JPH0289047A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve decolorability by processing without exerting adverse influence on photographic characteristics and to improve sharpness and color reproducibility by incorporating at least one kind of specific dyes and at least one kind of another specific dye into the photographic sensitive material. CONSTITUTION:The photographic sensitive material contains at least one kind of the dyes expressed by formula I and at least one kind of the dyes expressed by formula II. In formulas I, II, X, X' denote a hydrogen atom, amino group, etc.; Y, Y' denote a hydrogen atom, alkyl group, etc.; Z, Z' denote a hydrogen atom, amino group, etc.; R1, R3 denote an alkyl group, aryl group, etc.; R2, R4 denote a hydrogen atom, alkyl group, etc.; L1 to L5 denote a methine group; (l), (m) denote 0 or 1; (n) denotes 1 to 3; M<n+> denotes n-valent cation; R11, R13 denote an aliphat. group, arom. group, etc.; R12, R14 denote an aliphat. group, arom. group, etc. The silver halide color photographic sensitive material which is greatly improved in color reproducibility and sharpness is obtd. in this way and the after-colors after processing are decreased.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide color photographic light-sensitive material having good halation and color reproducibility.

(Prior Art) In a silver halide photographic light-sensitive material, a photographic emulsion layer or other Iml is used for the purpose of absorbing light in a specific wavelength range.
Coloring is often done.

A colored layer called a filter no is provided on the side far from the support to control the spectral composition of light incident on the photographic emulsion layer. between the photographic emulsion layer and the support, or the photographic emulsion layer of the support, in order to prevent blurring of the image, that is, no-ration, which is caused by reflection from the surface of the photographic emulsion layer and entering the photographic emulsion layer again. An anti-halation layer called an anti-halation layer is provided on the opposite side.

Due to the scattering of light in the photographic emulsion layer (reduction in image sharpness (this phenomenon is generally called irradiation))
In order to prevent this, the photographic emulsion layer is also colored.

These layers to be colored are often composed of hydrophilic colloids, and therefore, for coloring them, a water-soluble dye is usually included in the layer. This dye must satisfy the following conditions.

(I) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. In other words, it has an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense.
For example, it should not cause a decrease in sensitivity, latent image regression, or fog.

(3) No harmful coloration remains on the photographic material after processing by being bleached or dissolved away during the photographic processing process.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and in particular oxonol dye y#+, which has a pyranolone nucleus, has the property of being decolorized in a developer containing sulfites. , 4. It has been used as a useful dye for dyeing light-sensitive materials because it rarely has a negative effect on true emulsions. For example, British Patent No. rot, its no.
7, reference λ issue, same t, 3 it, rru issue, same/, 33!
, 7 Tata issue, same/, 3rj, 37/ issue, same/, $47.
Kol≠ issue, same/, μis, ioλ issue, same/, ni 13゜574, JP-A No. 41,130, Mukai Hirotar i
I, Hiroko O, No. 11-141.233, JP-
///, No. 0, AJ-273.1 core number, ≦3
-/3rippri No. 3, U.S. Patent No. 3゜Cohiro7. /No.27,
Same 3. Examples of dyes used include Hirotori, Rirr, Dohiro, 071, and Ri33.

(Problem to be Solved by the Invention) Usually, the pigments constituting a subtractive color photographic image are approximately H2
Haboj2, a yellow pigment with absorption maximum at 0~Hiroshi & Onm
Habot, a magenta dye with absorption maximum at 0-j70nm
There are three types of cyan dyes that have an absorption maximum between po and 700 nm, but the shapes of the spectral absorption curves of these dyes that are actually observed are quite wide in terms of wavelength, and there are yc% and undesirable absorptions outside the necessary absorption region. have. When using the aforementioned oquinol dye with a pyrazolone nucleus as a filter dye to remove this undesirable absorption and control the original spectral composition, the dye may have an inappropriate absorption wavelength or even if the absorption wavelength is appropriate, In addition, the rapid development processes that have become popular in the United Kingdom do not completely decolorize during processing, resulting in undesirable residual color in the processed image. l.

No. 712.163, same/, 12/, No. 013, same/
,! The oxonol dye having a hydroxy-7-pyridone nucleus described in 7.1, R.Tata, etc. has an absorption wavelength that could not be achieved with the oxonol dye having a pyrazolone nucleus fa, so it is useful as a filter dye for controlling the spectral composition. It's not neat. However, this type of dye is used in the photographic emulsion layer to prevent irradiation.
If used as a sensitizing dye, it may have little effect on the photographic emulsion itself, but on a spectrally sensitized emulsion, it may cause spectral sensitization in unnecessary areas or cause the sensitizing dye to be desorbed.
However, this method has the disadvantage of causing a decrease in sensitivity, and a solution to this problem has been desired.

Therefore, it is an object of the present invention to solve the following problems:
The object of the present invention is to provide a silver halide color photographic light-sensitive material that does not give any color, has excellent decolorization properties during processing, and has improved sharpness and color reproducibility.

(Means for Solving the Problems) In a photographic light-sensitive material having at least one silver halide emulsion layer on a support, the photographic light-sensitive material comprises at least one dye represented by the following general formula (I3) and the following general formula (
A silver halide color photographic material containing at least one of the dyes represented by n).

General formula (I) (in the formula, x and x' are each a hydrogen atom, a hydroxyl group, a carboxyl group, -C00R1, -CORt, -CONH2, -CO
NR, R2 represent an alkyl group, an aryl group or an amino group, Y and Y' each represent a hydrogen atom, an alkyl group, an aryl group or an amino group, and 2%2' represents a hydrogen atom, a cyano group, a carboxyl group, Sulfo group, amino group, -
COOR3, -COR3, R4R4 -C0~H2, -CO represents R3R4, an alkyl group or an aryl group. R1s R3 each represents an alkyl group or an aryl group, and R2 and R4 each represent a hydrogen atom, an alkyl group or an aryl group.
3, R4, R5 each represent a methine group, l, m each represent Q or /, nn/, 2 t'X j
f2r: Representation, Mn represents an n-valent cation.

General formula (■) -CONR15R16, R15R16 to -NR15CO
, -8O2R17, -COR17・ - to Rts CO
R1?・- to R16S 02 R17・cyano group (here %R15, R16 represents a hydrogen atom, aliphatic group or aromatic group, R17 represents an aliphatic group or aromatic M, R
15 and crazy 16 or R16 and R17 are connected! Or Aj
It may form an i-ring. ), n1%n2 represents 0 or /, and M represents hydrogen or other monovalent cation.
is the same as the definition in general formula (I). Next, the dye represented by the general formula (I) will be explained in detail.

