JPH03198050A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a photographic sensitive material ensuring high coupling reactivity and high dye absorption density by incorporating a specified cyan dye forming coupler into an emulsion layer or other layer. CONSTITUTION:When at least one silver halide emulsion layer is formed on a substrate to obtain a color photographic sensitive material, a cyan dye forming coupler represented by formula I is incorporated into the emulsion layer or other layer. In the formula I, R<1> is alkyl, alkenyl, cycloalkyl, etc., R<2> is a group substitutable on the benzene ring, each of R<3> and R<4> is H, alkyl, alkenyl, cycloalkyl, etc., R<5> is aryl, L is O or S, Z is H or a group releasable by coupling and l is an integer of 0-4. A sensitive material ensuring high coupling reactivity and high dye absorption density is obtd.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material containing a novel phenolic cyan dye-forming coupler. (Prior art) When a silver halide photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic-grade amine developer and a dye-forming coupler (hereinafter referred to as coupler) react to form a color image. be done. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce blue, green, and red, color images of yellow, macenta, and cyan, which are complementary colors, are formed, respectively. Phenol derivatives or naphthol derivatives are often used as couplers to form cyan images. In color photography, one-color-forming couplers are added to the developer solution or incorporated into the light-sensitive photographic emulsion layer or other color image-forming layer, and react with the oxidized product of the color developer formed by development. This forms a non-diffusible dye. The reaction between the coupler and the color developing agent takes place at the active site of the coupler, and a coupler having a hydrogen atom at the active site is a 4-equivalent coupler, i.e. stoichiometrically requires 4 moles of development to form 1 mole of dye. It requires silver halide with a nucleus. On the other hand, those having a group that can leave as an anion at the active site are 2-equivalent couplers, that is, couplers that stoichiometrically require only 2 moles of silver halide having a development nucleus to form 1 mole of dye. Therefore, compared to a 4-equivalent coupler, the amount of silver halide in the photosensitive layer can be generally reduced and the film thickness can be made thinner, making it possible to shorten the processing time of the photosensitive material and further improving the sharpness of the color image formed. improves. By the way, among cyan couplers, naphthol type couplers are used because the absorption of the generated dye image has a sufficiently long wavelength, there is little overlap with the absorption of the macenta dye image, and the coupling reactivity with the oxidized form of the color developer is low. Since it can be selected up to high prices, it has been widely used for photographic purposes, mainly color negative films. However, dye images obtained from naphthol-type couplers tend to be reduced and faded by divalent iron ions that accumulate in tired bleach or bleach-fix baths (referred to as reductive fading), and their heat fastness is poor. , improvements were strongly desired.・On the other hand, U.S. Patent No. 4,333,999 has a p-cyanophenylureido group at the 2-position and a ballast group (
A phenol type cyan coupler having a carbonamide group which is a diffusion resistance imparting group) is disclosed. These couplers undergo a bathochromic shift when the dyes associate in the film, giving dye images with excellent hue, and are also excellent in fastness, so they are widely used as couplers to replace the naphthol-type cyan couplers. It's starting to happen. (Problems to be Solved by the Invention) However, in recent years, the performance requirements for photographic materials have been severe, and these couplers have not been sufficient, and higher coupling reactivity and higher dye absorption density have been continuously sought. U.S. Pat. No. 4,772,543 discloses a 2-(phenylureido)-phenol type cyan coupler having an alkylamido group substituted with a substituted phenoxy group or a substituted phenylthio group at the 5-position. Also, JP-A-63
No. 161450 discloses a 2-(4-cyanophenylureido)-phenol type cyan coupler having an alkylamido group substituted with a substituted phenoxy group or a substituted phenylthio group at the 5-position. However, these cyan couplers did not provide a satisfactory answer to the above requirements for higher coupling reactivity and higher dye absorption density. An object of the present invention is to provide a silver halide color photographic light-sensitive material containing a novel cyan coupler that satisfies the above requirements for a cyan coupler that provides high coupling reactivity and high dye absorption density. (Means for Solving the Problems) In order to achieve the above object, the present inventors have carried out research and development, and as a result, they have found that the acyl group is particularly at the ortho position of the phenyl group in the 5-ballast group of the 2-ureido cyan coupler. It has been discovered that by introducing a group, a cyan coupler can be obtained which provides high coupling reactivity and high dye absorption density, and the present invention has been completed. That is, the above object is a color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the same layer as the emulsion layer or a different layer having the following formula (I
) This was achieved by a silver halide color photographic light-sensitive material characterized by containing a cyan dye-forming coupler represented by: General formula (RI01 (Formula, l' (l represents an alkyl group, alkenyl group, cycloalkyl group, or aryl group, R3 represents a group that can be substituted on the Benyan ring, R3 and 1 (4 is a hydrogen atom) , or represents an alkyl group, alkenyl group, cycloalkyl group, or aryl group, R3 and R4 may be the same or different, R% represents an aryl group, L is an oxygen atom or sulfur represents an atom, Z represents a hydrogen atom or a coupling-off group, I
l is an integer from 0 to 4. ) In E, the groups defined as R1 to R' further include those having a substituent. The cyan coupler represented by general formula (I) will be explained in detail below. In general formula (I), R1 is preferably a linear or branched alkyl group having a total number of carbon atoms (hereinafter referred to as C number) of 1 to 36 (more preferably 6 to 24), or More preferably a linear or branched alkenyl group having 6 to 24 carbon atoms, a 3 to 12-membered cycloalkyl group having 3 to 36 carbon atoms (more preferably 6 to 24 carbon atoms), or a 3 to 12-membered cycloalkyl group having 6 to 36 carbon atoms (more preferably 6 to 24 carbon atoms) represents an aryl group (6 to 24), and these represent substituents (e.g. halogen atom, hydroxyl group, carboxyl group, sulfo group, cyano group, nitro group, amino group, alkyl group, alkenyl group, alkynyl group, cycloalkyl group) group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl R1 is preferably a Straight chain, branched chain or substituent (alkoxy group, alkylthio group, aryloxy group, arylthio group, alkylsulfonyl group,
an alkyl group having an arylsulfonyl group, an aryl group, an alkoxycarbonyl group, an epoxy group, a cyano group, or a halogen atom [e.g., n-octyl, n-decyl,
n-dodecyl, n-hexadecyl, 2-ethylhexyl, 3.5.5-1-limethylhexyl, 3,5.5-trimethylhexyl, 2-ethyl-4-methylpentyl, 2
-hexyldecyl, 2-hebutylundecyl, 2-octyldodecyl, 2,4.6-trimethylhebutyl, 2.
