JPH02281203A - Color filter - Google Patents

Abstract

PURPOSE:To obtain a color filter having superior surface smoothness by incorporating a compd. formed by the coupling reaction of a specified precursor compd. with the oxidized product of a color developing agent into image elements having one color and incorporating at least one kind of fluorine-contg. surfactant. CONSTITUTION:When a color filter is formed on a transparent substrate by color development, at least one kind of practically colorless compd. formed by the coupling reaction of a precursor compd. represented by formula I with the oxidized product of a color developing agent in a color developing soln. is incorporated into image elements having at least one color and at least one kind of fluorine-contg. surfactant is also incorporated. In the formula I, R is optionally substd. alkyl or aryl substd. at the active site and X is a group of atoms required to form a 5- or 6-membered hetero ring contg. at least one N, S or O atom. The resulting color filter has superior surface smoothness.

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to a color filter, and more particularly to a color filter suitable for use in a color liquid crystal display. [Background of the Invention] As a method for manufacturing color filters, Japanese Patent Application Laid-open No. 55-63
As disclosed in No. 42, there is an external color development method using a color silver salt photographic material. However, in the method described in the above-mentioned patent, relief occurs between pixels having different spectral characteristics, which is a major cause of deterioration in image quality, especially after producing a color liquid crystal display. That is, in a color liquid crystal display, the spectral characteristics based on the orientation of liquid crystal molecules are determined by the voltage applied to the liquid crystal layer, and the voltage is influenced by the thickness of the liquid crystal layer. Therefore, when a difference in level occurs between pixels of a color filter, the spectral characteristics of each pixel after producing a color liquid crystal display are different from desired ones, resulting in deterioration of image quality. Therefore, in order to solve the above problem, the inventors developed a coupler (hereinafter referred to as a vise coupler) that forms a substantially colorless compound by coupling reaction with an oxidized form of a color developing agent in an external color developer. proposed that the B (blue), G (green), and R (red) pixels of a color filter selectively contain the coupling product of the optical coupler (Patent Application No. 63). -241800). However, it has been found that the above-mentioned product precipitates and crystallizes on the surface of the color filter, creating convex portions on the surface and impairing its smoothness. Another disadvantage is that the product precipitates from the light-sensitive material layer into the external color developing solution, significantly accelerating fatigue of the developing solution. [Object of the Invention] An object of the present invention is to provide a color filter with excellent surface smoothness. Another objective is to provide a color filter that is low cost and has stable performance. [Structure of the Invention] The above object of the present invention is to provide a color filter consisting of three primary colors of light, which is produced by color development using a silver halide photosensitive material having a photosensitive agent layer provided on a light-transmitting substrate. , (i) at least one color pixel contains at least one substantially colorless compound formed by a coupling reaction between a precursor compound represented by the following general formula [l] and an oxidized product of a color developing agent, and (2) Achieved by a color filter characterized by containing at least one fluorine-containing surfactant. General formula [I] In the formula, R is an alkyl group (including substituted alkyl groups) or an aryl group (including substituted aryl groups) substituted at the active site.
, X represents a group of atoms necessary to form a 5- to 6-membered heterocyclic nucleus containing at least one nitrogen atom, sulfur atom, or oxygen atom (the heterocyclic nucleus further forms a fused ring with another ring) or may have a substituent on the ring). The present invention will be explained in more detail below. The V-eye coupler represented by the general formula [1] has the compound dissolved in whole or in part in the treatment liquid on the ring or on the alkyl group represented by R, if necessary, and the compound has a substituent group having a molecular size and shape that renders it immobile in the emulsion layer after coupling with the oxidized form of the color developing agent. Examples of the substituent include organic groups having 6 to 24 carbon atoms. More preferable examples of the optical coupler represented by the general formula [1] according to the present invention include the following general formulas [2] to

[9]
It is a compound represented by the general formula [2] and [3]
Compounds represented by are preferred. General formula (9) R. O In the above general formula, R is the same as defined in general formula C1). R1 represents a substituted or unsubstituted alkyl group or aryl group. R2 represents a substituted or unsubstituted alkyl group, aryl group, alkylamino group, arylamino group, acylamino group, ureido group, cyano group or carbamoyl group. R and R2 or R8 at adjacent positions may be combined to form a ring. R5 represents a substituted or unsubstituted alkyl group or aryl group. A more preferred compound is a coupler represented by the following general formula [1O] in general formula [2]. General formula [lO] In the formula, R has the same meaning as R in general formula [1], and R2
represents a hydrogen atom, a halogen atom, and an alkyl, asacoxy, alkylamide, arylamide, alkylsulfonamide, arylsulfonamide, alkoxycarbonyl, carbamoyl, or sulfamoyl group, and R
5 represents a noalkyl group having 8 or less carbon atoms, an aralkyl group having 10 or less carbon atoms, or an aryl group, and n represents an integer of 0 to 5. These alkyl groups, alkoxy groups, aralkyl groups, and aryl groups may further have a substituent. Preferred examples of R5 include groups such as methyl, ethyl, benzyl, phenethyl, phenyl, and tolyl. Specific examples of the compound represented by the general formula [1] according to the present invention are shown below. E-1 E E E E E E E E E WE-31 WE-32 The processing solution containing the V eye color coupler according to the present invention may be the same as or different from the external developer or the black and white developer for SDB, but depending on the processing process. The same is preferable from the viewpoint of simplification and reduction of process cost. The amount used is preferably 10g or less per treatment liquid IQ, and 0.
