JPS6091355A - Silver halide color photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic material using a two- equiv. cyan coupler having excellent colorability and dispersibility by introducing a phenyl ureide group and acyl amino group. CONSTITUTION:The compd. which has a phenyl ureide group substd. with a halogen atom in the 2nd position of phenol, has an acyl amino group in the 5th position and has the group such as -SR' in the 4th position and is expressed by the formula I is used as a cyan dye forming coupler. R in the formula I denotes a substd. or unsubstd. alkyl group, aryl group or heterocyclic group, X denotes a halogen atom, R' denotes an substd. or unsubstd. alkyl group, aryl group, alkinyl group, cycloalkyl group or heterocyclic group and n denotes 1-5 integer. When n is >=2, X may be the same or different.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention This invention relates to a silver halide color photographic photosensitive material containing a cyan dye-forming coupler, particularly a novel λ common cyan coupler.

(Description of the Prior Art) When a silver halide photographic material is exposed to light and then subjected to color development, an oxidized aromatic-grade amine developer and a dye-forming coupler react to form a color image. Generally, in this method, a subtractive color reproduction method is used, and in order to reproduce i', green, and red, yellow, magenta, and cyan colors 11. !
II image is formed.

Phenol derivatives or naphthol derivatives are often used as couplers to form cyan images. In color photography, color-forming couplers are added during development α, but they are incorporated in the light-sensitive photographic emulsion layer or other color image-forming layers 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 this active site is an equivalent coupler, i.e., the theoretical stoichiometric amount of ψmol to form 1 mole of dye. This method requires silver halide having development nuclei of . On the other hand, a coupler having an anion and a group capable of dissociating at the active site is a 1-double coupler, that is, a 1
It is a coupler that requires only 2 moles of silver halide having development nuclei to form one mole of dye, and therefore, compared to the Hong Kong coupler, it can generally reduce the silver halide ridges in the photosensitive layer and reduce the film thickness. Since it can be made thinner, processing time for the photosensitive material can be shortened, and the sharpness of the color image formed can be improved. Typical examples of such leaving groups are listed below: US 8'F3,737. The JIA number has a sulfonamide group, in the US, J'l-J, 7≠ri, 7
3≠ has an imide group, US%d'l'J, 412.
No. 3.11 contains a sulfonyl group, and US Patent J, #74.
．． j4λ has an aryloxy group, as described in U.S. Patent J, J
//, Hiroshi 76 has an acyloxy group, and U.S. Patent 3,
21≠.

≠No. 37 has a thiocyano group, as described in U.S. Patent U, 03J,
The Jat No. has an inthiocyanate group, as stated in the US patent≠
04A1. , 173, a sulfonyloxy group is used in U.S. Pat. Cocoa, No. 6111 has an alkylthio group, JP-A-Shoj, 2-! /ri3 has a thiocarbonyloxy group, JP-Ko-Shoj7-μAOj has a haaralkenylcarbonyloxy group, JP-Ko-Ko-Jl-co1txr has an acylamino group, JP-Ko-Ko-J/-jJrJf, %Ko-Sho 57-6337
has an aminomethyl group, JP-A-4Z7-J7≠, 2j1
The same j7-co0003 has a heterocyclic oxy group, US Patent 3.227,! ! /, Tokukai Shoj, 2-taOri 3 pieces,
Same 13 7? ? "N same! J-10! 2, 16. Same j4f
f-/≠73t1 jII-At/2, same 5s-31
071, same j1-Aj ri j7, same j4-/ri 3 j1 same j
1. -6j3ri, ・Same 14-/24≠3, Same It-J7
/4'7, same zt-rootrt,, M Kosho 10-/
Ko03341. Same j hiro-371λλ, same lt-6ri de, same j7-39311. A substituted alkoxy group is known for j7-da6o6o.

Furthermore, by appropriately selecting all the leaving groups, it is possible to apply, for example, a diffusion transfer method in which the leaving group contains a diffusible dye moiety and the leaving dye is used to form a dye image of the diffusible dye on the image-receiving layer. This type of coupler is also called a diffusible dye-releasing coupler, and is described, for example, in U.S. Pat.
No. 227,510, No. 3.71. J, IIA, U.S. Defense Patent Application No. 1 00,022, British W “No.
, 330゜jko≠%. Matachiru's colored 2-equivalent coupler is dye 1#! There is a mask effect for color correction. The red coupler is called a colored coupler, for example, JP-A-Sho J/-2t.
It is described in the 03 Hiro issue.

