JPS6287959A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To increase the sensitivity of a silver halide color photographic sensitive material and to improve the quality of an image by incorporating at least one kind of specified cyan dye forming coupler into the sensitive material having at least one silver halide emulsion layer on the support. CONSTITUTION:This silver halide color photographic sensitive material having at least one silver halide emulsion layer on the support contains at least one kind of cyan dye forming coupler represented by th formula (where R1 is a 1-3C aliphatic group, R2 is halogen, an aliphatic group, an aliphatic oxy group, carbonamido, sulfonamido, carbamoyl, sulfamoyl or an aliphatic oxycarbonyl group, R3 is a ballast group and m is an integer of 0-3). The silver halide particles in the silver halide emulsion may be fine particles of <=about 0.1mum particle size or coarse particles of about 10mum diameter on a projection. The emulsion may be a monodispersion type emulsion having a narrow distribution or a polydispersion type emulsion having a wide distribution. The sensitive material the high sensitivity and the quality of an image is improved.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a novel cyan dye-forming coupler (
The present invention relates to a silver halide color photographic light-sensitive material which has high sensitivity, excellent image quality, and improved processing suitability by using a cyan coupler (hereinafter referred to as a "cyan coupler").

(Prior Art) When a silver halide color photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic-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 blue, green, and red, images of yellow, magenta, 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.

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 are non-diffusible by reacting with the oxidized form of the color developer formed by development. forms a pigment.

The reaction between the coupler and the color developing agent takes place at the active sites of the coupler, and couplers with hydrogen atoms at these active sites are equivalent couplers, i.e., stoichiometrically, 4 moles of developing agent are required to form 1 mole of dye. It requires silver halide with a nucleus.

On the other hand, those having a group capable of leaving as an anion at the active site are 2-equivalent couplers, that is, couplers that require only 2 stoichiometric moles of silver halide having development nuclei to form 1 mole of dye. However, compared to equivalent couplers, the amount of silver halide in the photosensitive layer can generally be reduced and the film thickness can be made thinner, which makes it possible to shorten the processing time of the photosensitive material and further improve the color image formed. The sharpness of the image is improved.

Conventionally, phenolic couplers and naphthol couplers have been used as cyan dye-forming couplers. In particular, naphthol couplers have an absorption maximum (λ
max), long wavelength, small absorption in the edge region, excellent color reproducibility, and many couplers with excellent color development have been discovered and have been widely put to practical use, especially in color negative light-sensitive materials.

However, this naphthol coupler, specifically λ-alkylcarbamoyl/-naphthol coupler or phenol coupler, is used in the bleaching or bleach-fixing process of the color development process, in the bleaching or bleach-fixing solution or fatigue. If the oxidizing power is weak, it has the disadvantage that sufficient color image density cannot be obtained by rubbing.This phenomenon is caused by the reduction of cyan dye by ferrous ions generated during the bleaching or bleaching process. Fading is said to be one of the causes.

A phenolic coupler having a ureido group at the 2nd position and a carbonamide group at the 5th position was developed with the aim of overcoming such drawbacks, as disclosed in Japanese Patent Application Laid-open No. 36-6J/34, the same! 7
−． 204LJμ3 cedar, same j7-20≠5ti-t,
, No. 67-20≠jvj, No. jf-332≠R, No. 31-33.230, etc. Although such couplers have the advantage that the color images are resistant to light, heat, and humidity, they do not have sufficient coloring properties even when used as divalent couplers. The disadvantage was that it was not possible to obtain Such drawbacks of couplers have been undesirable in photographic light-sensitive materials, as they result in lowered sensitivity and lowered image quality.

On the other hand, US Patent No. 3. ≠, r f , /7
3, JP-A No. 39-1036 Compound Example C-/l and JP-A No. 9011AI Compound Example C-23, i.e., 2-arylcarbamoyl-1
-Naphthol couplers are less prone to reductive fading of dyes during the above-mentioned bleaching or bleach-fixing treatments, and are superior in terms of color development compared to 2-ureido-j-carbonamidophenol couplers; The performance was still insufficient to be used in photographic light-sensitive materials that have recently become more sensitive and improved in image quality, as the image density was not sufficient or the sensitivity was not sufficient.