．． A range of 0.01 to 2 g is more preferable. The fluorine-containing surfactant according to the present invention may be used in the photosensitive agent layer, in the external developer, or both in the photosensitive layer and in the external developer; It is preferable to use it in the agent layer. In the present invention, a fluorine-containing surfactant (hereinafter simply referred to as a fluorine-containing compound) is defined as having at least one, preferably three or more, fluorine atoms and at least one, preferably three, carbon atoms in the molecule. It is a compound and also contains a polymer compound having a fluorine atom and a carbon atom in its main chain or side chain. For fluorine-containing compounds, U.S. Pat. No. 3,589,906
No. 3,666.478, No. 3,754,924, No. 3,775,126, No. 3,850,640,
West German Patent Publication No. 1,942,665, No. 1,961,6
No. 38, No. 2,124,262, British Patent 1, 30
0. No. 356, Belgian Patent No. 742,680, Japanese Unexamined Patent Publication No. 1973
-7781, 48-9715, 49-4673
No. 3, No. 4C1-133023, No. 50-99529
No. 50-113221, No. 50-160034, No. 51-43131, No. 51-129229, No. 51-10641'1, No. 53-84712, No. 5
No. 4-111330, No. 56-109336, No. 59
-No. 30536, No. 59-45441, Special Publication No. 1977-
No. 9303, No. 48-43130, No. 59-5887
Those listed in the number etc. can be used. 0M2COOCH2(CF2)8H NaO3S-CHCOOCH2(CFx
) a HC8F,,302NC)+2c)12(O
C3H6)50HC2)IS CI(2COOCH2(CF2)<H NaO,S CHCOOCH2(CF2)4HCH2
COOCHz(CF2)aH NaO,S CHCOOCHz(CFz)aHCF3
(CF2)s(CH2)+oCOONaCQCFz(C
FCF2) tcOOH H (CF2) locOONa HOOC (CF2CF), COOH Q Cρ (CF.CF) ICF2GOOK I2 CF3 (CFz) acH= CH (CHz) scOON
aCF3(Cjz)sCF(CHx)+oCOONaC
F. CF, (CF2)ycON(CHx)2cOONaCH
. C(2(CFz)acOONa CF3(CF2)3CH2CH2SO2NCH2COO
Na2H5 CF3(CFz)ysO□NcH2cOONaC x
H s CF, (CFz)ysOzN(CHg)acOOKC2
1(6 CF3(CF2), SO2NCI(2GOOKC.H. CF, (CF2)7So.NCOOK C.I7 CF3(CF2)7SO□NCH2So,HC2H. CF3(CF2)acON(CH2)2sOJ2H5 F -30 (SO3Na is o-, m- or p CF3(CF2)7SO3K CF, (CF2)ncH20sO3NaCF3(CF2
)6cOo(CH2)3sO3NaH(CF2)6CH
20(CH2)3SO3NaC+ 6H33cHcOO
cH2cFs03Na CI6H33CHCONHCH2CF2CF2Ho 3
Na CF3 (CF2), 5O2NCH2CH, 03O3HH
3rd position) H(CFx)scH2P(hH2 1((CF2)6PO3Na2 CF3(CF2)+2cOo(CH2CH20)20H
CF3(CF2)6CON(CH2)20(CH2CH
20) 8HCH. 2F5 CF3 CF3 cmc-CHF-CF3 C2F5 CH20(CH2CH20)7HCF3
CCCHF CF3 C2F5 Coo(CH2CH20)IHxF s 0ONa CF. C-CH-CF0ONa2F502F. CF3(CF2)7SO2N(CH,)20(CH,C
H20)2. HJ5 CF3 (CF, ri6cOo(CH2CH20)gcH3
H(CF2CF2)6CH20H H(CF2), CH20H CF3(CF2)6C00(CH2CHO)4(OH2
CH20)2oHH3 CF3(CF2)6C○○(CH2CHO)3(CH2
CH20)I. (C112), CH. CH3 CF 3 (CF 2 ) 7 S O2N H (CH2
), NΦ(CH3)3 bow θC2F. 03Na 2F5 (CH3COO)2CH(CF,)8CF3CH2CH
20H F-59 (CF3)2CFO(CF2)2CH2CH(CH2)
8COOH(CFri2CFO(C,F2)2C;H2C
O(CH2)scOOHH(CF2), C)120CI
(2'C)Ic)12SO3KH H CF3 H CF3 0(CHzCH20)aH These fluorine-containing compounds are described, for example, in US Pat. No. 2,559.
No. 751, No. 2,567.011, No. 2,732.3
No. 98, No. 2,764.602, No. 2,806,86
No. 6, No. 2,809,998, No. 2゜915.376
No. 2,915,528, No. 2,934,450, No. 2937.098, No. 2,957,031, No. 3,472,894, No. 3555.089, Special Publication No. 1977- No. 37304, JP-A No. 47-9631, Journal of the Chemical Society (J, Che
m, Soc, ) 1950, p. 2783, same 1957
, pp. 2754 and 2640, Journal of
The American Chemical Society (J, Am
er, Chem, Soc,) volume 79, page 2594 (1
957) and oil chemistry (J, Japan Oil Ch.
It can be synthesized according to the method described in Vol. 12, p. 653, etc. The amount of the fluorine-containing compound used in the present invention is 0.1 mg-log, preferably 1 mg to 1 g, per 1 m 2 of the silver halide photosensitive material. When added to a color developing solution, it is preferably 0.1 to 20 g per 1 ρ of the developing solution.
0.2 to 5 g is more preferable. The fluorine-containing compounds of the present invention may be used in combination of two or more. There are no restrictions on the method of adding the fluorine-containing compound of the present invention, such as adding it as a solution in water or an organic solvent, adding it as a powder or suspension by grinding it with a por mill, sand mill, etc., or adding it as a powder or suspension by dissolving it in a high-boiling organic solvent. , a method of adding it as an oil-in-water type emulsion, etc. is used. Regarding the silver halide photosensitive material In the present invention, a silver halide photosensitive material having a photosensitive layer (referred to as an emulsion layer) formed by coating a silver halide emulsion on a light-transmitting substrate is used. The light transmitting substrate used may be transparent or semitransparent as long as it has light transmittance. Furthermore, since the color filter is sometimes exposed to high temperatures during the vapor deposition process of transparent electrodes, it is preferable that the material of the light-transmitting substrate has good heat resistance. 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. The light-transmitting substrate can be used in the form of a plate, sheet, 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, but it is usually 0.5 μm to 10 m.