4.6.8-tetramethylnonyl, benzyl, 2-phenethyl, 3-(t-octylphenoxy)propyl,
3-(2,4-di-t-pentylphenoxy)propyl, 2-(4-biphenyloxy)ethyl, 3-dodecyloxypropyl, 2-dodecylthioethyl, 9°10
-Epoxyoctadecyl, dodecyloxycarbonylmethyl%2-(2-naphthyloxy)ethyl], unsubstituted or substituted (e.g. halogen atom, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group or alkoxycarbonyl group) [e.g., allyl, 10-undecenyl, oleyl, citronellyl, cinnamyl], a cycloalkyl group that is unsubstituted or has a substituent (halogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, or aryloxy group) [For example, cyclopentyl, cyclohexyl, 3,5-dimethylcyclohexyl, 4-t-
Butylcyclohexyl J, or an aryl group that is unsubstituted or has a substituent (halogen atom, alkyl group, alkoxy group, alkoxycarbonyl group, aryl group, carbonamide group, alkylthio group, or sulfonamide group) [e.g. phenyl, 4-dodecyl oxyphenyl, 4
-biphenylyl, 4-dodecanesulfonamidophenyl, 4-t-octylphenyl, 3-pentadecylphenyl]. In general formula (I), R3 is a group that can be substituted on the benzene ring, preferably a group selected from the above substituent group A, and when β is plural, Hs may be the same or different. R8 is more preferably a halogen atom (F, C11, Br, 1), a C1-24 alkyl group (e.g. methyl, butyl, shi-butyl, shi-octyl,
2-dodecyl), C3-24 cycloalkyl group (e.g. cyclopentyl, cyclohexyl), C1-24
alkoxy groups (e.g. methoxy, butoxy, dodecyloxy, benzyloxy, 2-ethylhexyloxy,
3-dodecyloxybroboxy, 2-dodecylthioethoxy, dodecyloxycarbonylmethoxy), C number 2~
24 carbonamide groups (for example, acetamide, 2-ethylhexanamide, trifluoroacetamide) or C1-24 sulfonamide groups (for example, methanesulfonamide, dodecanesulfonamide, toluenesulfonamide). In general formula (I), 2 is preferably an integer of 0 to 2, more preferably an integer of 0 or 1. In general formula (I), R'' and R4 are hydrogen atoms, C number is 1
~36 (preferably 1 to 24) alkyl group, C2~
36 (preferably 2 to 24) alkenyl group, C number 3 to
36 (preferably 5 to 24) cycloalkyl group, C 7 to 36 (preferably 7 to 24) aralkyl group, or C 6 to 36 (preferably 6 to 24) aryl group, and these groups may be substituted with a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, or an alkoxycarbonyl group. Examples of R and R4 include a hydrogen atom, methyl, ethyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, allyl, hexenyl, phenoxymethyl,
Examples include cyclopropyl, cyclopentyl, cyclohexyl, hexadecyl, benzyl, phenethyl, phenyl, tolyl, 4-methoxyphenyl, and the like. R3 and R4 are preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably a hydrogen atom or an alkyl group. In the general formula (+), L represents an oxygen atom or a sulfur atom, preferably an oxygen atom. In the general formula (+), R1 preferably has 6 to 36 carbon atoms.
, more preferably represents an aryl group of 6 to 15, and may be substituted with a substituent selected from the above substituent group A or may be a fused ring. Here, as a preferable substituent,
Halogen atom (F, CI2.3r,!), cyano group, nitro group, acyl Jλ (e.g. acetyl, benzoyl),
Alkyl groups (e.g. methyl, butyl, trifluoromethyl, trichloromethyl), alkoxy groups (e.g. methoxy, ethoxy, butoxy, trifluoromethoxy)
, alkylsulfonyl groups (e.g. methylsulfonyl, propylsulfonyl, butylsulfonyl, benzylsulfonyl), arylsulfonyl groups (e.g. phenylsulfonyl, p-tolylsulfonyl, p-chlorophenylsulfonyl), alkoxycarbonyl groups (e.g. methoxycarbonyl, butoxycarbonyl), Sulfonamide group (
(e.g. methanesulfonamide, trifluoromethanesulfonamide, toluenesulfonamide), carbamoyl groups (e.g. N,N-dimethylcarbamoyl, N-phenylcarbamoyl) or sulfamoyl groups (e.g. N,
N-dimethylcarbamoyl, N-phenylsulfamoyl). R1 is preferably a phenyl group having at least one substituent selected from a halogen atom, a cyano group, a sulfonamide group, an alkylsulfonyl group, an arylsulfonyl group, and a trifluoromethyl group, and more preferably a 4-cyano group. Phenyl, 4-cyano-3-halogenophenyl, 3-cyano-4-halogenophenyl, 4-alkylsulfonylphenyl, 4-alkylsulfonyl-3-halogenophenyl, 4-alkylsulfonyl-3-alkoxyphenyl, 3-alkoxy- 4-Alkylsulfonylphenyl, 3.4-dihalogenophenyl, 4-halogenophenyl, 3.4.5-)-dihalogenophenyl, 3.4-dicyanophenyl, 3-cyano-4,5-dihalogenophenyl, 4 -trifluoromethylphenyl or 3-sulfonamidophenyl, particularly preferably 4-cyanophenyl, 3-cyano-
4-halogenophenyl, 4-cyano-3-halogenophenyl, 3,4-dicyanophenyl or 4-alkylsulfonylphenyl. - In formula (I), Z represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter); preferred examples of the coupling-off group include a halogen atom,
0RII 5RII-OCR”-0SO,R”-N
COR"1 C2-36 alkenyl group, C3-36 cycloalkyl group, C6-36 aryl group, or C2-36 aryl group
6, and these groups may be substituted with a substituent selected from Group A. Z is more preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, or an alkylthio group. , particularly preferably a hydrogen atom, a chlorine atom, a group represented by the following formula (I1), or a group represented by the following formula Hn). General formula (I1) An arylazo group having 6 to 30 carbon atoms, a heterocyclic group having 1 to 30 carbon atoms and bonded to the coupling active position (position where Z is bonded) with a nitrogen atom (e.g. succinimide, phthalimide, hydantoinyl, pyrazolyl, 2-benzotriazolyl), and the like. Here, R'' is an alkyl group having 1 to 36 carbon atoms.

