JPH0473750A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain cyan images having a high sensitivity and high density and excellent color reproducibility, light resistance, heat resistance and moisture resistance by incorporating a specific cyan color image forming coupler into the above photosensitive material. CONSTITUTION:The cyan coupler expressed by formula is incorporated into this material. In the formula, A denotes a residual group of the cyan coupler; L denotes straight chain or branched alkylene group of >= 3 total C; R denotes a straight chain or branched alkyl group, cyclic alkyl group, aryl group. Since this coupler has high solubility, the coupler does not precipitate and flocculate in the process of applying silver halide color photographic emulsion layers on a base and drying the coating. The coupler has the excellent transparency of color developed dye images and has a high color developing speed and color developing efficiency. Further, the decreasing of the amt.of a high boiling point solvent is possible and the properties of the emulsion films improve. The color reproducibility, light resistance, heat resistance and moisture resistance are, therefore, improved together with the sensitivity.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide color photographic light-sensitive material containing a novel cyan coupler with excellent dispersibility.

(Prior Art) In general, aromatic -
Using a grade amine compound, especially an N,N-disubstituted paraphenylene diane compound, as a developing agent, silver halide grains of a photographic emulsion that have been exposed to light or chemically fogged are reduced, and at the same time, oxidation products of the developing agent and oxidized products of the developing agent are produced. A process is utilized which provides cyan, magenta and yellow dye images by reaction with couplers. For example, a phenol FAR or a naphthol derivative is used as the coupler 7 to form a cyan dye image.

Various methods have been devised for adding a coupler to a photographic emulsion layer, but one method involves introducing a lipophilic ballast group into the coupler molecule, dissolving it in an Im-containing solvent, and adding it by emulsifying and dispersing it. is useful.

The following properties are necessary for a coupler having a lipophilic ballast group in order to produce a color light-sensitive material with excellent photographic properties.

That is, (I) the coupler and the coloring dye produced in color development have high solubility in the high boiling point organic solvent used for dispersing the coupler.

(2) High stability after dispersion in silver halide photographic emulsion;
In addition, a stable coating film can be obtained without precipitation of coupler crystals even after coating and drying on a support.

(3) It has excellent diffusion resistance and does not diffuse into other layers.

(4) It has a high camping activity with the oxidation product of the developing agent and has excellent color development.

(51 The color dye image has excellent spectral absorption characteristics, high color density, and is robust to light, heat, and temperature.

(6) It can be obtained in high yield by a simple synthetic method from inexpensive raw materials.

etc.

In order to improve these characteristics, many attempts have been made to modify the structure of the ballast group of cyan couplers.
No. 46384 (US-4゜266.0!, No. 9), Special Publication No. 46-19035 (tJs3,619.196)
, Special Publication No. 48-25932 (US3,785.828
No.), Japanese Patent Application Publication No. 48-71640 (US3,919,9
No. 75), US 2,908.573, Br1t 96
9°921, US3,488,193, [JS35
No. 85.035, US 3.658.537, US 3,
No. 632.347, US 3,684,515, US 3
．． No. 762.921, OI-32062,350, U
S2.993.79], LIS3, 135.609, LIS3. 278. No. 306 and the like can be mentioned.

However, the conventionally known cyan couplers having a ballast group have some drawbacks and do not fully satisfy the above-mentioned necessary properties. Many of these cyan couplers having a lipophilic ballast group have insufficient camping reaction activity with the oxidation product of the developing agent when dispersed in the emulsion layer, or have insufficient solubility in the coupler solvent. In many cases, the dispersibility in the emulsion or coating film was poor, or precipitation or aggregation occurred. Furthermore, many of the conventional cyan couplers are difficult to synthesize and expensive, and also have problems in terms of suitability for production.

(The purpose of the present invention is to provide a coupler capable of obtaining a cyan image with high sensitivity, high density, and excellent color reproducibility, light resistance, heat resistance, and moisture resistance.) The object of the present invention is to provide an emulsion and an excellent method for producing an emulsion that does not cause aggregation and precipitation of couplers during the production of the emulsion.

(Means for Solving Problem R) These objects of the present invention have been achieved by a silver halide color photographic light-sensitive material containing a cyan coupler indicated by the following symbol (+).

-Archive (I) % Formula % In the formula, A is a cyan coupler residue, L is a straight chain or branched alkylene group having a total of 3 or more carbon atoms, R is a straight chain or branched alkyl group, cyclic alkyl group, aryl Representing a group, (
R may have one or more substituents. ) Couplers useful in the present invention are particularly represented by the following general formula (II) among cyan color-forming compounds having at least one -CON H(-L-)-OC-R group other than at the coupling position. Compounds are preferred.

-Archive (U) R,R,X In the formula, R represents a linear or branched alkyl group, a cyclic alkyl group, or an aryl group. L represents a straight chain or branched alkylene group having a total of 3 or more carbon atoms.

X represents a hydrogen atom or a substituent that can be removed during the color development process. R+, Rz, Rs and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a heterocyclic group,
It represents an amino group, a carbonamide group, a sulfonamide group, a sulfamyl group, or a carbamyl group. W represents a nonmetallic atom necessary to form a 5- or 6-membered ring.

R,, L, X, R, , R1, R3, R, and W will be described in more detail.

R is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms (e.g. methyl, isopropyl,
tert-butyl, hexyl, dodecyl, 1-hexylnonyl, etc.), cyclic alkyl groups (e.g. cyclopentyl, cyclohexyl, norbornyl, etc.), aryl groups (
For example, a phenyl group, a naphthyl group, etc.), and these represent a halogen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group, a carboxyl group, an alkylthiocarbonyl group, a ruthiocarbonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, ureido group, urethane group, thiourethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkyl It may be substituted with an amino group, dialkylamino group, anilino group, hydroxo group, mercapto group, etc.

1 represents a straight or branched alkylene group having a total of 3 or more carbon atoms; in the case of a straight chain alkylene group, it is fullkylene having 3 to 12 carbon atoms, preferably 3 to 6 carbon atoms; in the case of a branched alkylene group, The main chain has 1 to 12 carbon atoms, preferably 2 to 6 carbon atoms, and the branched chain has 1 to 12 carbon atoms, preferably 1 to 3 carbon atoms.

To give a more specific preferable example, in CONII Honri-Umbrella Car QC-R, *-L-Motoichi is (a) *4CL)its (
b) * - (CHrto4 books (c) bookflcH
gsu, II (d) l (CHz) - Chapter (e
) CH3(f) CL book-GHzC
H-Umbrella Car Car-CH-CHt-Umbrella Car (i) Ctli (j)
CHiCH.