It is within the range of m. In particular, when glass is used as a light-transmissive substrate for a liquid crystal color display, the thickness is preferably within the range of 0.3 to 2 mm. 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 ±0.1 μm. In the present invention, it is preferable to provide a backing layer for the anti-plane layer on the surface of the light-transmissive substrate opposite to the surface on which the emulsion layer is formed. In this case, the dye or pigment contained in the banking layer is preferably a non-diffusible dye or pigment. Specifically, a carbon black dispersion can be suitably used. The carbon planar dispersion liquid may be produced by either the furnace method or the channel method, and for example, "Diablack" (manufactured by Mitsubishi Kasei Corporation) can be suitably used. The non-diffusible dye or pigment is contained in the backing layer in a state dispersed in a hydrophilic colloid, but it must not be eluted into each processing solution even after development. The light absorption properties of the dye or pigment used vary depending on the spectral absorption properties of the silver halide emulsion used in the present invention, but for example, when using a silver halide emulsion that has not been spectral sensitized with a sensitizing dye, It is preferable that the material absorbs light of 500 nm or less. Furthermore, the backing layer may contain a UV absorber. Ultraviolet absorbent L, TEHA, such as rtlVINtn M
S-40J (manufactured by BASF), rTINUVIN-PJ
(manufactured by Ciba Geigy). Non-diffusible dyes or pigments and ultraviolet absorbers are known high-boiling organic solvents and low-boiling organic solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexane, tetrahydrofuran, carbon tetrachloride, chloroform, etc. After dissolving in a solvent, it is mixed with an aqueous gelatin solution containing a surfactant, and then a stirrer and a homogenizer are used.
After emulsifying and dispersing it using a dispersing means such as a colloid mill, a flow jet mixer, or an ultrasonic dispersion device, it is used by adding it to a coating composition for a hydrophilic colloid backing layer. The amount of non-diffusible dye or pigment used is preferably 1 mg or more, particularly preferably 1 mg or more per 100 cm 2 of the light-transmitting substrate. Although the emulsion layer can be directly coated on the surface of the light-transmitting substrate, it is also possible to provide a subbing layer between the emulsion layer and the light-transmitting substrate. The subbing layer strengthens the adhesive force between the emulsion layer and the light-transmitting substrate, and if the surface of the light-transmitting substrate is rough, it smoothes the rough surface. Materials forming this undercoat layer include, for example, gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymer, polyvinylidene chloride copolymer, and polyvinylidene chloride copolymer. Mention may be made of acrylamide. The thickness of the undercoat layer is preferably thin considering the spectral characteristics of the color filter, and is usually 1 μm or less, preferably within the range of 0.05 to 0.5 μm. The silver halide emulsion layer used contains at least silver halide and a water-soluble binder, but may further contain a dye having a silver salt dye bleaching action. 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 desirable to use a silver halide with a small average grain size, and in particular, a silver halide with a small average grain size. It is preferable to use a so-called Lippmann emulsion having a luminance of less than lum. If the average particle size of silver halide is large, the image quality, mainly in terms of graininess, of the resulting color filter may deteriorate. Examples of the water-soluble binder include gelatin, albumin, casein, cellulose derivatives, starch derivatives, sodium alginate, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid copolymers, and polyacrylamide. These may be used alone or in combination of two or more. Among these, gelatin is preferred. One of the preferred embodiments of the present invention is that a silver halide emulsion layer contains a dye exhibiting a silver salt dye bleaching action. Examples of such dyes include phthalocyanine dyes,
Examples include azo dyes. Among azo dyes, bisazo dyes are particularly preferred, and are -No2H 2-COCH,H Compound QC) 13 0CH. OCH. -QC)I. 0CR2C) 120H OCR. -QC)I. -OCH. OCH, CH20H -OCR. -QC)l. 0CH3 QC) Is -0CI(3 OCH3 OCH3 OCH3 C〇- CO O- O O2- O2- CO CO O2 O The silver halide emulsion in the present invention contains silver halide, a water-soluble binder, and a dye ( The weight ratio of silver halide):(water-soluble binder) is 1 = 6 to 8:11, the weight ratio of dye to silver halide is 1/10 to 50, and the weight ratio of dye to water-soluble binder is 1/100. The emulsion layer is preferably formed by applying the emulsion onto the light-transmitting substrate using a conventionally known coating method such as a spinner coating method or a spray coating method. The thickness of the emulsion layer thus formed is usually in the range of 0.3 to 10 μm in terms of dry thickness.
If it is less than 3 μm, sufficient color development may not be achieved, while if it exceeds 10 μm, the light transmittance may decrease and the brightness of the color filter may become insufficient. In particular, in the present invention, the thickness of the emulsion layer is set to 0.5 to 3 μm.
By keeping it within this range, the spectral characteristics of the resulting color filter can be improved. One of the preferred embodiments of the present invention is a method described in detail above, in which the emulsion layer is processed using a silver halide photosensitive material in combination with an external color development method and a silver salt dye bleaching method. However, when this method is adopted, it is preferable to carry out processing using the silver salt dye bleaching method after all processing steps using the external color development method are completed. Next, a preferred embodiment of the production method of the present invention will be explained in this order by dividing it into a processing step using an external color development method and a processing step using a silver salt dye bleaching method. (Processing step using external color development method) In this method, it is preferable that all colored parts formed on the light-transmitting substrate by external color development method be formed in advance before applying the silver salt dye bleaching treatment. . Specifically, the silver halide photosensitive material is subjected to mask exposure for forming pixels, and then developed with a developer containing a color-forming coupler to form a colored portion. Exposure Processing Exposure methods that can be employed in the present invention include, for example, methods used in normal pattern exposure such as contact exposure, proximity exposure, and step exposure. In the pattern exposure, for example, as shown in FIG. 1, a photomask 14 is placed on a silver halide photosensitive material 13 having an emulsion layer 12 containing the silver salt dye exhibiting a bleaching action and laminated on a light-transmitting substrate 11. This is done by placing the photomask 14 on the photomask 14 and applying light from above. With this operation, 7
Portions 16 of the emulsion layer to be exposed corresponding to openings 15 provided in the otomask 14 can be selectively exposed. The size of the portion 16 to be exposed, that is, the size of the opening 15, can be appropriately set depending on the use of the color filter to be manufactured. However, if the width of the opening 15 is narrower than the wavelength of the light source used for exposure, effective exposure cannot be performed, so the width of the opening 15 is made wider than the wavelength. Since silver halide has effective photosensitivity to light in the range of 340 to 420 nm, the width of the opening 15 is usually 340 Hm or more, and considering its use as a color filter, The thickness is preferably 1 μm or more. In addition, in the case of a color filter for a liquid crystal display, in order to effectively reproduce colors by additively mixing red, blue, and green colored parts, the width of the opening 15 should be set to 10 mm.