[In the formula, R1″ is a halogen atom, a cyano group, a nitro group,
an alkyl group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylsulfonyl group, a carbonamide group, a sulfonamide group, an alkoxycarbonyl group, a carbamoyl group, a sulfamoyl group, or a carboxyl group, where m represents an integer of O to 5; When m is plural, R
11 may be the same or different, ] General formula (I■) R1''-O-TC).-y Hts 14 1 P-, 11111 and R16 each represent a hydroxyl group, an alkyl group, an aryl group, an alkoxy In the general formula (!1), R13 is preferably a halogen atom, an alkyl group (e.g. methyl, t-butyl, L-octyl, pentadecyl). , alkoxy groups (e.g. methoxy, n-butoxy, n-octyloxy, benzyloxy, methoxyethoxy), carbonamide groups (e.g. acetamide, 3-carboxypropanamide) or sulfonamide groups (e.g. methanesulfonamide, toluenesulfonamide, p-dodecyloxybenzene sulfonamide), particularly preferably an alkyl group or an alkoxy group. 0m is preferably an integer of 0 to 2, more preferably an integer of O or 1. , R1 and/or R'4 represent a monovalent group, preferably an alkyl group (e.g. methyl, ethyl, n-butyl, ethoxycarbonylmethyl, benzyl, n-decyl%n-dodecyl), an aryl group (e.g. phenyl, 4-chlorophenyl, 4-methoxyphenyl), acyl groups (e.g. acetyl, decanoyl, benzoyl, pivaloyl) or carbamoyl groups (
For example, N-ethylcarbamoyl, N-phenylcarbamoyl), and SR'' and R14 are more preferably a hydrogen atom, an alkyl group, or an aryl group. '' is preferably an alkyl group, an alkoxy group, an alkenyloxy group, an aryloxy group, or a substituted or unsubstituted amino group, and more preferably an alkoxy group or a substituted or unsubstituted amino group. In the general formula (Il+), n preferably represents an integer of 1 to 3, more preferably l. Specific examples of R1 in general formula (I) K are shown below. CH3 -H- Below are specific examples of 2 in general formula (I). 1 So-QCCM. -050, CH3 10CHtCHtOCHs -OCH2COOCHs -0CI(, C00H -OCHICH Hit SO YiCM. -OCH, CH! SCH, C00H -OCH, CH Snow NH30, CH3 -5CI(, C00C, Hs -5CH2COOH -SCHχCH,C00H -5CHCOOH OH3 -SCH,CH,OH OH -5CH2CHCH,OH -OCIImCOOCJs-sOH -0CII*cOOc, IIm-t When Z is a coupling-off group, a photographically useful group (e.g. developing It is preferable not to contain inhibitor residues, dye residues).Specific compound examples of the cyan coupler of the present invention are shown below.Example 3Example 4Example 9Example 10Example 11Example 12 5 Example 6 Example 7 Example 8 Example 13 Example 14 Example 16 Example 17 Example 18 Example 19 8H+7-n Synthesis examples of couplers of the present invention are shown below to further explain the present invention.Synthesis Example Synthesis of Exemplary Coupler 1 Nitrogen Stream Below, potassium carbonate (
In the presence of 3.8 g of I and 0.10 mcijN, ethyl 2-bromotetradecanoate (33.5 g, 0.10 mon) was added dropwise, and the mixture was stirred at 80°C for 2 hours. After cooling, add water and extract twice with ethyl acetate. Wash the organic layer three times with water,
The solvent is distilled off under reduced pressure. Residual ethanol (200 ships)
A 5N aqueous sodium hydroxide solution (I
00mQ,) and stir for 2 hours. Add water and extract twice with ethyl acetate. The organic layer is washed with 1N diluted hydrochloric acid, water, and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and methylene chloride (l OOm), N, N
-Dimethylformamide (Imλ, ) was added, and oxalyl chloride (I5cc) was added dropwise at room temperature for 15 minutes.
Stir for an hour. The solvent was distilled off under reduced pressure to obtain a crude product of 2-(2-benzoyl-5-methoxyphenoxy)tetradecanoyl chloride (44.0 g, 86%). 5-Amino-2-[3(4-cyanophenyl)ureido]phenol (23.0 g, 0.086 m
on) of N,N-dimethylacetamide (200 mN,
) A crude product of 2-(2-benzoyl-5-methoxyphenoxy)tetradecanoyl chloride was added dropwise to the solution at room temperature over 30 minutes, and after the dropwise addition, the mixture was stirred at 60°C for 2 hours. After cooling, add water and extract twice with ethyl acetate. The organic layer was washed with O,I dilute hydrochloric acid, water, and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure and the residue was recrystallized from acetonitrile to give Exemplified Compound 1.
(57.3g, 81%) was obtained. In the present invention, the cyan coupler is generally used in an amount of 0.002 to 0.3 mol, preferably 0.01 to 0.2 mol, per mol of photosensitive silver halide. The coating amount per square meter is 0.01 to 5 mmol, preferably 0.1 to 2 mmol. The cyan coupler of the present invention can be introduced into a photosensitive material by an oil-in-water dispersion method. A weight ratio of 2.0 to zero high boiling point organic solvent to coupler can be used. Preferably 10
A high boiling point organic solvent of from 0 to 0 can be used, and compared to other cyan couplers having a similar structure, even a small amount of a high boiling point organic solvent of O, I to 0 can be used. A feature of the color photographic material of the present invention is that a stable dispersion can be obtained without using a high-boiling organic solvent. In the present invention, the coupler solvents listed below can be used, but for cyan couplers, phthalate esters (e.g. dibutyl phthalate, di-2-ethylhexyl phthalate, didodecylphthalate, ethyl phthalylethyl glycolate) ), fatty acid esters (e.g., hexyl tetradecanoate 2-ester, di-2-
Ethylhexyl adipate, di-2-ethylhexyl sebacate, 2-edylhexyl 9.10-epoxystearate), benzoic acid esters (e.g. 2-ethylhexyl sebacate, dodecylbenzoate, hexadecyl-4-hydroxybenzoate, etc.), phenols (
For example, 2.4-pentylphenol, 2.4-
dinonylphenol, 2,4-didodecylphenol, etc.) and chlorinated paraffins (e.g.