(Problems to be Solved by the Invention) The first object of the present invention is to provide a silver halide color photographic material with high sensitivity and improved image quality by using a new cyan coupler.

A second object of the present invention is to use a novel cyan coupler to reduce fatigue during bleaching or bleach-fixing processes.
- It is an object of the present invention to provide a silver halide color photographic material in which the cyan coloring density decreases extremely little even when a bleaching or bleach-fixing solution with weak oxidizing power is used.

(Means for Solving the Problems) The object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, which is represented by general formula (1). This is achieved by a silver halide color photographic material containing at least one cyan dye-forming coupler.

General formula [1] ■ In the formula, R1 is an aliphatic group having carbons i/ to 3, R2 is a halogen atom, aliphatic group, aliphatic oxy group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group or an aliphatic oxycarbonyl group, R3 represents a ballast group, and m represents an integer from O to 3. However, the total number of carbon atoms in (R2)m does not exceed j.

Here, the aliphatic group refers to a linear, branched or cyclic group,
Refers to saturated and unsaturated aliphatic hydrocarbon groups (the same applies hereinafter).

The substituents R, , I't2 and R3 in general formula (1) will be described in detail below.

R1 is an aliphatic group having up to 3 carbon atoms, and specific examples include methyl, ethyl, propyl, isopropyl, allyl, pro/grugyl, 2-methoxyethyl, 3-hydroxyethyl, 3-chloroethyl, etc. can be mentioned.

R2 is a halogen atom (e.g. fluorine, chlorine, bromine, etc.),
Aliphatic groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, trifluoromethyl, allyl, acetamidomethyl, etc.), aliphatic oxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, impropoxy, inpropoxy, in butoxy, aryoloxy, propargyloxy, methoxyethoxy, ethoxyethoxy, 3-chloropropoxy, etc.), carbonamide groups (e.g. acetamide, propanamide, butanamide, trifluoroacetamide, hydroxyacetamide, chloroacetamide, isobutanamide, etc.) ), sulfonamide groups (e.g. methylsulfonamide, ethylsulfonamide, butylsulfonamide, etc.), carbamoyl groups (
For example, methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, etc.), sulfamoyl groups (such as methylsulfamoyl, dimethylsulfamoyl, dimethylsulfamoyl, etc.) and aliphatic oxycarbonyl groups (
For example, methoxycarbonyl/, ethoxycarbonyl. m is an integer from 0 to 3, and when m is plural, the plural R2s may be the same or different from each other. R
3 represents a ballast, that is, a group having the size and shape necessary to impart diffusion resistance to the coupler; specifically, an aliphatic group having from ♂ to 3 carbon atoms, and an aliphatic group having from 10 to 3 carbon atoms;
Mention may be made of aromatic groups with a carbon number of up to 6 and heterocyclic groups with a carbon number of from .theta. to 36. The term "aliphatic group" as used herein has already been defined and may be used as a substitute. The term "aromatic group" refers to a substituted or unsubstituted monocyclic or condensed ring group. The term "heterocyclic group" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group.

In the compound represented by the general formula (1), m is preferably O, and R3 is preferably an aliphatic hydrocarbon group. More preferably R3 is a hydroxy group.

Carboxy group, sulfo group, carbonamide group, aliphatic oxycarbonyl group, sulfonamide group, carbamoyl group, sulfamoyl group, heterocyclic group, halogen atom, aliphatic sulfonyl group, aliphatic sulfinyl group, aliphatic oxy group, f is an aliphatic group substituted with an aliphatic thio group, and among them, an aliphatic group substituted with a carboxy group or a carbamoyl group is particularly preferable.

The coupler represented by the general formula (1) is a substituent (2 bonded to each other via a divalent or more than divalent group in 3).
(or a polymeric coupler bonded to the main chain of the polymer via a linking group in R3. In this case, the number of carbon atoms mentioned in R3 may be The range may be outside the specified range.

Specific examples of the compound represented by general formula (1) are shown below.

0CH2CH2SCHC12H25 (210OH QCH2CH2SO2C1□H25 0OH OC112C) 12NH8O2C, 2H25 General formula [■
The compound represented by ] is generally synthesized by method A or B shown below.

Rad (VI: 00H phenol-sano-→ g Here, X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a tosyloxy group, etc.).