It is preferable to set the thickness to 00 μm or less, particularly preferably 500 μm or less. Other conditions such as exposure time and light source can follow normal conditions. The non-processing color development method is a method in which a dye is dyed or precipitated into an emulsion layer by performing development using a developer containing one or more color couplers. The developer used contains at least a color forming coupler and a developing agent. As a developing agent, C.E.K. Meese, T.H. James (C, E, Ni, 1Jees an
dT. The Theory of the Photographic Process, 3rd Edition (The Theory of the Photographic Process) by James H.
of the Photographic Process
ss 3rd, Edition) J, pages 293 to 298, and specific examples include [1] 4-amino-3-methyl-N-(2-hydroquinethyl)aniline Sulfate (2) N-ethyl-N-methoxyethyl-3-methyl-
p-phenylenediamine/p-toluenesulfonate (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 hydrochloride, 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. The developing agent in the developing solution is usually used in a content within the range of 0.1 to 10 g in the developing solution 1Q. If the content of the developing agent is less than 0.1 g, effective development may not be possible, and even if more than 10 g is used, not only will no significant improvement in developability be observed, but depending on the type of developing agent. may not dissolve sufficiently. In particular, it is preferable to use the developing agent in the developer solution Ia in an amount of 0.5 to 7 g, and it is particularly preferable to use the developing agent in the range of 1 to 5 g. By setting the amount of the developing agent within this range, regardless of the type of color forming coupler used,
Development time at normal density is within an appropriate range (e.g. 1 to I
(within a range of 0 minutes), resulting in very good workability. Furthermore, by keeping it within this range, the coloring property becomes particularly good. The color forming coupler 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 at least 16 part thereof is dissolved in the developer. This is an external coupler, and any known external coupler can be used. Among the above-mentioned color couplers, examples of yellow couplers include ketomethylene compounds (e.g. σ-(4-
(carboxyphenoxy)-α-pivaloyl-2,4-dichloroacetanilide); furthermore, U.S. Pat.
'306, No. 3,619,189, Special Publication No. 40-3
Those described in No. 3775 and No. 44-3664 can be used. Examples of magenta coloring couplers include active methylene compounds (for example, pyrazolones such as 1-(2,4,6-dolichlorophenyl)-:3-(p-nitroanilino)-5-pyrazolone, 7-chloro- 3-phenyl6-ituprobyl-IH-pyrazolo[5,l-cl-1,24
- pyrazoloazoles such as triazoles and cyanoacetanilides), furthermore OLS 2,016,587, U.S. Pat.
No. 52.896, No. 3,615,502, Special Publication No. 1977
-133111 etc. can be used. Furthermore, examples of cyan color-forming couplers include phenol compounds (e.g., 2-acetamido-4,6 dichloro-5-methylphenol) and naphthol compounds (e.g., N-(2-acetamidophenethyl)-1-
hydroxy-2-naphthamide),
Also, U.S. Patent No. 3,002,836, U.S. Patent No. 3.54255
No. 2, British Patent No. 1,062.190, etc. can be used. In addition to the above, rThe Theory of
the Ph. tographic Process 3rd Edi
tionJ (cited above), Chapter 17. It is also possible to use those described on pages 382-395. In the developer, the total content of color forming couplers in the developer 112 is preferably set within the range of 0.1 to 20 g. If it is less than 0.1 g, the color may not develop sufficiently, while if it is more than 20 g, so-called fogging may occur. Particularly in the present invention, by controlling the total content of color forming couplers in the developer IQ within the range of 0.2 to log, a color filter with less color turbidity and good spectral characteristics can be obtained. The blending ratio of color-forming couplers exhibiting different color development in this developer can be appropriately set in consideration of the color-forming properties of the color-forming couplers used. For example, when combining a cyan color-forming coupler and a magenta color-forming coupler, the weight ratio of both is usually 1:9 to 7:3.
Preferably it is within the range of 1:9 to 4:6. Further, when a cyan color-forming coupler and a yellow color-forming coupler are combined, the weight ratio of both is usually in the range of 1:9 to 7:3, preferably 1:9 to 4:6. Furthermore, when combining a magenta coloring coupler and a yellow coloring coupler, the weight ratio of both is usually 9:1 to 2:8,
Preferably it is within the range of 8:2 to 6:4. When combining a color-forming coupler, a magenta color-forming coupler, and a yellow color-forming coupler, it is preferable to mix approximately the same amount of each of the three. In addition, the blending weight ratio of the total amount of color couplers and the developing agent in the developer that can be suitably used in the external color development method of the present invention depends on the type and content of the color couplers and the developing agent, etc. The weight ratio of the color forming coupler and the developing agent can be set appropriately in consideration of the above, but usually the weight ratio of the color forming coupler and the developing agent is within the range of 1:9 to 9:1. Additionally, the developer may contain preservatives (e.g., sodium sulfite,
diethylhydroxylamine), accelerators (e.g. alkaline agents such as sodium hydroxide), control agents (e.g. potassium bromide, potassium iodide), auxiliary agents (e.g. polyethylene glycol nanowater conditioner, citrazic acid, imidazole) It may also contain additives contained in ordinary external developers, such as color toning agents such as derivatives. A developer can be prepared by dissolving the above components in water. Note that the developer should be used at a normal operating temperature (for example, 10 to 40°C).