High boiling point organic solvents such as paraffins (0-70% by weight) are preferred. The cyan coupler of the present invention can be used in any of the light-sensitive emulsion layer, non-light-sensitive emulsion layer, and intermediate layer, but it is preferable to add it to the light-sensitive emulsion layer. It is more preferable to use it by adding it into the layer. The cyan coupler of the present invention may be used alone as a cyan coupler, or may be used in combination with other cyan couplers. Preferred cyan couplers that can be used in combination include 1-naphthol type cyan couplers, 5-amide-
1-Naphthol type cyan coupler (US Pat. No. 69089)
No. 9, JP-A No. 64-78252), 2-ureidophenol type cyan coupler (described in JP-A No. 64-2044, etc.). film, color negative film,
Color reversal film, color can be directly applied to positive photosensitive materials. Application to color negative film is particularly preferred. The silver halide emulsion of the light-sensitive material used in the present invention may be of any halogen composition, such as silver iodobromide, silver bromide, silver chlorobromide, or silver chloride. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (Shell) [-layer or multiple layers] A particle with a so-called layered structure in which the halogen composition is different, or a structure having a non-layered portion with a different halogen composition inside or on the surface of the particle (if it is on the surface of the particle, the edge of the particle , a structure in which portions of different compositions are joined on a corner or surface) can be appropriately selected and used. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When silver halide grains have the above-mentioned structure, even if the boundaries between parts with different halogen compositions are clear boundaries, the boundaries may be unclear due to the formation of mixed crystals due to compositional differences. It is also possible to actively have continuous structural changes. The halogen composition differs depending on the type of photosensitive material to which it is applied. For example, printing materials such as color paper are mainly based on silver chlorobromide emulsions, while photographic materials such as color negatives are mainly based on silver iodobromide emulsions. used. Furthermore, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more,
More preferably 95 mol% or more. Such a high silver chloride emulsion preferably has a structure in which the localized silver bromide layer is provided inside and/or on the surface of the silver halide grains in a layered or non-layered manner as described above. The halogen composition of the localized layer preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. These localized layers can be located inside the grains or on the edges, corners, or surfaces of the grain surfaces, and one preferred example is one in which they are epitaxially grown on a part of the corner of the grains. Average grain size of silver halide grains used in the present invention (
In the case of spherical or nearly spherical particles, the particle diameter is taken as the particle size, and in the case of cubic particles, the particle size is taken as the particle size, and it is the average based on the projected area. In the case of tabular grains, it is also expressed in terms of spheres. ) is preferably 2 μm or less and 0.1 μm or more, particularly preferably 1.
It is 5 μm or less and 0.15 μm or more. The particle size distribution can be narrow or wide, but
A so-called monodisperse silver halide emulsion in which the value (variation rate) obtained by dividing the standard deviation value of the grain size distribution curve of the silver halide emulsion by the average grain size is within 20%, particularly preferably within 15%, is used in the present invention. It is preferable to do so. In addition, in order to satisfy the target gradation of a light-sensitive material, two or more types of monodisperse silver halide emulsions with different grain sizes are used in an emulsion layer having substantially the same color sensitivity (monodispersity is defined as the above-mentioned type). (preferably one with a variable rate) can be mixed in the same layer or coated in separate layers. Furthermore, two or more types of polydisperse silver halide emulsions or a combination of a monodisperse emulsion and a polydisperse emulsion may be mixed or layered for use. The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, rhombidodecahedral, dodecahedral, etc.).
r ) crystals or coexistence of these crystals, or irregular (irre) crystals such as spherical
It may have a crystalline form (gular), or it may have a composite form of these crystalline forms. Also, tabular grains may be used. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Nα17643
(December 1978), pp. 22-23. “1. Emulsion preparation
ion and types)”, and the same Na187
16 (November 1979), 648 pages, graphic “
"Physics and Chemistry of Photography", published by Ballmontel (P, Gl.
afkides. Chemie et Ph1sique Photog
Rahique, Paul λ(ontel, 1
967), Duffin, “Photographic Emulsion Chem J.” Published by Focal Press (G, F, Duffin. Photographic Emulsion Chem.
(Focal Press. 1966)), Making and Coating of Photographic Emulsions by V. L. Zelikman et a!, Focal Press (Focal Press. 1966).
and CoatingPhotographic Em
uldion, Focal Press,
(1964) and others. U.S. Patent No. 3,574,628, U.S. Patent No. 3,655.39
No. 4 and British Patent No. 1. 413. Monodispersed emulsions such as those described in No. 748 are also preferred. Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Cutoff, Photographic Science and Engineering.
engineering), 14th
Vol. 248-257 (I970); U.S. Patent No. 4,
434゜226, 4,414,310, 4,4
33.048, British Patent No. 4,439,520, and British Patent No. 2,112,157. The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Also, mixtures of particles of various crystal forms may be used. The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Nα1
7643 and Nα1B716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. Additive type title RD 17643 RD 1871
61 Chemical sensitizers Page 23 Page 648 Right column 2
Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 Right Column 4 Brightener Page 24 5 Antifog Agent Pages 24-25 Page 649 Right Column ~
and stabilizer 6 light absorber, fu pages 25-26 page 649 right column ~
Ilter dye, page 650, left column, ultraviolet absorber 7, stain inhibitor, page 25, right column, page 650, left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column lO binder page 26 Same as above 11 Plasticizer, lubricant page 27 page 650 right column 12 Coating aid,
Pages 26-27 Page 650 Right column Surfactant 13 Static inhibitor Page 27 Same as above In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Pat.
It is preferable to add to the photosensitive material a compound that can be immobilized by reacting with formaldehyde as described in No. 35,503. Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nal 7643, ■-C-G. Yellow couplers include, for example, U.S. Patent Section 3.93.
No. 3,501, No. 4,022,620, No. 4,3
No. 26,024, No. 4.401゜752, No. 4,
No. 428,961, Japanese Patent Publication No. 5B-10739, British Patent No. 1. 425. No. 020, No. 1.476.76
No. 0, U.S. Patent Section 3.973.968, U.S. Pat.