Examples include C11°. Among them, branched alkylene chains such as (e) to (j) are particularly preferred.

X is a hydrogen atom or a substituent that can be removed during the color development process, and is a halogen atom (e.g., chloro, bromine, etc.), a thiocyano group, an acyloxy group (e.g., acetoxy, dodecanoyloxy, benzoyloxy, etc.), or an aryl group. Oxy group (e.g., phenoxy, p-chlorophenoxy, p-nitrophenoxy, etc.)
, alkoxy groups (e.g., ethoxy, 2-bromoethoxy, methoxyethoxycarbamoyl, methoxy, β-
methanesulfonaminoethoxy, callevobyldimethoxy, α-triarylmethoxy, etc.), arylazo groups (
For example, substituted and unsubstituted phenylazo, naphthylazo, etc.), alkylthio groups (for example, carbon 4-18
alkylthio, etc.), ruthio groups (e.g., substituted and unsubstituted phenylthio, etc.), heterothio groups (e.g., substituted and unsubstituted phenylthio, etc.),
For example, benzothiazolylthio, benzoxazolylthio, benzimidazolylthio, phenyltetrazolylthio, etc.), acylamino groups (e.g., haloalkylacylamino, etc.), sulfonamino groups (e.g., methanesulfonamino, phenylsulfonamino, etc.),
It represents an alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), an arylcarbonyloxy group (eg, phenylcarbonyloxy group, etc.), and the like.

R1, R2, R3, and R4 are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkylthio group, a heterocyclic group, an amino group, a carbonamide group,
Represents a sulfonamide group, sulfamyl group, or carbamyl group. For example, R+ represents any of the following groups.

Hydrogen atoms, halogen atoms (e.g. chloro, brome, etc.)
, primary secondary or tertiary alkyl groups having 1 to 22 carbon atoms (e.g. methyl, propyl, isopropyl, n-butyl, nibutyl, tert-butyl, hexyl, dodecyl, 2-chlorobutyl, 2-hydroxyethyl) ,2
-phenylethyl, l-(2,4,6-1lichlorophenyl)ethyl, 2-aminoethyl, etc.), alkylthio groups (e.g. hexadecylthio, etc.), alkoxy groups (e.g. methoxy, butoxy), aryl groups (e.g. phenyl, -methylphenyl, 2゜4.6-)lichlorophenyl, 3,5-dibromophenyl, 4-trifluoromethylphenyl, 2-trifluoromethylphenyl,
3-trifluoromethylphenyl, naphthyl, 2-chloronaphthyl, 3-ethylnaphthyl, etc.), heterocyclic groups (e.g., benzofuranyl group, furanyl group, thiazolyl group,
henzothiazolyl group, naphthothiazolyl group, oxasilyl group, henzoxazuryl group, naphthoxazolyl group,
pyridyl group, quinolinyl group, etc.), amino group (e.g. amino, methylamino, diethylamino, dodecylamino, phenylamino, tolylamino, 4-(3-sulfobenzamide)anilino, 4-cyanophenylamino,
2-trifluoromethylphenylamino, henzothiazurylamino, etc.), carbonamide groups (e.g., alkylcarbonamide groups such as ethyl, carbonamide, decylcarbonamide, or phenylethylcarbonamide, etc.), phenylcarbonamide, 2, 4.6-1-
Lichlorophenylcarbonamide, 4-methylphenylcarbonamide, 2-ethoxyphenylcarbonamide,
3-[α(2,4-di-tert-amylphenoxy)acetamide] phenylcarbonamide, or an arylcarbonamide group such as naphthylcarbonamide, or thiazolylcarbonamide, benzothiazolylcarbonamide, naphthothia Heterocyclic carbonamide groups such as prylcarbonamide, oxacylylcarbonamide, benzoxasilylcarbonamide, imidazolylcarbonamide, or benzimidaprilcarbonamide, etc.), sulfonamide groups (e.g., butylsulfonamide, dodecylsulfonamide, or Alkylsulfonamide groups such as phenylethylsulfonamide, phenylsulfonamide, 24.6-drichlorophenylsulfonamide, 2-methoxyphenylsulfonamide, 3-carboxyphenylsulfonamide,
or an arylsulfonamide group such as naphthylsulfonamide, or thiazolylsulfonamide, benzothiazolylsulfonamide, imidapril sulfonamide,
a heterocyclic sulfonamide group such as benzimidazolylsulfonamide or pyridylsulfonamide),
Sulfamyl groups (e.g., alkylsulfamyl groups such as propylsulfamyl, octylsulfamyl, pentadecylsulfamyl, or octadecylsulfamyl, phenylsulfamyl, 2,4.61-lichlorophenylsulfamyl) , 2-ethoxyphenylsulfamyl, or naphthylsulfamyl, or an arylsulfamyl group such as thiazolylsulfamyl, hendithiaprylsulfamyl, oxacylylsulfamyl, benzimidazolylsulfamyl, or pyridyl. heterocyclic sulfamyl groups such as sulfamyl groups) and carbamyl groups (alkylcarbamyl groups such as ethylcarbamyl, octylcarbamyl, pentadecylcarbamyl or octadecylcarbamyl, etc., phenylcarbamyl or 2,4. An arylcarbamyl group such as 6-dolychlorophenylcarbamyl, or a heterocyclic group such as thiazolylcarbamyl, benzothiaprilcarbamyl, oxacylylcarbamyl, imidasilylcarbamyl or henzimidaprilcarbamyl group, etc. carbamyl group).

Examples of R, , R, and R4 include those exemplified for R3.

W represents a nonmetallic atom necessary to form a 5- or 6-membered ring as shown below. Namely, Hensen ring, noclohexene ring, socrobentene ring, thiatur ring, oxazole ring, imidazole ring, pyridine ring, virol ring, etc. Among these, the Hensen ring is preferred.

Since the coupler of the present invention has high solubility, the coupler is sufficiently dispersed in the coated film during the process of coating and drying the silver halide color photographic emulsion on the support, and does not cause precipitation or aggregation, resulting in color-forming dye images. It can exhibit many excellent color photographic properties, such as excellent transparency, color development speed, and color development efficiency.

Furthermore, by using the coupler according to the present invention, it is possible to reduce the amount of high boiling point solvent, and this reduction will improve the physical properties of the emulsion film, as well as improve the 'iRH' of the emulsion film, improve resolution, and improve color development, fixing, etc. It is possible to speed up the processing.

