JPH02266351A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material free from deterioration of color development density and increase of minimum density even at the time of processing the photosensitive material with a color developer substantially not containing a benzyl alcohol by processing the photosensitive material containing at least one of couplers in combination with a specified color-nondeveloping compound with the color developer substantially not containing the benzyl alcohol. CONSTITUTION:The photosensitive material containing at least one of the couplers in combination with at least one of the color nondeveloping compounds represented by formulae I - IV is processed with the color developer substantially not containing the benzyl alcohol. In formula I - IV, each of R<1> and R<8> is an aryl or heterocyclic group; each of R<2> and R<5> is an alkyl, aryl, or heterocyclic group; each of R<6> and R<7> is an alkyl, aryl, alkoxy, or aryloxy group; each of R<9> and R<10> is H, or an alkyl or aryl group; and Y is -CO- or -SO2-, thus permitting sufficient color development density to be attained by the absence of benzyl alcohol.

Description

Detailed Description of the Invention (Prior Art) A silver halide color sensitive material consists of three types of silver halide emulsion layers selectively sensitized to have sensitivity to blue light, green light, and red light. A photosensitive layer consisting of is coated on the support.

In order to form a color photographic image, photographic couplers of three colors, yellow magenta and cyan, are contained in the photosensitive layer, and the exposed photosensitive material is subjected to color development processing using a so-called color developing agent.

The oxidized product of the aromatic primary amine undergoes a coupling reaction with the coupler to give a coloring dye, but the coupling rate at this time is as fast as possible (it is preferable to give a high coloring density within a limited development time). .

As couplers for photographic light-sensitive materials, oil-soluble couplers have been proposed that are dissolved in high-boiling point or low-boiling point organic solvents, emulsified and dispersed, and incorporated into emulsion layers. however,
When these couplers are used, there is a problem that the color developing agent has low fresh oil properties, so that it is difficult to penetrate into the coupler-dispersed oil droplets, resulting in a decrease in color density.

For this reason, various developing agent penetrating agents have been studied, and in particular, a method of adding benzyl alcohol to a color developer is widely used.

However, diethylene glycol or the like is required as a solvent since hydrangyl alcohol has low water solubility. However, these compounds have a pollution load value of BOD, C
Since the OD is high, it has been desired to remove benzyl alcohol for the purpose of reducing the pollution load.

Furthermore, even if such a solvent is used, it takes KIIi time to dissolve the benzyl alcohol, so it has been desired to remove the benzyl alcohol from the processing liquid for the purpose of reducing the liquid preparation work.

However, if benzyl alcohol, which is a color development accelerator, is removed, the color development will be significantly reduced.

In order to solve this problem, a technique has been disclosed in which a combination of color development accelerators is used, but sufficient effects cannot be obtained. (Japanese Patent Publication Nos. 51-12422, etc.) (On the other hand, as a technique for using additives in photosensitive materials, the techniques described in European Patent Publication No. 14 No. 309,158, No. 309,159, and No. 309.160 have been disclosed. However, it is not possible to predict the effects of the present invention from this).

In this sense as well, there has been a desire to develop a technique that does not contain alcohol and can provide sufficient color density.

(Problems to be Solved by the Invention) The object of the present invention is to provide a silver halide color photographic material that does not cause a decrease in color density and an increase in minimum density even when processed with a color developer that does not contain alcohol. The aim is to provide a processing method for

(!! Means for Solving Problem 1) The object of the present invention is to provide a support with a silver halide emulsion layer and a yellow dye-forming coupler selected from a magenta dye-forming coupler and a cyan dye-forming coupler. In a method for processing a silver halide color photographic light-sensitive material containing at least one coupler, at least one of the couplers has at least one of the following formulas (1) and (II).
, (III) or reformed] in combination with a non-color-forming compound, and the light-sensitive material is processed with a color-forming developer substantially free of benzyl alcohol. This is achieved by a method for processing photographic materials.

General formula (1) % Formula % [In the formula, R1 represents a substituted or unsubstituted aryl group or heterocyclic group, and R2 represents a monosubstituted or unsubstituted alkyl group, aryl group, or heterocyclic group, respectively. However, R2 does not contain a carboxyl group.] General formula (II) R3-MHSO2-R' [In the formula, R3 and R4 each independently represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. However, R3 and R4 are not both alkyl groups at the same time.] General formula [m] [In the formula, R5 is a substituted or unsubstituted purkyl group, aryl group, or heterocyclic group, and R6 and R7 are each independently substituted or unsubstituted alkyl group, aryl group,
R6 and R7 each represent an alkoxy group or an aryloxy group, and R6 and R7 may be bonded to each other to form a ring with the group ']\General formula (IV) [In the formula, R8 is substituted or unsubstituted. , R9 and RIG each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group or aryl group, and Y represents -ω- or -h-, respectively. A non-color-forming compound refers to a compound that does not undergo a coupling reaction with an oxidized product of an aromatic primary ion developer during color development, or does not substantially contribute to the color density even if it undergoes a coupling reaction.

In the above, "contained in combination" means included in the same layer, more preferably in a mixed state.

In the above description, "substantially free of benzyl alcohol" means that the content of mensyl alcohol per 11 color developing solutions is 2j17 or less, more preferably 0.
01 ml or less, particularly preferably 0.

In the above, the heterocyclic group refers to N, 0, 8. P, Ss, T.O.
It means a 3- to 8-membered (preferably 5- to 7-membered) optionally fused cyclic group containing at least one hetero atom selected from the atomic group in the ring.

- Compounds represented by formulas (1), (II) and (III) [detailed explanation below].

In general formula (1), R1 preferably has 6 to 6 carbon atoms.
24 substituted or unsubstituted aryl groups (e.g. phenyl, p-tolyl, m-tolyl, 4-cyanophenyl, 4
-nitrophenyl, 4-ri-4qphenyl, 4-fluorophenyl, 3.4-9 chlorophenyl, 2.5 a-J
) Ri: f-lophenyl, 2,4-dicyclophenyl, 2
, 4.5~Tolic gastrointestinal 2X nil, 2゜4-difluorophenyl, 2.5-5) Fluorophenyl 3.4-1)
Fluorophenyl, 3-cyanophenyl A/, 3-
tIJ fluoromethylphenyl, 4-chloroc! -3-cyanophenyl, 3-ri1-4-cyanophenyl, 3.
4-dicyanophenyl, 4-(N-propylcarbamoyl)phenyl, 4-acetylphenyl, 4-d/tanoylphenyl, 4-ethylsulfonylphenyl, 4-ethyl7enyl, 4-hexylphenyl, 4- t-butylphenyl, 4-octylphenyl, 4-methoxyphenyl, 4-butoxy7enylne, or carbon atoms a1-24
is a substituted or unsubstituted heterocyclic group (for example, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-quinolyl, 3-thienyl, 2-thiazolyl, 2-benzodeazolyl), and R2 preferably has 1 carbon atom. ~24 linear, monobranched, or cyclic substituted or unsubstituted alkyl groups (e.g., methyl, n-+-(antyl, etc.).

n-heptyl. n-undecyl, 1-ethylinchyl,
phenoxymethyl, indyl, cyclohexyl, 4-t
-/tylcyclohexyl, trictetramethyl, trifluoromethyl, heptafluoropropyl), number of carbon atoms: 6
~24 substitutions or none.

Substituted aryl groups (e.g. phenyl up-tolyl).

4-hexylphenyl, 4-hebutylphenyl.

4-octylphenyl, 4-chlorophenyl, 3゜4-
Dicyanophenyl, dichlorophenyl.

Pentafluorophenyl, 4-methoxyphenyl.

4-methoxyphenyl, 4-nitrophenyl), or a substituted or unsubstituted heterocyclic group having 1 to 24 carbon atoms (
For example, 2-pyridyl, 3-pyridyl.

4-pyridyl, 2-furyl, 2-thienyl). −
In formula (1), R1 is more preferably a substituted aryl group having 6 to 18 carbon atoms, particularly preferably a small number of electron-withdrawing substituents (preferably a fluorine atom,
#11/g atom, A elementary atom, iodine atom, cyano group, nitro group, trifluoromethyl group.

acyl group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group), and R2 is more preferably a linear, branched or cyclic substituted group having 1 to 18 carbon atoms. It is an unsubstituted alkyl group or a substituted or unsubstituted aryl group having 6 to 18 carbon atoms.

In general formula (II), R3 and R4 are preferably linear, branched, or cyclic substituted or unsubstituted alkyl groups having 1 to 24 carbon atoms (e.g., methyl, n-phthyl, n-
-Okudel, 2-ethylhexyl.

n-dodecyl, n-sadecyl, cyclohexyl, benzyl, trifluoromethyl, diethyl metho, 2-hexyldecyl), substituted or unsubstituted aryl groups having 6 to 24 carbon atoms (e.g. phenyl * p −)! J
4-cyanophenyl, 4-chlorophenyl, 1-naphthyl 3.4-0chlorophenyl, 4-fluorophenyl, 4-nitrophenyl, 4-ethylphenyl, 4-
hexylphenyl, 4-methoxyphenyl, 4-octylphenyl) or substituted or unsubstituted heterocycles having 1 to 24 carbon atoms (e.g. 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-quinolyl, 3-thienyl.

2-thiazolyl, 2-indithiazolyl), more preferably a linear, branched or cyclic substituted or unsubstituted alkyl group having 1 to 18 carbon atoms, or a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms. is an aryl group.