In A, in reaction (1), a and b are reacted without a solvent or using a solvent such as benzene, toluene, xylene, acetonitrile, etc. to obtain C. Then in reaction (11) C
and alcohol R3-OH are dehydrated and condensed using para-toluenesulfonic acid as a catalyst and a solvent such as benzene, toluene, xylene, etc. to obtain the target product dQ. R3 can also be further chemically transformed to obtain the desired performance in d.

In reaction curve (B), e and R3-X are reacted in a solvent such as dimethylformamide or dimethylacetamide in the presence of a base such as sodium hydroxide, potassium hydroxide, or sodium methoxide to obtain ". Then the reaction Qφ
Then, f and phenol are reacted in a solvent such as acetonitrile or toluene by adding thionyl chloride to obtain g. reaction(
In V), g and Nirin b are reacted under the same conditions as in reaction (1) to obtain the target product d. A synthesis example is shown below.

(Synthesis Example) Synthesis Example/-Synthesis of Exemplary Compound (2)-/, 4! -dihydroxy-2-naphthoic acid phenyljθ
1 was dispersed in 1/00 ml of toluene, and phenetidine≠7y was added dropwise while heating and refluxing under a nitrogen stream. After heating under reflux for 3 hours, toluene was distilled off. Methanol to the residue, 2
! ;Odl, f was added to crystallize, and the precipitated crystals were filtered and dried to give 2-(2-ethoxyphenylcarbamoyl)-/,4
377 4-naphthohydroquinone was obtained.

! -(2-ethoxyphenylcarbamoyl)-/, IJ
- Naphthohydroquinone 37y, Bromohydrin 37.
39 and paratoluenesulfonic acid λjy, toluene, 2
0011t was added, and the mixture was heated and refluxed under a nitrogen stream, and the generated water was removed using a water separator and an e-lator. After heating for 3 hours and cooling, the precipitated crystals were overdried to give ≠-(2-bromoethoxy)-2-(2-ethoxyphenylcarbamoyl'
) -/--1)-3ty of phthol was obtained.

≠-(2-Bromoethoxy)-λ-(2-ethoxyphenylcarbamoyl)-/-1-phthol λ/, Jy and 2-mercaptomyristate ethyl/7.3y, Impropatool λ00d was added and heated under a nitrogen stream. Potassium hydroxide // under reflux.

A solution of 2y in 10d of water was added dropwise. After heating under reflux for an hour, the mixture was cooled, neutralized with concentrated hydrochloric acid, and the precipitated coarse crystals were filtered.

The crude crystals were dissolved in a mixed solvent of ethyl acetate and acetonitrile, purified with activated carbon, and then crystallized.

The precipitated crystals were filtered with C, washed with acetonitrile, and then dried to obtain the desired exemplary compound f21k, 23y.
Obtained. Melting point: 10~/10°C Elemental analysis value (C35H47NO6S) Synthesis example λ - Synthesis of exemplified compound (3) The mixture was heated under reflux for 70 hours under a nitrogen stream. Toluene was distilled off, and the residue was crystallized from a mixed solvent of ethyl acetate and n-hexane. The precipitated crystals were temporarily dried to obtain 2-(2-propoxyphenylcarbamoyl)-71 μm naphthohydroquinone.

λ-(,!-Proboxyphenyl Rubamoyl)-/
, Hiro-Naphthohydroquinone 429, Bromohydrin 3
Toluene 20% to 26% Tata and paratoluenesulfonic acid
0d was added, and the mixture was heated and refluxed under a nitrogen stream, and the produced water was removed using a water pump. After heating under reflux for 2 hours, toluene was distilled off, and 200 ml of ethyl acetate was added for crystallization. The precipitated crystals were temporarily dried to give μm(2-bromoethoxy)-1-(2-propoxyphenylcarbamoyl).
−/− 371 naphthol were obtained.

≠-(,2-bromoethoxy)-λ-(,2-propoxyphenylcarbamoyl)-nonaphthol 2.2.2
Ethyl p and 2-mercaptomyristate/7.3j)
Improper tools,! The mixture was heated to reflux under a nitrogen stream, and a water/lθd solution of potassium hydroxide was added dropwise. After heating under reflux for μ hours, the mixture was cooled, concentrated hydrochloric acid was added, and the precipitated crude crystals were filtered out. The solution was heated and dissolved in crude crystalline acetonitrile (JOOd), mixed with activated carbon, concentrated to about 20 oytt, and crystallized. The precipitated crystals were allowed to pass, washed with ace-1-nitrile, and dried to obtain the desired exemplified θ compound (2).
2θ0.2 was obtained.