It is used after adjusting the pH value in C) using sodium hydroxide or the like so that the pH value falls within the range of 9.0 to 13.0. In the method of the present invention, pixels can be formed by external color development using the developer as described below, for example. First, the silver halide photosensitive material is pattern-exposed by a conventional method (first exposure). After performing the first pattern exposure, a first development of the exposed area is performed using a developer containing the color forming coupler. For example, by performing development using a developer containing a cyan coupler and a magenta coupler as color couplers (previous developer), the exposed area is developed blue. Further, by using a developer (green developer) containing a cyan color-forming coupler and a yellow color-forming coupler, the exposed area is developed green. Further, by using a developer (red developer) containing a magenta color-forming coupler and a yellow color-forming coupler, the exposed area is developed in red. Also, a developer containing a cyan coloring coupler (cyan developer)
, by using a developer containing a magenta color-forming coupler (magenta developer) and a developer containing a yellow color-forming coupler (yellow developer), the exposed areas become cyan and cyan, respectively.
Developed to magenta and yellow colors. The first exposed area is developed using any one of a cyan developer, a magenta developer, a yellow developer, a blue developer, a green developer, and a red developer depending on the purpose. After the first exposed area is developed in this way, the photosensitive material is usually immersed in a stop solution containing an acid such as acetic acid to stop the reaction accompanying the development, then washed with water, and then, usually, a bleach solution is added. Alternatively, by dipping in a black and white developer to prevent color turbidity in the first development area during the second and subsequent development processes, and then washing with water and drying, red, blue, green, cyan, magenta, and yellow colors can be created. The first one having any pixel of
Forms colored parts. Next, using a photomask, the unexposed area adjacent to the first exposed area is pattern-exposed in the same manner as the first exposure, and then a developer other than that used in the first step is used. Develop using one of the following. Further, if desired, a second colored portion can be formed by performing steps such as immersion in a bleach solution or a black and white developer, washing with water, and drying. Similarly, the unexposed portion adjacent to the second colored portion is exposed in a pattern, and then developed using a developer other than that used in the first and second steps. Further, if desired, a third colored portion can be formed by performing steps such as dipping in a bleach solution or a black and white developer, washing with water, and drying. In one example of a preferred embodiment of the present invention, after forming the first to third colored portions as described above, a silver salt dye bleaching treatment described in detail below is performed. (Processing step by silver salt dye bleaching method) In this method, after forming all the colored parts by the external color development method, a silver salt dye bleaching process is performed to remove the silver salts contained in the silver halide photosensitive material. Decolorizes pigments that exhibit a pigment bleaching effect. The processing steps by the silver salt dye bleaching method include at least black and white development, dye bleaching, and silver bleaching in this order. Next, the processing steps by the silver salt dye bleaching method will be divided into black and white development processing, dye bleaching processing, and silver bleaching processing, and will be explained in this order. Black-and-white development processing In this method, the photosensitive material is subjected to image exposure in the same pattern as the desired colored part pattern among the patterns of each colored part formed by the above-mentioned external color development method.
A black-and-white development process using a black-and-white developer is performed to form a reduced silver image on the light-sensitive material. The black and white developer used is, for example, a developing agent [hereinafter referred to as developing agent (D). ], a developing aid, a preservative, a so-called developing antifoggant, an alkaline buffer, and, if necessary, a solvent for the developing agent (D) and the developing aid. Examples of the developing agent (D) include hydroquinone, chlorohydroquinone, and catechol. Examples of the development aid include pyrazolone, pyrazolone derivatives, metol, and the like. Preservatives include sulfites, ascorbic acid, and the like. Examples of the development antifogging agent include bromide and benzotriazole. Examples of alkaline buffers include carbonates, hydroxides, phosphates, borates, and metaborates. Examples of the solvent for the developing agent (D) and the developing aid include ethylene glycol, triethanol, and jetanol. An example of the content of the various components in the black and white developer is 1 to 20 g of developing agent (D). Development aid 0.
05-8g/α, preservative 1-120g/α, development antifoggant 0.001-5g/α, alkaline buffer 0.1-
The amount is 50 g/α, and when a solvent for a developing agent and a developing aid is used, the amount is 1 to 20 mQ/Q of the solvent. The black-and-white development process is usually carried out by immersing the image-exposed photosensitive material in a black-and-white developer at 20 to 60° C. for 10 to 200 seconds. Photosensitive material (A) image-exposed by this black-and-white development process
A reduced silver image (silver negative image) is generated inside. After the black-and-white development process, a washing process is usually performed, and then a dye bleaching process, which will be described in detail below, is performed. Dye Bleaching Process In the dye bleaching process, a dye bleaching solution is used to bleach the pigment of the dye contained in the light-sensitive material. That is, this dye bleaching process is a process in which a positive image of the dye is formed by bleaching the dye in the dye contained in the image-exposed light-sensitive material in the portion containing a large amount of image silver. The dye bleach solution used contains, for example, a bleaching agent, a silver salt or a compound forming a silver complex, and a dye bleach accelerating catalyst. Examples of bleaching agents include mineral acids such as hydrochloric acid, sulfuric acid, and nitric acid; organic acids such as sulfamic acid, succinic acid, and acetic acid. Examples of compounds that form silver salts or silver complexes include potassium bromide, potassium iodide, urea, thiourea, semicarbazide, thiosemicarbazide, and the like. Examples of dye bleaching accelerating catalysts include pyrazine, naphthazine, quinoline, quinoxalines, phenazines, anthraquinones, naphthoquinones, indophenazines, N
-Substituted isoalloxazines, floquinoxalines, chietukizalines, diphenyl derivatives, triphenylmethane derivatives, lumazines, alloxazines, cinnolines, orthophenylenediamine derivatives, etc. (U.S. Pat. No. 2,270,118, 2,410.02
No. 5, No. 2,541゜884, No. 2,627,461
No. 2,669,517, British Patent No. 657,374
No. 711.247, Japanese Patent Publication No. 45-22195, etc. ). Examples of the contents of the various components in the dye bleaching solution include: 1 to 20 g/I2 of bleach, 0.1 to 20 g/(1) of silver salt or a compound forming a silver complex, and 0.1 g/(1) of dye bleach accelerating catalyst. 001-10g/it'.Dye bleaching treatment is usually carried out at 20-60°C and 10-20g/it'.
