JPH03209464A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a dye image superior in spectral absorption characteristics and storage stability by incorporating a specified yellow coupler in a blue- sensitive photosensitive layer. CONSTITUTION:The blue-sensitive photosensitive layer contains the yellow coupler represented by formula I and the yellow coupler represented by formula II, and in formulae I and II, R1 is aryl or tertiary alkyl; R2 is F, alkyl, aryl, or the like; R3 is a group substitutable on the benzene ring; X is H or a group to be released by the coupling reaction with the oxidation product of an aro matic primary amine color developing agent; l is an integer of 0 - 4, Y is same as R3; (m) is an integer of 0 - 4; and Z1 is a nonmetallic atomic group necessary to form a ring, thus permitting the obtained photosensitive material to be supe rior in spectral absorption characteristics and storage stability of a dye image.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, a silver halide color photographic light-sensitive material that has good spectral absorption characteristics, excellent color reproducibility, and storage stability. The present invention relates to a silver halide photographic material that completely forms a dye image with excellent properties.

[Conventional technology]

In color photographic paper used for direct viewing, yellow couplers, magenta couplers, and combinations of shea/coupler are usually used as couplers that form all the coloring dyes. Of these, magenta couplers have recently been developed, unlike conventional j-pyrazolone magenta couplers,
Pyrazoloazole magenta couplers have been developed which are advantageous in terms of color reproducibility because the coloring dyes do not have sub-absorption near 30 nm.

On the other hand, for yellow couplers, the maximum absorption wavelength of the coloring dye formed is generally located on the long wavelength side with respect to the absorption characteristics that are preferable from the viewpoint of color reproducibility.

A yellow coupler which has a maximum absorption wavelength in a short wavelength and is preferable in terms of color reproduction is disclosed in Japanese Patent Application Laid-open No. 1999/-/73≠Tata. However, a problem with these yellow couplers whose maximum wavelength is short wavelengths is that the resulting dyes do not have sufficient fastness to light and heat. For this reason, there has been a need for a technique to improve the fastness of dyes formed from the above-mentioned short-wave yellow couplers.

[Problems to be solved by unexploded fJA] The purpose of the present invention is to provide a silver halide photographic material in which the formed dye has excellent spectral absorption characteristics and the dye image has excellent storage stability. be.

[Means to solve the problem]

The objects of the present invention were achieved as follows. That is, (1) a silver halide photographic light-sensitive material comprising at least n of each of a blue-sensitive halogen/silver emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive halogen/silver emulsion layer on a support, Previously recorded sensitive emulsion skin is Yellow Turnip 2 of the following -ff formula (1)
A silver halide photographic material containing at least one of - and at least one of the following yellow couplers (■).

General formula (1) [In the formula, R1 is an aryl group Ifc is a tertiary alkyl group,
R2 is a fluorine atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, a dialkylamine group, an alkylthio group, or an arylthio group, R3 is a group t that can be substituted on the benzene ring, and X is a hydrogen atom l or aromatic It-LO- represents an integer of a group capable of being separated in a coupling reaction with a dispersion of a primary amine-based active drug. However, when l is plural, the plural R3s may be the same or different. ] General formula CII) [In the formula, Y is a substitutable group on the benzene ring, m
is an integer from 0 to 4A. However, when m is plural, the plural Y's may be the same or different.

21 represents a nonmetallic atomic group necessary to form a ring] (2) The oil-soluble substance coexisting and dispersed with the yellow couplers of the above-mentioned -Momona (1) and the above-mentioned -Momona (If) is The weight ratio is 01jj or less with respect to the total weight of the yellow coupler of the above-Momona CI) and the above-mentioned -Momona (If), and the yellow coupler of the -Momona CI) and the -ff formula (n) The silver halide photographic material as described in (1) above, wherein the total amount of 2- is 0°1017 m2 or more.

Compound (1) used in the present invention will be explained in more detail.