In general formula (In), R5 is R in general formula CI)
1, and R6 and R7 are preferably linear, branched or cyclic substituted or unsubstituted alkyl groups having 1 to 24 carbon atoms (e.g. methyl, ethyl, butyl, n-
octyl, 2-ethylhexyl, n-dodecyl), substituted or unsubstituted aryl groups having 6 to 24 carbon atoms (e.g. phenyl jp-tolyl).

p-/p-phenyl, p-isopropylphenyl), linear, branched or cyclic substituted or unsubstituted alkoxy groups having 1 to 24 carbon atoms (e.g. methoxy, ethoxy, n-cytoxy, Methoxyethoxy.

n-octyloxy, 2-ethylhexyloxy.

n-dodecyloxy) or a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms (e.g. phenoxy*p-)lyloxy, p-isopropylphenoxy, p-
-chlorophenoxy), more preferably a linear, branched or cyclic substituted compound having 1 to 18 carbon atoms.
R6 and R7 are unsubstituted alkoxy groups or substituted or unsubstituted aryloxy groups having 6 to 18 carbon atoms;
and may form each other.

In General 2α], R8 has the same meaning as R1 in general formula (1)K, R9 and RIO are preferably a hydrogen atom or a group having the same meaning as R3 or R4, and more preferably R9 is a hydrogen atom and R is Straight chain, branched or cyclic device having 1 to 18 carbon atoms 4g8 - Unsubstituted alkyl group or substituted or unsubstituted aryl group having 6 to 18 carbon atoms, and Y is -GO-.

Specific examples of compounds represented by the general formula CI), (I[), (1) or α] are shown below, but the present invention is not limited thereto.

Specific examples of compounds represented by general formula (I) ■-13 NCQNBCOC12E2B-n ■-15 ■-16 ■-17 ■-18 ■-19 -2O NCGNuCOQCsH□7-n Nc (SiNacoQc, a□3-n NC<IshiNfiCO00C8H07 NO-c)-MHmo)(J NO-c)-NHCOQCOOC4H.

CFs-C>NHCO8CrH15-nC/ C/ Specific example 02H of the compound represented by general formula (II).

■-15 ■-16 ■-17 ■-18 ■-19 ゜-C8E1. so, NmGi CH, -Q-so2NH-C)-C2E.

c1! n,,Qso2Nnc4g,-nOso2sac
, H,-n cl-(lOl)-so, NBc12E12. -nC
1esozNklC16H8s -”-Formula (111)
Specific examples of compounds represented by formula (■) - Specific examples of compounds represented by formula (■) ■-25 C4Hs1-c)-NHCONH-cN-The compound represented by formula (1) is a carboxylic acid ester or a carboxylic acid ester and amines, -formula (I
The compound represented by f) is produced by the reaction of 9 sulfone chlorides or sulfonic acid esters with a heptadane, -
The compound represented by formula (III) can be prepared by reacting phosphoric acid esters or phosphoric acid esters with amines.
The compounds represented by formula y can be synthesized by reacting carbamoyl chlorides, sulfamoyl chlorides, carbamate esters, isocyanates, and amines. At this time, the solvent (for example, inzene,
Toluene, dP silene, ether, tetrahydrogen, dioxane, acetonitrile, N-dimethylformamide), N,N-dimethylacedoj), N
, N/-dimethylimidacillin-2-one, [methylene chloride, tetraroform] can be used as necessary.

In addition, bases or catalysts (e.g. triethylamine, pyridine, N-ethylmorpholine, sodium carbonate, potassium carbonate, DBU, DBN) are used in these reactions.
, p-dimethylaminopyridine, imidazole, N
, N-dimethylaniline, tetramethylurea, tetramethylguanidine) may be used.The reaction temperature is -78℃.
-200°C, usually -20°C to 150°C.

The amount of the compound represented by formula (1), (I[), (I[I) or α] added to the photosensitive material is 0.01F-1ON per dye-forming turnip j-IJF in the same layer. Yes, preferably 0. III to 5ji, more preferably 0
．． 0 pigment forming power puller which is 2-3I and general formula (1),
(II).

The compounds represented by crrn t or α] may be dissolved together, emulsified and dispersed, and applied, or may be dissolved separately, emulsified and dispersed, and then mixed and applied, but the former method is preferred.

The compound represented by the general formula [1], (fl), l) or (g) can be added to any layer in the light-sensitive material, but is preferably a light-sensitive silver halide emulsion layer or a layer adjacent thereto. .

Specific examples of dye-forming couplers used in the present invention are Research Disclosure (RD) Nl 17643,
(2) In addition to those described in the patents listed in C to G, the following may be mentioned.

Examples of yellow dye-forming couplers include U.S. Pat. No. 3,933,501, U.S. Pat. No. 4.022.620, U.S. Pat.
British Patent No. 4,248,961, Japanese Patent Publication No. 10739/1983, British Patent No. 1,425.020, British Patent No. 1,476.
No. 760, U.S. Patent No. 3.973.968, U.S. Patent No. 4.
Preferred are those described in European Patent No. 314,023, European Patent No. 4.511.649, European Patent No. 249.473A, and the like.

As magenta dye-forming couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, as disclosed in U.S. Pat.
, No. 310.619, No. 4, No. 351, No. 897,
European Patent No. 73.636, US Patent No. 3.061,4
No. 32, No. 3.725.067, Research Disclosure No. 24220 (June 1984), JP-A No. 60-33552, Research Disclosure Seed 24230 (June 1984), JP-A No. 60-43
No. 659, No. 61-72238, No. 60-35730
No. 55-118034, No. 60-185951, U.S. Patent No. 4.500.630, U.S. Patent No. 4.540,
No. 654, No. 4.556.630, International Publication 08
Particularly preferred are those described in No. B104795.

Cyan dye-forming couplers include phenolic and naphthol couplers, and are described in U.S. Pat. No. 4.052.
．． No. 212, No. 4.146.396, No. 4,22
No. 8°233, No. '4,296.200, No. 2.
No. 369.929, No. 2.801.171, No. 2
．． 772.162, 2.895°826, 3,772,002, 3.758.308, 4.334.011, 4.327.173,
West German Patent Publication No. 3,329,729, European Patent No. 12
1, 365^, US Patent No. 249.4538, US Patent No. 3,446.622, US Patent No. 4.333.999,
Same No. 4.775.616, Same No. 4.451.559, Same No. 4,427.767, Same No. 4.690.889
No. 4.254. No. 212, same No. 4.296.1
99, JP-A No. 61-42658, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are recommended in Research Disclosure 17643.
- Section G, U.S. Patent No. 4.163.670, Japanese Patent Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4.138.258, British Patent No. 1.146,36
No. 8 is preferred, and also US Pat. No. 4.7
No. 74.181, a coupler that corrects unnecessary absorption of a color-forming dye by a fluorescent dye released upon coupling, and a coupler that can react with a developing agent to form a dye, as described in U.S. Pat. No. 4,777.120. It is also preferred to use couplers in which a dye precursor group is present as a leaving group.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Patent No. 4.366.237 and British Patent No. 2,125.
．． 570, European Patent No. 96, 570, West German Patent (
The one described in Japanese Publication No. 3.234.533 is preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat.
No. 4.576°910, British Patent No. 2.102.
It is described in No. 173, etc.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors include the aforementioned RD 17643.
, Patents described in sections ■ to F, Japanese Patent Application Laid-Open No. 57-15194
No. 4, No. 57-154234, No. 6G-184248
No. 63-37346, U.S. Patent No. 4,248,96
2, 4°782, 012 is preferred.

Couplers that release a nucleating agent or a development accelerator imagewise during development include British Patent No. 2,097,140;
No. 2.131.188, JP 59-157638
No. 59-170840 is preferred.

Other couplers that can be used in the photosensitive material of the present invention include competitive couplers described in U.S. Pat. No. 4,130,427, U.S. Pat. , DIR redox compound releasing couplers, DIR coupler releasing couplers described in JP-A-60-185950, JP-A-62-24252, etc.,
DIR coupler releasing redox compound or DIR redox releasing redox compound, European Patent No. 173゜3
Coupler that releases a dye that removes and restores color by H as described in No. 02^, R, D, Ishi 11449, Ishi 24241, JP-A-61
-201247 etc. bleach accelerator releasing couplers,
Ligand-releasing couplers described in U.S. Pat. No. 4,553,477, leuco dye-releasing couplers described in JP-A-63-75747, U.S. Pat. No. 4.774.18
Couplers that emit fluorescent dyes as described in No. 1 can be mentioned.

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

Examples of high boiling point solvents used in the oil-in-water dispersion method are described in U.S. Pat. No. 2,322.027 and the like.

Specific examples of high-boiling organic solvents with a boiling point of 175°C or higher at normal pressure used in the oil-in-water dispersion method include phthalic acid esters (dibutyl phthalate, dicyclohexyl phthalate, di-2-ethylhexyl phthalate, decyl phthalate). , bis(2,4-sheet amyl phenyl) phthalate, bis(2,4-di-t-amylphenyl) isophthalate, bis(1,1-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-ethylhexylphenyl phosphonate, etc.), benzoic acid esters (to 2-ethyl xyl benzoate,
dodecyl benzoate, 2, ethylhexyl-p-hydroxybenzoate, etc.), amides l! (N,N-diethyldodecaneamide, N,N-diethyllaurylamide, N-tetradecylpyrrolidone, etc.), alcohols or phenols! (Isostearyl alcohol, 2.
4-di-t@rt-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, instearyl lactate, trioctyl citrate, etc.), aniline derivatives ( N, thonbutyl-2-
butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopropylnaphthalene, etc.), and the like. 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, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, dimethylformamide, and the like.