[In the formula, R11 and R13 represent an aliphatic group or an aromatic group, [(I2,1(I4 is an aliphatic group or an aromatic group, OR1
5C00Rt5, - to R15R16, X, X', Y
S Y', Z, Z', Rt, Rffi, R,
, R, is an unsubstituted alkyl group (for example, methyl, ethyl, n-butyl, isopropylcyclohexyl), a substituted alkyl group with F as one substituent,
Halogen atoms such as C1 and Br (e.g. 2-chloroethyl, trifluoromethyl, 1.1,2.2-tetrafluoroethyl), phenyl groups (e.g. benzyl, phenethyl, 4-chlorobenzyl, 2-sulfobenzyl, 4- sulfobenzyl, 4-sulfophenethyl, 4-(3-sulfopropyl)oxybenzyl), hydroxyl groups (e.g. 2-hydroxyethyl, 3-hydroxypropyl), cyano groups (e.g. 2-cyanoethyl), carboxylic acid groups (e.g. carboxymethyl , 2-carboxyethyl, 4-carboxybutyl, l-carboxyethyl), sulfonic acid groups (e.g. sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl), alkoxy groups (e.g. 2-
methoxyethyl, 2-(2-hydroxyethoxy)ethyl), amino groups (e.g. 2-dimethylaminoethyl, 2
-diethylaminoethyl) or ester groups (e.g. ethoxycarbonylmethyl, methoxycarbonylmethyl, 2
-hydroxyethoxycarbonylmethyl)) is preferred.

X, X', Y, Y', Z, Z', Rt, Rt
.

The aryl groups represented by R, , R, are each unsubstituted aryl group (e.g. phenyl, naphthyl) substituted aryl group (
As a substituent, halogen atoms such as F, C1, B (e.g. 2,5-dichlorophenyl, 4-chlorophenyl),
Hydroxyl groups (e.g. 4-hydroxyphenyl), carboxylic acid groups (e.g. 2-carboxyphenyl, 3,5-dicarboxyphenyl), sulfonic acid groups (e.g. 3-sulfophenyl, 4-sulfophenyl, 2,5-disulfophenyl) ), alkoxy groups (e.g. 4-methoxyphenyl, 4-
(3-sulfopropyloxy)phenyl, 4methoxy-
3-sulfophenyl), an alkyl group (e.g. P-tolyl, 2-methyl-4-sulfophenyl), an amino group (e.g. 4-dimethylaminophenyl, 4-diethylaminoethyl), a cyano group (e.g. 4-cyanophenyl) or ester group (e.g. 4-ethoxycarbonylphenyl))
is preferred.

The methine group represented by LL, Lx, L3, L-1Ls is preferably an unsubstituted methine group, but may have a substituent (for example, methyl, ethyl, 2-sulfoethyl).

Mll+ represents a monovalent (n represents 1.2.3) cation (e.g. H'', Na'', K'', Ca'' carboxylic acid group, or at least one sulfonic acid group or carboxylic acid group) More preferably, Z and Z' represent a cyano group or a substituted or unsubstituted carbamoyl group, and Y and Y' have at least one sulfonic acid group or carboxylic acid group. It represents a group.

Specific examples of the dye represented by general formula (I) are shown below.

(HOCH!)4P'').

When the general formula (I) has a carboxylic acid or a sulfonic acid, these acids may form salts (for example, inorganic salts such as sodium, potassium, ammonium, etc., or organic amine salts such as triethylammonium, pyridinium, etc.) even when they are free acids. You can leave it there.

Preferred among general formula (I) are x, x'Y, Y'
, Z or Z' is a sulfonic acid group or Cz II
s C2HszHs Cz Hs! -3 C11□ H1 CIlICOOK CI, COO to CMICOOK cozcoo ■ ■ ■ CIIgCH*5OJa CH*CHiSOJa ■ ! -8 CII*C1hOH CHzCH*OH Hs H3 C! II S xHs CHyoC11xSOJ CIl□CIh5OsK ■ CH3 C11゜■ C, II S Cz 11 s! ! ■ ■-18 CHzCII*C00Na CHiCHxCOONa C1lzCHiSOJa CIIxCIIiSOJa 1lz CI+.

Ct)Is J.S. CHzCIIzSOJ CIlICII□SO3 l-30 CIl□CD! 5O3K C) IxCHz SOJ ■ CZ II% C! IIs ! ■-36 H ! ■ Cz It's C! II S zHs Ni+ zHs C11zCIItCII□0■ CHICOOK CIIzCIItSOJa ■-46 Cx tl 5 CHIC11□CIItO1l CH,C00K CIIzCHzSO:+Na zils ! -42 Hz CH! ■ CI II% C,H.

CHtCHO5Osx CHICIlISO3 Dyes represented by the general formula (N) are described in U.S. Pat.
, No. 62/, No. 312, 163, No. 62/, r7ri,
222, and the hydroxypyridones used to synthesize the dye represented by the general formula (I) are described in "Heterocyclic Compounds - Viridine and Its Visiting Conductors - Vol. 1," edited by Talinsberg. Part 3” (Interscience Publishing, IYT, 2nd Year 2nd, Journal of the American 1 Keba Cal Society (J, Am.

Chem, Soc, )/ri 4t3 years, 6j volume, 4444
2 pages, Journal of the Chemical Technology
and Biotechnology (J, Chem, Tech
.

Biotechnol, ) / 9K6, vol. 36, ai
.

Page, Tetrahedron/ri4
4th year - Volume! 4Lj page, No. 2127 in Tokko Sho t/-,
West German patent @λ, /j, No. 2.4/2, 2.3ψri, 7
No. 02, same company, Oλ, Hirot No., US patent 3.7t3
．． It can be synthesized by the method described in No. 170 and the like.

Next, the dye represented by the general formula (I1) will be explained in detail.