In the general formula [,1], 1 is preferably an aryl group having 6 to λ carbon atoms (e.g., phenyl, p-tolyl,
〇-tolyl, goumetquinphenyl, comethoxyphenyl, ≠-butoxyphenyl, μm octyloxyphenyl, ≠-hexadecyloxyphenyl, l-naphthyl) or a tertiary alkyl group of several h to 2t carbon atoms (e.g. “-” Butyl, t-pentyl, t-hexyl, /, /, J
, J-tetramethylbutyl, l-adamantyl, /, /
-cy'f-λ-chloroether, cophenoxycobropyl, bicyclo[co,λ,λ]octan-1-yl).

In general formula (1), R2 is preferably a fluorine atom,
Alkyl groups having l-co≠ carbon atoms (e.g. methyl, ethyl, isopropyl, t-butyl, cyclopentyl, n-
octyl, n-hexadecyl, be/zyl], aryl groups having 6 to λμ carbon atoms (e.g. phenyl, p-tolyl,
0-tolyl, methoxyphenyl), 7 to carbon atoms
Alkoxy groups such as methoxy, ethoxy, butoxy, rhooctyloxy, n-tetradecyloxy,
benzyloxy, methoxyethoxy), carbon atoms 6~
2μ aryloxy group (e.g. phenoxy, p-tolyloxy, 0-tolyloxy, p-methoxyphenoxy, p-dimethylaminophenoxy, m-”'entadecylphenoxy), dialkyl with 8 carbon atoms λ ~ 2≠ Amino group (e.g. dimethylamino, diethylamino, pyrrolidino, lysine, morpholino), number of carbon atoms l-λ≠
alkylthio groups (e.g. methylthio, butylthio, n
-octernao, n-hexadecylthio) or arylthio groups having 6 to 2μ carbon atoms (e.g. phenylthio,
≠-Methoxyphenylthio, Hiroshi-t-7'terphenylthio, 4'-)"f sylphenylthio)".

In the general formula CI), R3 is preferably tL< is a halogen atom (7 atoms, chlorine atom, bromine atom, iodine atom), an alkyl group with the number of carbon atoms/-2≠ (e.g. methyl, t-butyl, n- dodecyl), aryl group with t-, 2 carbon atoms (91, e.g., phenyl, p-1'), p-dodecyloxyphenyl), alkoxy group with carbon atom/~-24c (for IPIJ, methoxy% n- butoxy, n-octyloxy, n-tetradecyloxy, benzyloxy, methoxyethoxy), aryloxy groups having 6 to 3 carbon atoms (e.g. phenoxy, pt-butylphenoxy, ≠-butoxyphenoxyquine, carbon atoms Alkoxycarbonyl group of number 2 to λ≠ [e.g. ethoxycarbonyl,
dodecyloxycarbonyl, /-(dodecyloxycarbonyl]ethoxycarbonyl], an aryloxycarbonyl group having 7 to λ≠ carbon atoms (9Il, t[phenoxycarbonyl, ≠- to monooctylphenoxycarbonyl,
carbonyl, ≠-di-t- is methylphenoxycarbonyl), a carbonamide group having a carbon atom number of /-2 [e.g., acetamide, piparoylamino, benzamide, coetherhexanamide, tetradecaneamide, /-(2,
≠-Gt- is methylphenoxy)butanamide, J-
(,2,Hiroji-t-nimethylphenoxy7)butanamide, 3-dodecylsulfonyl-cometherpropanamide], sulfonamide group with carbon atoms/~co≠ (e.g. methanesulfonamide, p-toluenesulfonamide,
hexadecanesulfonamide), number of carbon atoms l ~ co≠nocarhamo (l group CPI, HN-methylcarbamoyl, N
-tetradecylcarbamoyl, N,N-dihexylrubamoyl, N-octadecyl-N-methylcarbamoyl, N-phenylcarbamoyl), sulfamoyl group having O≠ carbon atoms (e.g. N-methylsulfamoyl,
N-phenylsulfamoyl, N-acetylsulfamoyl, N-propanoylsulfamoyl, N-hexadecylnulfamoyl, N,N-dioctylsulfamoylba alkylsulfonyl group with 7 carbon atoms/~co≠ ( For example, methylsulfonyl, benzylsulfonyl, hexadecylsulfonyl), arylsulfonyl 1 having 6A-2≠ carbon atoms (IJ, tt'? phenylsulfonyl tp-tolylsulfonyl, p-dobufursulfonyl, p-methoxynulfonyl), 118i FZ/~-2≠ freido group (e.g. 3-methylureido, 3-phenylureido, 3,3-dimethylfreido, 3-tetradecylureido), null 7 amoylamine group having carbon atoms Q≠ (
For example, N, N-dimethylsulfamoylamino), alkoxycarbonylamino group with carbon atoms λ~2≠ (for example, methoxycarbonylamino, imbutoxycarbonylamino, dodecyloxycarbonylamino), nitro group, number of carbon atoms /~-2≠ heterocyclic group (e.g. ≠-pyridyl, λ-thienyl, 7-talimide, octadecylsuccinimide), cyano group, carbon atom number/P-λ anlu group (for example, PJ acetyl, benzoyl, dodecanoyl),
Acyloxy groups with carbon atoms/-2≠ (if kept, acetoxy, benzyloxy, dodecanoyloxy), alkyl/l/sulfonyloxy groups with carbon atoms 1 to -24L 7 groups (
methylsulfonyloxy, heisubylsulfonyloxy)xfc is arylnulfonyl having 6 to -≠ carbon atoms, t-? Shili (1FIJ, ttf p-)
luenesulfonyloxy, p-dodecylphenylsulfonyloxy].