Preferred are those described in European Patent No. 4,023, European Patent No. 4,511,649, European Patent No. 249°473A, and the like. As the magenta coupler, 5-pyrazolone and pyrazoloazole compounds are preferred, and U.S. Patent Section 4,31
No. 0,619, No. 4.351°897, European Patent No. 73,636, U.S. Patent Section No. 3,061,432, No. 3.125,067, Research Disclosure Nα24220 (June 1984) ), JP-A-60-3
No. 3552, Research Disclosure Nα242
30 (June 1984), Japanese Patent Publication No. 60-43659,
No. 61-72238, No. 60-35730, No. 55
-118034, 60-185951, U.S. Patent Section 4.500,630, 4.540.654,
No. 4,556,630, International Publication WO381047
Examples include phthol couplers described in No. 95, etc.
U.S. Patent Sections 4.052.212 and 4.146.3
No. 96, No. 4,228,233, No. 4. 296
．． No. 200, No. 2,369,929, No. 2,8
No. 01.171, No. 2,772,162, No. 2,
No. 895,826, same No. 3. 772. No. 002, No. 3,758,308, No. 4,334.011,
No. 4,327,173, West German Patent Publication No. 3,329
, 729, European Patent No. 121.365A, European Patent No. 24
No. 9.453A, U.S. Patent Section 3,446,622, U.S. Pat.
Same No. 4.451.559, No. 4.427,767, No. 4,690,889, No. 4. 254. 2
No. 12, No. 4.・No. 296,199, JP-A-61-4
Those described in No. 2658 and the like are preferred. Colored couplers for correcting unnecessary absorption of color-developing dyes are described in Research Disclosure Nα17643 Section ■-G, U.S. Patent No. 4,163°670, and Japanese Patent Publication No. 5
No. 7-39413, U.S. Patent No. 4,004,929,
Same No. 4. 138. No. 258, British Patent No. 1,146
, No. 368 is preferred. Additionally, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774.181, and couplers that react with developing agents as described in U.S. Pat. No. 4,777.120. It is also preferable to use a coupler having as a leaving group a dye precursor group capable of forming a dye. Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4,368,237 and British Patent No. 2,125.
, 570, European Patent No. 96,570, and German Patent Publication No. 3.234,533 are preferred. Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576.910, British Patent No. 2,102
, No. 173, etc. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers releasing development inhibitors are described in RD l 764 as previously described.
3. Patents listed in sections ■ to F, JP-A-57-1519
No. 44, No. 57-154234, No. 60-18424
No. 8, No. 63-37346, No. 63-37350,
U.S. Patent No. 4248.962, U.S. Patent No. 4,782,012
Preferably, those listed in No. Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097.140;
No. 2,131,188, JP 59-157638
No. 59-170840 is preferred. Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130.427, U.S. Pat. , DIR redox compound emitting couplers described in JP-A-60-185950, JP-A-62-24252, etc., DIR coupler-emitting coupler D
IR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173,30
2A, couplers R, D, Nα11449, which release dyes that fade after separation as described in No. 313,308A;
Bleach accelerator releasing coupler described in JP-A-61-201247, etc., U.S. Patent No. 4,553,477
Ligand-releasing coupler described in JP-A-63-75
Couplers that emit leuco dyes as described in US Pat. No. 747, couplers that emit fluorescent dyes as described in US Pat. No. 4,774,181, and the like. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling organic solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like. Further, the process and effects of a latex dispersion method as one of the polymer dispersion methods, and specific examples of latex for impregnation are described in US Patent No. 4. 199. No. 363, West German Patent Application (OLS)
No. 2,541.274 and No. 2,541,230
Regarding dispersion methods using organic solvent-soluble polymers, PCT International Publication No. WO38100723 describes, for example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (
diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. a2-ethylhegicyl benzoate, 2,4-dichlorobenzoate) (2-ethylhexyl acid), alkylamides (e.g. diethyl laurylamide), fatty acid esters (e.g. dibutoxyethyl dibutoxylate, di-2-ethylhexyl tetradecanoate, 2-hexyldecyl tetradecanoate, tributyl citrate, diethyl azelate) ), chlorinated paraffins (
paraffins with a chlorine content of 40% to 80%), trimesic acid esters (e.g. tributyl trimesate), or organic solvents with a boiling point of 30°C to 150°C, such as lower alkyl acetates such as ethyl acetate and butyl acetate, propion The amount ranges from 0.001 to 1 mole per mole of ethyl acid, secondary butyl alcohol, methyl imbutyl ketone, β-ethoxyethyl acetate, and silver methylcellosol, preferably from 0.01 to 0 for yellow couplers. .5 mole, 0 for magenta coupler
．． 003 to 0.3 mol, and 0 for cyan couplers
．． 002 to 0.3 mol. The color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-212248, and JP-A-1-8
1 described in No. 0941. 2-benzisothiazoline-
3-one, n-butyl, p-hydroxybenzoate,
It is preferable to add various preservatives or antifungal agents such as phenol, 4-chloro/L/-3,5-dimethylphenol, 2-phenoxyethanol, and 2-(4-thiazolyl)benzimidazole. The photographic material used in the present invention is coated on a commonly used plastic film (cellulose nitrate, cellulose acetate, polyethylene terephthalate, etc.), a flexible support such as paper, or a rigid support such as glass. For details on the support and coating method, see Research Disclosure Volume 176 Item 1764
3 Described in Section XV (p. 27) Section X■ (p. 28) (December 1978 issue). The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Further, metal complexes such as (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used. Specific examples of organic antifade agents are described in the following patent specifications: Hydroquinones are disclosed in U.S. Patent No. 2,360,290;
2,418.613, 2,700.453, 2,701.197, 2.728,659
No. 2,732,300, No. 2,735,76
No. 5, No. 3,982.944, No. 4,430,4
25, British Patent No. 1,363,921, U.S. Patent No. 2.710.801, U.S. Pat. U.S. Patent No. 3°432.30
No. 0, No. 3,573,05.0, No. 3,574,
No. 627, same No. 3. 698. No. 909, No. 3, 7
No. 64,337, JP-A-52-152225, etc.