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

These couplers can also be impregnated into rhodapuru latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution.

Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W (+88100723) are used. In particular, the use of acrylamide polymers is preferred from the viewpoint of color image stabilization.

The light-sensitive material of the present invention has few silver halide emulsion layers (both IF
There is no particular restriction on the number or order of the silver halide emulsion layer and the non-photosensitive layer, as long as fJ is provided.A typical example is to use a support with substantially the same color sensitivity. However, it is a silver halide photographic light-sensitive material having at least one light-sensitive layer consisting of a plurality of silver halide emulsion layers having different photosensitivity, and the light-sensitive layer is one of blue light, green light, and red light. In multilayer halogen and silver oxide color photographic materials, the unit photosensitive layers are generally arranged in order from the support side: a red-sensitive layer, a green-sensitive layer, and a green-sensitive layer. , are arranged in order of blue sensitivity. However, depending on the purpose, the 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 layers.

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

The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
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.

A plurality of silver halide emulsion layers constituting each unit photosensitive layer are composed of a high-speed emulsion layer and a low-speed emulsion layer, as described in West German Patent No. 1.121.470 or British Patent No. 923.045. A two-layer structure can be preferably used0
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.
-112751, 62-200350, 62-
As described in Nos. 206541 and 62-206543, 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 Ji (BH) / high sensitivity green sensitive layer (GH) / low sensitivity green sensitive layer (GL)
/High-sensitivity red-sensitive layer (RH) /Low-sensitivity red-sensitive layer (R
L) or Bll/BL/GL/G■/R11/
I? In order of L or BH/BL/GH/GL/RL/R
They can be installed in the order of H, etc.

Further, as described in Japanese Patent Publication No. 55-34932, from the side farthest from the support, the blue-sensitive layer/GH/R
They can also be arranged in the order of H/GL/RL. Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/I? They can also be arranged in the order of L/Gll/R1i.

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 it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464,
In the same color-sensitive layer, medium-sensitivity emulsion layer/high-sensitivity emulsion layer/low-sensitivity emulsion layer may be arranged in this order from the side remote from the support.

In addition, they may be arranged in the following order: high-speed emulsion layer/low-speed emulsion II/middle-speed emulsion layer, or low-speed emulsion layer/middle-speed emulsion layer/high-speed 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.

When the photographic light-sensitive material of the present invention is a color negative film or a color reversal film, preferred silver halide contained in the photographic emulsion layer is silver iodobromide, silver iodo, containing about 30 mol% or less of silver iodide. Silver chloride or silver iodochlorobromide. Particularly preferred is silver iodobromide or silver iodochlorobromide containing from about 2 mole percent to about 25 mole percent silver iodide.

When the photographic light-sensitive material of the present invention is a color photographic paper, the silver halide contained in the photographic emulsion layer is composed of silver chlorobromide or silver chloride that does not substantially contain silver iodide. It can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is less than 1 mole %, preferably less than 0.2 mol %.The halogen composition of these silver chlorobromide emulsions is optional. Silver bromide/silver chloride can be used. This ratio can vary widely depending on the purpose, but the silver chloride ratio is 2 mol%.
The above can be preferably used. For light-sensitive materials suitable for rapid processing, so-called high silver chloride emulsions containing a high silver chloride content are preferably used. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.For the purpose of reducing the amount of replenishment of the processing solution, the silver chloride content is 98 to 100 mol%. Almost pure chloride emulsions such as those having the following properties are also preferably used.

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 a polydisperse emulsion or a monodisperse emulsion.

Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD) Ha17643
(December 1978), pp. 22-23, 'I, Emulsion preparation and
d types)”, and the same Na 1B716
(November 1979), page 64B, “
"Physics and Chemistry of Photography", published by Paul Montell (P, G1a
fkides+ Ch@mic at Ph1slqu
e PhoLograph-ique, Paul M.
ontel+ 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (G, P, Duffin.

Photographic [! mulsion
Chemistry (Focal Press.

(1966)), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (V, L, Zelik
Making and Coa
ting Photographic Es+ulsi
on+ 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 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science
ence and I! ngineer1ng),
Vol. 14, pp. 248-257 (1970); U.S. Patent Nos. 4,434.226, 4,414.310, 4
, 433,048, 4,439,520 and British Patent No. 2.112.157.

The crystal structure may be --like, the inside and outside may have different halogen compositions, it may be a layered structure, or silver halides with different compositions may be joined by epitaxial bonding. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide.

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

The silver halide emulsion used is usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. Additives used in such processes are subject to Research Disclosure Ha
17643 and k 18716,
The relevant sections are summarized in the table below.

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

1 plate of mask ■ 1 cup of anus chemical sensitizer Page 23 Page 648 Right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649, right column 4 Brightener Page 24 5 Antifogging agent Pages 24-25 Page 649 right column ~ and stabilizer 6 Light absorber, filter dye, ultraviolet absorber 7 Anti-stain agent Page 25 right column Page 650 left ~ Right column 8
Dye image stabilizer 25 pages 9 Hardeners 26 pages 10 Binder 26 pages 11 Plasticizers, lubricants 27 pages 651 pages left column Same as above 650 pages right column pages 25-26 649 pages right column - 650 pages left column 12! ! Fabric aids, pages 26-27, page 650, right column, surfactant 13, static, page 27, same, top frame fixing agent.In addition, in order to prevent deterioration of photographic performance due to formaldehyde gas, U.S. 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 color photosensitive material of the present invention includes JP-A-63-2577
No. 47, No. 62-272248, and JP-A-1-8
1,2-benzisothiazoline-3 described in No. 0941
-one, n-butyl p-hydroxybenzoate, phenol, 4-chloro-3,5-dimethylphenol,
2-phenoxyethanol, 2-(4-thiazolyl)
It is preferable to add various preservatives or fungicides such as 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, page 28 of 17643, and the same! 4111871
6, from the right column on page 647 to the left column on page 648.

In the photosensitive material of the present invention, the total film thickness of the entire aqueous colloid layer on the side having the emulsion layer is preferably 28 μm or less, more preferably 23 μm or less, even more preferably 20 μm or less, and the film swelling rate T1/.

is preferably 30 seconds or less, more preferably 20 seconds or less.

The film thickness means the film thickness measured at 25° C. relative temperature and 55% humidity (2 days), and the film swelling rate TI/l can be measured according to a method known in the art. For example, Photographic Science and Engineering (Photogr, SclEng,) + Vol. 19, 2 by A. Green et al.
It can be measured by using a swellometer (swelling needle) of the type described in No., pp. 124-129, and TI/1 is the maximum swelling film reached when treated with a color developer at 30°C for 3 minutes and 15 seconds. 90% of the thickness is defined as the saturation film thickness, and the time required to reach this film thickness of Tl/1 is defined.

The membrane swelling rate T'i 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%. The swelling rate can be calculated from the maximum swollen film thickness under the above-mentioned conditions according to the formula: (maximum swollen film thickness - film thickness)/film thickness.

The color photographic material according to the present invention includes the above-mentioned RD,
Nil 17643, pages 28-29, and Ha 1
The color developer can be developed by the usual method described in the left column to right column of 615 of 8716, but the color developing solution does not substantially contain benzyl alcohol.

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. Although aminophenol compounds are also used as color developing agents, p-phenylenediamine compounds are preferably used, and typical examples include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N-
β-hydroxyethylaniline, 3-methyl-4-amino-N, ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-β-
Examples include methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Among these, 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline sulfate is particularly 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, benzothiazoles or mercapto compounds. If necessary, various preservatives such as hydroxylamine, diethylhydroxylamine, sulfites, hydrazines such as N,N-biscarboxymethylhydrazine, phenyl semicarbazides, triethanolamine, and catechol sulfonic acids, ethylene glycol, alkaline solvents such as diethylene glycol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, auxiliary developing agents such as the competitive coupler l-phenyl-3-pyrazolidone, tackifiers, amino acids. Various chelate compounds represented by polycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids,
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N,N
, N-trimethylenephosphonic acid, ethylenediamine-N
, N,N,N-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or 7-minophenols such as N-methyl-p-aminophenol. It can be used alone or in combination.

These color developing solutions and black and white developing solutions generally have a pn of 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material to be processed, but it is generally less than 32% per square meter of the light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
It can also be lower than N1. 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, the above aperture ratio is preferably 0.1 or less,
More preferably, it is 0.001 to 0.05. As a method for reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the surface of the photographic processing solution in the processing tank, there are also methods for reducing the aperture ratio.
Method using a movable lid described in No. 2033, JP-A No. 6
The slit development processing method described in No. 3-216050 can be mentioned. Reducing the aperture ratio is preferably applied not only to both color development and black and white development steps, but also to all subsequent steps, such as bleaching, bleach-fixing, fixing, washing, 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 (bleach-fixing process), or in order to speed up the process, it may be carried out in two ways: bleach-fixing process after bleaching process. Depending on the purpose, treatment may be carried out in consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. Examples of bleaching agents that can be used include compounds of polyvalent metals such as iron (III), peracids, quinones, nitro compounds, etc. 9 Typical bleaching agents include organic complex salts of iron (I[I), such as ethylenediamine tetra Use of aminopolycarbon rIIg such as acetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, or complex salts such as citric acid, tartaric acid, malic acid, etc. I can do it. Among these, aminopolycarboxylic acid iron (fir) if salts, including ethylenediaminetetraacetic acid iron(III) complex salt and 1,3-diaminopropanetetraacetic acid iron(III) complex salt, are used from the viewpoint of rapid processing and environmental pollution prevention. Preferred further aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions. These aminopolycarboxylic acid iron (rin)! 1 pH of bleach or bleach-fix solution using salt
is usually 4.0 to 8, but it is also possible to process at an even lower pH for speeding up the process.

