler used. For example, when combining a cyan coupler and a magenta coupler, the weight ratio of both is usually 1
:9 to 7:3 (preferably l:9 to 4:6). Further, in the case of a combination of a cyan coupler and a yellow coupler, the ratio is usually within the range of 1:9 to 7:3 (preferably 1:9 to 4:6). Further, in the combination of magenta coupler and yellow coupler, the ratio is usually 9:1 to 8:2 (preferably 8:2 to
6:4). And cyan coupler,
When combining the magenta coupler and the yellow coupler, it is preferable to mix approximately the same amounts of the three couplers.

Furthermore, the weight ratio of the total amount of coupler to the developing agent in the developer can be set as appropriate by taking into account the type and content of the coupler and developing agent.
Usually, the compounding weight ratio of the coupler and the developing agent is adjusted to 1
:9-9:1 (preferably l:5-5)
: within the range of 1).

Furthermore, the developer for color filters contains preservatives (for example,
sodium sulfite, diethylhydroxylamine), accelerators (e.g. alkaline agents such as sodium hydroxide),
Control agents (e.g. potassium bromide, potassium iodide), auxiliary agents (e.g. water conditioners such as polyethylene glycol,
It may also contain additives contained in ordinary external developers, such as color toning agents such as citradinic acid and imidazole derivatives.

The developer should be used at normal operating temperatures (e.g. 20-35°C).
It is used after adjusting the pH value using sodium hydroxide or the like so that the pH value is within the range of 9.0 to 13.0.

A silver halide photosensitive material used to produce a color filter using a color filter developer has a light-transmitting support and an emulsion layer coated on the support.

The support of the silver halide photosensitive material has light transmittance. Furthermore, when assembling a liquid crystal color display or the like, the color filter may be exposed to high temperatures during the vapor deposition process, so it is preferable that the material for the support has good heat resistance.

Examples of materials constituting such a light-transmitting support include polymeric compounds such as polyethylene terephthalate, polystyrene, polycarbonate, and cellulose acetate;
Examples include glass (eg, borosilicate glass, etc.), inorganic materials such as quartz and sapphire, and the like. The light-transmitting support can be used in the form of a plate, sheet, or film using the above-mentioned materials.

The thickness of the light-transmitting support can be appropriately set depending on the application, but it is usually preferably 0.5 μm" 10 mm. Particularly in the case of a liquid crystal color display, the thickness is 0.3 μm.
It is preferable to use a light-transmitting support with a thickness of ~2 mm.

The support needs to be optically transparent and therefore
In the present invention, not only a transparent support but also a translucent support can be used. Note that a light-transparent para-kink layer for antihalation may be provided on the surface of the light-transparent support on which the emulsion layer is not provided. Furthermore, the light-transmitting support may be colored within a range that does not impair the properties of the color filter.

Although the emulsion layer can be directly coated on the light-transmitting support, the emulsion layer can also be provided via a subbing layer in order to reinforce the adhesive force between the emulsion layer and the support.

Examples of materials forming the subbing layer include gelatin, albumin, casein, cellulose derivatives, starch derivatives,
Examples include sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, and polyacrylamide. The undercoat layer is preferably thin considering the spectral characteristics of the color filter, and is usually 1 μm or less (preferably 0.05 to 0.5 μm or less).
μm).

The emulsion layer is a layer in which silver halide is dispersed in a water-soluble binder, and can be formed by coating a known silver halide. However, in the present invention, in order to obtain a color filter with good spectral characteristics, it is desirable to use silver halide with a small average particle size.
It is preferable to use a so-called Lippmann emulsion having an average grain size of 0.1 μm or less.

As the silver halide, those used in ordinary photographic materials can be used. Namely, silver chloride, silver iodide, silver bromide, silver chloroiodide, silver chlorobromide and silver iodobromide can be mentioned. These can be used alone or in combination, and it is particularly preferable to use silver bromide or silver iodobromide.

As the water-soluble binder in the emulsion layer, ordinary binders can be used. Examples include gelatin albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, and polyacrylamide. These can be used alone or in combination. Among these water-soluble binders, gelatin is particularly preferred.

The emulsion layer contains the above silver halide and water-soluble binder.
It is desirable that the weight ratio be 6 to 8:1.