In the general formula (1), l is preferably an integer of /''l or ko.

In the general formula (1), X is preferably a group (referred to as a leaving group) that can be separated by a coupling reaction with an oxidized product of an aromatic primary amine developer, and specifically a halogen atom (fluorine , chlorine, bromine, iodine
a heterocyclic group bonded to the coupling active position at the nitrogen atom of
Aryloxy group having 6 to 24 carbon atoms, arylthio group having 1-λ carbon atoms (fpH, phenylthio, p-butylphenylthio, p-/lorophenylthio, p-carboquinphenylthio) , number of carbon atoms l
Acyloxy group with ~λ≠ (eg, acetoxy, benzyloxy, dodecanoyloxy), alkylsulfonyloxy group with number of carbon atoms/~ (eg, methylsulfonyloxy, butylsulfonyloxy, dodecylnulfonyloxy), 7 arylsulfonyloxy groups having 6/-1≠ carbon atoms (crab benzenesulfonyloxy, p-chlorophenylnulfonyloxy) or m/~ carbon atoms
Examples of heterocyclic oxy groups include 3-pyridyloxy, /
-phenyl-/, 3. (Hiro-tetrazole-yyloxy), and more preferably a heterocyclic group or an aryloxy group bonded to the coupling active position through a nitrogen atom.

When X is a nitrogen ring group bonded to the coupling active position with a nitrogen atom, X contains, in addition to the nitrogen atom, a heteroatom selected from oxygen, iota, nitrogen, phosphorus, selenium, and tellurium. A substituted or substituted monocyclic or fused heterocyclic ring having a j to 7-membered ring, examples of which include succinimide, maleimide, 7-talimide, diglycolimide, pyrrole, pyrazole, imidazole,
l.

Tip 4c-triazole, tetrazole, indole,
Benzopyrazole, benzopyrazole, benzotriazole, imidazolidine-J, 4L-dione, oxazolidine-2,≠-dione, theazolidine-, Hiro-dione, imidazolidin-1-one, oxazoline-coone, thiazolin-2-one, Benzimidazoline-o/, Be/Zoxazoline-λ-one, Be/Zoteazoli/
---On, Corpyroline-Yoichio/, λ-Imidazoli/-! -one, indoline-kott 3-dione, 2, t-
Examples include dioxypurine, paraban FR1i*2+≠-triacylysia J, j-dione, λ-pyridone, pyridone, copyrimidone, 6-pyridazone, copyrazone, and the like, and these heterocyclic groups may be substituted. Examples of substituents include hydroxyl group, carboxyl group, sulfo group, and amino group (for example, amino, N-methylamino, N
In addition to (1N-dimethylamino, N,N-diethylamino, anilino, pyrrolidino, piperidino, morpholino), there are the substituents listed above for R3.