Spiroindanes are described in U.S. Pat. No. 4,360,589, and p-alkoxyphenols are described in U.S. Pat. No. 2.735.
, 765, British Patent No. 2,066, J75, JP-A-59-10539, JP-A-57-19765, etc. Hindered phenols are disclosed in U.S. Patent No. 3゜700.4.
No. 55, JP-A No. 52-72224, U.S. Patent No. 4,22
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3,457,079, U.S. Pat. No. 56-21144, etc., and hindered amines are disclosed in U.S. Patent No. 3,336.1.
No. 35, No. 4,268,593, British Patent No. 1.3
No. 26,889, No. 1,354,313, No. 1,
No. 410,846, Japanese Patent Publication No. 51-1420, Japanese Patent Publication No. 1973
No. 8-114036, No. 59-53846, No. 5
No. 9-78344, etc., metal complexes are disclosed in U.S. Patent Box 4,0.
No. 50,938, British Patent No. 4,241,155, British Patent No. 2,027, British Patent No. 731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with a coupler and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet absorber into the cyan coloring layer and the layers on both sides adjacent to it. As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533,7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3,314°794, U.S. Pat. No. 3,352.
681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. No. 3,705,805 and 3,707,395). (as described in US Patent Box 4,045,229), butadiene compounds (such as those described in US Pat. No. 3,700,455), or benzoxidol compounds (such as those described in US Pat. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted with specific waste. Among these, benzotriazole compounds substituted with the above-mentioned oryl group are preferred. As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Vuis (Academic Press, published in 1964). The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N,N, -
Diethylaniline, 3-methyl-4-amino-N-ethyl N-β-hydroxyethylaniline, 3-methyl-4
-Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides or p-toluenesulfonic acid Examples include salt. Two or more of these compounds can be used in combination depending on the purpose. The color developer may contain pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or antifoggants such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. If necessary, hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, triethylenediamine (l,4-diazabicyclo[2°2.2]octane), etc. Various preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, fogging agents such as competing couplers sodium boron hydride, Auxiliary developing agents such as l-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, l-hydroxyethylidene-1,
1-diphosphonic acid, nitrilo-N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N. Representative examples include N', N'-tetramethylenephosphonic acid, ethylene diamine-di(0-hydroxyphenylacetic acid), and salts thereof. Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as l-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination. The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
It can also be less than ml. When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer. After color development, the photographic emulsion layer is usually bleached. The bleaching treatment may be carried out simultaneously with the fixing treatment, or may be carried out separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents include iron (■) and cobalt (
III), compounds of polyvalent metals such as chromium (■), copper (n), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (III) or cobalt (III), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, l,3-diaminoacetic acid; Aminopolycarboxylic acids such as propanetetraacetic acid, glycol ether diamine tetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates, unitrobenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron(III) complex salts and persulfates, including ethylenediaminetetraacetic acid iron(III) complex salts, are preferable from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(II) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron(III) complexes is usually 5.5 to 8, but in order to speed up the processing, the pH can be lowered. . A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary. Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, JP-A-53-95630, Research Disclosure No. Nα17.129 (I97
Compounds having a mercapto group or disulfide bond as described in Jp.
Thiourea derivatives described in No. 61; JP-A-58-1623
Iodide salt described in No. 5; West German Patent No. 2,748°430
Polyoxyethylene compounds described in No. 1973-
Polyamine compounds described in No. 8836; bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Pat. No. 3,893,858 and West Patent No. 1.
, 290° 812 and JP-A-53-95630 are preferred. Additionally, U.S. Patent No. 4,552゜8
Compounds described in No. 34 are also preferred. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography. Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred. The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
on Engineers Vol. 64, p. 248-25
3 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. In addition, isothiazolone compounds and thiabendazoles described in JP-A No. 57-8542,
Chlorine-based disinfectants such as chlorinated sodium isocyanurate,
Others, such as benzotriazole, Hiroshi Horiguchi, "Chemistry of anti-bacterial and anti-mildew J (1986), Sankyo Publishing, edited by Hygiene Technology Association, "Sterilization of microorganisms, sterilization, anti-mold technology J (I982), Kogyo Gijutsudai, Japan anti-bacterial “Encyclopedia of antibacterial and fungicidal agents J (I)” edited by Hui Gakkai
9B6) can also be used. The pH of the washing water in the processing of the photosensitive material of the present invention is 4 to 4.
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15 to 45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-5B-14834, and JP-A-60-22'0345 can be used. Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. . It is also possible to add various botanical agents and antifungal agents to this stabilizing bath. The overflow liquid from water washing and/or replenishment of the stabilizing liquid can be reused in other processes such as the desilvering process. The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compound described in No. 7, No. 3,342,
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15.159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719.4B2, JP-A-53-1
Examples include urethane compounds described in No. 35628. The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are JP-A-56-64339, JP-A-57-144547,
and No. 5B-115438. Various processing solutions in the present invention are used at temperatures of 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. Further, in order to save silver on the photosensitive material, a treatment using cobalt intensification or hydrogen peroxide intensification as described in German Patent No. 2,226,770 or US Pat. No. 3,674,499 may be carried out. (Example) Next, the effects of the present invention will be specifically explained by examples, but the present invention is not limited to these. Example! A monochromatic photosensitive material consisting of two layers, an emulsion layer and a protective layer, on a subbed cellulose triacetate support (Sample 1)
01-108.1'lO-12) were prepared with the compositions shown below. Values other than couplers are expressed in units of g/3. (For silver halide, values are shown in terms of silver) Emulsion layer Silver iodobromide emulsion (silver iodide 2 mol%, average grain size 0.3 μm) Silver 0.8 Yaratin
1.2 coupler (see Table 1) sol/m” unit 0.001 Dibutyl phthalate 0.3 Protective layer Seratin 0.9 Polymethyl methacrylate particles (1.5 μm in diameter) 0.41-oxy-3 , 5-dichloro-5-sodium triazate 0.04 Next,
Sample 109 was prepared in the same manner as Sample +01 except that dibutyl phthalate was not added to the emulsion layer. Color photosensitive material thus prepared (Sample 101-
112) at an exposure intensity of 4 using a continuous moisture wedge.