Melting point g~'? 2°C Elemental analysis values (C36H, NO6S) The cyan coupler of the present invention achieves the purpose of the present invention by using 0.002 to 0.3 mol per 1 mol of photosensitive halogen (t[) in the layer to be introduced. can do.

Couplers of the present invention and couplers that can be used in combination are:

It can be introduced into the photosensitive material by various known dispersion methods, such as a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. In the oil-in-water dispersion method, after dissolving either a high-boiling point solvent with a boiling point of /7j'C or higher and a low-boiling point so-called auxiliary solvent alone or in a mixture of the two, the presence of a surfactant is determined. It is then finely dispersed in an aqueous medium such as water or an aqueous gelatin solution. Dispersion may be accompanied by phase inversion and, if necessary, co-solvent distillation.

It may be used for application after being removed or reduced by noodle washing or ultrafiltration.

Specific examples of dove-boiling organic solvents include heptatarate esters (dibutyl phthalate, dicyclohexyl phthalate,
(di-2-ethylhexyl phthalate, didodecyl phthalate, etc.), esters of phosphoric acid or phosphonic acid (triphenyl phosphate, tricresyl phosphate,
λ-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-λ-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-X-ethylhexylphenyl phosphonate, etc.)
, benzoic acid esters (-monoethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl-p-
hydroxyhenzoate, etc.), amides (diethyldodecanamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (stearyl alcohol, l,≠-di-tert-amylphenol, etc.),
Aliphatic carboxylic acid esters (dioctyl azelate,
(crycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives (
N, N-dibutyl-λ-butoxy, 3-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and as auxiliary solvents, solvents with a boiling point of about 30° to about Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

In the silver halide color photographic material of the present invention, any of silver halide 7 such as silver halide, silver iodobromide, silver chlorobromide, silver chloroiodobromide, silver arsenic chloride, and silver chloroiodide is used. Silver iodobromide is preferable for high-sensitivity light-sensitive materials. In the case of silver iodobromide,
The silver iodide content is usually ≠ θ morti or less, preferably 2
It is 0 molti or less, more preferably 10 molti or less.

The above-mentioned silver halide grains may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape, or may have a twin crystal shape. It may be one with crystal defects such as planes or a composite form thereof.

Also, mixtures of particles of various crystal forms may be used.

The grain size of the silver halide described above may be fine grains of about 0.07 microns or less, dog-sized grains with a projected area diameter of up to about 10 microns, monodisperse emulsion with a narrow distribution, or polydisperse with a wide distribution. An emulsion may also be used.

Further, tabular grains having an aspect ratio of j or more may be used in the above emulsion layer.

The crystal structure of the emulsion grains mentioned above may be uniform, or may be composed of different halogen compositions inside and outside (or may have a layered structure). o, z7.i≠6, US Patent No. 3,!;0.
f, 0ls1, 4≠, ≠≠≠.

It is disclosed in Japanese Patent Application No. ♂77 and Japanese Patent Application No. 31-2≠, r4Lg. Further, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as Rodin buttons or lead oxide may be bonded.

The above-mentioned emulsion may be of a surface latent image type in which a latent image is formed on the surface, or an internal latent image type in which a latent image is formed inside one grain, or a type in which both the surface and interior K have latent images.

The silver halide photographic emulsion that can be used in the present invention can be produced using any known method, for example, Research Disclosure % /7 Otsu Otsu, No. /7 Otsu p3 (February 1971), 22-23 Page, “■.

Emulsion Preparation
n and Types)” and the same, vol. 117, No.
, / g 7 /6 (15'7P year//month), 6≠g
You can follow the method described in Tei.

The photographic emulsion used in the present invention is based on "Physics and Chemistry of Photography" by Grafkide, published by Ballmo Methyl Co., Ltd. (p.
Des, Chimie et Physiqueph
otographique Paul Monte
G, F, Duffin, Photo
graphicEmulsion Chemistry
y (Focal Press.