R11% R12, R13, R14s R15% The aliphatic group represented by R16 and R17 may be any linear, branched or cyclic alkyl group, aralkyl group, alkenyl group, such as methyl, ethyl, n-butyl, benzyl. , 2-sulfoethyl, μm sulfobutyl, λ-sulfobenzyl, 2. Hiro-disulfobenzyl, Hiro-sulfophenethyl, cocalpoquinethyl, carboxymethyl,
Examples of M include trifluoromethyl, dimethylaminoethyl, and λ-hydroxyethyl. 1 R11%R12%R13s R14%R15%R16,
Examples of the aromatic group represented by R17 include o, phenyl, cafthyl, sulfophenyl, 3-sulfophenyl, J, r-disulfophenyl, ≠-carboxyphenyl, ! , 7-disulfo J-? Examples include groups such as niathyl.

It is formed by connecting R15 and at6, and R16 and R17! Or as a t-membered ring, a pyrrolidine ring, a piperidine ring,
Examples include a biaridon ring and a morpholine ring.

H as a monovalent cation other than hydrogen represented by MΦ,
Examples include Na■, KΦ, LiΦ, HN (C2H51P, etc.).

In general formula (■), preferred are R11 and R1
3 is at least one sulfonic acid group or carboxylic acid group fj
l: represents an alkyl group or an aryl group, and particularly preferred is one in which all and R13 represent an aralkyl group having at least one sulfonic acid group or carboxylic acid group. Examples of dyes represented by general formula (It) are shown below.

These dyes are covered by British Patent No. rot, its/
,/77, tLt29, direction/, 331r, 7
Tata issue, fEiJ/, 311.37/ issue, same/, Hiro A7
．． Jl Hiro issue, same/, '133, No. 102, same/, 11
3゜j/A No., Japanese Unexamined Patent Publication No. 1it-41730, zr-
/l, /233 issue, same number j2-20330, direction j9-i
iitqQ, Mukai 4J-273j core, AJ-/3
It can be synthesized by the method described in R.P.

When using the dyes represented by the general formulas (N and (■)) as filter dyes, iranion prevention dyes, or antihalation dyes, any effective dye can be used; It is preferable to use the dyes in the range of θ, Or or 3.0.The ratio of the dyes (I) and (■n) is, by weight, the general formula +1 to the dye of the general formula (nJ). ) is preferably in the range of 0.1 times to io times. Attachment 7: The JO period may be any step before coating.

The dye '#+ according to the invention can be dispersed in emulsion j-other hydrophilic colloid layers (interlayers, protective layers, antihalation layers, filter layers, etc.) in various known ways.

(2) A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which the dye is dissolved or dispersed in an aqueous solution or a solvent v'C and then used in an emulsion layer or a hydrophilic colloid If4. Appropriate medium, 1? If it is, methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, JP-A-1-9? No. It, U.S. Patent 3. It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, pyridine, etc., or a mixed solvent thereof, as described in No. 1, No. 30.

(2) A method in which a hydrophilic polymer having a charge tv opposite to that of the dye ion is made to coexist with l111 as a mordant, and the dye is localized in a specific layer by interaction with the dye molecule.

A polymer mordant is a polymer containing a secondary or tertiary atom group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a μ-class cationic group, and a molecular size of 10,000 or more, particularly preferably 10,000 or more. It is something.

For example, vinyl pyridine polymers and vinyl pyridinium cationic polymers described in US Pat.

Vinylimidazolium cationic polymer disclosed in /217,316 etc.; US Patent 3°tλt,
A polymer mordant capable of crosslinking with gelatin, etc., as disclosed in No. 45'44, etc.; r, Tata J, Tokukaisho! μ-/1122 is an aqueous sol type mordant type disclosed in the specification etc.; US Patent 3. Water-impossible mordants disclosed in US Patent U,/At
, a reactive mordant capable of covalently bonding with the dye disclosed in No. 7 Otsu, etc.; British Patent No. 6r! Polymers derived from ethylenically unsaturated compounds having dialkylamanoalkyl ester residues as described in , ≠ 7j; Reaction of polyvinyl alkyl ketones with aminoguanidine as described in British Patent No. 1rzo, 211 The product obtained by; US Patent 3, a4Lt,
Examples include polymers derived from 2-methyl-7-vinylimidazole as described in No. 237.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may also be oligomers or polymers.

For details on this one combination, please refer to JP-A-1.0-/! No. 37 (Fuji 4 Shin Film ■), dated January 2, 1925, and is described on page 1 to page 7 of the specification of λ.

In addition, in the hydrophilic colloid dispersion obtained above, for example, Tokkosho! Hydrosyl, a lipophilic polymer described in No./-32rjj, may be added.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used.

The silver halide grains in the photographic emulsion may be so-called regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be one with crystal defects such as twin planes or a composite form thereof. Also, mixtures of particles of various crystal forms may be used.

The silver halide grains may be fine grains with a grain size of about 0.1 micron or less, large grains with a projected area diameter of about 10 microns, monodisperse emulsions with a narrow distribution, or monodisperse emulsions with a wide distribution. It may also be a polydisperse emulsion.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, such as Research Disclosure,
Volume 176, N1117643 (December 1978),
pp. 22-23, “1. Emulsion production
Preparation and Types)”
and the same, vol. 187, Seed 1B716 (November I979)
), page 64B.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Phys
ique Photographique Paul
Montel, 1967), “Photographic Emulsion Chemistry” by Duffin, published by Focal Press (G, F, Du
ffin.

Photographic EIIpulsion
Chemistry (Focal Press1966
), "Production and Coating of Photographic Emulsions" by Zelikman et al., published by Focal Press (Sill, Zelika+an'etal
, Making and Coating Photo
graphic Emulsion+Focal P
(Res+ 1964). That is, acidic method, neutral method,
Any method such as ammonia method may be used, and methods for reacting soluble silver salt and soluble halogen salt include one-sided mixing method,
Either a simultaneous mixing method or a combination thereof may be used. A method in which zero particles are formed under an excess of negative ions (so-called back mixing method) may also be used. As a type of simultaneous mixing method, it is also possible to use a method in which PAg in the liquid phase in which silver halide is produced is kept constant, that is, a so-called Chondrald double jet method. According to this method,
A silver halide emulsion with a regular crystal shape and nearly uniform grain size can be obtained.

In addition, known silver halide solvents (for example, ammonia, Rodankali or U.S. Pat. Showa 54-100717
Physical ripening can also be carried out in the presence of thioethers and 1,000-ion compounds) as described in No. 1983 or JP-A-54-155828. This method also yields a silver halide emulsion with a regular crystal shape and a nearly uniform grain size distribution.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling PAg and pH during grain formation. For more information, see Photographic Science and Engineering (Photographic Science and Engineering).
5science and Engineering) No. 6, pp. 159-165 (I962); Journal of Photographic Science (Journal
or Photographic 5science)
+ l 2 @, pages 242-251 (I964), US Patent No. 3.655.394 and British Patent Series 1.41
No. 3,748.