A two-equivalent coupler whose separation product has the effect of inhibiting development is called a development inhibitor-releasing coupler, and is called a development inhibitor-releasing coupler. Since development is suppressed in proportion to the amount of silver, it has the effect of making the image finer, adjusting the gradation, and improving color reproducibility. It can also be used in a diffusion transfer method by utilizing the effect on adjacent layers. This type of coupler is described in U.S. Patent No. 3.2.27.
．． No. 13≠, or in Japanese Patent Application Laid-Open No. 22333, West German Patent Publication No. ≠lμ, oo6.

As described above, two-equivalent couplers tend to be widely used because they are inherently superior to conventional couplers and have a variety of applicability.

On the other hand, a phenolic cyan coupler having a ureido group at the 2-position and an acylamino group at the j-position has a higher color produced after color development than other phenolic cyan couplers or naphthol couplers. It is said that JP-A-Sho!t-Ar13≠, JP-A 57-20≠54t3, JP-A 57-204Ajll≠, JP-A 7-koO≠jFj, JP-A 1-332+9, JP-A 31-3
32!0゜same j♂-33231. same! l-33,232
Couplers described in et al. are known, including some two-equivalent cyan couplers.

However, the conventionally known ureido group at the 2-position, j
Many of the phenolic two-equivalent cyan couplers that have an acylamino group in the position have insufficient coupling reactivity, give significant color strength, have poor dispersibility and cause coating failures, or are defective in the coupler itself. It has the disadvantage that it is not stable and cannot be stored for a long period of time, and the stability of the color image formed after color development against heat or light is still not sufficient for long-term storage.

(Objective of the Invention) The first object of the present invention is to improve such conventional drawbacks and to provide a silver halide color photographic light-sensitive material using a novel 2-equivalent cyan coupler which has extremely excellent color development and dispersibility. Our goal is to provide the following.

Another object of the present invention is to provide a coupler that exhibits almost no decrease in color density even when treated with a bleaching solution having weak oxidizing power or a bleaching solution that is exhausted.

DESCRIPTION OF THE INVENTION It has been found that the objects of the present invention are achieved by a cyan dye-forming coupler represented by the following general formula CI) and a silver halide color photoreceptor containing the same.

General formula (1) In the formula, R represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, X represents a halogen atom, and L/ is a substituted or unsubstituted alkyl group, aryl group. , represents an alkenyl group, a cycloalkyl group, or a heterocyclic group, n represents an integer from / to j, and n is 2 or more, and X may be the same or different. n will be explained in detail.

In the general formula (1), 几 is a chain or cyclic alkyl group, preferably a carbon number/~2 alkyl group (for example, a methyl group,
butyl group, pentadecyl group, cyclohexyl group, etc.),
Aryl group (e.g. phenyl group, naphthyl group, etc.),
or a heterocyclic group (e.g., 2-HiIJ sil &, 4'
- Piridil! , -z-7xyl group, co-oxazinol group, 2-imidazolyl group, etc.), and these represent an alkyl group, aryl group, heterocyclic group, alkoxy group (e.g., methoxy group, dodecyl group, λ-methoxyethoxy group, etc.). ), aryloxy group (e.g., phenoxy group, 2゜4'-di-tert-amylphenoquine group, λ, ≠-di-tert-octylphenogyshi group, 3-1ert-butyl-hiro-hydroxyphenoxy group, naphthyloxy 7 cancer, etc.), carboxy groups, carbonyl groups (e.g., acetyl groups, tetradecanoyl groups, benzoyl groups, etc.), ester groups (e.g., methanesulfonyl groups, phenoxycarbonyl groups, acetoxy groups, penzoyloxy groups, butoxysulfonyl groups, toluene) sulfonyloxy mfx etc.)
, amide group (e.g., acetylamino group, ethylcarbamoyl group, methanesulfonylamide group, butylsulfamoyl group, etc.), imide group (e.g., succinimide group, hydantoinyl group, etc.), sulfonyl group (e.g., methanesulfonyl group), It may be substituted with a substituent selected from a hydroxy group, a cyano group, a nitro group, and a halogen atom.

X represents a halogen atom (CF, α or Br), preferably F or α. In addition, the number of substituents is /−j
However, more preferably n==/~3, and the substitution positions are preferably the 3-position, the a-position and the j-position with respect to the ureido group. Further, when n is 2 or more, they may be the same or different.