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

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
, No. 290,812, No. M2.059,988, vP
No. 53-32736, No. 53-57831, No. 5
No. 3-37418, No. 53-72623, No. 53-9
No. 5630, No. 53-95631, No. 53-1042
No. 32, No. 53-124424, No. 53-14162
Compounds having a mercapto group or a disulfide group as described in No. 3, No. 53-28426, Research Disclosure No. 1k17129 (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 the iodide salts described in 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 No. 5-8836; Others No. 49-42.434, No. 49-59.644, No. 5
No. 3-94,927, No. 54-35.727, No. 55
Compounds described in No. 26.506 and No. 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. 58, West German Patent No. 1.290.812, Japanese Unexamined Patent Publication No. 1983
Preferred are the compounds described in US Pat. No. 4,552,834.
These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for maximum shadows.

In addition to the above-mentioned compounds, bleach and bleach-fix solutions contain 8! It is preferable to include an acid, and a particularly preferable organic acid is a compound having an acid dissociation constant (pKa) of 2 to 5, and specifically, acetic acid, propionic acid, etc. are preferable.

Examples of fixing agents used in fixing solutions and bleach-fixing solutions include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used. Among them, ammonium thiosulfate is the most widely used. It is also preferable to use a combination of thiosulfate, thiocyanate, thioether compounds, thiourea, etc. As a preservative for fixing solutions and bleach-fixing solutions, sulfites, bisulfites, carbonyl bisulfite adducts, or European patented The sulfinic acid compounds described in No. 294769^ are preferred. Furthermore, various aminopolycarboxylic acids and residual phosphonic acids are preferably added to the fixing solution and bleach-fixing solution for the purpose of stabilizing the solution.

The total time for 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 ~
The temperature is 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 process, it is preferable that the stirring be as strong as possible.A specific method for strengthening the stirring is the treatment on the emulsion surface of the photosensitive material described in JP-A-62-183460 and JP-A-62-183461. A method of colliding liquid jets, a method of increasing the stirring effect using a rotating means as described in JP-A No. 62-183461, and a method of moving the photosensitive material while bringing the emulsion surface into contact with a wiper blade provided in the liquid. , a method of improving the stirring effect by creating turbulence on the surface of the emulsion, and a method of increasing the circulation flow rate of the entire processing liquid. Such agitation enhancement means include bleaching solutions,
It is effective in both bleach-fixing solutions and fixing solutions. Improved agitation speeds up the supply of bleach and fixing agent into the emulsion film,
It is thought that this increases the desilvering rate as a result. Also,
The agitation improvement means described above are more effective when a bleach accelerator is used, and can significantly increase the accelerating effect and eliminate the fixing inhibiting effect of the bleach accelerator.

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 a photosensitive material conveying means as described in Japanese Patent Laid-open No. 191259-1912. This effect is particularly effective in shortening the processing time in each step and reducing the amount of processing solution replenishment.

It is standard practice for the silver halide color photographic material of the present invention to undergo a water washing and/or stabilization process after desilvering treatment. The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. this house,
The relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is J
own-al of the 5ociety
or Motion Picture an
d ele-vision Engineers Vol. 64, P, 248-253 (May 1955 issue)
It can be determined using the method described in .

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 water residence time in the tank, bacteria propagate and the generated suspended matter becomes a layer on the photosensitive material. In the processing of the color photosensitive material of the present invention, such problems can be solved by:
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 incyanurate, and other benzotriazoles described in the issue, Hiroshi Horiguchi, "Chemistry of antibacterial and fungicidal agents J (1986), Sankyo Publishing, Hygiene Technology" “Sterilization, sterilization, and anti-mildew technology for microorganisms,” edited by the Society (1982)
Industrial Technology Society, Japan Society of Antibacterial and Mildew Akebono “Encyclopedia of Antibacterial and Antifungal Agents” (
It is also possible to use the fungicides described in (1986).

The p8 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 2
A range of 30 seconds to 5 minutes is selected at 5 to 40°C. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water.

In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-854
All known methods described in No. 3, No. 5B-14834, and No. 60-220345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be performed. An example of this is a stabilization bath containing a dye stabilizer and a surfactant, which is used as a final bath for color photographic materials. Examples of the dye stabilizer that can be used 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 resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in other processes such as the decomposition 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 a color developing agent, it is preferable to use various precursors of the color developing agent. U.S. Patent No. 3.342,59
Indoaniline compounds described in No. 7, No. 3.342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. and No. 15.159, aldol compounds described in No. 13,924, U.S. Patent No. 3
．． Metal salt complex described in No. 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35628.

The silver halide color light-sensitive material of the present invention may contain various types of l-phenyl-3, if necessary, for the purpose of promoting color development.
- Pyrazolidones may be incorporated.

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

Each birch treatment solution in the present invention is used at a temperature of 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but it is possible to use a higher temperature to accelerate the treatment and shorten the treatment time. Conversely, by lowering the temperature, it is possible to improve the image quality and the stability of the processing solution.

In addition, West German Patent No. 2.226.7 was developed to save silver on photosensitive materials.
70 or US Pat. No. 3,674,499 using cobalt intensification or hydrogen peroxide intensification.

Further, the silver halide photosensitive material of the present invention is disclosed in U.S. Patent No. 4,
No. 500.626, JP-A No. 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.

(Left below) Example 1 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support laminated on both sides with polyethylene. ! The heavy liquid was prepared as follows.

1st layer coating liquid preparation yellow coupler (ExY> 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cp
d-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 cc of 10% sodium dodecylbenzenesulfonate.
The mixture was emulsified and dispersed in 185 cc of a 10% aqueous gelatin solution. On the other hand, silver chlorobromide emulsion (cubic, average grain size 0.8
A 3-near mixture of 8- and 0.70-(f!
i molar ratio) 0 The coefficient of variation of the particle size distribution is 0.08 and 0.
．． For each emulsion, 0.2 mol % of silver bromide was added (localized on the grain surface), and the following blue-sensitive sensitizing dye was added per 1 mol to 2.0 x 10-' mol for large-sized emulsions, respectively. In addition, for small size emulsions, 2.5
A sample was prepared in which sulfur sensitization was performed after adding 10-' moles of X.

The above emulsified dispersion and this emulsion were mixed and dissolved to prepare a first coating solution having the composition shown below.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-8-triazine sodium salt was used.

The following spectral sensitizing dyes were used in each layer.

Blue-sensitive emulsion layer Green-sensitive emulsion layer (per mole of silver halide, 4.0 x 10-' moles for large size emulsions, 5.6 for small size emulsions)
XIO-' mol) and (2.0 XIO-' mol each for large size emulsions and 2.5 1
B, 5 X 10-' mol per mole of red-sensitive emulsion layered silveride, ? ,7
X10-'mol, 2.5X10-'mol were added.

The following dyes were added to the emulsion layer to prevent erasure.

(per mole of silver halide, 0.9X10-' mole for large emulsions and 1 mole for small emulsions)
．． For the red-sensitive emulsion layer, the following compounds were added to the halogenated
2.6 x 10-'' moles were added per mole of F1.

In addition, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added to each of the blue-sensitive emulsion layer, green-sensitive emulsion layer, and red-sensitive emulsion layer (layer structure) The composition of each layer is shown below, and the numbers are Application amount (g/rrf)
The silver halide emulsion represents the coating amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] -th layer (blue-sensitive layer) Said silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Coupler (EXY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (
Solv-1) 0.35 Color image stabilizer (Cpd-7) 0.0
6 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Splv-1) 0.16
Solvent (Solv-4) 0.
08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1lfi compound (Ag molar ratio) of average grain size of 0.55n and 0.39-) Coefficient of variation of grain size distribution are 0.10 and 0.08,
(Each emulsion contained 8 mol% of AgBrO locally on the grain surface) 0.12 Gelatin
l, 24 magenta coupler (EXM
) 0.20 color image stabilizer (Cpd-2
) 0.03 color image stabilizer (Cpd
-3) 0.15 color image stabilizer (C
pd-4) 0.02 Color image stabilizer (CPd-9) 0.02 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-2) 0.4
0 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber CUV-1> 0.47 Color mixing prevention agent (Cpd-5) 0.0
5 solvent (Solv-5)
0.24 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of one with an average grain size of 0.584 and one with an average grain size of 0.45n (Ag molar ratio) with a grain size distribution of 0. The coefficient of variation is 0.09 and 0.11,
(Each emulsion contained 0.6 mol% of 8gBr locally on a part of the grain surface) 0.23 gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-
6) 0.17 color image stabilizer (Cp
d-7) 0.40 color image stabilizer (
Cpd-8) 0.04 solvent (S
olv-6) 0.15 Sixth layer (R outside vA @ collection layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing inhibitor (Cpd-5) 0.02
Solvent (Solv-5) 0.
08 Seventh layer (protective layer) Gelatin 1.3 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 1=1 mixture (molar ratio) of 0.17 liquid paraffin and 0.03 (ExM) Magenta coupler (ExY) l:1 mixture of yellow coupler (molar ratio) (ExC) Cyan coupler l R'''Cd1s 2:4:4 mixture (Cpd) Color image stabilizer (Cpd-6) Color image stabilization rule 2: = 4 mixture (weight ratio) (Cpd-7) ) Color image stabilizer (CHffi-CH)-= (Cpd-8) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd -5) Color mixture prevention agent 0■ (Cpd-9) Color image stabilizing agent (Uly 1) Ultraviolet absorber 4 = 2:4 mixture (weight ratio) (Solv-1) t\I medium (Solv-5 ) Solvent (Solv-2) Solvent C00CJtt (CHt)m 0OCJ1 (Solv-6) 2:l mixture (volume ratio) of solvent (Solv-3) Solvent (Solv-4) Solvent Then, each layer solvent is shown in Table 1. Similar photosensitive materials were prepared except that the compound of the present invention was used as shown in , and a sensitometer (manufactured by Fuji Photo Film Co., Ltd., F'WH type, light source color temperature 32001C) was used for each sample. Gradation exposure was applied using a three-color separation filter for sensitometry.The exposure was carried out at an exposure time of 0.1 seconds and an exposure amount of 2500M5.Then, the following treatment was performed. .