Specific examples of the novel cyan coupler included in the present invention are shown below, but the present invention is not limited thereto.

(i) C, H, 0CNI1 (i) CJwOCNH I SCHzCHxCOOH OCOCtNs 0CLCLSCHtCOOH H1 H C! H5 H H J CI+.

-ni+she In the above formula, A, L and R have the same meanings as explained in general formula (I), and Y represents a chloro or bromine atom.

Next, specific synthesis examples will be shown for typical couplers used in the Examples, but other couplers can also be synthesized in a similar manner.

(I1 Synthesis of Compound 3 445.5 g of phenyl ester 1 and 290.1 g of isopropanolamine were dissolved in 600 g of acetonitrile.
The mixture was heated to reflux for an hour. After cooling with water, the precipitated crystals were collected and dried to obtain 342 g of Compound 3. a+p, 162-5°C (2) Synthesis of Compound 5 341 g of hydroxyl compound 3 and 231 g of 2-he-bovine sildecanoyl chloride were heated under reflux for 2 hours in 88 °C of acetonitrile, and after cooling with water, the precipitated crystals were collected. After drying, 437 g of Compound 5 was obtained.

(3) Synthesis of Compound 6 370 g of nitro compound 5, 6 g of 10% Pd-C catalyst, and ethyl acetate I/O were placed in an autoclave and hydrogenated at 50° C. for 3 hours.

After completion of the reduction, the catalyst was separated from the furnace, and the residual aroma obtained by concentrating the furnace liquid under reduced pressure was crystallized with n-hexane, and the precipitated crystals were collected.
After drying, 327 g of amine compound 7 was obtained. mp, 9
5-Bure (4) Synthetic amine form of exemplary coupler (20) 720
．． Dissolve 8 g in 60 ρ of dimethylformamide, and add 7.0 g of concentrated hydrochloric acid while cooling with water. 6ml was added. Furthermore, an aqueous solution of 2.7 g of sodium nitrite and 10 - of water was added dropwise over 20 minutes.
Stirring was continued for 0 minutes to prepare a diazo solution.

Meanwhile, add 79.7 g of pyridone and 13 g of sodium acetate to 30 g of water.
11 dimethylformamide 30R1, and after heating and dissolving, cooling on ice, and stirring at 10° C. or lower, the above diazo solution was slowly added. After continuing stirring for an additional 15 minutes, the mixture was extracted with ethyl acetate and washed with water three times. The m-layer was concentrated under reduced pressure, and the residual aroma was crystallized from methanol-ethyl acetate.
The precipitated crystals were collected and dried to obtain the example coupler (20).
21.

2g was obtained. mP, 117-9°C The light-sensitive material of the present invention is provided with at least one silver halide emulsion layer of a blue-sensitive layer, a green-sensitive layer, and a red-sensitive layer on a support. Generally, there are no particular restrictions on the number and order of the silver halide emulsion layers and non-photosensitive layers. A typical example is a silver halide photographic material having on a support at least one photosensitive layer consisting of a plurality of silver halide emulsion layers having substantially the same color sensitivity but different sensitivities. The photosensitive layer is a unit photosensitive layer sensitive to blue light, green light, or red light, and in a multilayer silver halide color photographic light-sensitive material, the photosensitive layer is generally a unit photosensitive layer. A red-sensitive layer, a green-sensitive layer, and a blue-sensitive layer are arranged in this order from the support side. However, depending on the purpose, the above-mentioned order of installation may be reversed, or the order of installation may be such that different photosensitive layers are sandwiched between the same color-sensitive layer.

Non-photosensitive layers such as various intermediate layers may be provided between the above-mentioned silver halide photosensitive layers and between the uppermost layer and the lowermost layer.

The intermediate layer includes JP-A-61-43748 and JP-A-59-2.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain a commonly used color mixing inhibitor.

The plurality of silver halide emulsion layers constituting each unit photosensitive layer are disclosed in West German Patent No. L12L470 or British Patent No. 92
As described in No. 3,045, a two-layer structure consisting of a back-sensitive emulsion layer and a low-sensitivity emulsion layer can be preferably used. Usually, it is preferable to arrange the layers so that the photosensitivity decreases toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-11
No. 2751, No. 62200350, No. 62-2065
As described in No. 41, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support.

As a specific example, from the side farthest from the support, low sensitivity blue sensitive layer (BL) / high sensitivity blue sensitive layer 1! (BH) / High sensitivity green photosensitive layer (G) I) / Low sensitivity green photosensitive layer (GL
)/high sensitivity red sensitive JW (RH)/low sensitivity red sensitive layer (I?L) or Bit/BL/GL/G)I
/l'lH/RL order, or BH/BL/IJ/GL
/RL/RH, etc.

Furthermore, as described in Japanese Patent Publication No. 55-34932, blue-sensitive N/GH/R
They can also be arranged in the order of H/GL/RI. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/RL/GH/R1 (blue-sensitive layer/GL/RL/GH/R1) may be arranged in this order from the farthest side from the support. can.

In addition, as described in Japanese Patent Publication No. 49-15495, the upper layer is a silver halide emulsion layer with the highest sensitivity, the middle layer is a silver halide emulsion layer with lower sensitivity, and the lower layer is more sensitive than the middle layer. An example is an arrangement consisting of three layers with different photosensitivity, in which a silver halide emulsion layer with a low density is disposed and the photosensitivity gradually decreases toward the support. Even when composed of 3N having different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, a medium-temperature emulsion layer/high-speed emulsion layer/low-speed emulsion layer may be arranged in this order from the side remote from the support.

In addition, high-sensitivity emulsion layer / low-sensitivity emulsion layer / medium-sensitivity emulsion layer,
Alternatively, the layers may be arranged in the following order: low sensitivity emulsion N/medium sensitivity emulsion layer/high sensitivity emulsion layer.

Furthermore, even in the case of four or more layers, the arrangement may be changed as described above.

As mentioned above, various layer structures and arrangements can be selected depending on the purpose of each photosensitive material.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing about 30 mol% or less of silver iodide. . Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 10 mole percent silver iodide.

Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof.

The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be on the polydisperse pore side or as a monodisperse emulsion.

Examples of silver halide photographic emulsions that can be used in the present invention include Research Disclosure (RD) N.

17643 (December 1978), pp. 22-23, I
Emulsion preparation
n and types)” and the same Nα18716
(November 1979), 648 pages, Nα307
105 (November 1989), pp. 863-865,
and the graphic “Physics and Chemistry of Photography”, published by Beaumontel (P, Glafkides, Chemie
et Ph1sique Photographique
E, Paul Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F
, Duffin Photographic Emul
sion Chemistry (Focal Pre
ss1966)), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (ν 1. Zelik
Manetal. Making and coating
g Photographic Emulsion,
Focal Press, 1964).