Monodispersed emulsions that can be used in the present invention include silver halide grains having an average grain size of more than about 0.05 μm;
Emulsions of which at least 95% by weight are within ±40% of the average grain size are typical. Furthermore, the average particle size is 0.1
An emulsion can be used in which the silver halide grains have a particle size of 5 to 2 .mu.m and at least 95% by weight or (grains number) of at least 95% of the silver halide grains are within a range of ±20% of the average grain size. A method for producing such an emulsion is described in U.S. Patent No. 3,574°628.
No. 3,655,394 and British Patent Series 1,4
No. 13,748.

Also, JP-A-48-8600, JP-A-51-39027,
No. 51-83097, No. 53-137133, No. 5
No. 4-48521, No. 54-99419, No. 58-3
Monodisperse emulsions such as those described in No. 7635 and No. 5B-49938 can also be preferably used.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described by Gutoff, Photographic Science and Engineering.
ence and Engineering) + 14th
Vol. 248-257 (I970): US Patent No. 4.
434゜226, 4,414,310, 4,4
No. 33.048, No. 4,439,520 and British Patent No. 2,112.157. When tabular grains are used, there are advantages such as improved covering power and improved color sensitization efficiency with sensitizing dyes.
, 434, 226.

It is also possible to use particles whose crystal shape is controlled by using a sensitizing dye or certain additives in the particle formation process.

The crystal structure of these emulsion grains may be --like, the inside and outside may have different halogen compositions, or they may have a layered structure.
No. 46, U.S. Patent No. 3.505.068, U.S. Patent No. 4,44
No. 4,877 and Japanese Patent Application No. 58-248469.

Furthermore, silver halides of different compositions may be joined by epitaxial joining (for example, silver halides,
These emulsion grains, which may be grafted with compounds other than silver halides, such as lead oxide, are described in U.S. Pat.
, No. 684, No. 4.142.900, No. 4,459,
No. 353, British Patent No. 2,038,792, U.S. Patent No. 4.349.622, No. 4,395,478, No. 4433.501, No. 4,463,087, No. 3
．． It is disclosed in JP-A-59-162540, etc.

Furthermore, photosensitive nuclei (Ag*S, Ag
It is also possible to use a grain structure having a so-called internal latent image type grain structure in which silver halide is further grown on the periphery after the formation of silver halide (n, Au, etc.).

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

These various emulsions may be either a surface latent image type in which a latent image is formed mainly on the grain surface or an internal latent image type in which a latent image is formed inside the grain.

Furthermore, the direct reversal emulsion may be a solarization type, an internal latent image type, a photofog type, a nucleating agent type, or a combination of these types.

Among these, an internal latent image type emulsion that has not been fogged in advance is used, and is fogged by light before or during processing.
Alternatively, it is preferable to directly obtain a positive image by fogging using a nucleating agent.

The unfogged internal latent image type silver halide emulsion used in the present invention is an emulsion containing silver halide in which the surface of the silver halide grains is prefogged (and the latent image is mainly formed inside the grains). However, more specifically, a certain amount of silver halide emulsion is coated on a transparent support,
This sample was exposed to light for a fixed time of 0.01 to 10 seconds, and was then placed in the following developer A (internal type developer) for 20 minutes.
The maximum density measured by the usual photographic density measuring method when developed at 18°C for 6 minutes is obtained when a similarly exposed sample is developed at 18°C for 5 minutes in the following developer B (surface type developer). Preferably those with a concentration at least 5 times greater than the maximum concentration, more preferably at least 10
It has twice the concentration.

Internal developer A Metol 2g Sodium sulfite (anhydrous) 90g Hydroquinone
8g Soda carbonate (-water salt)
52.5gKBr
5gKI
Add 0.5g water If
Surface type image liquid Metol 2.5g! -Ascorbic acid 10gNaBO, -4Hz
0 35g KBr
Add 1g water
Specific examples of the 1N internal latent image type emulsion include British Patent No. 1011062 and U.S. Patent No. 2.592゜2.
Examples of the core/shell type silver halide emulsions include conversion type halogenated agents and core/shell type silver halide emulsions described in No. 50 and No. 2,456.943. JP 47-32813, JP 47-32814, JP 52-134721, JP 52-156614, JP 53-60222, JP 53
-66218, 53-66727, 55-12
No. 7549, No. 57-136641, No. 58-702
No. 21, No. 59-208540, No. 59-21613
No. 6, No. 60-107641, No. 60-247237
No. 61-2148, No. 61-3137, Special Publication No. 56-18939, No. 5B-1412, No. 5B-1
No. 415, No. 5B-6935, No. 58-108528
No. 61-36424, U.S. Patent No. 320631
No. 3, No. 3317322, No. 3761266, No. 3
No. 761276, No. 3850637, No. 392351
No. 3, No. 4035185, No. 4395478, No. 4
No. 504570, European Patent No. 0017148, Research Disclosure Magazine No. 16345 (I977
Examples include the emulsions described in (November 2013).

In order to remove soluble silver salts from the emulsion before and after ripening, Tardel water washing, flocculation sedimentation method, ultrafiltration method, etc. can be used.

The emulsion used in the present invention is usually one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such a process are described in the aforementioned Research Disclosure N1117643 (December 1978) and Research Disclosure Nα18716 (November 1979), and the relevant parts are summarized in the table below.

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

Additive type RD17643 RD187
161 Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Anti-fogging agents and stabilizers 6 Light absorbers, filter dyes UV absorbers 7 Anti-stinting agents 8 Dye image stabilization Agent 9 Hardener 10 Binder Page 23 Page 648 Right column Same as above Pages 23-24 Page 648 Right column - Page 649 Right column Page 24 Page 24-25 Page 649 Right column Page 25-26 Page 649 Right column - Page 650 Left column 25 True right column Page 25 Page 26 Page 26 Page 650 Left to right column Page 651 Left column Same as above 11 Plasticizer, lubricant Page 27 Page 650 Right column 12 1! Fabric aid, surface pages 26-27 Same as above Active agent 13 Static prevention page 27 Same as above agent In addition to the yellow coupler mentioned above, various color couplers can be used in the color photographic light-sensitive material of the present invention, and specific examples thereof are mentioned above. Research Disclosure (RD)
) Ishi 17643, described in the patents listed in ■-C to G.