Photographic properties were evaluated based on two points: Dmin (minimum density) and Dmax (i & large density) for each layer of B, G, and R. In addition, the optical image fastness evaluation was 9.5 million lux, Xθ
Fade meter is the percentage of the drop from the point giving the initial density of 165 for the yellow image after 90 hours of irradiation.
I asked for it.

The results are shown in Table 1.

Processing 1 and 1-1 Process and Plate MXJL"ta2xf amount color development 35℃ 45 seconds 161d l?!
Bleach fixing 30-35℃ 45 seconds 215dl?
ffi rinse ■ 30-35℃ 20 seconds □ 1
0 j! Rinse■ 30-35℃ 20 seconds □t
o f rinse■ 30-35℃ 20 seconds 350d
10 j! Drying: 70-80 DEG C. for 60 seconds.The amount of replenishment was per photosensitive material Ml (3-tank countercurrent flow method from rinsing ■ to ■) was used.The composition of each processing solution was as follows.

Left j: Go former 1st wave water Ethylenediamine-N,N.

N, N-tetramethylene phosphonic acid potassium bromide triethanolamine sodium chloride Ku' C Otoya filter hill 800 d 800 d 1.5 g 2.0 g 0.015 g 8.0 g 12.0 g 1.4 g potassium carbonate N-ethyl-N-(β-methyl Tansulfonamidoethyl )-3-methyl-4- Aminoaniline sulfate N, N-bis(carboxy methyl)hydrazine Fluorescent whitening M (WRITEl 4B.

25 g 25 g 5.0 g 7.0 g 5.5 g 7.0 g Add water and pH (25℃) 1000 m 6.0 Uλ hill (tank liquid and replenisher liquid are the same) Ion exchange water (calcium , magnesium is 3 p each
pm or less) Add water to 1000d 1ooold pH (25℃) 10.05 10.45 U Sadahooka C Tank liquid and replenishment liquid are the same) Water Ammonium thiosulfate (70%) Sodium sulfite ethylenediaminetetraacetic acid iron (Ill) 00 m 100 1d T g Ammonium 5 g Disodium ethylenediaminetetraacetate g As is clear from Table 1, it can be seen that the light-sensitive material using the compound of the present invention has improved color development. Furthermore, the compound of the present invention was also found to have an improving effect on yellow light image fastness.

Example 2 On a subbed cellulose triacetate film support,
Sample 201, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared.

(Composition of photosensitive layer) The coating amount is expressed in g/rd unit of silver for silver halide and colloidal silver, and the amount expressed in g/rd unit for coupler additive and gelatin. Regarding the dye, the number of moles is expressed per 111 moles of halogen in the same layer. Note that the symbols indicating additives have the meanings shown below. However, if a substance has multiple effects, one of them is listed as a representative.

UVi ultraviolet absorber, So I vs high boiling point organic solvent, ExF; dye, Ex S; sensitizing dye, Ex C
; Cyan coupler, ExM; Magenta coupler ExY
; Yellow coupler, Cpd; Additive 1st layer (Halley cidin prevention layer) Black colloid il O, 15
Gelatin 2,9U V-
10,03 UV -20,06 UV -30,0? 5olv-20,08 Ex F -10,01 Ex F -20,01 2nd layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Agf 4 mol%, uniform-Agl type, equivalent sphere diameter 0 .4 μm Coefficient of variation of 1 sphere equivalent diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.4 Gelatin 0.8E x
S -12,3X10-' ExC-10,17 ExC-20,03 ExC-30, 13 No. 37J (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core-shell ratio 2:1
internal high Agl type, equivalent sphere diameter 0.65βm, coefficient of variation of equivalent sphere diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.65 Silver iodobromide emulsion (Agf 4 mol%) , uniform Agl type, equivalent sphere diameter 0.4 μm, coefficient of variation of equivalent sphere diameter 37%, plate-shaped particles, diameter/thickness ratio 3.0) Coated silver amount 0.1 Gelatin 1.0ExS-
12X10-' Ex S-21, 2X10-'ExS-52Xl0-' BXS-77 Sensitive emulsion layer) Silver iodobromide emulsion (Ag1 6 mol%, core-shell ratio 2:1
internal high Agl type, equivalent sphere diameter 0.7 μm, coefficient of variation of 1 sphere equivalent diameter 25%, plate-shaped particles, diameter/thickness ratio 2.5) Coated silver amount 0.9 0.8 1.6X1G-' 1.6X10 -'1.6X10-' 6 Xl0-' 0.07 0.05 0.07 0.20 4.6X10-' Gelatin xS-I X5-2 xS-5 xS-7 xC-I xC-4 olv-I olv-2 pd-7 5th layer (intermediate layer) Gelatin V-4 V-5 pct-1 Polyethyl alcohol olv-1 0,6 0,03 0,04 0,1 Relay latex 0.08 0.05 6th layer (Low-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 pm, coefficient of variation of equivalent sphere diameter 37%, plate-like grains, diameter/thickness ratio 2. 0) Coated silver amount 0.18 Gelatin 0.4ExS-3
2X10-'ExS-47XfO-'ExS-51xxo-' ExM-50,11 ExM-70,03 ExY-80,01 Solv-10,09 Solv-40,01 7th layer (mid-sensitivity green emulsion Layer) Silver iodobromide emulsion (Agl 4 mol%, core shell ratio 1:
1 surface height Agl type, equivalent sphere diameter 0.5t1ms, coefficient of variation of equivalent sphere diameter 20%, plate-shaped particles, diameter/thickness ratio 4.0) Coating jilt O, 27 Gelatin 0.6ExS-3
2X10-'ExS-47X10-'ExS-51XIO-' Ex M -50,17 ExM-70,04 Ex Y -80,02 Solv-10,14 Solv-40,02 8th layer Emulsion layer) Iodobromide daughter milk jl'l (Multilayer structured grains with Ag1 8.7 mol%, silver ratio 3:4:2, Ag! content from inside to 24
Mol, 0 mol, 3 mol%, equivalent sphere diameter 0.7 μm, coefficient of variation of equivalent sphere diameter 25%, plate-like particles, diameter/thickness ratio 1.6) Coating IN1 0.7 Gelatin 0.8E x S
-45,2X10'''xS-51XIO-' ExM-50,I ExM-60,03 ExY-80,02 ExC-10,02 ExC-40 ,01 Solv-10,25 Solv-20,06 So 1 v-40,01 Cpd-71XIO-' 9th layer (middle layer) Gelatin 0.6Cp d
-10,04 Polyethyl acrylate latex 0.12Sol
v-10,02 10th layer (donor layer for interlayer effect on red-sensitive layer) Silver iodobromide emulsion (Ag1 6 mol%, internal high AgT type with core-shell ratio 2:l, equivalent sphere diameter 0.7 μm, equivalent to sphere) Coefficient of variation in diameter 25%, plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0.68 Silver iodobromide emulsion (Agl 4 mol%, uniform Agl type, equivalent sphere diameter 0.4 pm, equivalent sphere Coefficient of variation in diameter 37%, plate-like particles, diameter/thickness ratio 3.0) Coated silver amount 0.19 Gelatin 1.0BxS-3
6X10-' ExM-100,19 Solv-10,20 11th layer (yellow filter layer) Yellow colloidal silver 0.06 Seven Latin 0.8Cpd-20,1
3 Solv-10,13 Cp d -10,07 Cp d -60,002 H-10.13 12th layer (low-range blue emulsion N) Silver iodobromide emulsion (Ag14.5 mol%, uniform -Agl Type, equivalent sphere diameter 0.7 pm, coefficient of variation of equivalent sphere diameter 15%, plate-like grains, diameter/thickness ratio 7.0) Coated silver amount 0.3 Silver iodobromide emulsion (Agl 3 mol%, uniformly Agl Mold, equivalent sphere diameter 0.3 μm Coefficient of variation of 1 sphere equivalent diameter 30%, plate-shaped particles, diameter/thickness ratio 7.0) Application II amount 0.15 Gelatin 1.8ExS-
69X10-' ExC-10,06 ExC-40,03 ExY-90,14 ExY-110,89 S o I v -10,42 13th layer (middle layer) Gelatin 0.7EXY-1
20,20 Solv-10,34 14th JIl (High sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type, equivalent sphere diameter 1.0 μm, coefficient of variation of equivalent sphere diameter 25%, Multitwinned plate-like grains, diameter/thickness ratio 2.0) Coated silver amount 0
．． 5 Gelatin 0.5ExS-
61XIO-' ExY-90,01 ExY-110,20 ExC-10,02 Solv-10,10 15th layer (first protective layer) Fine grain silver iodobromide emulsion (Ag [2 mol%, homogeneous Agl type,
Equivalent sphere diameter 0.07ttm) Coated silver amount 0.12 Gelatin 0.9U V
-40,11 UV-50,16 Solv-50,02 H-10,13 Cpd-50,10 Polyethyl acrylate latex 0-09 No. 16
Layer (second protective layer) Fine-grain silver iodobromide emulsion (Ag1 2 mol%, uniform-Agl type, equivalent sphere diameter 0.07 tt m) Coated silver amount 0.3
6 Gelatin 0.55 polymethyl methacrylate particles (diameter 1.5 pn) 0.2H-
10,17 In addition to the above components, each layer contains an emulsion stabilizer Cpd-3.
(0,07g/po), surfactant cp ci-4 (0,
03g/i), 1,2-benzisothiazoline-3-
on (average 200 ppm relative to gelatin), n-
Butyl p-hydroxybenzoate (approximately 1.OOOp
pm), and 2-phenoxyethanol (between approx.
0OOpp■) was added.