U.S. Patent Nos. 3,574,628 and 3,655.39
Monodisperse emulsions such as those described in No. 4 and British Patent No. 1,413.748 are also preferred.

Tabular grains having aspect ratios of about 3 or greater can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering), Vol. 14, pp. 248-257 (I970); U.S. Patent No. 4
．． No. 434,226, No. 4,414.310, No. 4,
433.048, 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 above-mentioned emulsions may be of the surface latent image type that forms latent images primarily on the surface, of the internal latent image type that forms inside the grains, or of the type that has latent images both on the surface and inside the grains, but negative-tone emulsions It is necessary that Among the internal latent image type emulsions, a core/shell type internal latent image type emulsion described in JP-A-63-264740 may be used. A method for preparing this core/shell type internal latent image type emulsion is described in JP-A-59-133542.

The thickness of the shell of this emulsion varies depending on the development process, etc., but is preferably from 3 to 40 nIl, particularly preferably from 5 to 20 om.

The silver halide emulsion used is usually one that has been subjected to physical training, chemical ripening, and spectral sensitization. Additives used in such processes are Research Disclosure Sou 17
643, Doshu 18716 and Doshu 307105, and the relevant parts are summarized in the table below.

The photosensitive material of the present invention includes grain size, grain size distribution, halogen composition, grain shape,
Two or more types of emulsions differing in at least one characteristic of sensitivity can be mixed and used in the same layer.

Silver halide grains covered with grain surfaces as described in U.S. Pat. No. 4,082,553, U.S. Pat. No. 4,626,4
Silver halide grains and colloidal silver with covered grain interiors described in No. 98 and JP-A No. 59-214852 are preferably used in a photosensitive silver halide emulsion layer and/or a substantially non-photosensitive hydrophilic colloid layer. Can be used.

Silver halide grains with a puffed interior or surface are defined as
refers to silver halide grains that can be developed (non-imagewise). The yI method for producing silver halide grains in which the inside or surface of the grains is covered is described in US Pat. No. 4,626,498 and Japanese Patent Application Laid-Open No. 59-214852.

Core with fogged grain interior/Scheroda The silver halides forming the inner core of the silver halide grains may have the same halogen composition or different halogen compositions. As the silver halide coated inside or on the surface of the grain, any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide can be used. Although there is no particular limitation on the grain size of these fogged silver halide grains,
The average particle size is preferably 0.01 to 0.75 μm, particularly 0.05 to 0.6 μl. The grain shape is not particularly limited and may be regular grains or polydisperse emulsions, but may be monodisperse (at least 95% of the weight or number of silver halide grains is within ±40% of the average grain size).
% or less).

It is preferred for the present invention to use non-photosensitive V&grain silver halide. Non-photosensitive fine-grain silver halide is a material that is not exposed to light during imagewise exposure to obtain a dye image.
These are fine silver halide grains that are not substantially developed in the development process, and are preferably not fogged.

The fine grain silver halide has a silver bromide content of 0 to 100 mol %, and may contain silver chloride and/or silver iodide, if necessary. Preferably, it contains 0.5 to 10 mol% of silver iodide.

The fine grain silver halide preferably has an average grain size (average diameter equivalent to a circle of projected area) of 0.01 to 0.5 μm, and preferably 0.01 to 0.5 μm.
0.02 to 0.2 μm is more preferable.

Fine-grain silver halide can be prepared in the same manner as conventional photosensitive silver halide. In this case, the surface of the silver halide grains does not need to be optically sensitized, nor is spectral sensitization necessary. However, prior to adding this to the coating solution, it is preferable to add a known stabilizer such as a triazole-based, azaindene-based, hendziadurium-based, or mercapto-based compound, or a zinc compound. This layer containing fine silver halide grains can preferably contain colloidal silver.

The silver hair coated with the photosensitive material of the present invention is preferably 6.0 g/M or less, most preferably 4.5 g/M or less.

Known photographic additives that can be used in the present invention are also described in the three Research Disclosures mentioned above, and the relevant descriptions are shown in the table below.

In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, US Patent No. 4,411.987 and 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. 435,503.

The photosensitive material of the present invention includes U.S. Patent No. 4.740.454, U.S. Pat.
It is preferable to contain a mercapto compound described in JP-A No. 1283551.

A compound that releases a fogging agent, a development accelerator, a silver halide solvent, or a precursor thereof irrespective of the amount of developed silver produced during the development process, which is described in JP-A-1-106052, is added to the light-sensitive material of the present invention. It is preferable to contain.

The photosensitive material of the present invention is disclosed in International Publication No. WO88104794 and Japanese Patent Application Publication No. 1999-1999. It is preferable to include a dye dispersed by the method described in Japanese Patent Application No. 1-502912 or a dye described in BP No. 317.308A, US Pat.

Various color couplers can be used in the present invention, specific examples of which can be found in the aforementioned Research Disclosure N.
α17643, ■-C-C1 and Nα307105
, ■-C-G.

As a yellow coupler, for example, U.S. Patent Box 3.93
No. 3,501, No. 4,022,620, No. 4.3
No. 26,024, No. 4.401,752, No. 4.
No. 248.961, Japanese Patent Publication No. 58-10739, British Patent Box No. 1.425,020, British Patent Box No. 1,476.760, US Patent Box No. 3.973,968, Japanese Patent No. 4.314.
No. 023, No. 4, 5], No. 1,649, European Patent No. 2
49, No. 473A, etc. are preferred.

As magenta couplers, 5-pyraduron and birazoroadurone compounds are preferred;
No. 0,619, No. 4,351.897, European Patent Box No. 73.636, US Patent Box No. 3,061,432, US Patent No. 3725.067, Research Disclosure No. 24220 (June 1984) ), Japanese Patent Application Publication No. 1986
-33552, Research Materials Closure No.
, 24230 (June 1984), JP-A-60-4
No. 3659, No. 61-72238, No. 60-3573
No. 0, No. 55-118034, No. 60-185951
No. 4500.630, U.S. Patent No. 4,540,
No. 654, No. 4,556.630, International Publication WOS
Particularly preferred are those described in No. 8104795 and the like.

Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Patent Box 4,052.212.
No. 4.146.396, No. 4.228.23
No. 3, No. 4.296.200, No. 2,369.9
No. 29, No. 2,801.171, No. 2.772,
No. 162, No. 2.895,826, No. 3,772
, No. 002, No. 3.758.308, No. 4,33
4.011, 4.327.173, West German Patent Publication No. 3329.729, European Patent Publication No. 121.365A
No. 249453A, U.S. Patent Box 3,446.6
No. 22, No. 4,333.999, No. 4,775,
No. 616, No. 4.451.559, No. 4,427
．． No. 767, No. 4.690,889, No. 4.25
No. 4212, No. 4,296,199, JP-A-61-
Preferred are those described in No. 42658 and the like. Furthermore, JP-A-64-553, JP-A-64-554, JP-A-64-555
Pyrazoloazole couplers described in US Pat. No. 64-556 and imidazur couplers described in U.S. Pat.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576910, British Patent No. 2.102.1
No. 37, European Patent No. 341188A, etc.

Couplers whose colored dyes have appropriate diffusivity include U.S. Patent Box 4,366.237 and British Patent Box 2,125.
．． Preferred are those described in No. 570, European Patent No. 96.570, and German Patent Publication No. 3.234,533.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure No. U.S. Patent Box 4,004,929, U.S. Patent No. 4,138,25
No. 8, British Patent Box 1,146,368 is preferred. In addition, there are couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during combing, as described in U.S. Patent Box 4,774,181, and U.S. Patent Boxes 4 and 7.
It is also preferable to use a coupler having as a leaving group a dye precursor group capable of reacting with a developing agent to form a dye as described in No. 77,120.

Compounds that release photographically useful residues upon coupling can also be preferably used in the present invention.

DIR couplers that release development inhibitors are the aforementioned RD
17643, ■-F section and the same No. 307105,
■-Patent listed in Section F, JP-A-57-151944
Preferred are those described in U.S. Pat. No. 57-154234, U.S. Pat.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent Box No. 2.097,140;
No. 2,131.188, JP 59-157638
No. 59-170840 is preferred.

Also, JP-A-60-107029, JP-A No. 60-2523
Compounds that release fogging agents, development accelerators, silver halide solvents, etc. through redox reactions with oxidized developing agents described in Japanese Patent Laid-open Nos. 40, 144940 and 1-45687 are also preferred.

Other compounds that can be used in the light-sensitive material of the present invention include the competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , the multi-equivalent couplers described in JP-A-60-185950, etc.
DIR redox compound releasing couplers, DIR coupler releasing couplers, DI described in JP-A-6224252 etc.
R coupler-releasing redox compounds or DIR redox-releasing redox compounds, couplers that release dyes that change after separation as described in EP 1733028 and EP 313,3084; 2
No. 4241, a bleach accelerator releasing coupler described in JP-A-61-201247, etc. Gantt-releasing coupler described in U.S. Pat. No. 4,555,477, etc., JP-A-63-757
Couplers that emit leuco dyes as described in US Pat. No. 4774.181 and couplers that emit fluorescent dyes as described in US Pat.

The coupler used in the present invention can be introduced into the light-sensitive material by a known dispersion method.

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027 and the like.

The boiling point at normal pressure used in the oil-in-water dispersion method is 175'
Specific examples of high-boiling-boiling, organic 7-volume agents of C or higher include phthalic acid esters (dibutyl phthalate, dichlorohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-t-amyl phenyl) )
phthalate, bis(2,4-di-t-amyl phenyl) isophthalate, bis(I,1-diethylpropyl) phthalate, etc.), esters of phosphoric acid or phosphonic acid (
Triphenyl phosphate, tricresyl phosphate, 2-ethylhexyl diphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phospho7-ate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylhendzoate, 2-ethylhexyl-p)
-hydroxyhenzoate, etc.), amide'R (N, N
-diethyldodecaneamide, N,IJ diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol,
2,4-di-tert-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N,N-diptyl-2-butoxy-5-tert~octylaniline, etc.), hydrocarbons @ (paraffin, dodecylbenzene,
diisopropylnaphthalene, etc.).

Further, as the auxiliary solvent, an organic solvent having a boiling point of about 30"C or higher, preferably 50"C or higher and about 160"C or lower, can be used. Typical examples include ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, and cyclohexanone. , 2-ethoxyethyl acetate, dimethylformamide, and the like.

Specific examples of the latex dispersion process, effects, and latex for impregnation include U.S. Pat. It is described in.

The color photosensitive material of the present invention contains phenethyl alcohol and JP-A-63-257747, JP-A-62-272248
1,2-benzisothiaprin-3-one, n-butyl p-hydroxyhenzoate, phenol, 4-chloro-3,5 described in JP-A-1-80941
-dimethylphenol, 2-phenoquineethanol, 2
- It is preferable to add various preservatives or antifungal agents such as (4thiazolyl)benzimidazole.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, and color reversal paper.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, No. 17643, page 28, same No. 187
16, page 647 right column to page 648 left column, and Nα3
07105, page 879.

In the light-sensitive material of the present invention, the total thickness of all the hydrophilic colloid layers on the side having the emulsion layer is preferably 284 m or less, more preferably 23 μm or less, even more preferably 8 μm or less, particularly preferably 16 μm or less. . Further, the membrane swelling rate T172 is preferably 30 seconds or less, more preferably 20 seconds or less. The film thickness is 25°C relative 1? degree 55%”JAW
Means the film thickness measured under (2nd day), and the film swelling rate T I
/2 can be measured according to techniques known in the art. For example, Knee Green (A, Gr.
Photographic Science and Engineering (Photogr, Sci, E
T1/2 can be measured by using a swellometer (swelling membrane) of the type described in NG, ), Volume 19, No. 2, pages 124-129, and T1/2 can be measured using a color developer at 30°C for 13 minutes.
90% of the maximum swollen film thickness reached when treated for 5 seconds is defined as the saturated film thickness, and is defined as the time required to reach 1/2 of the saturated film thickness.

Membrane swelling rate TI/. can be adjusted by adding a hardening agent to gelatin as a binder or by changing the aging conditions after coating. Further, the swelling rate is preferably 150 to 400%. Swelling rate is the maximum swelling Wi! under the conditions mentioned above. , the thickness can be calculated according to the formula: (maximum swelling film thickness - film thickness)/film thickness.

The photosensitive material of the present invention has a hydrophilic colloid layer (with a total dry thickness of 2 μm to 20 μm) on the side opposite to the side having the emulsion layer.
It is preferable to provide a back layer (referred to as a back layer). This back layer contains the aforementioned light absorber, filter dye, ultraviolet absorber, anti-statink agent, hardener, binder, plasticizer,
It is preferable to contain a lubricant, a coating aid, a surface active agent, etc. The swelling ratio of this bank layer is preferably 150 to 500%.