When X represents an aryloxy group, X is the number of carbon atoms t
-λ is an aryloxy group, and when X is a heterocyclic group, it may be substituted with a group selected from the above-mentioned substituent group. Substituents include carboxyl group, nurpho group, cyano group, nitro group, alkoxycarbonyl group, halodef octad, carbo/amide group, sulfonamide group, carbamoy/'i, sulfamoyl group, alkyl group, alkylsulfonyl group, aryl The primary sulfonyl group is preferably an afur group.

Next, regarding each of the substituents 1, 2, R3 and X described above, fi which is particularly preferably used in the present invention
Let's talk about the target of the t substituent.

- In the pattern (1), R1 is particularly preferred; , t-butyl group is most preferred I
Yes.

In the general formula [1), R2 is particularly preferably a methyl group, ethyl group, alkoxy group, aryloxy group I or dialkylamino group, butyl group, ethyl group, alkoxy group, aryloxy group or dimethylamino group. is most preferred.

- In the pattern (I), kL3 is particularly preferably an alkoxy group, a carbo/amide group or a sulfonamide group.

In general formula (III), X is particularly preferably a heterocyclic group with 91 atoms bonded to the coupling active position or an aryloxy group.

When X is the above-mentioned heterocyclic group t-6, X is preferably represented by the following -mona (III).

- Monna (I[I) In the general formula (1), Z2 is 9, 5 kL6kL7 Was. Here, R4, R5, R8 and Ro represent a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylnulfonyl ay+h amino group, R6 and R7 represents a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an ary-k/Ck-honyl group, or a t*h alkoxycarbonyl group; and □ represent a hydrogen atom, an alkyl group or an aryl group. R10 and "11 may be bonded to each other to form a benzene ring.

R4 and R5, R5 and R6, R6 and n, y or R4 and R8
are bonded to each other to form rings (cyclobutane, cyclohexane, cyclohebutane, cyclohexene, pyrrolidine,
piperidine).

-Among the heterocyclic groups grouped in the pattern (III), particularly preferable ones include i where z2 can be expressed in the general formula (III).
! I am Motoki Kiba.

Total carbon atoms i of the heterocyclic group represented by general formula (III)
is λ~ko≠, preferably Hiroshi~koO1, more preferably j
~/6. - Ibarawasa nru (! nest ring group) in Monna (II), nuccinimide group, Frey/imide group, 7-talimide group, l-methylimidazolidine-kotsuhiro-dion-3-yl group, / - Benzyl imidazolidine,
4A-dione-3-yl group,! ,! -dimethyloxazolidine-2゜μm di/-3-yl group, j-methyl-j
-propyloxazolidine-λ, ≠-dione-3-yl group,! , j-dimethylthiazolidine-, l-dione-
3-yl group, jl'-dimethelimidazolidine, 4
A-dione-3-yl group, 3-methylimidazolidinetrione-/-yl group, '121≠-triacylidine-3
．． ! -dione-triacylidine-3, ! -Zion-≠-
yl group, /-be/zi-2-phenyl7. λ, ≠-triacylidine-J, J-dio/-μmyl group, j-hequinyloxy/-methylizdazolidi/-1.

μmdione-3-yl group, /-be/jirou-ethoxyimidazolidine-λ, ≠-dio7-J-(ru group, l-be/jirou!-dodecyloxyimidazolidine-co, ≠-
There is a diion-3-yl group.