V-1 0 words V-4 v-5 olv-1 tricresyl phosphate 5oJv-27 dibutyl tarate (t) (4■9 olv-5 trihexyl phosphate ExF-1 ExS-1 ExS-5 ExS-6 ExS- 7 (1;t1gJ3sξ1ltl'JL411s)3xS
-2 ExS-3 ExS-4 ExS-8 xC-1 xC-2 0 TsubaExC-3 ExC-4 0 Kidney (1) CJ drop (ni;su 1111 Vλh Shiichimeyo Shiki M- Shiwork xM-10 xY-8 xM-5 xM-6 xY-9 xY-11 Cpd-7 cp d-5 Cpd-1 Cpd-3 J13 " Cpd-4 Cpd-2 Cpd-6 CHm-01-Sow CHz-ωNHCHtCHi
-CIl-5ow C) It C0NHGHz (Preparation of samples 202 to 213) In sample 201, the fourth layer So1 mer 1 , 8o
1yv-2, 7th layer So1mer1, So1mer4.
8th layer Volv-1, 8o1v-2, 5olv-4,
It was produced in the same manner as Sample 201, except that part or all of Soxma-1 in the 12th layer was replaced with the compound of the present invention as shown in Table 2.

The thus prepared sample was wedge-exposed to sunlight, developed through the processing steps (I) and [[)K shown below, and the density was measured. The results are summarized in Table 3.

As a result, in the treatment step (II) <<containing alcohol), although color development is improved, a small Kffi concentration is also observed, making it impractical.

However, when the photosensitive material of the present invention is developed using Process 11 (I) that does not contain indyl alcohol, the minimum density is
(Color development can be improved.)

Processing step (1) Sample 201.205.209 was cut to a width of 35 m + width, a photograph of a subject that seemed to be standard was taken, and the cumulative replenishment amount of color developer was 30 j ( A running test was conducted until the tank capacity reached 3 times the tank capacity. After this running test, samples 201 to 213 were subjected to development treatment for color development evaluation.

Process Processing time Processing temperature Replenishment amount Color development 3 minutes 15 seconds 38℃ 451j bleaching 1 minute 00 seconds 38℃ 201j bleach fixing 3 minutes 15 seconds 38℃ 3011Ll water washing (114
0 seconds 35℃ (2+ to (1)-% countercurrent piping system.

Tank capacity 107? 4g e Washing with water (2) 1 minute 00 seconds 35℃ 30 resistance
41 stable 40 seconds 38℃ 20111j 4
/ dry a! 1 minute 15 seconds 55°C Replenishment amount is 35cm per width 1+r+length Next, write down the composition of the processing solution.

(Color developer) Mother solution (II) Replenisher (F) Diethylenetriaminepentaacetic acid l,Ol-hydroxyethylidene-1,1-3,0 diphosphonate Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide
Potassium 1,4 iodide
1.5■Hydroxylamine sulfate! 2.4
Add 4-[N-ethyl-N-β-hydro diethylamino]-2-methylaniline sulfate in 4.5 ml of 1.0 jpf1
10.05 (0! White liquor) Common to mother liquor and replenisher (Unit! Ferric ethylenediaminetetraacetate 1
20.0 Ammonium dihydrate 4.4 37.0 0.7 1.0/ 10.10 Ethylene diamine diacetic acid = 10.0 Sodium chloride Ammonium bromide 100.0 Ammonium nitrate Ammonia water (27%) Add water TeYi 10.0 15.0IIj 1.01 6.3 (Bleach-fix solution) Common to mother liquor and replenisher (Unit II) Ethylenediaminetetraacetic acid ferric ammonia water dihydrate Ethylenediamine ethyl acetate disodium salt Sodium sulfite fOsulfur IR ammonium aqueous solution Aqueous ammonia (27%) Add water to pH 50,0 5,0 12゜0 24 o, oIIIl 6,0- 1,01 7,2 (Washing solution) Mother liquor and replenisher common tap water to H Calcium and magnesium ions were extracted by passing water through a mixed bed column packed with a strongly acidic cation exchange resin (Amberlite R-120B manufactured by Rohm Ambehars) and an OH anion exchange resin (Amberlite IR-400). The concentration was adjusted to below 3 W/l, and then 20 νj of sodium isocyanurate dichloride and sodium sulfate o,is tvt were added.

The pH of this solution was in the range of 6.5-7.5.

(Stabilizing solution) Common to mother solution and replenisher solution (Unit: Formal 7 (3
7%) 2. (C10 (average degree of polymerization 10
) Add ethylenediaminetetraacetic acid O,OS disodium salt solution to pH i, og 5.0-8.0 Treatment step (n) Add indyl alcohol per color developer 11 to the color developer in treatment step (1). It was carried out in the same manner as the treatment step (1) except that it was added so that Ic was 1511117.

Example 3 A test was carried out in the same manner as in Example 2 except that the treatment step (1) of Example 2 was replaced by the following treated saliva.

As a result, as in Example 2, the minimum concentration did not increase (
, the effect of improving color development was observed.

Furthermore, when the development process was carried out by adding 15% of benzyl alcohol per color developing solution 11 in the processing step [phase], the minimum density became thicker (increased).

Processing process (■) Process Processing time Processing temperature Replenishment V Color development 55 seconds 42℃ 2311/Bleach
45 seconds 38℃ 5d Fixing 1 minute 30 seconds 38℃ 3017 Washing (1)
25 seconds 38℃ Water washing +21 25 seconds 38℃ 30rllll stability 25 seconds 38℃ 20m Drying 1 minute 55℃ , the amount of developer carried into the bleaching process, and the amount of fixing solution carried into the washing process 1 are 35++w+width photosensitive material 1.
They were 2.5 d and 2.0 − per m length, respectively.

(Color developer) Diethylenetriaminepentaacetic acid 1-hydroxyethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Human 90 Xylamine sulfate 4-(N-ethyl-N-β-Human 90 Add ethylamino)-2-methylaniline sulfate aqueous solution H Mother liquor 1.0fI 3.0 Ii 4, Og 30.0, F 1.41 1.5■ 2.4g 1.0g 10.09 Replenisher 1. 1.9 3.2I 4.92 30, OF 3.6g 17.1 F 1.01 10.14 (#4 white liquor) Mother liquor replenisher 1.3-Diaminopropanetetraacetic acid Ammonium bromide Ammonium nitrate Acetic acid (98% ) Add water to phi (adjust with aqueous ammonia) 2.81 76 g 90, F 110, O# 1, Ol 3.7 4.0Ii 160, OIi 1, Og 2.2 (Fixer) Ethylene diamine acetate Ammonium salt mother solution and replenisher common 1.71! Ammonium sulfite 14, O, F Ammonium thiosulfate aqueous solution (70011/1) 340 1! l Add water to H7.0 (Water wash) Common tap water for mother liquor and replenisher to B-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OR-type strongly basic anion exchange resin. (Same Amber Rai) IRA-
Water was passed through a mixed bed column packed with 400) to reduce the degree of calcium and magnesium ion penetration to 3"f/l or less, and then sodium incyanurate dichloride 20
q/l and 150w1 of sodium sulfate were added. The pa of this liquid was in the range of 6.5-7.5.

(Stabilizing solution) Mother solution and replenisher common surfactant 0.4g ethylene glycol Add 1.0g water
1,0j pH5,0-7,0 Example 4 A multilayer color photographic paper having the layer structure shown below was prepared on a paper support which was laminated on both sides with polyethylene and whose surface was subjected to corona discharge treatment. The coating solution was prepared as follows.