This is done by immersion in a dye bleach solution for 0 seconds. By this dye bleaching treatment, the silver-rich portions of the image-exposed photosensitive material are bleached to form a positive dye image. Black silver that is not used to bleach the dye may remain as it is. After the dye bleaching treatment, a washing treatment with water is usually performed, and then the silver bleaching treatment described below can be performed. Silver bleaching process Silver bleaching process is a process in which all black silver remaining in the image-exposed light-sensitive material that has been subjected to the dye bleaching process is rehalogenated. A silver source white liquor is used for this silver bleaching treatment. The silver source white liquor may be a conventionally known one, and for example, a bleaching liquor containing a ferric chelate of ethylenediaminetetraacetic acid can be suitably used. Silver bleaching is usually carried out at 18-60°C for 5-500 seconds. After performing the above processing, washing with water, fixing processing to remove silver halide in the photosensitive material, and further washing with water.
dry. (Regarding the exposure/processing process) Next, a preferred exposure/processing process in the present invention will be explained. For example, Table A shows the pattern of the exposure and processing process when forming a color filter having B (pixel for transmitting blue light), G (pixel for transmitting green light), and R (pixel for transmitting red light) shown in FIG. Shown below. Each colored part shown in the second factor is yellow pigment (M or M2)
, magenta dye (Yl or Y2) and cyan dye (C+
or C2), containing two different color pigments. Table A shows the method for forming each of these dyes. That is, in this method, after forming a dye image at the location indicated by GA in Table A by employing an external color development method,
A silver salt dye bleaching method is used to erase the color of the dye in areas other than the areas indicated by SDR, which exhibits a silver salt dye bleaching action. For example, in the pixel forming pattern shown in pattern example (3) in Table A, first, the blue light transmitting pixels are pattern-exposed in the manner described above in the first exposure/processing process. Thereafter, development is performed using an external developer containing a magenta color-forming coupler. Next, after the green light transmitting pixels are pattern-exposed in a second exposure/processing process, a development process is performed using an external developer containing a yellow color-forming coupler and a cyan color-forming coupler. Subsequently, after the red light transmitting pixels are pattern-exposed in a third exposure/processing process, development is performed using an external developer containing a yellow color-forming coupler and a magenta color-forming coupler. Finally, after the green light transmitting pixels and the red light transmitting pixels are pattern-exposed, the silver salt dye bleaching treatment is performed. Here, regarding the order of exposure and processing of blue light transmitting pixels, green light transmitting pixels, and red light transmitting pixels, silver salt dye bleaching treatment is performed after all external color development treatments are completed. There are no particular restrictions. Further, the arrangement of the blue light transmitting pixels, the green light transmitting pixels, and the red light transmitting pixels is not defined as shown in FIG. 2. (Others) In the method of the present invention, a red part (R), a blue part (B) and a green part (G
) were formed with gaps between them, pattern exposure was applied to these gaps, and then a developer containing a cyan coloring coupler, a magenta coloring coupler, and a yellow coloring coupler was used. By performing the development process, the red part (R) and the blue part (B
) and the green part (G), a light-impermeable section (black stripe) 33 can also be formed. Also in this case, the silver salt dye bleaching process is preferably carried out after all external development processes have been completed. Further, in the method of the present invention, it is also possible to perform an etching process on the color filter layer to remove unnecessary portions of the color filter layer, depending on the use of the color filter. Furthermore, the pixel formation mode may be either mosaic or striped. The color filter thus obtained can be suitably used, for example, as a filter for a liquid crystal color display as shown in FIG. That is, if the color filter 43 is arranged so that the color filter 43 and the liquid crystal 47 controlled by the electrodes 48a and 48b are sandwiched between the polarizing plates 46a and 46b as shown in FIG. Can be used as a filter. Furthermore, it can also be suitably used in place of other conventionally used color filters for image pickup tubes. [Example] Next, the present invention will be explained in more detail with reference to Examples. Note that % in the examples represents weight % unless otherwise specified. Example I Preparation of silver halide photosensitive material Silver iodobromide containing 4 mol% silver iodide was prepared by simultaneously adding an aqueous silver nitrate solution and an aqueous solution containing potassium bromide and potassium iodide to a 10% aqueous solution of gelatin. An emulsion (average particle size: 0.05 μm, gelatin concentration: 9%) was prepared. The addition conditions were regulated so that a Lippmann emulsion having an average grain size and diameter of 0.05 μm was obtained. The resulting silver iodobromide emulsion contained 28.3 mg per mole of silver.
of sodium thiosulfate pentahydrate was added thereto and chemically aged at 59.5°C for 45 minutes. Then, l-phenyl-5-mercaptotetrazole and l-carboxyethyl-34,5-hydroxybenzene were added to the emulsion at 141.5 mol/silver, respectively.
mg, 3.40g, and the following compound SC-
An emulsion coating solution was prepared by adding 15.9 g of 1 per mole of silver, and further adding 40 mg and 5 mg of the following compounds H-1 and H-'2 per 1 g of gelatin as hardeners, respectively. SC-1 H-1 ((CH* = CH302CHz) 3ccH2sO
*cH2cH2) 2NCH2CH2503K The obtained emulsion coating solution was coated on a 1.1 mm thick transparent borosilicate glass substrate (30 cm x 30 cm) to a dry film thickness of 3 μm, and a silver halide photosensitive film having an emulsion layer was formed. The material was prepared. The amount of silver coating is 1.5 g/m2, and the amount of pigment coating is 0.