Note that the emulsion layer may contain additives used in emulsion layers of ordinary light-sensitive materials.

The thickness of the emulsion layer is usually preferably 0.5 to 10 μm. If the thickness is less than 0.5 μm, sufficient color development may not be achieved, and if it is thicker than 10 μm,
The light transmittance may decrease and the brightness of the color filter may become insufficient. In particular, in the present invention, by setting the thickness of the emulsion layer within the range of 0.5 to 3 μm, the spectral characteristics of the resulting color filter can be improved.

The emulsion layer (and subbing layer) is coated using a conventional photographic material coating method.

The color filter of the present invention using the above silver halide photosensitive material and developer is produced as follows.

First, the silver halide photosensitive material described above is exposed in a pattern (first exposure).

Pattern exposure can be performed by a conventional method. For example, as shown in FIG. 2, a silver halide photosensitive material 2 having an emulsion layer 22 laminated on a light-transmitting support 21
By placing a photomask 24 on the photomask 24 and applying light from above the photomask 24, the portions 26 of the emulsion layer to be exposed corresponding to the openings 25 provided in the photomask 24 are selectively exposed.

The size of the scheduled exposure portion 26 in the color filter,
That is, the size of the opening 25 of the photomask can be appropriately set according to the intended use of the resulting color filter. However, if the width of the opening 25 is narrower than the wavelength of the structure used for exposure, effective exposure cannot be performed, so the width of the opening 25 is made wider than this wavelength. Since silver halide has effective photosensitivity to light of 340 to 420 nm, the width of the opening 25 is 340 nI.
11 or more, and furthermore, considering the use as a color filter, it is preferably 1 μm or more. Also,
In the case of a color filter for a liquid crystal display, the width of the opening 25 should be 1,000 μm in order to effectively reproduce colors by additively mixing the colored parts developed in red, blue, and green. It is desirable that the thickness be below (particularly desirably 500 μm or below).

Regarding other conditions such as exposure time and light source in manufacturing the color filter of the present invention, usual conditions can be followed.

After performing the first pattern exposure in this manner, a first development of the exposed portion is performed using a color filter developer. For example, by performing development using a developer (blue developer) containing a cyan coupler and a magenta coupler as couplers, the exposed portion is developed into a blue color. Further, by using a developer containing a cyan coupler and a yellow coupler (green developer), the exposed area is developed into green. Further, by using a developer containing a magenta coupler and a yellow coupler (red developer), the exposed areas are developed into red.

The first exposed area may be developed using any of the above-mentioned blue developer, green developer, and red developer.

Development can be carried out according to the overlay development method in ordinary photographic technology. For example, the development temperature is usually 10~
The 40°C1 development time is usually 30 seconds to 30 minutes.

After developing the first exposed area in this way, the silver halide photosensitive material is usually immersed in a stop solution containing acetic acid, sodium sulfate, etc. to stop the reaction involved in development, and then the silver halide photosensitive material is Rinse the material with water and dry.

In the emulsion layer of the silver halide light-sensitive material thus obtained, the pattern-exposed areas become colored areas that are colored in a color corresponding to the developer used.

By performing exposure and development as described above, it is possible to produce a color filter having a light-transmitting colored part of one color on the silver halide photosensitive material. When used as a color filter, colored portions of red, blue and green colors other than those formed in the first step are further formed on the silver halide photosensitive material.

That is, for example, using a 7-oto mask different from that used in the first step, the unexposed portion adjacent to the first colored portion formed in the first step is exposed in the same way as in the first exposure. pattern exposure according to the method and then development using one of the developers other than those used in the first step. Further, if desired, a second colored portion can be formed by performing steps such as immersion in a stop solution, washing with water, and drying.

Similarly, a third colored part is formed by exposing an unexposed part adjacent to the second colored part to pattern light and developing it using a developer other than that used in the first and second steps. be able to.

After forming the first to third colored parts in this way, a step of removing the silver component in the photosensitive layer (bleach-fixing step) is usually carried out.
Fix the colored parts.

In this way, a light-transmitting support 31 as shown in FIG.
A color filter having red (R), blue (B), and green (G) light-transmitting colored portions 32 formed thereon can be manufactured.