After exposure at 0 cm5, the following standard color development process was performed. Standard color development processing (temperature: 38°C) Color development 73 minutes 15 seconds Bleaching 6 minutes: 30 seconds Fixing 4 minutes 20 seconds Washing 5 minutes Stable 1 minute The composition of the processing solution used in each step was as follows. Color developer Diethylenetriamine Pentaacetic acid 1-Hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-ethyl-N-〇-hydroxyethylamino) 2-Methylaniline Add the sulfate water and p OL 10.0 106.0g 3.0mL 150, O wing 10, Og Add water 1.1llJ2
pH 4,2 Fixer Ethylenediaminetetraacetic acid disodium salt 1.0g Sodium sulfite 4.0g Ammonium thiosulfate aqueous solution (70%) 175.0rn1
Sodium bisulfite 4.6g Add water 1.0 flood pl+
6.6 Stabilized formalin (40%) 2.0ryt
Add 0.3 g of polyoxyethylene-p-thousononylphenyl ether (average degree of polymerization, 10) to obtain a sample that developed a cyan color in the Qu color development process (I01-
109) using a Fuji-type densitometer (FSD), the gamma value (slope of the sensitometric curve) and D max l
The maximum color density) was measured. The results are shown in Table 1, and each value is expressed as a relative value when the measured value of sample 101 is taken as 100. Table 1 Comparative coupler A: described in U.S. Pat. No. 4,333.999 Compound Example 7 Comparative coupler B: described in U.S. Pat. No. 4,772.543 Compound Example I Next, the maximum concentration part of the sample (lot-112) was measured at λm using a Hitachi U-3200 UV-visible spectrophotometer.
ax (maximum absorption value) was determined. Thermal fastness evaluation was performed using cyan-colored samples (+0l-11
2) was heated for 7 days at a temperature of 80° C. and a relative humidity of 70%, and the concentration was determined as a percentage of the drop from the initial concentration. However, a site with an initial concentration of 1.5 was used. Comparative coupler C: described in Compound Example 1 of JP-A-63-161450 From Table 1, when the compound of the present invention is used, the coupling reactivity is higher than when the comparative coupler is used.
In order to examine the resistance to reductive fading of images with high maximum color density, samples 101-112 were exposed to light using a continuous density wedge at an exposure intensity of 40 CmS, and then bleached with the following composition. A process similar to the standard color development process described above (hereinafter referred to as reduction fading process) was performed except that a liquid was used. Bleach solution Propylenediaminetetraacetic acid ferric ammonium salt 90g Propylenediaminetetraacetic acid ferric ammonium salt 15g Aqueous ammonia Ammonium tribromide 150g Ammonium nitrate
Add 10g water
11p8 4.2 Sample that developed cyan color by reduction fading treatment (+0l-1
12), D max using a Fuji densitometer (FSD)
(maximum color development density) was measured, and the ratio to Dmas of the corresponding sample (marker 0l-112) which was colored by the above-mentioned standard color development process was determined. Dmas (reduction fading treatment) Table 2 shows the λmax, color image retention rate, and reductive fading resistance thus obtained. Table 2 From Table 2, when the coupler of the present invention is used, the produced dye has a λIIIax of 685 to 7, which is suitable for negative photosensitive materials.
05n1m and comparative couplers A, 13 and C
It can be seen that the color image storage stability and resistance to reduction and fading are excellent compared to the case of using . Example 2 A multilayer silver halide photosensitive material (Sample 2) in which a photosensitive layer having the following composition was coated on an undercoated cellulose triacetate support-L.
01-211) were created. (Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/m"0 position, and for silver halide, it indicates the coating amount in terms of silver. However, for sensitizing dyes, the same layer The coating amount per mole of silver halide is shown in moles. First layer (antihalation layer) Black colloidal silver Silver 0.18 Gelatin Second layer (intermediate layer) 2.5-C-pentadecylhydroquinone 0. 18EX-1
0,07 EX-30,02 EX-120,002 U-10,06 LJ-20,08 U-30,10) IBs-10,10 HB S-2 Ceratin 3rd layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Sensitizing dye 1 Sensitizing dye +1 Sensitizing dye ■ Coupler (see Table 3) EX-10 B5-1 Seratin 4th layer (second red-sensitive emulsion layer) Emulsion G Sensitizing dye I Sensitizing dye II Sensitizing dye In coupler (see Table 3) EX-3 EX-4 EX-10 B5-1 0.02 0.88 Silver 0.25 Silver 0.25 6.9 Xl0-' 1.8 X 10- ' 3.1 Xl0-' 6.3 Xl0-'(thousand*/a+") o, oz. ◎, 060 0.73 Silver 1.0 5, I , 5 X -3 EX-4 [MiX-2 1Bs-1 1Bs-2 Gelatin 6th layer (intermediate layer) I', I3 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ 1.1 Silver 1.60 5.4XlO-'1.4XIO-'2.4XlO-' 0.010 o, oa. 0,097 0,22 0,10 1,39 0,040 0,020 0,68 0°3.0× 1.0× 3.8× EX-6 EX-1 EX-7 EX-8 1BS-1 HB S -3 Ceratin 8th layer (second green-sensitive emulsion layer) Emulsion C Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ I": X-6 EX-8 EX-7 1-IBs-1 HB S - 3 Seratin 9th layer (third green-sensitive emulsion layer) Emulsion E Sensitizing dye V Sensitizing dye ■ 0,260 0.02+ 0,030 0,025 0.100 0.0+0 0.53 Silver 0.45 2, IX 10-' ?, 0XlO-' 2.6X 10-' 0, 094 0.0+8 0, 026 0, +60 o, ooa O143 Silver 1.2 3.5X In-'8.0XlO-'' Sensitizing dye ■ EX-13 EX-14 EX-II EX-1! 1r3S-1 HB S-2 Seratin 10th layer (yellow filter layer) Madder colloidal silver EX-5 B5-1 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion Δ Emulsion B Emulsion F Sensitizing dye ■ EX-9 EX-8 B5-1 Gelatin 3.0 0.07 0.07 3.5X 10-' 0.72 0.042 G, 28 0.94 12th layer (second blue-sensitive emulsion layer) Emulsion G Sensitizing dye■ EX-9 EX-10 B5-1 Gelatin 13th layer (third blue-sensitive emulsion layer) Emulsion II Sensitizing dye ■ EX-15 ++13S-1 Ceratin 14th layer (first protective layer) Emulsion l J -4 3-5 HB S -1 Ceratin 15th layer (Second protective layer) Polymethyl acrylate particles (diameter approximately 1.5 μm) Silver 0.45 2, IX 10-' 0, 154 0, 007 0.05 0.56 Silver 0.77 2.2XlO-' 0. 20 0.07 0.69 Silver 0.5 σ, 11 0.17 0.05 0.85 0.54 5-1 0.20 Gelatin 1.20 In addition to the above two ingredients, each layer contains a gelatin hardening agent H-1 and a surfactant were added. X-1 I X-2 11 X-3 H X-4 12 υ-1 -2 J-3 C++l5OSO,eu-4 Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye 1 Sensitizing dye ■ ItI angry dye ■ Sensitizing dye ■ -t -1 At this time, all of the samples 201 to 211 prepared in A1 except the support and the dowel layer of the support The dry film thickness of the coating layer is 16.5LL.