1 (, / is an alkyl group having 1 to /I carbon atoms (e.g., methyl group, ethyl group, n-propyl group, i-propyl group, n
-butyl group, i-butyl group, t-butyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, etc.), alkenyl group having 1 to 1 carbon atoms (for example, propenyl group) , butenyl group, octenyl group, etc.), aralkyl group having a carbon number of 1 to 1 (e.g., benzyl group, phenylethyl group, etc.), an aralkenyl group having a carbon number of /-/I, phenylpropenyl-Afx, etc.), cycloalkyl group (e.g., cyclopentyl group, cyclohexyl group, methylcyclohexyl group, zocloheptyl group, etc.), an aryl group with carbon number t to cog (e.g., phenyl group, ≠-nitrophenyl group, naphthyl group, etc.), or j negative or t Member ring heterocyclic group (in addition to one nitrogen atom, this heterocycle may further contain an oxygen atom, a sulfur atom, and/or a nitrogen atom, and may also be fused with a benzene ring or a heterocycle) ). Examples of the heterocycles constituting these heterocyclic groups include pyrrole, imidazole, pyrazole, triazole, tetrazole, thiazole, megizazole, thiadiazole, oxadiazole, benzimidazole, pentthiazole, benzoxazole, pyridine, pyrazine, and pyrimidine. , triazine, quinoline and the like.

Here, the alkyl group represented by R', alkenyl group,
Aralkyl groups, aralkenyl groups, cycloalkyl groups, aryl groups, and heterocyclic groups each include a 1a substituent such as a halogen atom (such as fluorine, chlorine, or bromine), a cyano group, a hydroxyl group, an alkoxy group (such as a methoxy group, an ethoxy group, etc.). , propyloxy group, butoxy group, octyloxy group, etc.), aryloxy group (e.g., phenoxy group, etc.)
, acyloxy group (e.g., acetyloxy group, propionoyloxy group, butyroyloxy group, benzoyloxy group, etc.), acylamino group (e.g., formamino group, acetylamine group, propionoylamino group, benzoylamino group, etc.), Sulfonamide group (e.g., methylsulfonamide group, octylsulfone amide group,
benzenesulfonamide group, etc.), sulfamoyl group (
For example, unsubstituted sulfamoyl group, methylsulfamoyl group, ethylsulfamoyl group, furobylsulfamoyl group, phenylsulfamoyl ah, etc.)1. Sulfonyl group (e.g., methylsulfonyl group, ethylsulfonyl group, octylsulfonyl group, Hensensulfonyl group, etc.)
, carbonyl group, sulfo group, nitro group, arylthio group (e.g., phenylthio group, etc.), alkylthio group (e.g., methylthio group, ethylthio group, etc.), carbamoyl group (e.g., eva, ethylcarbamoyl group, quenylcarpamoyl group, etc.) , alkoxycarbonyl groups (e.g., evaporation, methylsulfonyl groups, ethoxycarbonyl groups), sulfinyl groups (e.g., methylsulfinyl groups, phenylsulfinyl groups), heterocyclic groups (e.g., pyrazolyl groups, triazolyl groups, etc.), etc. may be replaced with These substituents may be further substituted with these substituents, and two or more substituents may be substituted at the same time, and in this case, the substituents may be the same or different.

The compound represented by the general formula [1] (hereinafter referred to as the coupler of the present invention) has a phenylureido group substituted with a halogen atom at the 2-position of the phenol, and an acylamino group at the j-position, -8 with general formula (1) in the j position
11. It is characterized by having groups such as ', and it is thought that this is the reason why the rather good l characteristics were obtained.

In other words, the colorless 2-equivalent cyan coupler of the present invention has excellent coloring properties, extremely high sensitivity, gradation, and maximum density IW.
[silver halide contained in the re-emulsion] can be completely reduced, and it is suitable not only for normal processing but also for rapid processing. Furthermore, it has excellent solubility in high-boiling organic solvents, good dispersion stability in photographic emulsions, and does not cause capri or color staining on the photosensitive layer.

The dye obtained from the cyan coupler of the present invention is
It has excellent fastness against heat and humidity, exhibits sharp absorption without unnecessary light absorption, and has good spectral absorption characteristics. Furthermore, the coupler of the present invention has one property in that even when processed with a bleaching solution having weak oxidizing power or a bleaching solution that is exhausted, there is almost no low F color density.