1st layer coating liquid preparation Yellow coupler (ExY) 60.0 g and anti-fading agent (Cpd-1) 28.0 g ethyl acetate 15
Add and dissolve 0 cc, 1.0 cc of solvent (Solv-3), and 3.0 cc of solvent (U-1), and add this solution to 450 cc of a 10% aqueous gelatin solution containing sodium dodecylbenzenesulfonate, and then add it to an ultrasonic homogenizer. The resulting dispersion was mixed into a silver chlorobromide emulsion (silver bromide 0.7 mol %) containing the following blue-sensitive sensitizing dye.
A 1st layer coating liquid was prepared by mixing and dissolving 0 g of the 1st layer.

Coating solutions for the second to seventh layers were also prepared in the same manner as the coating solution for the first layer. The gelatin hardening agent for each layer is 1.2-
Bis(vinylsulfonyl)ethane was used.

The following spectral enhancing dyes were used in each layer.

Blue-sensitive emulsion layer; anhydro-5,5'-dichloro-3,
3'-disulfoethyl thiacyanine hydroxide green-sensitive emulsion layer; anhydro-9-ethyl-5,5'-diphenyl-3,3'-disulfoethyl oxacarbocyanine hydroxide red-sensitive emulsion layer i3,3'- diethyl-5-methoxy-9
, 11-neobentylthiadicarbocyanine iodide The following materials were also used as stabilizing agents in each emulsion layer.

was used.

[3-carboxy-5-hydroxy-4-(3-(3-
Carboxy-5-oxo-1-(2,5-bisulfonatophenyl)-2-pyrazolin-4-ylidene)-1-propenyl)-1-pyrazolyl]benzene-2,5-disulfonate-disodium salt N,N' -(4,8-dihydroxy-9,10-dioxo-3,7-cissulfonatoanthracene-1,5-diyl)bis(aminomethanesulfonate)-tetrasodium salt [3-cyano-5-hydroxy-4- (3-(3-cyano-5-oxo-1-(4-sulfonatophenyl)-
2-pyrazolin-4-ylidene)-1-pentanyl)-
1-pyrazolyl]benzene-4-sulfonate ~ sodium salt and the following as an irradiation prevention dye (N composition) The composition of each layer is shown below, and the numbers are coating fit (g/I
The silver halide emulsion represented by Tr) represents the coating amount in terms of silver.

Support Paper laminated on both sides with polyethylene, surface treated with corona discharge Support Layer (blue sensitive layer) Silver chlorobromide emulsion described above (AgBr O, 7 mol %, cubic, average grain size 0.94) 0 .29 Gelatin 1.80 Yellow coupler (Ext) 0.60 Anti-fading agent (Cpd-1) 0.28 Solvent (Solv-3) 0.01 Solvent (II-1) 0.03 Second layer (color mixing prevention layer ) Gelatin O, SO color mixing inhibitor (Cpd-2) 0.055 Solvent (Solv-1) 0.03
Solvent (1-1) 0.15 Third layer (green-sensitive layer) Above-mentioned silver chlorobromide emulsion (AgBr O, 7 mol%, cubic, average grain size 0.45 m) 0.18
Gelatin 1.86 magenta coupler (!IxM) Anti-fading agent (Cpd-3) Anti-fading agent (Cpd-4) Solvent (Solv-1) Solvent (1-1) Fourth layer (color mixing prevention agent) Gelatin color mixing prevention agent (Cpd-2) Ultraviolet absorber (UV-1) Ultraviolet absorber (GV-2) Solvent (Solv-1) Solvent (Solv-2) Fifth layer (RFI sensitive layer) The above-mentioned silver chlorobromide emulsion (AgBr Average particle size 0.5g) Gelatin cyan coupler (lxc-1) Cyan coupler (ExC-2) Antifading agent (Cpd-1) Solvent (III-1) 0.27 0.17 0.10 0.2 0. 03 1.70 0.065 0.45 0.23 0.05 0.05 4 mol%, cubic, 0.21 1.80 0.26 0.12 0.20 0.16 Solvent (Solv-2) Color development Accelerator (Cpd-5) 6th layer (UV absorbing layer) Gelatin UV absorber (UV-1) UV absorber (UV-2) Solvent (Solv-1) Solvent (Solv-2) 7th layer (protective layer ) Gelatin 0.09 0.15 0.70 0.26 0.07 0.30 0.09 1.07 (ExY) Yellow coupler α-Vivalyl α-(3-benzyl-1-hydantoinyl)-2-chloro- 5-(β-(dodecylsulfonyl)
Butyramide J aceto 7 dilide (Ext) Magenta coupler 7-chloro-6-ituprobyl-3- (3-[(2-
Butoxy-S-(L-octyl)benzenesulfonyl]propyl)-! H-pyrazolo(5,l-dan)-1,
2,4-) Riazole(!1xc-1) Cyan coupler 2-pentafluorobenzamide-4-chloro-5(2
-(2,4-di-tert-amylphenoxy)-3-
Methylbutyramidephenol (ExC-2) Cyan coupler 2,4-dichloro-3-methyl-6-[α-(2,4-
Di-tart-amylphenoxy)butyramide]phenol (Cpd-1) anti-fading agent-(CL-CHh- C0NHCaH*(n) Average molecular weight 80,000 (
Cpd-2) Color mixing inhibitor 2.5-di-tert-octylhydroquinone (Cp
d-3) Anti-fade agent 7.7'-dihydroxy-4,4,4',4'-tetramethyl-2,21-spirochroman (Cpd-4) Anti-fade agent N-(4-dodecyloxyphenyl)- Morpholine (Cpd-5) Color accelerator p-(p-)luenesulfonamide) phenyl-dodecane (Solv-1) Solvent Di(2-ethylhexyl) phthalate (Solv-2) Solvent Dibutyl phthalate (Solv-3) Solvent (l-nonyl)phthalate (Solv-4) solvent N,N-diethylcarbonamido-methoxy-2,4-
Di-t-amylbenzene (UV-1) UV absorber 2-(2-hydroxy-3,5-di-tert-amylphenyl)benzotriazole (UV-2) UV absorber 2-(2-hydroxy-3, 5-tert-butylphenyl)benzotriazole These samples were exposed to light in the manner described in Example 1;
Separately, a sample of the above photosensitive material subjected to imagewise exposure is subjected to continuous processing (running test) using a paper processing machine until twice the tank capacity for color development is refilled in the following processing steps, and then processed. A color image was obtained.

Processing ■ 1 degree solid color development 35℃ 45 seconds 161M11741! Bleach fixing 30-36℃ 45 seconds 215m 1171 stable ■
30~37℃ 20 seconds -101 stable ■ 30~3
7℃ 20 seconds -10f stable■ 30~37℃ 20
seconds -io x stable■ 30~37℃ 30 seconds 24
8d No. 1 Drying 70-85'C 60 seconds Umbrella Replenishment amount per light-sensitive material (4 tank countercurrent system from stable ■ to ■) The composition of each processing solution is as follows.

Sadate Niri l Oka LIL Oka Sarako Wataru Mizu
800d 800d ethylenediaminetetraacetic acid 2.0g 2.0g5.
6-Sihydroxybenzene-1.2.4-trisulfone M O, 3 g 0.3 g Triethanolamine 8.0 g 8.0 g Sodium chloride 1.4 g Potassium carbonate
25g25gN-ethyl-N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate 5.0g 7.0gdiethylhydroxylamine 4.2g 6.0gFluorescent brightener (4,4 '- Diaminostilbene type) 2.0g Add 2.5g water 1000d 1000dpH
(25℃) 10.05 10.45
Two beans and five hills (tank fluid and replenishment fluid are the same) water
400 dAmmonium thiosulfate (70% [wt/vol) 100
td Sodium sulfite iron ethylenediaminetetraacetate (I[[) Ammonium ethylenediaminetetraacetic acid dinatrirum Add glacial acetic acid water to pH (25°C) MC tank solution and replenisher are the same) Formalin (37%) Formalin-sulfite adduct 5- Chloro-2-methyl-4-ifthiazolin-3-one 2-methyl-4-isothiazolin-3-one Add sulfuric acid water and pit (25°C) 7 g 5 g g g 1000 d 5.40 0.1 g 0 .7 g 0.02 g 0.01 g 0.005 g 1000 d 4.0 When the processed photosensitive material was evaluated in the same manner as in Example 1, it showed the same color development and image durability as in Example 1. Improvement effects were observed.

Also, instead of the solvent in each layer, the compound of the present invention, I-
2, I-8, l-12, l-15, It-5゜n-8,
H-12, M-5, ■-9, ■-1, F/-5, IV-
A similar effect was confirmed using No. 16.

(Example 5) A multilayer color photosensitive material having each layer having the composition shown below was prepared on a 127 μm thick triacetic acid CEL P film support coated with an undercoat, and designated as Sample 101.

The numbers represent the amount added per ml.