It was 24g/m2. The photosensitive material thus produced was designated as Photosensitive Material-1. In addition, in the manufacturing process of Sensitive Material-1, a 1% solution of a surfactant containing each of the compounds shown in Sensitive Materials 2 to 9 in Table 1 was added to the emulsion coating solution, and the volume of the emulsion coating solution per mole of silver was determined. Photosensitive materials-2 to 9 were prepared in the same manner except that the amount of water added was adjusted so that the volume was the same as the volume of the emulsion coating solution in the manufacturing process of photosensitive material-1. The amount of silver is 15g/
n+2, the amount of dye applied was 0.24 g/m2, and the amount of fluorine-containing compound applied was 90 mg/m'. The silver halide photosensitive materials mentioned above all have a backing layer on the surface of the borosilicate glass substrate opposite to the surface having the emulsion layer. The formation of this backing layer will be explained next. Add the following dispersion of compound Y-1 to an aqueous gelatin solution, and add 40 mg each of hardeners H-1 and H-2.
Here, the amount of gelatin added to the aqueous gelatin solution was adjusted in advance so that it was 5%. Also, the amount of Yl added in 100 m of the aqueous gelatin solution (the amount of Yl added in 2 was 1%).
．． It was 35%. Thereafter, this aqueous gelatin solution was applied to the borosilicate glass substrate and dried to form a backing layer. Y-
The amount of 1 added was lomg/d+++''.The above-mentioned dispersion liquid was dissolved per 1g of Y-1 in 1g of tricresyl phosphate and 4.29v2 of ethyl acetate, and then 0.83g of seratin and 0.83g of triisopropyl β were added. - 2.63 m of 5% aqueous solution of sodium naphthalene sulfonate
Addition and mixing to an aqueous solution containing C and water 8.4mα
After ultrasonic dispersion at ℃, ethyl acetate was removed, and water was added to make 17.6 mff, and three colors (blue), G (green), and R (red) were prepared as shown in Figure 2. A method for manufacturing a color filter having a mosaic pattern will be described below. The size of each pixel is 150μm×15
It is 0 μm. On each of the above silver halide photosensitive materials, one side or 150μ
A chromium mask for a color filter having a square opening of m in size was overlaid, and a first exposure was performed using a tungsten lamp. Exposure was carried out at a position corresponding to part B in the second area. The exposed photosensitive material is heated to the following magenta color developer at 23°C.
immersed in water for 3 minutes. Magenta color developer composition Magenta coupler...0.26g6-
t-Butyl-7-chloro-3-(3-methylbutyl) I
H-pyrazolo[3,2-c]-1,2,4-triazole coupler (WE-20)...0.
6g developing agent・・・・・・・・・・・・ 2,0g4
-Amino-3-methyl-N-ethyl-N-β methanesulfonamide ethylaniline 11/2 sulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3. 00mff Anhydrous sodium sulfate...20.0g Sodium bromide...1.0g Sodium sulfite...
......1O, 00g ethylene glycol...
...10.0+nQ polyethylene glycol...
・・・ Add 2.0g water
Note that sodium hydroxide was added to the above magenta color developer to adjust the pH value at 25°C to 12.0. Next, after washing with water for 1 minute, bleaching was performed by immersing it in a silver source white liquor having the following composition for 3 minutes, washing with water for 4 minutes, and then drying to form a blue part on the substrate (first treatment )
. Silver source White liquor composition Ethylenediaminetetraacetic acid iron (I[I) ammonium salt.
・・・・・・・・・200.0g Ammonium bromide・・・・・・・・・ 1O, 0g Glacial acetic acid・・・・・・・・・・・・・・・・・・・・・・・・ 1000+n++ Add water to set If. , pH=6. using ammonia water.
Adjust to 0. Next, another chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was part G in FIG. 2, and a second exposure was performed. The photosensitive material subjected to the second exposure was immersed in a yellow color developer having the composition shown below at 23°C for 3 minutes, washed with water for 1 minute, and then bleached, washed with water, and dried in the same manner as the first time, and then placed on a substrate. A green part was formed on (second treatment). Yellow color developer composition Yellow coupler... 1.5ga-(
4-carboxyphenoxy)-αpivaloyl-2,4-
Dichloroacetanilide developing agent・・・・・・・・・
... 2.0g 4-amino-3-methyl-N-ethyl-N-β methanesulfonamidoethylaniline φ11/
Disulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3.00 m 12 Anhydrous sodium sulfate 20.0 g Sodium bromide ...3.0g sodium sulfite
・・・・・・・・・ 10.00g ethylene glycol・
...... IO, Om (2 polyethylene glycol... Add 2.0g water
Note that by adding sodium hydroxide to the above yellow color developer, the pH value at 25°C is 12.
．． I adjusted it so that it was 0. Next, another chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was the R area in FIG. 2, and a third exposure was performed. The photographic material subjected to this third exposure was immersed in a red color developer having the composition shown below at 23°C for 3 minutes, and then washed, bleached, washed with water and dried in the same way as the second exposure, and then placed on a substrate. A black part was formed (third process). Red color developer composition Magenta coupler...0.28g6-
t-Butyl-7-chloro-3-(3-methylbutyl)l
H-pyrazolo[3,2-c14,2.4-triazole coupler (WE-20)...0.
32g yellow coupler・・・・・・・・・ l-4
2gσ-(4-carboxyphenoxy)-αpivaloyl-2,4-dichloroacetanilide developing agent...
・・・・・・・・・ 2.0g4-amino-3-methyl-
N-Ethyl-N-β-methanesulfonamide ethylaniline 11/2 sulfate l hydrate Sodium nitrilotrimethylenephosphonate (40% aqueous solution) 3-03-0O anhydrous sodium sulfate・・・・・・・・・ 20.0g Sodium bromide ・・・・・・・・・・ 3.0g Sodium sulfite・
・・・・・・・・・ 10.00g ethylene glycol・
...... lo, 00mQ polyethylene glycol... Add 2.0g water
112 Furthermore, by adding sodium hydroxide to the above red color developing solution, the pH value at 25°C is 12,
I adjusted it so that it was 0. Next, a chrome mask for a color filter was placed on the photosensitive material after the above processing so that the exposed area was the R area in FIG. 2, and a fourth exposure was performed. The photosensitive material subjected to the fourth exposure is processed at 330C as follows to form a red part (fourth exposure).