On the other hand, the aforementioned US patent≠, 3.33. Tatata, Tokukai Akira! 17-. 20g 5μ3, same 57-2017! rg≠,
Same j7-. 20uju! , same 3g-, JJ, 2 geta, same jlr-33260, ([T33g-332!/, same j
Even when compared with the λ win-lose cyan couplers described in No. 1-3323, 2, etc., the effect of the coupler of the present invention was completely deplorable.

Next, specific couplers included in the scope of the present invention will be illustrated, but the couplers of the present invention used in the present invention are not limited to these.

The coupler of the present invention can be synthesized by various methods, and typical synthesis routes and synthesis examples are shown below.

Synthesis Example/(Synthesis of Exemplified Compound 1) N-dodecylthiophenol 13y was dissolved in tetrahydrofuran≠00ql, and the resulting solution was added with 1,0% NaH oil composition and 2oy, and j-chloro- 2-
Methyl-nitropenzoxazole 1ooy, dimethylformamide soo, I! The reaction solution was added dropwise to the bath solution at room temperature and stirring was continued for 3 hours. The reaction solution was poured into hydrochloric acid water and the precipitated crystals were collected to obtain Form A/A69.

Next, 811” ”f S
A mixture of 100 liters of i and x tanol was reacted at 700C for a long time, and the precipitated crystals were washed with water several times to form 8 pieces 1319.

Next, add g total toluene jθ□si to Form B/3, heat m + under, and add p-chlorophenylisocyanate soy.
And toluene! A solution of 0yHl was added dropwise and the reaction continued for 1 hour. After lowering the temperature to room temperature, the precipitated crystals were separated, and dimethylacetamide J j O@l was added to 3 g of C-form/Hiroshi and 3 g of palladium-carbon catalyst to obtain C-form l≠3y, and catalytic reduction was carried out in an autoclave. I did this. After the hydrogen for one theoretical run is consumed,
Catalysts are distributed from house to house, and the resulting P-relatives are 2-(λ,
ert-amylphenoxy)hexanoyl chloride? j
f was added and reacted for 2 hours at t o Oc. The reaction solution was poured into water, extracted with ethyl acetate, washed with water, and concentrated under reduced pressure. The resulting residue was subjected to chromatography using a silica gel column. Exemplary compound (1) was obtained by concentrating the fractionated solution g under reduced pressure. 737g was obtained.

Elemental analysis value (C331-174N3 (J4Sα) Cal
cd C;7/, ri4 HiLI N:4t,73;
Ju, 0/Found C; 7/, A9 H; tjON
;J7/CI! ;3J and other couplers could be synthesized in the same manner.

The photographic hole fi11 made using the present invention may contain a color image forming coupler other than the present invention. The coupler preferably has a hydrophobic, non-diffusing type called a pallast group in the molecule. The coupler may be a monoequivalent or two-equivalent to silver.

It may also contain a colored coupler that has a color correction effect, or a coupler that releases a development inhibitor during development (so-called DI coupler).

The coupler may be such that the product of the coupling reaction is colorless.

*A known open-chain ketomethylene coupler can be used as the color-forming coupler. Among these, benzoylacetanilide and biparo-f-acetanilide compounds are advantageous.

As the magenta coloring coupler, pyrazolone compounds, indacylon compounds, cyanoacetyl compounds, etc. can be used, and pyrazolone compounds are advantageous for Il'r. In addition, virazole-based compounds, pyrazoloimidazole-based compounds, pyrazolo-pyrazole-based compounds, and the like are also advantageously used.

As a cyan color-forming coupler, a phenolic compound is used,
Puchtorund compound 1, etc. can be used.

In addition, colored couplers and DII are also couplers (D couplers that release highly diffusive development inhibitory substances)
etc. can also be used together.

In addition to the DIR coupler, the light-sensitive material may also contain a compound that releases a development inhibitor upon development; for example, as described in US Pat. λri 74 Hiroj No., same J, J 75',
j-29, West German 't'R1' entry/exit ii (OL
S ) J・≠/7. Rig No., JP-A Shoj, 2-/s2
7/ issue and JP-A-11-11 can be used in JP-A No. 7//A.

Two or more couplers of the present invention may be contained in the same layer. The same compound may be combined in one or more layers of different lambda.

The couplers of this invention generally contain 2
×70-3 moles! X10 'I'd prefer it/×
If 10-2 moles are added, 'tX10-'' moles are added.

When used in combination with the above couplers, the couplers that produce the same color υ) It is preferable that all the colorings fall within the above range.