As magenta couplers, 5-pyrazolone and pyrazoloazole compounds are preferred, and US Pat.
0,619, European Patent No. 4,351°897, European Patent No. 73,636, US Patent No. 3,061,432, US Patent No. 3,725,067, Research Disclosure N1124220 (June 1984) ), Japanese Patent Application Publication No. 1986
-33552, Research Disclosure N11
24230 (June 1984), JP-A-60-4365
9, U.S. Patent No. 4,500,630, U.S. Patent No. 4,54
Particularly preferred are those described in No. 0.654.

Cyan couplers include phenolic and naphthol couplers, and are disclosed in U.S. Pat. No. 4,052,212.
No. 4,146,396, No. 4.228,23
No. 3, No. 4,296,200, No. 2.369.92
No. 9, No. 2,801゜171, No. 2.772.16
No. 2, No. 2゜895.826, No. 3,772.0
No. 02, No. 3.758,308, No. 4,334,
No. 011, No. 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121°365A, U.S. Patent No. 3,446,622, No. 4,333,
No. 999, same No. 4. No. 451.559, same No. 4,42
Those described in No. 7,767, European Patent No. 161.626A, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are described in Research Disclosure No. 17643.
- Section G, U.S. Patent No. 4,163゜670, Special Publication No. 1983
-39413, U.S. Patent No. 4,004,929, U.S. Patent No. 4,138.258, British Patent No. 1,146,36
The one described in No. 8 is preferred.

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, and German Patent Publication No. 3,234,533 are preferred.

Typical examples of polymerized dye-forming couplers are U.S. Pat. No. 3,451,820; U.S. Pat. No. 4,080.211; U.S. Pat.
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 releasing development inhibitors include the aforementioned RD17643,
Patents listed in Sections ■-F, Japanese Patent Application Laid-Open No. 57-151944
Preferred are those described in No. 57-154234, No. 60-184248, and U.S. Pat.

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. 4.310,618, DIR redox compound releasing couplers as described in JP-A-60-185950, etc., and releasing dyes that recolor after separation as described in European Patent No. 173.302A. Examples include couplers.

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.

The steps, effects, and latex for impregnation of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. etc. are listed.

The light-sensitive material of the present invention includes dyes other than the above-mentioned dyes that prevent irradiation and halation, ultraviolet absorbers, plasticizers, optical brighteners, matting agents, air fog inhibitors, coating aids, and hardening agents. , antistatic agents, slipperiness improvers, various development accelerators, etc. can be added. Representative examples of these additives are listed in Research Disclosure magazine N111764.
3■-■ pages 225-27 (published in December 1978), and 18716 (published in November 1979) p647
-651.

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

Multilayer natural color photographic materials usually have a red-sensitive emulsion layer on a support,
It has at least one green-sensitive emulsion layer and at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as necessary. The preferred order of layer arrangement is red sensitivity, green sensitivity, and blue sensitivity from the support side, or green sensitivity, red sensitivity, and blue sensitivity from the support side. Further, each of the above emulsion layers may be made up of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may exist between two or more emulsion layers having the same color sensitivity. . Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler.

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

In the photographic light-sensitive material of the present invention, the photographic emulsion layer and other layers are described in Research Disclosure Magazine k17643v section (2).
Published in December 1978) on page 28, European Patent No. 0,102,253, and JP-A-61-97655.
It is coated on the support described in No. Also, Research Disclosure Magazine N1117643XV Section P2B~2! I
N: The coating method described above can be used.

The present invention can be applied to various color photosensitive materials.

For example, color negative film, color print film, color reversal film for slides or television,
A typical example is color reversal paper. The present invention can also be applied to full-color copying machines and color hard copies for storing CRT images.
Journal disease! The present invention can also be applied to black-and-white photosensitive materials using a mixture of three-color couplers, such as those described in No. 7123 (published in July 1978).

The present invention is preferably applied directly to positive photosensitive materials.

When the photosensitive material of the present invention is a direct positive, fogging treatment is performed by the following "photofogging method" and/or "chemical fogging method". After imagewise exposure, development processing and/or
Or done during the development process. The imagewise exposed light-sensitive material is immersed in a developer solution or a pre-bath of the developer solution, or is taken out from the solution and exposed before drying, but it is most preferable to expose the material in the developer solution.

As a light source for fogging exposure, a light source within the sensitivity wavelength of the photosensitive material may be used, and -M may be any of fluorescent lamps, tungsten lamps, xenon lamps, sunlight, and the like.

These specific methods are described, for example, in British Patent No. 1,151,
No. 363, Special Publication No. 45-12710, No. 45-127
No. 09, No. 58-6936, JP-A No. 48-9727, No. 56-137350, No. 57-129438,
No. 58-62652, No. 58-60739, No. 58
-70223 (corresponding U.S. Patent No. 4.440°851)
, No. 58-120248 (corresponding European Patent No. 89101A
2) etc.

For photosensitive materials sensitive to all wavelength ranges, such as color photosensitive materials, Japanese Patent Application Laid-open Nos. 56-137350 and 5B-702
A light source with high color rendering properties (as close to white as possible) as described in No. 23 is preferable, and the illuminance of the light is 0.01 to 200.
0 lux, preferably 0.05 to 30 lux, more preferably 0.05 to 5 lux is suitable. For light-sensitive materials that use emulsions with higher sensitivity, low-light exposure is preferable. Adjustment of illuminance can be done by changing the luminous intensity of the light source, attenuating light using various filters, or changing the light-sensitive material. The distance between the photosensitive material and the light source, and the angle between the photosensitive material and the light source may be changed. Further, the illuminance of the fogging light can be increased continuously or stepwise from low illuminance to high illuminance.

It is preferable to immerse the light-sensitive material in a developer solution or a pre-bath solution, and to irradiate the light-sensitive material after the solution has sufficiently penetrated into the emulsion layer of the light-sensitive material.

In the present invention, the nucleating agent used when carrying out the so-called "chemical fogging method" can be contained in the light-sensitive material or in the processing solution for the light-sensitive material. Preferably, it can be incorporated into the photosensitive material.