A color filter was obtained having a mosaic pattern of three colors: Geography), B (blue), G (green), and R (red). Black and white development 1 minute water wash 1 minute dye bleach 1 minute water wash 1 minute silver
Bleach 6 minutes in water
Wash, fix for 1 minute, wash with water for 1 minute
Drying for 4 minutes The bath used for each treatment had the following composition. Black and white developer composition Sodium sulfite 10g Hydroquinone 10g Potassium hydroxide (48
% aqueous solution) 5+++Q diethylene glycol
20m12 Jimaison
0.7g sodium carbonate 2
Add 0g potassium bromide 2g thiadiazole 0.05g water
1 (1 Dye bleaching solution composition 96% sulfuric acid 40m + 2 Potassium iodide 15g2.3.6- Add trimethylquinoxaline 2g water
112 Silver bleaching solution composition Pure water 800tQ Sodium ferricyanide 206g Sodium bromide 15g Borax
Add 1g water
Adjust Q (p)I to 8.0 using an aqueous potassium hydroxide solution. ) Fixer composition Ammonium thiosulfate 175.0g Sodium sulfite 8.5g Sodium metasulfite 2.3g Add water
lQ (adjusted to pH=6.0 using acetic acid)
After the color filter was prepared, the backing layer was completely removed by impregnating the backing layer with a 3% aqueous solution of sodium hypochlorite and wiping it off with gauze. The color filters obtained in this way were sample No.
1 to 9. In the manufacturing process of samples No. 1 to 9, photosensitive material sample N
2.5, and the amount of color coupler in the magenta color developer and the red color developer and the type and amount of the coupler were changed as shown in Table 2.
0 to 17 were produced. However, Sample Nos. 10, 12, 14 and 16 use photosensitive material samples No.: 2, and Samples No. 11, 13.
15 and 17 are shown in Table 2: Amount of color coupler in magenta color developer and red color developer, type and amount of viscous coupler, type and amount of coupler and developing agent in each external type developer, and previous sample No. 1 to 1. Sample No. 1, except that the types and amounts of couplers and developing agents in the magenta color developer, yellow color developer, and red color developer in the manufacturing process of No. 9 were changed as shown in Table 3.
In the same manner as ~9, color filter sample No. 18~
Sample No. 1 of the obtained color filter
26, blue light (B), green light (G), red light (
As a result of scanning the density of blue light transmitting pixels and red light transmitting pixels using a microdensitometer with an aperture scanning area of 250 μm2 using R), the difference in concentration between samples in each pixel was determined by the concentration distribution [ (Standard deviation) / (Average concentration) x 100] ±
It was small, within 3%. Further, for each sample, the difference in level between each pixel and the state of the protrusion formed on the sample surface of each pixel were examined using a Clear Step manufactured by Rank Taylor Hobson Co., Ltd. The step difference between each pixel when protrusions were ignored was within 0.05 μm in all color filter samples. or,
The presence of protrusions is shown in Table 4. In each color filter sample, for each blue light transmitting pixel and red light transmitting pixel, each side of a 500-pixel square pixel and horizontally on the l line at the center of the pixel. , measured by the above device, 0
．． The number of protrusions larger than 1 μm and 0.2 μm is shown as an average value for one pixel. Table 4 Number of protrusions within one pixel From the results in Table 4, the number of protrusions on the sample surface after color filter production is very small in the samples of the present invention. In addition, after preparing the sample of the color filter, the turbidity of the magenta color developing solution and the red color developing solution was measured using a turbidity meter 30 minutes after development. Compared to the developer used to create the sample, the level of turbidity in the developer was very low, and it was almost transparent. When 10 identical samples were prepared in the sample preparation process for each color filter, this tendency was further expanded. In addition, when the same measurements as shown in Table 4 were performed on the 10th color filter sample, the number of protrusions on each pixel tended to increase in each sample, but the sample of the present invention showed a tendency to increase.
It increased by 0 to 50% compared to the first sample, whereas it increased by 100 to 180% in the comparison sample. As described above, in the present invention, the color filter surface exhibits excellent smoothness, and the fatigue of the developer is small, and the number of times the developer needs to be replaced is reduced, thereby reducing manufacturing costs.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing an example of pattern exposure in the manufacturing method of the present invention, and FIG. 2 is a cross-sectional view showing an example of a color filter obtained by the manufacturing method of the present invention.
FIG. 3 is a cross-sectional view showing another example, and FIG. 4 is a cross-sectional explanatory view showing an example of a liquid crystal color display using a color filter obtained by the manufacturing method of the present invention. 11... Light-transmitting substrate 12... Emulsion layer 13...
Silver halide photosensitive material 14... Photomask 15... Opening 16... Area to be exposed 21.31
...Light-transparent substrate 22.32...Colored part 33...
・Black stripe 43...Color filters 46a, 46b...Polarizing plate

Claims (1)

[Scope of Claims] A color filter consisting of three primary colors of light, produced by color development using a silver halide photosensitive material having a photosensitive layer on a light-transmissive substrate, [1] having the following general formula: [1]
[2] At least one color pixel contains at least one substantially colorless compound formed by a coupling reaction between a precursor compound represented by the formula and an oxidized product of a color developing agent; A color filter characterized by containing a fluorine surfactant. General formula [1] ▲ Numerical formulas, chemical formulas, tables, etc. is a group of atoms necessary to form a 5- to 6-membered heterocyclic nucleus containing at least one nitrogen atom, sulfur atom, or oxygen atom (the heterocyclic nucleus may further form a fused ring with another ring) , and may have a substituent on the ring). ]