``Production and Coating of Photographic Emulsions'' by Zelikman et al.
, for Focal Press (V, L, Zelikmane
tal, Making and Coating p
photographicEmulsion, pocal
press, /ri6t1. ), etc., as appropriate.

In preparing the photographic emulsion used in the present invention, various silver halide solvents (for example, ammonia, Rodankali, or U.S. Pat. No. 3.27/, 157, JP-A-Sho!/
-/, No. 2360, JP-A No. 53-h Jin 0g, JP-A No. 3
3-/4t≠3/7 issue, JP-A Sho, 5≠-1007/7 or JP-A Shojhiro-/! Thioether compounds and thione compounds described in No. 3g2g etc.) can also be used.

Furthermore, as a monodispersed emulsion, the average particle diameter is approximately θ.

Emulsions with silver halide grains larger than 7 microns, at least 5% by weight of which are within ±tAO% of the average grain diameter are typical. Average particle diameter is 0.23-
．． Emulsions can be used in the present invention having silver halide grains of at least 2 microns or at least 7j by weight or (number of grains) within the range of average grain diameter ±1 OS.

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 present.

The emulsion used in the present invention is one that has undergone physical ripening, chemical ripening, and spectral sensitization.

The additives used in such processes are based on the research and research mentioned above.
Disclosure No. / 7g 113 ( / 9
7g/February) and the same No./g 7/Otsu (/
1/month in 1977), and the relevant sections are summarized in the table below.

Known photographic additives that can be used in the present invention are also listed in the one Research Disclosure mentioned above, and their locations are shown in the table below.

Additive type RD/7 Otsu 4'3 RD/11'
7/Otsu/ Chemical sensitizers, 23 Tei 6≠Right column 2 Sensitivity increasing agents Same as above 3 Spectral sensitizers, , 23-2μ pages Otsu≠The right column of the page~Supersensitizers 6≠Right column of the next page ≠ Brightener
λj Anti-fogging agent j4'-2≠Page A77?77
? And stabilizer O light absorber, F! J-CoO page 1,149 Right column ~ Ilter dye AJO left column Ultraviolet absorber 7 Anti-stin agent 2! ;Page right column 6! ;0 page left~
Right column g Dye image stabilizer 2j Teita Hardening agent Page 2 tji Page left column/θ
Binder 26 Sada Same as above/l Plasticizer, lubricant λ7 Sada 80 right column/2 Coating aid,
Table jA-, page 27 Same surface active agent/3 Static prevention,! Page 7 Stopping Agent As the yellow coupler that can be used in the present invention, a typical example is a hydrophobic acylacetamide coupler having a ballast group. A specific example is US Patent No. 2.
≠07.210, 2017.0.57, and 3.263.306. The use of two-equivalent yellow couplers is preferred for the present invention, and U.S. Pat.
No. 3. No. 33.301 and No. ≠, 02λ.

Is it the oxygen atom separation type yellow coupler described in No. 620, etc., or Tokuko Sho 3g-1073? No., U.S. Patent No. ≠, uO/, 732, No. 1A, 326.0211-
No., RD/Zθ33C1 (7 years μ month), British Patent No. 1
．． ≠No. 25,020, West German Application Publication No. j,! /ri, 97
No. 7, No. 2,261, 3 Otsu No. 1, No. -132, j
No. 7 and No. 2≠33. A typical example is the nitrogen atom separation type yellow coupler described in ♂ No. 12 and the like. α-Pivaloylacetanilide couplers Coloring dyes have excellent fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include intazolone-based or cyanoacetyl-based couplers, preferably j-pyrazolone-based and pyrazoloazole-based couplers, which have a ballast group and are hydrophobic. The j-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, or from the viewpoint of the hue and color density of the coloring dye.
3ii, og No. 2, og No. 2, 3≠3,703, og No. 2
．． 1.00,7gg, 2.90g, 373, 3.06λ, 1s63, 3. /j2,lf! ;
1z No. 3,936,075, etc. As a leaving group for a bimodal j-pyrazolone coupler, the nitrogen atom leaving group described in US Pat. ;/, l! Particularly preferred is the ruthio group described in No. 7. The j-virazolone coupler having a ballast as described in European Patent No. 73.636 provides high color density. Examples of pyrazoloazole couplers include birazolohenzimitazoles described in U.S. Pat. No. 3.061.4t32, preferably pyrazolo (J, /-c) described in U.S. Pat. No. 3,723,0ls7. (/.