Here, the "nucleating agent" is a substance that acts to directly form a positive image during surface development of an internal latent image type silver halide emulsion that has not been fogged in advance. In the present invention, fogging using a nucleating agent is particularly preferred.

When incorporated into a light-sensitive material, it is preferably added to the latent type halide emulsion layer, but as long as the nucleating agent is adsorbed to the silver halide by diffusion during coating or processing, it may be added to other layers. For example, it may be added to an intermediate layer, undercoat layer or bank layer.

When the nucleating agent is added to the processing solution, it may be contained in the developer solution or a low pH prebath as described in JP-A-58-178350.

Furthermore, two or more types of nucleating agents may be used in combination.

Regarding the nucleating agent used in the present invention, JP-A-63-10
No. 6506, and in the same specification, it is particularly preferable to use compounds represented by general formulas (N-1) and (N-11).

When a nucleating agent is included in a sensitive material, the amount used must be halogenated! ! The amount per mole is preferably 10-'' to 10-8 mol, more preferably to-' to 10-3 mol.

In addition, when adding a nucleating agent to the processing solution, the amount used is:
It is preferably from to-'' to 10-3 mol, more preferably from 10-? to 10-4 mol per 12.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but P-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-Hydroxyethylaniline, 3-methyl4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino/-N-ethyl-N-
Examples include β-methoxyethylaniline and their sulfates, hydrochlorides, and P-)luenesulfonates. Two or more of these compounds can be used in combination depending on the purpose.

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 aminophenols such as N-methyl-p-aminophenol. Alternatively, they can be used in combination.

The pH of these color developers and black and white developers is generally 9 to 12. Although the amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, it is generally 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher,
You can also do the following:

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 include iron (■) and cobalt (Il).
l), Chromium (Vl),! Compounds of polyvalent metals such as 1i1(II), peracids, quinones, nitro compounds, etc. are used.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
Urnalof the 5ociety of Mo
tion Picture and Televisi
onEngineers Volume 64, P, 24B-2
53 (May 1955 issue).

(Example) The present invention will be explained in detail below using examples.

Example 1 Paper support laminated on both sides with polyethylene (thickness 10
0 micron) on the front side, apply the following four layers from the first no.
A color photographic material was prepared in which the back side was coated with 5 to 6 N tubes in multiple layers. The polyethylene on the coating side of the first layer contains amorphous titanium as a white pigment and a small amount of ultramarine as a bluish dye (the chromaticity of the surface of the support is L* a"
b'' yarn was III, 0.-0.20.-0.71).

(Photosensitive layer composition J Below are the ingredients and application! (,9/m2 unit).

Regarding silver halide, the coating amount is shown in terms of silver. The emulsions used in each layer were prepared according to the manufacturing method of emulsion EM/.

However, the four-layer emulsion used was a Lippmann emulsion that was not surface chemically sensitized.

1st layer (antihalation/l111) black colloidal silver...0.10 gelatin
... 0.70 2nd layer (intermediate layer) Gelatin ... 0.70 3rd layer (low sensitivity red sensitive layer) Odor spectrally sensitized with red sensitizing dye (ExS-/, λ, 3) Silver chloride (average particle size 0.2 μμ, size distribution [coefficient of variation Jr%, octahedral 2.1 0.0 Silver chlorobromide spectrally sensitized with Hong red sensitizing dye (ExS-/, Ko, 3) (Silver chloride! Morch, average particle size O, aOμ
, size distribution IQ%, octahedron)...
o, or gelatin... /, 00
Cyan coupler (Ex C-/, Ko, 3f/:
/:O12) ... 0.30 Anti-fading agent (Cpd-/, -13, reference equivalent) o, ir Anti-stinting agent (Cpd-j) 1 0.003 Coupler dispersion medium (Cpd-6J ・0. 03 Coupler solvent (So IV-/, J, 7 equivalents)・
・ ・ 0. /2 μth layer (high sensitivity red sensitivity 1@) Silver bromide spectrally sensitized with red sensitizing dye (ExS-/, Ko, 3) (average grain size o, toμ, size distribution/!俤, 8 Face piece) ・ ・ ・ 0, / Gugelatin ・ ... /, 00 cyan coupler (Ex C-/ , ko, 3 /:/
:0. λ) ・ ・ e O, 30 anti-fading agent (cpct-/, 2.3, da-yari) ・ 0. Ir coupler dispersion medium (cpct-a) -0,03 coupler solvent (Sol v-i%, 2.3 equivalents)
θ, / 2 1st layer (middle layer gelatin...i, o.

Color mixing prevention agent (Cpd-7)... o, or Color mixing prevention agent solvent (Solv-≠, 5 equivalents) o, it Polymer latex (Cpd-r) ・ ・ ・ 0. 10 6th layer (low-sensitivity green-sensitive layer) Silver bromide (
Average particle size θ, λ! μ, size distribution Ir, octahedral] ... 0.0 Hong green sensitizing dye (ExS-≠j spectrally sensitized chlorobromide@(silver chloride j morch, average particle size O0≠Qμ, size Distribution io%, octahedron)・・
・ o, ot gelatin ... o, t.

Magenta coupler (ExM-/, λ, 3 equivalents)・・
・0. // Anti-fading agent (equivalent amount of cpa-ta, 26)...
o, ip stain inhibitor tcpd-10, //, /λ, 13 at 1
0 Near: 7: / Ratio Den l -O, O+25 Coupler dispersion medium (cpa-j) ・ ・ ・ o, or Coupler solvent (Solv-tl, A present) ・ ・ ・
Q, /! No. 71- (High sensitivity green-sensitive layer) Silver bromide (
Average particle size o, t μ, size distribution 16 cm, octahedral) ... 0. IO gelatin...
・o,t.

Magenta coupler (ExM-/,!, 3 equivalents)...
O0// Anti-fade agent (Cpd-ta, 2 in equal amounts) ・ ・ ・ O, l Anti-fading agent (Cpd-10, 11% lλ, 13 in 10N:7:/ratio) Exposure 0.02j Coupler Dispersion medium (Cpd-A...O, O coupler medium (Solv-41, 11)...
Q + l evening ♂ 1- (the same layer as the middle j-n 5th layer (yellow filter layer) yellow colloidal silver ・ Q, / cogelatin
... 0.07 color mixture prevention agent (Cpd-7)
... 0.03 Color mixture inhibitor solvent (Solv4I, 1st m) ... 0.10 Polymer latex (Cpd-r) 0.07 1st orn (intermediate layer) 2nd layer (low sensitivity) same as 1st jI@ Silver bromide (average grain size Q, ≠θμ, size distribution Ir,
Octahedron)... 0.07 blue sensitizing dye (ExS-1%
Spectrally sensitized silver chlorobromide (silver chloride r morti, average grain size 0.10μ, size distribution/1%, octahedral)
・ ・ 0, / Hiro Gelatin o, r.