The above-mentioned couplers can be introduced into the silver rhodanide pore layer by known methods such as US '1/rλ, 322°027
The method described in this issue is used. For example, phthalate alkyl esters (e.g. dibutyl tucrate, dioctyl phthalate), phosphate esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate) , benzoic acid esters (e.g. octyl benzoate),
Alkylamides (e.g. diethyl laurylamide),
Fatty acid esters (e.g. dibutoxyethyl succinate, dioctyl azelate), or boiling points of about 30
°C to /j O, 'C organic solvents, such as lower alkyl acetates such as ethyl acetate, butyl acetate;
After being dissolved in ethyl flupionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be mixed and used.

It is also possible to use a dispersion method using a polymer as described in 1st Kaisho J/-391RJ3 and JP-A-KOKAI-TATA≠3.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution.

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g. those described in U.S. Pat.
3,312゜6t1), benzophenone compounds (for example, those described in JP-A No. 6-27rv), cinnamic acid ester compounds (for example, U.S. Pat. No. 3,701.101, J, 707) , No. 371), butadiene compounds (e.g., those described in U.S. Pat.
Jt, 2 Kota), or benzoxyzole compounds (e.g., U.S. Patent J, 700, ≠
rs) can be used. Furthermore, US Patent 3. Hirotata, No. 7A2, JP-A-5≠-Hiro1531
You can also use those listed in this issue. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These UV absorbers may be mordanted into certain layers.

The photographic emulsion used in the present invention is P, Glafkid
Ch1mie et Physique Pho by es
tographlque (published by Paul Monte 1, / 1967), G, F'.

Photographic Emuls by Duffin
ionChemistry('I”he Focal
Published by Press, /ri, <A year), V, Lr, Z
Making and by el ikman et al
Coating PhotographicEmul
Sea bream can be trimmed using the method described in John Phys.

In the present invention, silver halide emulsions with regular crystal shapes and nearly identical grain sizes can also be used.

Two or more silver halide emulsions formed separately may be mixed and used.

In the coupler of the present invention, tabular grains, especially grains with a grain size/thickness ratio of 5 or more, especially t or more, account for 10% of the total projected area.
It may be used in combination with the emulsions mentioned above.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be added.

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing capri and stabilizing photographic performance during the manufacturing process, storage or photographic processing of the light-sensitive material. . ffz Azoles such as benzothiazolium hanawa, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, fluoromobe/zimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothi°diazoles , aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially l-
Phenyl! -mercaptotetrazoles); mercaptopyrimidines; mercaptotriazines; )
(tetrazaindenes), pentaazaindenes, etc.; adding many compounds known as antifoggants or ambo agents, such as benzenethiosulfur, onic acid, benzenesulfinic acid, benzenesulfonamide, etc. I can do it. For example, U.S. Clock 3rd Month 1.4A7 No. 3. Those described in Riko, Rihiro No. 7, Tokko Shoj2-2g, and A60 can be used.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion layer of the photosensitive lunar composition of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, and thiomorpholine. , quaternary ammonium salt compounds, urethane derivatives, urea derivatives, imidazole conductors, 3-pyrazolidones, and the like.

The photographic emulsions used in this invention may be spectrally sensitized with methine dyes and others. Dyes that may be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex melonanine dyes, holopolar cyanine dyes, hemicyanino dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are cyanide dyes, merocyanine dyes and complex merocyanine dyes. For these pigments, any of the nuclei commonly used for cyanine pigments can be used as basic heterogeneous nuclei. That is, pyrroline nucleus, oxazinone nucleus, thiacillin nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; nuclei in which aliphatic hydrocarbons are fused to these nuclei; and nuclei in which aromatic hydrocarbon rings are fused to these nuclei, i.e., indolenine nuclei , benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, knzothiazole nucleus, naphthothiazole nucleus,
A benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazoline-j-one nucleus, a thiohydantoin nucleus, and a cortioxazoline-J nucleus as a nucleus having a ketomethylene structure.
, 4t-dione nucleus, thiazolidine-X, a-dione nucleus,
J-allergic nuclei such as rhodanine nuclei and thiobarbic acid nuclei can be applied.

These sensitizing colors J&;i may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization.

Along with the sensitizing dye, a color g that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are used for 44.

In the photographic material produced using the present invention, the photographic emulsion layer and other hydrophilic colloid layers may contain a stilbene-based, triazine-based, oxazole-based, or coumarin-based brightener. These may be water-soluble,
A water-insoluble brightener may also be used in the form of a dispersion.