The color photographic material according to the present invention includes the above-mentioned RD, N
α17643, pages 28-29, same No. 18716, 651 left column to right column, and same No. 307105, 8
It can be developed by the usual method described on pages 80-881.

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 are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl- 4-amino-N-ethyl-β-
Hydroquine ethylaniline, 3-methyl-4-amino-
Examples include N-ethyl-Nβ-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-methoxyethylaniline, and their sulfates, hydrochlorides, and ρ-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-Nβ
-Hydroxyethylaniline sulfate is preferred, and two or more of these compounds may be used in combination depending on the purpose.

The color developer may contain pHM buffers such as alkali metal carbonates, borates or phosphates, chloride salts, bromide salts,
It is common to include development inhibitors or antifoggants such as iodide salts, benzimidazoles, hendithiazoles or mercapto compounds. In addition, if necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as 11.11-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, ethylene glycol, etc. , organic carriers such as diethylene glycol, hensyl alcohol salts, development accelerators such as amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as l-phenyl-3-pyrazolidone, tackifiers, amino acids, etc. Various chelating agents such as polycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, and hydroxyethyliminodiacetic acid. Acetic acid, hydroxyethylidene-1.1
- Diphosphonic acid, nitrilo-LN,L)rimethylenephosphonic acid, ethylenediamine-N,N,N,N tetramethylenephosphonic acid, ethylenediamine di(O-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples. .

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 dihydroxyhenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. They can be used alone or 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.
11tl! You can also do the following: 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.

The contact area between the photographic processing solution and air in the processing tank can be expressed by the aperture ratio defined below.

That is, Capacity of treatment liquid (cm') The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a barrier such as a floating lid on the surface of the photographic processing solution in the processing tank,
Method using a movable lid described in No. 033, JP-A-63
An example of this method is the Surimet development treatment method described in Japanese Patent No. 216050. Reducing the aperture ratio is important not only for both color development and black and white development processes, but also for subsequent processes,
For example, it is preferable to apply it to all steps such as bleaching, bleach-fixing, fixing, washing with water, and stabilization. Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which a bleaching treatment is followed by a bleach-fixing treatment. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. As the bleaching agent, for example, compounds of polyvalent metals such as iron ([[l]), peracids, quinones, nitro compounds, etc. are used. Typical bleaching agents include organic complex salts of iron (III), such as aminopolymer salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, and glycol ether diaminetetraacetic acid. Carboxylic acids or complex salts of citric acid, tartaric acid, malic acid, etc. can be used. Among these, aminopolycarboxylic acid iron (I [[) complex salts, including ethylenediaminetetraacetic acid iron (III) complex salt and 1,3-diaminopropane tetraacetate iron ([1) complex salt] are useful for rapid processing and environmental pollution prevention. Preferable from this point of view. In addition, iron aminopolycarboxylate (n[
) Complex salts are particularly useful in both bleach and bleach-fix solutions. The pl+ of the bleach solution or bleach-fix solution using these aminopolycarboxylic acid iron (I) complex salts is usually 4.0.
~8, but it is also possible to process at an even lower pH for faster processing.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their pre-bath, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290.812, No. 2,059.988, JP-A No. 53-32736, No. 53-57831, No. 53-
No. 37418, No. 53-72623, No. 53-956
No. 30, No. 53-95631, No. 53-104232
Compounds having a mercapto group or a disulfide group as described in Research Disclosure No. 17129 (July 1978), etc.;
Thiazolidine derivatives described in JP-A-50-140129; JP-A-45-8506, JP-A-52-20832
No. 53-32735, U.S. Patent No. 3,706,5
Thiourea derivatives described in No. 61: West German Patent No. 1,127
, 715 and JP-A-58-16,235; West German Patent Nos. 966.410 and 2,748.4
Polyoxyethylene compounds described in No. 30;
Polyamine compound described in JP-A-49-40,943, JP-A No. 49-59, JP-A No. 644, JP-A No. 53-94.927, JP-A No. 54-35,727, JP-A No. 5-8836;
Compounds described in Nos. 5-26.506 and 58-163.940: bromide ions, etc. can be used. Among these, compounds having a mercapto group or a disulfide group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as described in US Pat. No. 3,893.
No. 858, West German Patent No. 1.290.812, Japanese Unexamined Patent Publication No. 5
The compounds described in No. 3-95,630 are preferred. Furthermore,
Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material.

These bleaching accelerators are particularly effective when bleaching and fixing color brightening materials for photography.

In addition to the above-mentioned compounds, the bleaching solution and bleach-fixing solution preferably contain an organic acid for the purpose of preventing bleach staining. Particularly preferred organic acids have an acid dissociation constant (pKa) of 2.
~5, specifically acetic acid, propionic acid,
Hydroquine acetic acid and the like are preferred.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thionoanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. Further, a combination of thiosulfate, thiocyanate, thioether compound, thiourea, etc. is also preferred. As the preservative for the fixer and bleach-fixer, sulfites, bisulfites, carbonyl bisulfite adducts, or sulfinic acid compounds described in European Patent No. 294,769A are preferred. Furthermore, it is preferable to add various aminopolycarboxylic acids and organic phosphonic acids to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

In the present invention, the fixer or bleach-fixer contains p+1
For adjustment, a compound having a pKa of 6.0 to 9.0, preferably imidazoles such as imidazole, 1-methylimidazole, 1-ethylimidazole, and 2-methylimidazole, is added at 0.1 to 10 mol/! It is preferable to add.

The total time of the desilvering process is preferably as short as possible without causing desilvering defects. The preferred time is 1 minute to 3 minutes, more preferably 1 minute to 2 minutes. In addition, the processing temperature is 25°C ~
50°C, preferably 35°C to 45°C. In a preferred temperature range, the desilvering rate is improved and the occurrence of staining after processing is effectively prevented.

In the desilvering step, it is preferable that stirring be as strong as possible. Specific methods for strengthening agitation include the method of impinging a jet of processing liquid on the emulsion surface of the photosensitive material described in JP-A No. 62-183460, and the method described in JP-A No. 62-183.
No. 461, a method of increasing the stirring effect using a rotating means, and further improving the stirring effect by moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid to create turbulence on the emulsion surface. Examples include a method of increasing the circulation flow rate of the entire treatment liquid. Such means for improving agitation is effective for all bleaching solutions, bleach-fixing solutions, and fixing solutions. It is believed that improved stirring speeds up the supply of bleach and fixing agent into the emulsion film, and as a result increases the desilvering rate. Further, the above-mentioned tl stirring improving means includes:
It is more effective when a bleach accelerator is used, and the accelerating effect can be significantly increased and the fixing inhibiting effect caused by the bleach accelerator can be eliminated.