2, μ] Human Triazole Research Disclosure No. 2≠220 (/?gtA, Otsuzuki) and JP-A-60-3.33! Pyrazolotetrazoles described in λ and Research Disclosure, No. 2≠
230 (/rig≠June) and JP-A-60-≠36j
Examples include the pyrazolopyrazole domain described in No. Imidazo[/,
2-b] Preferred are pyrazoles, as described in European Patent No. 1/1
Pyrazolo(/, j-bJ(/.

2, μ] Triazole is particularly preferred.

Cyan couplers that can be used in combination with the cyan coupler of the present invention include phenolic couplers.

A specific example is U.S. Pat. No. 2,367, Octopus No. 7.

Same No. 29gθi, i”yi, Same No. 2,77.2./
No. 62, same No. 2. ♂ri! It is written in 1g2 Otsu issue etc. Cyan couplers, which are robust to humidity and temperature, are preferably used in combination; a typical example is U.S. Pat.
．． μ ≠ No. 6,622, same No. ≠.

333, Tade No. 7, same No. t, ≠! These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the j-position, which are described in J7, No. 7.47, and the like.

In order to correct unnecessary absorption of color pigments, it is preferable to use a colored coupler in combination with a color negative sensitive material for photographing to perform masking. Colored couplers are based on the research mentioned above.
Disclosure, No.

776≠3, described in items ① to G.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. μ3/, ♂ko 0 and Hiro the same, ogo.

, No. 211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 11.31+7,212.

Couplers that release photographically useful residues upon coupling may also be preferably used in the present invention. As a DIR coupler that releases a development inhibitor, the patented coupler described in the aforementioned Research Disclosure, No. /76≠3, Section Vll-F is useful.

The light-sensitive materials produced using the present invention contain hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, and sulfonamide phenols as color-fogging inhibitors or color-mixing inhibitors. It may also contain derivatives and the like.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Organic anti-fading agents include hydroquinones,
o-Hydroxychromans, t-hydroxycoumaran [
, spirochromans, p-alkoxyphenols, bisphenols, hindered phenols,
Typical examples include gallic acid derivatives, methylene dioxybenzenes, amine phenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Also, metal complexes typified by (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

The light-sensitive material according to the present invention includes, in addition to the silver halide emulsion layer,
It is preferable to provide appropriate auxiliary layers such as a protective layer, intermediate Jd, filter layer, antihalation layer, and back layer.

The color photographic material according to the present invention is disclosed in the above-mentioned Research Disclosure, No. /76μ3! g~2
The developing process can be carried out by the usual method described in the left column to the right column of the tsi page of the same page and No./g7/O. The color photographic light-sensitive material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, whitening and fixing treatment.

A bleach bath using a bleach accelerator may be followed by bleach fixing.

In the washing process, it is common to use countercurrent washing in tanks larger than one to conserve water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A No. 7-46≠3 instead of the water washing step. In the case of this process, 2~
? A countercurrent bath in the tank is required. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, membrane pu
(e.g. pHJ~g)
For example, borate, metaborate, borax, phosphate,
Typical examples include carbonate, potassium hydroxide, sodium hydroxide, ammonia water (used in combination with monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.) and formalin. In addition, water softeners (
Inorganic phosphoric acid, mininopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), fungicides (benzisothiazolinones, isothiazolones, etc.)
Various additives such as thiazoline benzimidazoles, halogenated phenols, etc.), surfactants, optical brighteners, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used in combination. Good too.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium periosulfate.

The present invention can be used in general silver halide color photosensitive materials such as color negative films, color to/on films, color positive films, color reversal films for slides, color reversal films for movies, and color reversal films for TV. In particular, when used in color negative films that require high sensitivity and high image quality, especially color reversal films, remarkable effects can be obtained in improving sharpness and graininess.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example/Samples 10/-/10, light-sensitive materials each consisting of layers having the compositions shown below, were prepared on a cellulose triacetate support. The couplers contained in the first layer are shown in Table 1.

1st layer: Silver iodobromide emulsion (silver iodide≠molti) Silver coating amount /, ≠≠jF / m
'Sensitizing dye I 91 moles ≠, s x io moles Sensitizing dye ■ record 1 mole /, j Completed acrylate particles (diameter approx./.