In carrying out the present invention, the known anti-fading agents listed in F may be used in combination, and the color stabilizers used herein may be used alone or in combination of two or more.

Known anti-fading agents include hydroquino derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, bisphenols, and the like.

The light-sensitive material produced using the present invention may contain a hydroquinone phenol derivative, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, or the like as a color anti-capri agent.

The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support.

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler. (6) However, different combinations may be used depending on the case. can.

Any known method can be used for the photosensitive phase photographic processing of the present invention. A known treatment liquid can be used. Processing temperatures usually range from 11'C to 300C (
: is chosen between /10( :lower temperature or z
o It may be a PA deer that exceeds 0c.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylene diamines (e.g., guamino-N, N-diethylaniline, 3-methyl-l-amino-N, N-diethylaniline, Hiro-amino-N-ethyl). -N-β-hydroxyethylaniline, 3-methyl-≠-amino-N-ethylupe β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-N-
β-methanesulfamide ethylaniline, ≠-amino-3-methyl-h-f-N-β-methoxyethylaniline, etc.) can be administered once a month.

Others written by L+F, A+Mason Pbotograp
hicProcessing Che+n1stry
λJ (published by lI'ocal Press, 1ytt)
J-222 Tribute, U.S. Patent No. 2/3.075, same.
jri J, 3t4A, 4? υi昭ψt-64A9JJ
You may use those listed in the No.

Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates and phosphates, development inhibitors or anti-capri agents such as bromides, iodides and organic anti-capri agents. It can also contain agents such as If necessary, water softeners, preservatives such as hydroxylamine, organic solvents such as benzyl alcohol and diethylene glycol, phenomenon accelerators such as polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, Competitive couplers, fogging agents such as sodium borohydride, auxiliary developers such as l-phenyl-3-pyrazolidone, to viscous loading, U.S. Patent Publication 013.7.
2J No. K iiL + port +) force & , lr y T
'S-based chelating agent German publication C0L8)2, ta,
2. It is also good to use the antioxidant IF agent described in Rizo No. C.

The copy of the emulsion layer after color development is usually bleached.

Bleaching treatment may be performed simultaneously with footwear treatment, or may be performed separately. As bleaching agents, compounds of polyvalent metals such as iron (ill), cobalt (ill), chromium (■), steel (II), polyvalent metals, quinones, nitroso compounds, etc. are used. For example, ferricyanide, dichromium, iron(II) or cobal (1)
organic complex salts, such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-,2-2-propanol-4-auto-Y acid; Acid complex salts; persulfates, permanganates; nitrosophenols, etc. can be used. Of these, especially useful are potassium ferricyanide, sodium ethylenediamine 400rIRtik (Ill), and ammonium ethylenediamine/tetraacetic acid rA(lit) salt. Iron (Ill) complex salt of ethylenediaminetetraacetate also has the advantage of being independent.
It is also useful in Shirabo fuji.

For bleaching or bleaching, use US 1 o'clock + i'l'','
Guco, jJO issue, same 3. λ≠l, No. 6, Tokuko Showa 11
In addition to the bleaching accelerators described in No. 1-1304 and tr"t Publication+j-11'31., and the thiol compounds described in JP-A-33-Aj7J, No. 2, various additives can also be added. .

Hereinafter, the F1 invention will be specifically described with reference to Examples, but the invention is not limited thereto.

Example 1 A sample was prepared by coating an emulsion layer and a retention layer on a cellulose triacetate film support in the following order.

In exemplary coupler (3)/339, dibutyl phthalate 1
Add 00cc and 100cc of ethyl acetate.

Dissolve in a heating bath at 0C, and add gelatin too much and 10 g of sodium dodecylbenzenesulfonate to the solution.
The mixture was mixed with an aqueous solution of o0c and stirred commercially using a homogenizer to obtain a fine coupler dispersion.

Silver iodobromide emulsion with silver iodide and silver bromide molar ratio of 6 pairs/kg
In addition, on the above support, the coating amount of coupler is 7X10
It was applied at a concentration of 'mol/m2.

A gelatin protective layer having a dry film thickness/μ was applied on top of this sample to prepare sample/A.

Samples iB and tc were prepared in a similar manner using example couplers (13) and (14) such that the coupler coating (mol/771) and the mixing ratio of coupler and silver were the same as sample/A. did.

In addition, as a comparison coupler, a coupler (101
), (102) and prepared samples /D and /E in exactly the same manner as sample /A.

t-c5t(□1 (101) After giving 20% C to these sample O-1 using the sensitometry query, 3Ir0C was added in the above treatment process.
Development processing was performed.