The automatic developing machine used for the photosensitive material of the present invention is
No. 0-191257, No. 60-191258, No. 60
It is preferable to have the photosensitive material conveying means described in Japanese Patent Application No. 191259. As described in the above-mentioned Japanese Patent Application Laid-Open No. 60-191257, such a conveying means can significantly reduce the carry-over of the processing liquid from the front bath to the rear bath, and is highly effective in preventing deterioration of the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of processing liquid replenishment.

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 varies widely depending 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 (stages), the replenishment method such as free flow or down flow, and various other conditions. Can be set to . Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnal of the 5ociety of
Motion Picture and Te1ev
ision Engineers Vol. 64, p. 24
8-253 (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 color photosensitive materials of the present invention, as a solution to these problems,
The method for reducing calcium ions and magnesium ions described in JP-A No. 62-288,838 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, etc., and penzotriadur, etc., described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (I986) Sankyo Publication, Hygiene technology synthesis [microbial sterilization, sterilization, and anti-mold technology, (I982)
Industrial Technology Center, Japanese Society of Antibacterial and Antifungal Research ``Encyclopedia of Antibacterial and Antifungal Agents'' (
It is also possible to use the fungicides described in I986).

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 30 seconds to 5 minutes at 25 to 40°C. A range is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 58-14834, and No. 60-220345 can be used.

Further, following the water washing process, a further stabilization process may be performed, such as a stabilizing bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photosensitive materials for photography. can be mentioned. Examples of the dye stabilizer include aldehydes such as formalin and glutaraldehyde, N-methylol compounds, hexamethylenetetramine, and aldehyde sulfite adducts.

Various chelating agents and antifungal agents can also be added 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.

When each of the above-mentioned processing liquids is concentrated by evaporation in processing using an automatic processor or the like, it is preferable to correct the concentration by adding water.

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 +- 14,85
0 and N (Schiff base-type compounds described in I15,159, aldol compounds described in I13,924, metal salt complexes described in U.S. Pat. No. 3,719.492, JP-A No. 5
Examples include urethane compounds described in No. 3-135628.

The silver halide color light-sensitive material of the present invention may optionally contain various types of 1-phenyl-3-
Pyrazolidones may also be incorporated.

Typical compounds are JP-A-56-64339 and JP-A No. 57-
No. 144547 and No. 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, a temperature of 33°C to 38°C is standard, 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. can be achieved.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500,626, JP-A-60-133449, No. 5
It can also be applied to the heat-developable photosensitive materials described in No. 9-218443, No. 61-238056, European Patent No. 210.66OA2, and the like.

(Examples) The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited thereto.

Example 1 Emulsions of couplers of the present invention and comparative couplers ~1
．． was obtained by dissolving the following oil phase and aqueous phase, mixing them, and emulsifying them with a household mixer.

(Oil phase) Cyan coupler EX-250, Og Coupler of the present invention or comparative coupler 10.0 g Ethyl acetate 150 cc (Aqueous phase) Bovine bone gelatin 100.0 g W-32
,0g water 100
After storing 0cc of these emulsions of A-L in a refrigerator at 7°C for 28 days, 200g was collected, heated and melted at 40°C, and dissolved for 48 hours. 200 cc of hot water was added to this, and the filter was passed through a Millipore EC filter (I° Oaa diameter) under reduced pressure to examine its permeability.

A-H prepared using the coupler of the present invention could be easily tPB'd without clogging and did not leave any residual odor on the filter.

On the other hand, the emulsion prepared using the comparative coupler produced solid matter, was severely clogged, and could not be filtered after a small amount of emulsion was passed through.

From the above results, it is clear that the coupler of the present invention has excellent precipitation stability when made into an emulsion.

R-4 21ts OCI (, C11,0 Example 2 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The number corresponding to each component indicates the coating amount expressed in g/rd unit, 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 mole units.

(Sample 101) 1st layer (antihalation layer) Black colloid m Silver o, 18 Gelatin 0.70 2nd layer (
Intermediate N) 2.5-di-pentadecylhydroquinone 0.18E X
-10,070 E -10 E 3゜lXl0-' 0.10 0.020 0.12 0.070 o, os.

O,070 0,060 gelatin 4th layer (second red emulsion layer) Emulsion C Sensitizing dye I Exacerbating pigment■ Sensitizing dye■ X-2 X-3 EX~10 Eχ-14 [J-1 gelatin 51st! (Third red emulsion N) emulsion Sensitizing dye I Sensitizing dye H Sensitizing dye■ X-2 0,60 1 barge 1.00 5.1X10-' 1.4X10-' 2.3X10-' 0.30 0.050 0.015 0.10 0.070 0.050 0.070 1.00 Silver 1.60 5.4X10-' ], 4XlO-' 2.4X10”’ 0.097 X-3 X-4 B5-1 B5-2 gelatin 6th layer (middle layer) X-5 B5-1 gelatin 7th layer (first green emulsion layer) Emulsion A Emulsion B Sensitizing dye■ Sensitizing dye V Sensitizing dye■ Eχ−1 X-6 X-7 X-8 B5-1 0.010 0.080 0.11 0.05 ],,OO 0,020 0,60 Silver 0.15 Silver 0,15 3, OX 10-5 1.0XlO-' 3.8 X to-' 0.26 0.030 0.025 0.10 B5-3 gelatin 811i! (Second green emulsion layer) Emulsion C Sensitizing dye■ Sensitizing dye V Sensitizing dye■ X-6 X-7 X-8 B5-1 B5-3 gelatin 9th layer (3rd green emulsion layer) Emulsion E Sensitizing dye■ Exacerbating pigment■ Sensitizing dye■ X-1 X-11 0°010 0.60 Silver 0.45 2, lX10-' 7.0X10-S 2.6X10-' 0.094 0.026 0.018 0.16 8.0X10-' 0.50 Silver 1.20 3.5X10-' 8.0X10-' 3.0X10-' 0.025 0.10 X-13 B5-1 B5-2 gelatin 10th layer (yellow filter layer) yellow colloidal silver X-5 B5-1 gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye■ X-8 Eχ-9 B5-1 gelatin 12th layer (second blue-sensitive emulsion layer) Emulsion G 0.015 0.10 0.10 0.80 Silver 0.050 0.080 0.030 0.60 Silver 0.080 Silver 0.070 Silver 0.070 3.5X10-' 0.042 0.72 0.28 1.10 Silver 0.45 Sensitizing dye■ EX-9 EX-10 B5-1 gelatin No. 13 (3rd blue-sensitive emulsion layer) Emulsion H Sensitizing dye■ EX-9 HB S-1 gelatin 14th layer (1st protection M) Emulsion I B5-1 gelatin 15th N (second protective layer) B-1 (diameter 1.7 μm) 2, l　X　10~4 0.15 7.0X10-' o os.