In addition to the above composition, a gelatin hardening agent H-/A and a surfactant were added to each gelatin layer containing 3 μm).

Compound sensitizing dye I used to prepare the sample: anhydro-3,! ;'-dichloro-3,
3'-di(γ-sulfopropyl)-7-nityruthiacarpocyanine hydroxide pyridinium salt was color-sensitized. =j
'-Dibenzothiamine hydroxide triethylamine salt) 1-/: (CH□-Cn2O2CH□CQNIICH
After exposing one sample /θl to /lθ obtained from 2+2 for sensitometry, the following development treatment (A
) was carried out at 3g0C.

／、Color development・・・・・・・・・・・・・・・・・・
・・・・・・ 3 minutes/3 seconds, bleach ・・・・
・・・・・・・・・・・・・・・・・・・・・ 6 minutes 30 minutes
Second 3, wash with water ・・・・・・・・・・・・・・・・・・
・・・・・・ 3 minutes/, 5 seconds ψ, fixation ・・・・
・・・・・・・・・・・・・・・・・・ q minutes 20 seconds j, wash with water ・・・・・・・・・・・・・・・・・・
...3 minutes/j seconds 6, stable...
7 minutes 3 seconds The composition of the treatment liquid used in each step is as follows.

Color developer sodium nitrilotriacetate i, oy sodium sulfite p, ay sodium carbonate
30. θ potassium tribromide
/, ≠7 hydroxylamine sulfate
2,≠1≠-(N-Ethyl-N-β-HydroxyethylRyomino) -1-Methyl-Roniline Sulfate ≠,3 Add water -'/2 Bleach solution Ammonium Bromide / O, Oy Ammonia water (2g) 23.0 (capital) Ethylenediamine-tetraacetic acid sodium iron salt /30. θ1 glacial acetic acid
Add li, θ flash water
/ 2 fixer sodium tetrapolyphosphate, x, oy sodium sulfite ≠, oy ammonium thiosulfate (70%) / 7j, Occ sodium biphosphite
<z, add 6y water
7 2 Stable formalin QCC water? In addition / 1. Next, develop in the same manner as in 1 except that the bleaching treatment plate in development [A] is changed to the following processing solution formulation (Development [:B)]
'r went. This bleaching solution is a schematic representation of a state in which a large amount of photosensitive material has been processed and is exhausted.

Treatment step (B) Bleach solution composition (D-/) Add 700 grams of water (D-/)
-, 2) Pour steel wool into (D-, ?) and seal it.

Release 1 Fe (M) - EDTA Fe (li) -
After EDTAI, this /θ0 was added to (D-/) to make the bleaching solution of treatment step (B).
It was treated in the same way as A).

Sample 10/treated in treatment steps (A) and CB)
The density was measured with red light at ~/10.

The results are shown in Table-/.

In Table 1, the relative sensitivity is expressed as a relative value of the reciprocal of the exposure value necessary to provide a density corresponding to [the lowest density factor 0°2]. Well, dye residual rate - treatment CB
) up to 11 degrees/treatment (maximum concentration at AJ x 100
Defined by

From the table - /, compared to the comparative coupler (A, l ~ [sample using EJ (10 / ~ / θj), the sample of the present invention ( / θ O ~ /
/θ) clearly has high sensitivity, and the decrease in color density is extremely small even with a tired bleaching solution.

CB) tc51111 [C] α (DJ (E.J. OCH2CH2so2c, □F125 Example Conducted on a Cuco triacetate film support.

A multilayer color photosensitive material 20/ was prepared, each layer having the composition shown below.