Yellow coupler (ExY-/, 2 equivalents)・・・
0,3 Anti-fading agent (Cpd-/da) 1 0.10 Anti-stinting agent (cpct-j,/J in l:j ratio
- 0.007 force puller dispersion medium (cp
a-≦J ・O; Silver (average particle size o, rjμ, size distribution it%, octahedral) ・ ・ ・ o, is Gelatin ... θ, t.

Yellow coupler (ExY-/, 2 equivalents)... 0
, 30 Antifading agent (Cpd-/IIt) ・ ・ o, i.

Anti-staining agent (cpct-t, /j in /:j ratio)
... 0.007 Force Blur dispersion medium (Cp
d-67 ・0.02 Coupler solvent (Solv-λ) ・o, i.

1st illtl (ultraviolet absorbing layer) Gelatin... /, 00 ultraviolet absorber (equal amounts of cpct-2, μ, /)...jo, t.

Color mixing inhibitor (Cp d -7,77 equivalent) ・ ・ ・
O, OS Dispersion medium (Cpd-6) ・・・ 0.02 Ultraviolet absorber solvent (Solv-2, 7 etc. M) ・ ・ ・ o
, or 1st≠j- (protective layer) Fine grain silver chlorobromide (silver chloride 27 molti, average size o, i
μJ...0.03 Acrylic modified copolymer of polyvinyl alcohol...0.0/ Equivalent amount of polymethyl methacrylate particles (average particle size λ, reference μ) and silicon oxide (average particle size jμ)
... 0.0! Gelatin...
/ , 10 gelatin hardening agent (t-1-/, H-2 equivalent) ・ ・ ・ o , it ZrJ * (44 layers) Gelatin ... λ, IO ultraviolet absorber (Cpd-2,4 (, 74th grade 1 break - o, r.

No. 741 (back protective layer) Equivalent amounts of polymethyl methacrylate particles (average particle size, reference μ) and silicon oxide (average particle size jμ)
・・・ o, or gelatin ・・・
λ, 00 gelatin hardening agent (H-/, H-2 equivalent)・
・ ・ O, l How to make emulsion EM-/Do not vigorously stir an aqueous solution of potassium bromide and silver nitrate into an aqueous gelatin solution 7! "C" was added simultaneously over a period of 73 minutes to obtain octahedral silver bromide grains with an average grain size of O0 h 0 μ. To this emulsion was added 0°3I of J,!-dimethyl- per 7 moles of silver.
7,3-thiazoline-λ-thione, t■ sodium thiosulfate and 7■ chloroauric acid (4! hydrate salt) were added sequentially to 7!0
Chemical sensitization treatment was performed by heating at C for 10 minutes.

The particles thus obtained were used as cores and further grown in the same precipitation environment as in the first precipitation to finally obtain an octahedral monodisperse core/shell bromide emulsion with an average particle size of 0.7 μm. The coefficient of variation in particle size was approximately IO%. This emulsion contains 1.0% per mole of silver. ! Sodium thiosulfate (2) and/and chloroauric acid <U* salt Jn9 were added and heated at 60°C for 6Q minutes to carry out chemical sensitization treatment to obtain an internal IIJ image type silver halide emulsion.

Each photosensitive layer contains ExZK-/ and ExZK- as nucleating agents.
2 to silver halide, respectively / , :>-3io-
2% by weight, 10 1 of Cpd-2λ as a nucleation accelerator
11% was used. In each layer, alkanol (Cpd-λ3, 1% co!) was used as a stabilizer in the silver 0genide and colloidal silver-containing layers.

This sample was designated as sample number 1.

In addition, samples in which 7 Iu of comparative and non-inventive dyes listed in Table 1 were added to the first NtlJ were designated as sample numbers λ to IQ, respectively.

The compounds used in Example gA+ are shown below.

ExS-J ExS-4 ExS-Hiroshi 03Na Cpd-/ 5O3H-N(C2H5)3 O3H pct-2 x-j book 5O3H・N(C2H5)3 Cpd-J 4-19 (t) Shi4tig (I7 Cpd-Pi Cpd-j H cpct-x Cpd-7 R cpct-// Cpd-/J Cpd-/3 H Cpd-r COOC2H5 cpct-2 Cpd-10 (-’sat t(t) Cpd-/Hiroshi cpct-/j H Cpd-/A Cpd-77 H Cpd-, 22 Cpd-23 Cpd-2 Hiroshi Cpd-λ Cpd λ 6 E x M -/ E x M-J (JC4Hg(n) C8H17 (g ExC-/ α ExC-2 L ExC-J ExY-/ α C3H1) (I) ExY-2 C81-11met) olv-t Di(2-ethylhexyl) sebake root ol trinonyl phosphate olv-3 ′)( 3-methylhexyl) phthalate - 5olv-μ 5olv-r olv-4 olv-7 H-/ -J ExZK-/ ExZK-x tricresyl phosphate dibutyl phthalate Trioctylphos 7ate Di(,2-ethylhexyl)phthalene root 7.2-bis(vinylsulfonyl) acetamido)ethane G, BU-DICHLOROCOHYD AKI C-1,3,j-triazine Na salt 7-(3-ethoxythiocarboni) Ruaminobenzamide) - Turmeth Ru-1 O-Prohagi Rui, i, i.

≠-tetrahydroacridinium trifluoromethanesulfonate 2-[gu(J-(j-(J-(t-(J-(cochrotor(/-dodecylox7carponylethoxycarbonyl)phenylcarbamoyl)]-Koichi Hydroxy7- /-naphthylthio)tetrazol-7-yl"phenyl)ureido"benzenesulfonamido)phenylJ-/-formylhydrazineSilver halide color photographic light-sensitive material prepared as above/-IO'lfAfter imagewise exposure, Continuous processing was carried out using an automatic developing machine according to the method described below until the cumulative amount of liquid replenishment reached three times the tank capacity.