Further, in the present invention, as shown in FIG. 4, red (R), blue (B) and green (G
) is formed with a gap therebetween, the gap is exposed to light in a pattern, and then developed using a developer containing a cyan coupler, a magenta coupler, and a yellow coupler. 42 red part (R
), a light-impermeable section (black stripe) 43 can also be formed in the gap between the blue part (B) and the green part (G).

The color filter thus produced can be effectively used as a color filter for a liquid crystal color display as shown in FIG. In FIG. 1, the symbol ■ is a light emitter, the symbol 2 is a polarizing plate that polarizes the light beam from the light emitter 1, and the symbol 3 is a polarizer that polarizes the light beam from the light emitter 2. This is a liquid crystal layer that selects transmission and non-transmission, and 4 is a color filter.

Furthermore, it can also be effectively used in place of color filters in conventionally used image pickup tubes and the like.

〔Effect of the invention〕

Since the dye obtained from the cyan coupler used in the present invention has low absorption in the blue and green parts, it is possible to obtain a color filter with increased transmittance of chromosomal light and green parts. Furthermore, since it has very good heat resistance, it is particularly excellent as a color filter for liquid crystal color displays that are exposed to high temperatures during vapor deposition processes.

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, methanol solution A of the coupler was mixed with developing agent aqueous solution B, water was added to make a total volume of 1Q, and sodium hydroxide was used for blue color development. Solution Composition Next, in the following green color developing solution composition, after adding the methanol solution A of the coupler to the aqueous developing agent solution B, the total volume was made up to 1Q with water, and the solution was diluted with pi (10,5
(25°C).

Composition of green color developing solution 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 that has been exposed for the first time is immersed in the blue color developing solution at 25°C for 3 minutes, and then the stop solution (lQ
A blue portion was formed on the substrate by immersing the substrate in a solution (containing 28% acetic acid 32IIIM and 45 g of sodium sulfate) 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, the film was immersed in a bleaching solution with the following composition for 5 minutes and a fixing solution for 5 minutes at 25°C (desilvering treatment).
A red area was formed on the support and designated as Sample 1 (comparison).

Bleach solution composition Ammonium bromide... 160.0g
Ammonia water (28%)・・・・・・25.0mρ
Ethylenediaminetetraacetic acid iron acetate sodium salt...
・・・・・・・・・130.0g Glacial acetic acid・・・・・・
・・・・・・・・・14. Add OmQ water and bring the total volume to 11
Set it to 2.

Fixer composition Sodium tetrapolyphosphate...2.0g Anhydrous sodium sulfite...Pa...4.0g Ammonium thiosulfate (70% aqueous solution) 175.0mff Sodium bisulfite... - Add 4.0g water to make the total amount 1Q.

Next, color filter samples 2 to 4 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 a side of 150 μm are uniformly formed over the entire tomo-silica glass substrate, and no color turbidity is observed in each color. There wasn't.

450 nm, 540 part of the blue filter of samples 1 to 4
Table 1 shows the results of measuring the spectral transmittance at nm and 630 nm.

Table 1 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 1-hydroxy-2-naphthamide cyan coupler.

In addition, each sample was placed in an oven and heated to 170-180℃ for 2 hours.
When the spectral transmittance at 650 nm of a part of the blue filter was measured after being maintained for a period of time, Samples 2 to 4 showed almost no difference from the data in Table 1, but Sample 1 (comparative coupler) showed a significant increase of 30%. This is because the dye obtained from the cyan coupler used in the present invention has excellent heat resistance.

Moreover, 450 nm of a part of the green filter of samples 1-4.

Spectral transmittance at 540 nm and 630 nm was also measured.

The results are shown in Table 2.

Table 2 From the results in Table 2, it can be seen that the color filter of the present invention also improves the transmittance of green light.

[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 the 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 part

Claims (2)

[Claims] (1) 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, a dye image corresponding to the pattern is formed by external color development. In the color mosaic filter obtained by repeating the same steps to form a pattern of at least two colors, and performing desilvering treatment after the final color development, the active sites are removed from the color developer. A color mosaic filter comprising at least one pyrazoloazole cyan coupler having at least one electron-withdrawing group and/or hydrogen-bonding group at a possible position. (2) The color mosaic filter according to claim 1, wherein the color developing solution contains at least one other coupler having a different hue of the coloring dye.