(Sample 20/) 1st; -; gelatin layer containing antihalation layer black colloid; 2nd layer; middle layer 2, gelatin layer containing J-G and an emulsified dispersion of monooctyl hydroquinone; 31st layer; 1st red Sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 5 mol%)...
Flavor application amount /, 6y/m” increase, 1 angular dye ≠, 3 x io ' mol sensitizing dye for 1 mole of sickle ■・・・・・・・・・・・・・・・For 1 mole of yen/ ,!;×10 Molar coupler EX-/・・・・・・・・・0 for 1 mole of button Molar coupler EX-, 2...Tagawa Gin 1 0.0 per mole
03 mole coupler EX-3...0.0002 moles per mole of silver ψ layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide: 10 moles)... ...Amount of trowel applied /, 147/m2 Sensitizing dye■...3 x 10 moles of sensitizing dye for 61 moles... ...for 1 mole of silver/
×10 Molar coupler A ・・・・・・・・・0 for 7 moles of silver
9012 mole coupler EX-, 2...For 1 mole of button...
θ, 00/Otsu mole jth layer; middle layer, ! 6th layer same as layer; 1st green-sensitive emulsion layer Silver iodobromide emulsion (iodide; ≠ morch)...
Trowel application - total /, 29/m2 Sensitizing dye■・・・・・・・・・J x 70 mol sensitizing dye 1'/・・・・・・・・・・・・・・・・・・・・・・・・・・・・J×70 mol sensitizing dye per 1 mol of trowel / 29/m2 ...Co x/θ for 1 mole of silver Molar coupler EX-4......O for 1 mole of silver, OS molar coupler EX-j...Saku1 0.00 moles per mole Coupler EX-A・・・・・・O, ooig moles per mole of silver 7th layer; 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide : Zamorchido......Silver coated t/, 311/m2 Sensitizing dye ■......3 x 10 mole increase per mole of scissors, sensitizing dye ■...・・・・・・・・・・2×10 moles per mole of silver Coupler EX-7・・・・・0.0% per mole of silver
0/7 Molar coupler EX-4......0.003 mol per 1 mol of gM G layer; Yellow filter single layer Seratin aqueous solution containing yellow colloid and λ, J-T
- Seventh gelatin layer containing an emulsified dispersion of octylhydroquinone; First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; 2 mol %)...
...Silver coating amount 0.777 m" Coupler EX-7...0.2 per 1 mole of silver!; Molar coupler EX-10...For 1 mole of silver 0.
0/! r mole 10th layer; 2'l! r-sensitive emulsion layer silver iodobromide (silver iodide; mole %)... Silver coating amount 0.6 f/m2 Coupler EX-T... Kawa... Per 1 mole of Senshi Te 0.
06 mol 1st/layer; First protective layer silver iodobromide (silver iodide 1 mol, average grain size θ, 07 μ)...
・・・・・・・・・ Trowel application-sha 0.3y/
7.2 layer of gelatin containing an emulsified dispersion of the m2 ultraviolet absorber UV-/; first protective layer applying a gelatin layer containing polymethyl methacrylate particles (diameter approx./, jμ);

In addition to the above composition, a ceratin curing agent H-/ and a surfactant were added to each layer.

The sample prepared as described above was designated as sample 20/.

Compound sensitizing dye used to prepare sample ■: Anhydrotor ethyl! ,! ;'-Cycloro3.3'-di(γ-sulfoflovir)oxacarpodianine sodium salt sensitizing dye 1v: Anhydro-! ,At,! r', A'-tetrachloro-7
,/'-diethyl-3,3'-di(β-[β-(γ-
sulfopropoxy)ethoxy]ethylimidazolocarpositin hydroxide sodium salt EX-COEX-3 EX-4' Coupler EX-I α Coupler EX-7 Coupler gx-,i' EX-/.

The coupler (A) of the qth layer of UV-/sample 20/ is shown in Table-λ.
Sample 20. l! ~, 210 were produced.

After exposing the obtained sample 20/~2.20 to light for sensitometry, two types of development processing [A] and CB) were performed in the same manner as in Example 1, and the density of the processed sample was measured using red light. was measured.

The results are shown in Table 2.

Samples using comparative couplers (AJ to [E]) from Preview Table-2 (
Samples of the present invention (206-21
No. 0) has high sensitivity, and the decrease in color density is extremely small even with a tired bleaching solution, and the effect of the present invention is clear.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material having at least one silver halide emulsion layer on a support, comprising the general formula [
A silver halide color photographic material containing at least one cyan dye-forming coupler represented by I. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aliphatic group having 1 to 3 carbon atoms, and R_
2 is a halogen atom, an aliphatic group, an aliphatic oxy group, an aliphatic oxycarbonyl group, a carbonamide group, a sulfonamide group, a carbamoyl group, or a sulfamoyl group, R
_3 represents a ballast group, and m represents an integer from 0 to 3. However, the total number of carbon atoms in (R_2)m does not exceed 5.