1st layer: Anti-scratch layer Black colloidal silver 0.25g Gelatin 1.9g U-10°04g U-2.0.1g U-30.1g O amount! -10.1g 21st: Intermediate layer gelatin 0.40gCpd
-D 10mg011-3
40mg Third layer: Intermediate layer covered fine grain silver iodobromide emulsion (average grain size 0.06μ, Agl content 17%) Silver amount 0
．． 05g gelatin 0.4g 1st layer: low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain size 0.4μ, Agl content 4.57μ) A mixture of monodisperse cubes and average particle size 0.3μ, Agl content 4.5 mol - l = 1 of monodisperse cubes) Silver amount 0.4g Ze2 Chia 0.8g Kabutsu C-10,20g Kabutsu C -90.05g 011-1 0. IOCgs layer: medium-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-1 and S-2 (average grain vkO, 5μ, Agl content 47 ruti monodisperse cubic) Silver amount 0 .4g gelatin
0.8g Coupler C-10.2g Coupler C-20.05g Turnip? -C-3 0.2Jr011
-1 0.1CC 6th layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes s-1 and S-2 (average grain size 0.7μ, Agl content 2 mol-monocarbon) Dispersed twin particles) Silver amount 0.4g gelatin 7
L1g Kazokabutsu 3
0.7g Kabutsu c-1o, 3g 7th layer: Intermediate layer gelatin 0.6g Dye D-
10.02g 8th layer: Silver iodobromide emulsion covered with intermediate layer (average grain size 0.06μ, Ag[
Gelatin LOgCpd-A
0.2g 9th layer: Low-speed green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-a and S-4 (average grain size 0.4μ, Agl content 4.57 11 mixtures of dispersed cubes and monodispersed cubes with an average particle size of 0.2μ and an All content of 4.5 mol) Silver amount 0.5g O, 25g 0.10g 0.10g 0.10g 0.03g 0.1g 0 .1g 0.1g 0.1g Gelatin coupler C-4 Coupler C-7 Kabutsu C-g pd-B pd-E pd-F pd-G pa -H 10th layer: Medium-sensitivity green-sensitive emulsion layer sensitizing dye S Silver iodobromide emulsion spectrally sensitized with -3 and S-4 (average grain size 0.5 μ, Agl content 3 mol - 〇 monodisperse cubic) Silver amount 0.4 g gelatin
0.6g Kapwo G-40, 1g Coupler 0-7 0.1g Coupler G-80, 1g Cpd-B O, 03gCp
d-ICQ, Ig Cpd-F 0. IKC! p
d -G O,05gCpd
-H0105g g11 layer: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion spectrally sensitized with sensitizing dyes S-3 and s-4 (average grain vko in terms of spheres, 6μ, Agl content 0.6μ,
Monodispersed flat plate with an average diameter/thickness of 7) Silver amount 0.5g Gelatin Log Kab 9-C
-40.4g Coupler C-70.2g Coupler C-80.2g Cpd-B 0.08gc
pd-E 0. IgCpd
-F 0. IgCpd-G
O,1gcpd-H0
, 1g 12th layer: Intermediate layer gelatin 0.6g Dye D-2
0.05g 13th layer: Yellow filter layer Yellow colloidal silver Silver amount 0.1g gelatin
11gcp(1-A
0.01g 14th layer: Intermediate layer gelatin 0.6g 15th layer:
Low-speed blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle size 0.4μ, Agl content 3 mol - 1:l mixture of monodisperse cubes and monodisperse cubes with average particle size 0.2μ, Ag content 0.6g Gelatin 0.8g coupler G
-50.6g 16th layer: Medium-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and 8-6 (
Monodispersed cubes with average particle size 0.5μ and AgI content 27 Roux) Silver content 0.4g gelatin
0°91 Cub 2-C-50, 3g Coupler G-60, 3g 17th layer: Highly sensitive blue-sensitive emulsion layer Silver iodobromide emulsion sensitized with sensitizing dyes S-5 and S-6 (
Average particle size when converted to spheres: 0.7 μ, Agl content: 1.5 molti,
Tabular grains with an average diameter/thickness of 7) Silver content: 0.4 g Gelatin: 12 g Coupler G-6
0.7g 18th layer: 1st protective film layer gelatin 0.7gU-10,
04g U-30,03K U-40,03g U-50,05g U-60,05g cpd-co, sg dye D-30,05g 19th layer: Fine grain silver iodobromide emulsion covered with second protective layer (Average particle size 0.06/
J, Agl content 1 mo, b%) Silver amount 0.1 g gelatin
0.4g 20th layer: 3rd protective layer gelatin 0.4g polymethyl methacrylate (average particle size 1.5μ) 0.1 and 4=6 copolymer of methyl methacrylate and acrylic acid (average particle size L5μ) 0 .1g silicone oil 0.03g surfactant"'-1
3.0 mg In addition to the above composition, gelatin hardening agent 5-1 and a surfactant for coating and emulsification were added to each layer.

Diptyl phthalate tricresyl phosphate Cpd-A %;! Coupler C-8 Cpd-B H Cpd-C Cpd-E Cpd-H Cpd-D D-7! -1 Next, the weight ratio of the oil in the fourth and fifth layers is 1/IK.
A similar photosensitive material was prepared except that the compounds of the present invention shown in Table 4 were used, and processed in the following processing steps.

Photographic properties are cyan density D min r D mA!
It is expressed as a relative sensitivity when the sensitivity of sample A is set as 100.

(Sensitivity was expressed as the relative value of the reciprocal within the exposure required to give Dmin K 0.5 plus 'density.)
After the treatment, the sample was left at 70° C. (15-20° RH) for 10 days, and the drop in concentration from the initial concentration of 1.5 was determined.

The degree of fading is 0sNa I asked for it. The results are shown in Table 4.

1st water wash Reversal Color development adjustment Bleach fix 2nd water wash 8 t B1 8I 8I 8I 8I 1st developer NitriloN, N, N -) rimethylene phosphonic acid 5
Sodium salt Sodium sulfite Hydroquinone mono, potassium sulfonate Potassium carbonate 1-phenyl-4-methyl-4-human tetraxymethyl-3
-Pyrazolidone Potassium bromide Potassium thiocyanate Potassium mother liquor 2.0g 0g 0g 3g 2.0g 2.5g 2g 2.0mg Reversal liquid Phosphonyl 5-sodium salt Stannous chloride dihydrate Logp-Aminophenol 0 .1g sodium chloride
sg glacial acetic acid 15
yn/replenisher 2.0g 0g 0g 3g 2.0g 4g 2g Voice 6,00〇 was adjusted with hydrochloric acid or sodium hydroxide.

Color developer mother solution Replenisher nitrilo-N,N,N-)limethylene 2. Og
2.0 g Phosphonic acid pentasodium salt Sodium sulfite 7.0 g
7.0g trisodium phosphate dodecahydrate 36
g 36g potassium bromide
10g potassium iodide 90g sodium hydroxide 3.0g
3.0 g Cytoxic acid 15 g
1.5gN-ethyl to β-methanesulfone
l1g l1gamidoethyl)-3-methyl-4~ Aminoaniline sulfate 3,6-cythiaoctay-1,8-1,0g
Add LOg diol water to 10100O!
10100O- was adjusted with hydrochloric acid or potassium hydroxide L80 12.00- was adjusted with hydrochloric acid or potassium hydroxide.

Adjustment solution Mother solution Replenishment solution Ethylenediaminetetraacetic acid・8.0 g
Add the same disodium salt/dihydrate sodium sulfite 12 g 1-thioglycerin 0.4 ml water to the mother liquor.
1000m/pH 6.20- was adjusted with hydrochloric acid or sodium hydroxide.

bleaching solution Ethylene chloride 4 acetic acid fist Disodium salt/dihydrate salt Ethylenediaminetetraacetic acid/FslQ Fecal ammonium dihydrate salt potassium bromide ammonium nitrate 2.Og 4.0g 120 g 240 g 00g 0g 00g 0g … 5.70 5.50 - was adjusted with hydrochloric acid or sodium hydroxide.

Fixer sodium thiosulfate sodium sulfite sodium bisulfite Mother liquor 0g 5.0g 5.0g replenisher Same as mother liquor -6,60 The voice was adjusted with hydrochloric acid or anthonia water.

Stable liquid mother liquor 5.0 mj O, 5 m4 Formalin (37 t) Polyoxyethylene-p-7nonoerphenylene ether (average degree of polymerization 10) Add water 10100 O
As is clear from Table 4, when a compound of the present invention is used in the replenisher mother liquor without adjustment, both color development and cyan image storage stability are improved.

Claims (1)

[Scope of Claims] A silver halide color photographic photosensitive material comprising at least one silver halide emulsion layer on a support and at least one coupler selected from yellow dye-forming couplers, magenta dye-forming couplers and cyan dye-forming couplers. In the material processing method, at least one of the above couplers is contained in combination with at least one non-color-forming compound represented by the following general formula [I], [II], [III] or [IV], and the photosensitive 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing the material with a color developing solution that does not substantially contain benzyl alcohol. General formula [I] R^1-NHCO-R^2 [In the formula, R^1 is a substituted or unsubstituted aryl group or heterocyclic group, and R^2 is a substituted or unsubstituted alkyl group, aryl group. or a heterocyclic group, respectively. However, R^2 does not contain a carboxyl group. ] General formula [II] R^3-NHSO_2-R^4 [In the formula, R^3 and R^4 each independently represent a substituted or unsubstituted alkyl group, aryl group, or heterocyclic group. However, R^3 and R^4 are never an alkyl group at the same time. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^5 is a substituted or unsubstituted alkyl group,
In the aryl group or heterocyclic group, R^6 and R^7 each independently represent a substituted or unsubstituted alkyl group, aryl group, alkoxy group or aryloxy group. However, R^6 and R^7 may be bonded to each other to form a ring with ▲numerical formula, chemical formula, table, etc.▼. ] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R^8 is a substituted or unsubstituted aryl group or heterocyclic group, and R^9 and R^1^0 are each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and Y represents -CO- or -SO_2-, respectively. ]