Color development 735 seconds bleach fixing Hiro Ol water washing (I) San OI water washing (λ) Hiro Ol drying 301 iroc /! 1 331 J# rO# J 00rnl/m 2 3+20 The washing water replenishment method is to replenish the washing water (K) and
, 2) was introduced into the washing bath (I), using a so-called countercurrent lighting system. At this time, the amount of bleach-fixing solution brought into the washing bath (I) from the constant whitening bath for photosensitive materials is 3jlR1/m2, and the ratio of the amount of washing water replenishment to the amount of bleach-fixing solution brought in is 1. Ta.

The composition of each treatment liquid was as follows.

Color developer D-Sorbit Sodium naphthalene sulfonate/formalin condensate Ethylenediamine Tetrakis methylene phosphonic acid Diethylene glycol Benzyl alcohol Potassium bromide Benzotriazole Sodium Mate N,N-bis(carboxymethyl)hydra o, irg o, 2Og o, irg o. Ethanolamine to ethyl-(β-methanesulfonamidoethyl)-3-methyl-μm aminoaniline sulfate Potassium carbonate Fluorescent brightener (diaminostilbene thread) Add water p)i (co!0C) Bleach-fix Liquid ethylenediamine ≠ acetic acid, λ sodium, λ hydrate ethylenediamine ≠ acetic acid, Fe (I113, Ako, Og 6.0y 6, Hirogoko, μy r, og!, r9 30.0g /, 09 2j, 011 7.2g / 000 formation / 000at IO0λj 10.7j Mother liquor Replenisher μ, Og Same as mother liquor 70.09 Ammonium cohydrate Ammonium thiosulfate (yoog/1) p-) Sodium luenesulfinate Potassium bisulfite! -Mercapto-7゜3, Hiro-Triacy/10go 20.09 20.0g o, zg Ammonium nitrate 10.09 pH (Jj 'C) 6.20 Washing water Mother solution and replenisher both tap water and d-type strong acid cation Replacement mjtit Rohm and Haas Amberlight 1L (-/λoB),! :
, 0Hffi7 anion exchange resin (Amberlite IR
Water was passed through a mixed bed column packed with -1700) to reduce the concentration of calcium and magnesium ions to 3 da/l or less, and then sodium dichloride iso7anurate -〇■/
l and gft sodium i, r1/It were added. The pH of this solution is 6. ! ~7°! It was within the range of

In order to evaluate the color reproducibility of the obtained sample, the following tests were conducted. A manuscript was prepared by photographing the Macbeth color checker using a color negative film (S) iR-700 manufactured by Fuji Photo Film ■) and printed on color paper (O20 manufactured by Fuji Photo Film ■).This manuscript was printed using a reflective printer. (sample 1) to (sample 10),
A color print v was produced by performing development processing in the processing steps shown below. The ay and color of the print were adjusted so that the gray scale of the neutral j of the Macbeth color checker on the original was set to gray of density /, 0 on the print. HVCviY was measured using the modified Munsell symbol for the colors/R of the Macbeth color chart on the resulting print, and the C@ is shown in Table 7. Does it mean that the higher the C value, the more saturated the sample reproduces the color? show. It was also confirmed that the magnitude of this value corresponds to the intensity of each color when visually viewing the print.

Furthermore, the degree of image staining due to dye residue on the color grid obtained after processing was compared. (Sample/) to (Sample 10) were exposed to white light at zooCMS, t7to'', 3200, and processed as described above.At this time, in order to emphasize the degree of contamination, the coloring process of the development process was standardized. The time was shortened from 73! seconds to 30 seconds. Under these conditions, there is almost no color development by the coupler, and the difference in density of the sample obtained can be considered to be the difference in the amount of dye residue used. C, T, and F (%) at a spatial frequency of 77 lines/min were determined and shown in Table 1.

The larger the C, T, and F numbers, the better the sharpness of the photosensitive material.

Table 7 shows that (I) or (I-a) alone cannot eliminate μ residual color and improve both sharpness and color reproducibility, whereas when the dye of the present invention is combined, there is no residual color. It can be seen that a photosensitive material with improved both sharpness and color reproducibility can be obtained.

(Effects of the Invention) According to the present invention, a silver halide color photographic material with significantly improved color reproducibility and sharpness can be obtained. Moreover, the above photosensitive material has reduced residual color after processing and is suitable for practical use.

Claims (1)

[Scope of Claims] A photographic light-sensitive material having at least one silver halide emulsion layer on a support, the photographic light-sensitive material comprising at least one dye represented by the following general formula (I) and the following general formula (II). A silver halide color photographic material containing at least one dye represented by: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X and X' are hydrogen atoms, hydroxyl groups, carboxyl groups, -COOR_1, -COR_1, -CONH_2,
-CONR_1R_2 represents an alkyl group, an aryl group, or an amino group, Y and Y' each represent a hydrogen atom, an alkyl group, an aryl group, or an amino group, and Z and Z' each represent a hydrogen atom, a cyano group, a carboxyl group, or a sulfonate group. group, amino group, -COOR_3, -COR_3, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲mathematical formulas, chemical formulas,
There are tables, etc. ▼, -SO_2R_3, -CONH_2, -CONR_3R_4, represents an alkyl group or an aryl group. R_1 and R_3 each represent an alkyl group or an aryl group, and R_2 and R_4 each represent a hydrogen atom, an alkyl group or an aryl group. L_
1, L_2, L_3, L_4, L_5 each represent a methine group, l and m each represent 0 or 1, n is 1,
2 or 3, and M^n^■ represents an n-valent cation. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1_1 and R_1_3 represent an aliphatic group or an aromatic group, R_1_2 and R_1_4 are an aliphatic group, an aromatic group, -OR_1_5-, -COOR_1_5, -NR
_1_5R_1_6, -CONR_1_5R_1_6,
-NR_1_5CONR_1_5R_1_6, -SO_
2R_1_7, -COR_1_7, -NR_1_6CO
R_1_7, -NR_1_6SO_2R_1_7, cyano group (here, R_1_5, R_1_6 represent a hydrogen atom, an aliphatic group or an aromatic group, R_1_7 represents an aliphatic group or an aromatic group, R_1_5 and R_1_6 or R_
1_6 and R_1_7 may be connected to form a 5- or 6-membered ring. ), n_1 and n_2 represent 0 or 1, and M^■ represents hydrogen or other monovalent cation. L_1, L_2, L_3, L_4, and L_5 have the same definitions as in general formula (I). )