It was ~1764μ. The prepared sample (201-2+1) has a size of 35 mm1l+
After cutting and processing, a red wedge exposure was applied. Next, the film was processed for 1 r using a cine type automatic developing machine according to the processing method shown in F. The samples to be evaluated for color development and f[ability were subjected to imagewise exposure until the cumulative replenishment of the color developing solution reached 3 times the capacity of the mother solution tank, and then the processing was carried out. Treatment process step Treatment time Treatment temperature Replenishment amount. Color development 3 minutes 15 seconds 37.8℃ 23d drift
White 40 seconds 38.0℃ 5ml fixation 1 minute 30 seconds 38.0℃ 30d water wash (I)
30 seconds 38.0℃ water washing (2) 30 seconds 38.0℃ 30m1 stable 30 seconds
38.0℃ 20m1 drying 1 minute 5
5°C *The amount of replenishment is per meter of 35+nm width.Water washing is a countercurrent method from (2) to (I). Tank capacity 0I2 5β 10β 5β 5β 2 The composition of the treatment liquid is shown below. (Mother liquor developer) Diethylenetriaminepentaacetic acid 1-hydroxyedylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 2-Methyl-4-[N-ethyl-N-(β- [Hydroxyethyl)amino] Add aniline sulfate solution to pH (Bleach solution) Mother solution (g) Replenisher solution (g) 1.0 +, 1 3.0 3.2 4.0 4.9 30.0 30.0 1 .4 1.5 mg 2.4 3.6 4.5 6.4 +, I [1,0 Flood 10.05 10.10 Mother liquor (g) Replenisher solution (gl 1.3-Propylenediaminetetraacetic acid ferric Ammonium monohydrate propylene diamine!, Co3 Tetraacetic acid Ammonium bromide 6111 Ammonium acetic acid (98%) Add water and pH [Ammonia water (27%) (Fixer) 144.0 2.8 84.0 30, 50.0 1.0] 4.0 206.0 4.0 +20.0 41.7 72.5 °C 1.0β 3.2 Common to mother liquor and replenisher (gl Ethylenediaminetetraacetic acid - ammonium salt ammonium sulfite Ammonium thiosulfate aqueous solution (700g/Il) Add water and H (Washing water) Mother liquor and replenisher common 1.7 14.0 340.0 mj2 1.0 7.0 Add tap water to H-type strongly acidic cation exchange resin (ROHMAND Haas Amberlite IR-120B) and OH type strongly basic anion exchange resin (Amberlite IR-120B)
400) to reduce the concentration of calcium and magnesium ions to 3 mg/12 or less, followed by 20 mg of sodium isocyanurate dichloride.
/I2 and 150 mg/β of leethrium sulfate were added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizing liquid) Common to liquid and replenishing liquid (Unit: g) Formalin (37% > 1.2 mA! Surfactant 0.4 (C+O11)
*+-0→Cl1-CIlaO)-r5-11] Ethylene glycol 1.0 Add water
In the 1.0 flood pH 5.0-7.0 treatment step, all samples (201-211) showed good color development, hue, and sufficient wax (maximum color density). For evaluation of heat fastness, cyan-colored samples (20+
-211), the color image residual rate was determined in the same manner as in Example 1. Reduction fading resistance was determined by exposing two samples each of Samples 201 to 211 to red light using a continuous density wedge. One sample was subjected to the standard color development process in Example 1, and the other was subjected to reductive fading treatment. It was obtained by doing the following. Table 3 shows the results of color image retention rate and reduction fading rate. Table 3 (Effects of the Invention) As is clear from the results below, when the compound of the present invention is used, the coupling reactivity and color density are high, the hue is good, and the color image storage property and It can be seen that a photosensitive material with high resistance to reduction and fading can be obtained. (Preferred embodiment of the present invention) 1. In the claims: -L in formula (I)
A silver halide color photographic material in which is an oxygen atom. 2. In the claims, β in general formula (I)
A silver halide color photographic material in which r↓ is 0 or 1. 3. In the claims - R in formula (I)
' and R4 are a hydrogen atom or a substituted or unsubstituted alkyl group, a silver halide color photographic light-sensitive material. 4. A silver halide color photographic light-sensitive material in preferred embodiment 3, wherein one of %R1 and R' is a hydrogen atom and the other is an unsubstituted alkyl group. 5. In the claims, I in general formula (I)
A silver halide color photographic material in which P is p-cyanophenyl group. 7. A novel method for obtaining a color image by developing a silver halide color photographic material in the presence of a cyan dye-forming coupler represented by formula (+). 8. In the claims, 2 in general formula (I)
A silver halide color photographic material in which is a hydrogen atom. ° “Itobariho 11 official book (method) Procedural amendment (voluntary) May 23, 1990

Claims (1)

[Scope of Claims] A color photographic light-sensitive material having at least one silver halide emulsion layer on a support, the same layer as the emulsion layer or a separate layer containing a cyan compound represented by the following general formula (I). A silver halide color photographic material characterized by containing a dye-forming coupler. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 represents an alkyl group, alkenyl group, cycloalkyl group, or aryl group. R^2 is a group that can be substituted on the benzene ring. R^3 and R^4 represent a hydrogen atom, or an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group, and R^3 and R^4 may be the same or different. May be.R
^5 represents an aryl group. L represents an oxygen atom or a sulfur atom. Z represents a hydrogen atom or a coupling-off group. l is an integer from 0 to 4. )