1 barb 0.77 2.2X10-' 0.20 0.070 0.60 Silver 0.20 0.11 O117 5,0X10-" 1.00 0.40 5.0X10-" B-2 (Diameter 1. 7 am) 0.1
0B -30,1O 3-10,20 Gelatin 0.40 Furthermore, W-1, W~2, W-
3, B-4, 113-5, F-1, F-2, F-3, F
-4, F-5, l-6, F-7, F-8, F-9, F-
10, F-11, F-12, F-13, and iron salt, lead salt, gold salt, platinum salt, iridium salt, and rhodium salt.

X l X (i) C, H, 0C1tH ]1 X X-7 zus C7! X H X X X Hi H CbH+1(n) H3 X H C,H.

ff1Is C,H,O3Oρ C11゜X l Dye■ Sensitizing dye■ ■ CH2=C)l Sow CHz C0NHCI
(.

CB! -CH 301CHt C0NH CHt CH.

L +CH, -C ]-11,000CH, -C +A OOH 0OCR3 x/y=10/90 Sensitizing dye■ CHt.

1lff +011□ ±1---1000CH.

+.

OOH 0OCL x/y=40/60 CHt CH3 (CHl), 5iO−+Si ±1 block−−−÷S i −0 ÷Coco−3i (C)I:+) 3 + CH2−CB −)− +CH2− CH ±7--1,000C) 12 CH ±AX/y=70/30 CaF+ , 5OJHCtlzCHzCHzOC1lz
C) IJ (CL) s0ONa NHCJ + z (n) NIIC AH5 Here, each coupler in the fourth layer is as follows (water phase), (oil phase)
Each solution was dissolved and mixed, emulsified using a household mixer, stored in a refrigerator at 7°C for 21 days, and then redissolved and added.

(Oil phase) X-2 X-14 X-10 Ethyl acetate (water phase) Pork skin gelatin water , 0g 800 cc 5, Og (Samples 102 to 109) The couplers of the present invention and comparative couplers shown in Table 2 were added to No. 4N of Sample 101 to prepare Samples 102 to 109.

Sample 101 was prepared in accordance with the method for sample 101, except that 5.0 g of the coupler of the present invention and the comparative coupler were added to the above (oil phase).

These samples were exposed to red imagewise light and subjected to the following color development process. Table 2 shows the logarithm of the reciprocal of the exposure amount that gives the cyan density (fog +0°2) as the relative sensitivity. Further, the value obtained by subtracting the yellow capri density from the yellow density at a cyan density of 1.5 is shown in Table 2 as the color turbidity.

Processing method Processing time Processing temperature 9 Replenishment amount 'lll Capacity 3 minutes 15
Seconds 37.8℃ 25d 1Of45 seconds 3
8℃ 5-4145 seconds 38℃
4145 seconds 38℃ 30d
4f 20 seconds 38 °C 21-step color development bleaching bleach-fixing (]) bleach-fixing (21 water washing (I) +21 20 seconds 38 °C 30d
21! Constant 20 seconds 38 ℃ 20
f27! Drying: 1 minute at 55°C Introduced to fixation (2).

In the above process, the amount of bleach-fix solution carried into the washing step was 2 ml per 1 meter length of the photosensitive material having a width of 35111 mm.

(Color developer) Mother er, (R)
Replenisher (g) Diethylenetriaminepentaacetic acid 5.0
6.0 Sodium sulfite 4.0
5.0 Potassium carbonate 30.0
37.0 Potassium Bromide 1.3
0.5 Potassium iodide 1.2■Hydroxylamine sulfur 9 salt 2.0 3.64-[N
-Ethyl-N-β-4,76,2hydroxyethylamino]-2-methylaniline sulfate Wash with water and add dry water and H (bleaching solution) 1.3-diaminopropanetetraacetic acid ferric ammonium hydrate 1.3-Diaminopropanetetraacetic acid Ammonium bromide Ammonium nitrate Ammonia water (27%) Acetic acid (98%) Add water and H (Bleach-fix solution) Ethylenediaminetetraacetic acid Ferric ammonia water dihydrate Ethylenediaminetetraacetic acid disodium salt 1.01 10.00 Mother liquor (g) 144.0 2.8 84.0 17.5 10.0 51.1 4.3 Mother liquor (g) 50.0 5.0 1, Oll 10.15 Replenisher ( g) 206.0 4.0 120.0 25.0 1.8 73.0 1, Ol 3.4 Replenisher (g) 25.0 Ammonium sulfite 12.0 20.
0 ammonium thiosulfate 290.0 mf
320. Oml water melt W1. (700g/A) Ammonia water (27%) 6.0 d 1
Add 5.0 ml water 1.07
! 1. off pH 6,88,0 (Washing water) Mother liquor and replenisher Common tap water was mixed with an H-type strongly acidic cation exchange resin (Amberlite JR-120 days, manufactured by Rohm and Haas) and an OH-type strongly basic anion exchange resin (Amberlite JR-120 days, manufactured by Rohm and Haas). Rai) I RA
Water was passed through a mixed bed column packed with -400) to reduce the concentration of calcium and magnesium ions to 3/1 or less, followed by sodium isocyanurate dichloride 20/l.
and sodium sulfate 150/1 were added. I of this liquid
) H was in the range of 6.5-7.5.

(Stable solution) Common to mother solution and replenisher solution (Unit: g) Formalin (37%) 1. 2TR1 surfactant 0.4 (C16112
, -0+ CH, C1,0-)ya I+ ) ethylene glycol 1° Add water and 1°07! H 5°7° From Table 2, it is clear that the samples using the couplers of the present invention have good coating properties and are excellent in color reproducibility as expressed by brown turbidity.

Procedural amendment

Claims (1)

[Scope of Claims] A silver halide color photographic material containing a cyan image-forming coupler represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, A is a cyan coupler residue, L is a straight chain or branched alkylene group with a total carbon number of 3 or more, and R is a straight chain or branched alkyl group , represents a cyclic alkyl group or an aryl group. (R may have one or more substituents.)