/, Color development...3 minutes/j seconds 2 a White...
... 6 minutes 30 seconds 3 Water washing ... 3 minutes 11 seconds IA Foot φ ... Take 30 minutes Water washing ... 3 minutes / j seconds 6 Cheap feet / 30 seconds Is it used for 1-3 minutes? The composition of the treatment liquid is as described above.

Color phenomenon 1 elephant maki nitrilo 3 nil sodium / , Of / Sodium sulfite Hiroshi, 01 / Sodium carbonate 30. Of potassium bromide 1. ≠y Hydroxyfluamine sulfate 2; '7 j/Hiro-(N
-Ethyl-N-β-hydroxydiethylamine) -No methylaniline sulfuric acid, sy Add water / e White liquid ammonium bromide /1,0. Oy A7-t1= Knee7 water (-2Ir4) 2s, occ
Ethylenediamine-tetraacetic acid sodium iron salt 130. O+! Ice intoxicating acid l≠, Occ Add water and add sodium tetrapolyphosphate to fixation 11 2. Of sodium sulfate g, oy ammonium thiosulfate (70 t) /7J, Occ Sodium thiosulfate a, ty Add water /1 Stabilizing solution hol, phosphorus 1. Occ Water was added and 1 liter of the prepared sample was measured using red light.

The results are shown in Table 1.

As can be seen from the table, the couplers of the present invention exhibit significantly improved sensitivity and higher maximum densities than the comparative couplers. Furthermore, the peak wavelength of the absorption spectrum of the coloring dye and the degree of cutting on the short wavelength side were also satisfactory.

Next, each developed film was tested for fastness. The fastness when the sample was left in the dark for t weeks at 70% 1 (to 0C), and the fastness when left in the dark for t weeks at 70% We examined the fastness of light when fully exposed to light for 6 days at 10,000 lux) and the rate of decrease in density 11 at initial concentration/0.
The intensifier of the N color light density in the fogged area after 17≠ days at °C (
Stin) +NII 511. Ta.

The results are shown in Table 2.

The heat resistance of the color image formed by the coupler of the present invention was sufficient, and there were few stains.

Example 2 A multilayer color photosensitive material sample was prepared on a cellulose triacetate film support, each layer having the composition shown below.

7th layer; no-ration prevention layer; gelatin layer containing black colloidal silver ILz layer; intermediate layer 2.3 gelatin layer containing an emulsified dispersion of 5-di-t-octylhydroquinone; 1st red-sensitive emulsion layer; Silver bromide emulsion (silver iodide; 5 mol%)...silver coating amount /
, f / tn 2 sensitizing dye l...Hiroshi for 1 mole of silver, jxlO mol sensitizing dye ■... for 1 mol of silver /, jxlO mol coupler (10/)... for 1 mol of silver 0.0q mole coupler EX-J...0.003 mole per mole of silver Casolar EX-T...4 moles of o, ooo per mole of silver a) 藉; Second red-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide i/(7 mol%)...silver coating amount
1. ≠y 7m 2 Sensitizing dye I...3x10 moles per mole of silver Sensitizing dye ■.../xlO moles per mole of silver Exemplary coupler (3)...0. 02λ mole coupler〇X-J... 010071 moles per mole of silver j7th layer; intermediate layer same as second layer; first green h&IL t-ttI layer silver iodolayer bromide emulsion silver; ≠mol%)...Silver coating amount /, 2f/m2 Sensitizing dye■...JXlo mole for 1 mole of silver Sensitizing dye■...For 1 mole of silver! ×/θ Molar coupler EX-u... 00 for 1 mole of silver OS Molar coupler EX-j... 0 for 7 moles of silver, OQJ
'Mole coupler EX-ta... o, oois mole 7j for 1 mole of silver; 2nd green-sensitive emulsion layer silver iodobromide emulsion (silver iodide; t mole)... silver coating amount /,
3y/yn2 Sensitizing dye ■... 3 x 10 moles per mole of silver Sensitizing dye ■... 10/, 2x/θ per mole of silver Molar coupler EX-7... relative to 1 mole of silver 0.077 mole coupler EX-t...0.003 mole coupler EX-to...0+0OO3 for 1 mole of silver
All mole B; yellow filter with yellow colloidal silver in a single-layer gelatin aqueous solution; 2. j-gee t-
Gelatin layer 2nd layer containing an emulsified dispersion of octopus hydroquinone; 1st sensitized milk layer Silver iodobromide emulsion (silver iodide; 6 mol%)...Silver coating amount 0,
797m2 Coupler EX-4...0.23 mole per mole of silver Coupler EX-2...0.0/! to 1 mole of silver! t mol 1st θ layer; 2nd H-sensitive emulsion layer Silver iodobromide (silver iodide 1 mol)... Silver coating amount 0, A f / m 2 Coupler EX-ff... 0003 mol 11th per 1 mol silver Layer; 1st If! , layered silver iodobromide (silver iodide 1 mol%, average grain f=, 0.07μ
)・・ Silver coating amount 0,597 m2 Gelatin layer 1st co-layer containing emulsified portion of ultraviolet absorber UV-/; 1st protective layer trimethylmethanoacrylate particles (diameter approx. 1).

Apply gelatin layer.

In addition to the above composition, gelatin hardener 1 (-/) and a surfactant were added to each layer. The sample prepared as described above was designated as sample (λA).

〇-Q O-0 Country (), 6 Taku's O ■ ■ 工■ t-% -ノ■! 1 0 Q Cabinet engineer I/1= 5 Q, ! Country -No1 @'s I went there.

l Color development...3 minutes 15 seconds 2. Bleached white... 30 seconds 3 Washing with water...3 minutes/j seconds Arrive at France in 30 minutes Wash with water...3 minutes lj seconds t Stability...3 minutes/j seconds The composition of the treatment liquid used in each step is as follows.

Color range 1 solution Sodium nitrilotriacetate i, op Sodium sulfite a, op Sodium carbonate 30.01 Potassium bromide /, 44f/ Hydroxylamine sulfuric acid λ, Hirof Der (N-ethyl-N-β-hydroxyethylamine /)-u-Methylaniline sulfate Hiroshi, 5g Add water /l Bleach solution Ammonium bromide 71080g Ammonia water (2!) 2! , Occ ethylenediamine-sodium tetraacetate /30. Of/ Glacial acetic acid 74'・Occ Add water / l Fixing solution Sodium tetrapolyphosphate λ, Of sodium sulfate ≠, Og fOwLm'77monium (70%) / 7 j
, OCC sodium sulfite ≠, AM Add water /71 Stabilizing liquid formalin 1. Occ Add water / β Example coupler (3) of the Vth layer of sample, 2A Example coupler (/J), Comparative coupler (10t), (10,2)
Sample 2B12C was prepared in the same manner as sample A except for changing to
,,2D was created.

Comparison coupler (lO
Sample 2E was prepared in the same manner as above except that the coating amount was changed to 0.031 mol per 1 mol of silver.

The obtained sample was exposed to white light and subjected to the same treatment as in Example/1, and the optical density was measured using red light to obtain the results shown in Table 3.

From the results in Table 3, the couplers of the present invention show a significant improvement in conversion to 1. Moreover, when comparing the S values of the sample λg (!: RIs4) in which the sensitivity was improved by increasing the amount of the comparative coupler applied, the sample A, 2jJ3ka0, 00 J', o, o
.

It can be seen that 1.2E is 0.0/j compared to that, and the graininess is also excellent.

Patent applicant η Photo Film Co., Ltd. Procedural amendment 1, case description Showa SR < 1 and V) Application No. 1P 6 6
No. 2, Title of the invention Silver halide color photographic material 3
, Part 1 related to the person making the amendment case Special #'r Applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (52
0) Tomisuri 'y''j Film Co., Ltd. 4, subject to correction
Column 5 of ``Detailed explanation of one invention in one specification'', content of amendment The description in the section of ``Detailed explanation of one invention in one specification'' is amended as follows.

l) Page 3, line 7 "Anion and" "As an anion" and correct it.

j) Page 3, line 1 "Sharpness" ``Sensai 1 Sword'' and correct it.

3) Page 6/line 3 “1st place” [2nd place] and correct it.

1st line of hat 1st page "λ-phenyl" "No frills" and correct it.

j) 1st/Wataru 7th line 1 Heterocycle” "With Peter Ring" and correct it.

Claims (1)

[Scope of Claims] A silver halogenide color photographic material containing a cyan dye-forming coupler represented by the following general formula (1). General formula CI) In the formula, R represents a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group, X represents a norogen atom, and R' represents a substituted or unsubstituted alkyl group, aryl group, or alkenyl group. represents a group, a cycloalkyl group, or a complex group, n represents an integer from / to j, and when n is 2 or more, X may be the same or different.