Among the above heterocyclic groups, an imidazolidi/-2,4-monodio/-3-yl group (for example, l-benzyl-imidazolidine-λ, ≠-dione-3-yl group) is the most preferred group.

When X is an aryloki group, μ-carboxylic enoxy group, ≠-methylsulfonylphenoquine group, Hiro-
(4L-benzyloxyphenylsulfonyl) phenoxy 7 groups, Gu (4L-hydroxyphenylsulfonyl) phenoxy 7 groups, λ-chloro μm (J-J Rolow Hirohiro-hydroxyphenylsulfonyl) phenoxy group, Hiro-methoxy carmel phenoxy 7 group, cochlorocoumethoxycarbonylphenoxy group, λ-acetamido-Hiroshi-methoxycarbonylphenoxy group, ≠-isopropoxycarbonylphenoxy group, Hiro-cyanophenoxy7 group, co(
N-(co-hydroxyether]carbamoyl]phenoquine group, Hiro-nitrophenoxy7 group, co, j-dichlorophenoxy group, co, 3゜j-trichlorophenoxy group, ≠-
Methoxy group, luponyl group, methquine phenoxy group, ≠−
(3-carboxypropanamide) phenoxy7 is the most preferred target.

The coupler represented by the general formula (1) may form a λ-mer 1 or a larger λ-mer which is bonded to each other via a substituent R□ and a group having a covalence or higher. In this case, the number of carbon atoms in each substituent group may be outside the range specified above.

When the coupler represented by the general formula (1) forms a multimer, a typical example is an addition polymer having a yellow dye-forming coupler residue or an ethylenically unsaturated compound* (yellow color-forming monomer) alone or in a copolymer. In this case, the multimer is a repeating unit of the general formula [■] t-tvt, - The yellow coloring repeating unit represented by -formation (fli') contains 71!1 or more in the multimer. Alternatively, it may be a comonomer containing i*x or one or more non-color-forming ethylene monomers as a copolymerization component.

General formula (■) In the formula, R1-) hydrogen atom, l-carbon alkyl group l
A represents a chlorine atom, A represents -CONH--coo-t or a substituted or unsubstituted phenylene group, a substituted or unsubstituted alkylene group, a phenylene group or an aralkylene group, and L represents a -CON)l--NHCON
H- -NHCOO--NHCO--0CONH--NH--
COO--0CO--CO--Q--8--80□--
6 tons) of NH80□-1 or -802NH-'. as
b% Ctx' or /l-indicated. Q represents a yellow coupler residue from which the compound represented by the formula CI) is removed.

As the multimer, a copolymer of a yellow color-forming monomer represented by a turnip 2-unit of the general formula (IV) and the following non-color-forming ethylene-like monomer is preferred.

Examples of the non-chromic ethylene mass polymer that does not couple with the formation product of aromatic-grade amine derivatives include acrylic acid,
α-Chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Amides or derivatives derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ether acrylate, n-propyl acrylate, n-butyl acrylate, t-buter acrylate, 1so-bunal acrylate, coethylhexyl acrylate, n-octyl acrylate, lacryl acrylate, methyl methacrylate, ethyl methacrylate-1', ``-butyl methacrylate and β-
hydroxy methacrylate), vinyl esters (e.g. vinyl acetate), vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile 1
Aromatic vinyl compounds (such as styrene and its derivatives, such as vinyltoluene, divinylinzene, vinylacetophenone and sulfostyrene), itaconic acid, citraco/@, crotonic acid, vinylidene chloride, vinyl alkyl ethers (?IJ, t[ vinyl ethyl ether), maleic acid ester, N-vinyl cobiro'))
% N-vinylpyridine and λ- and 1≠-vinylpyridine.

Particularly preferred are acrylic powder esters, methacrylic esters, and maleic esters. The non-color-forming ethylene-type top layer used here can also be used in combination with more than 100 g. If kept, methyl acrylate and bunal acrylate, bunal acrylate tonuterene, butyl methacrylate and methacrylic powder, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the field of polymer couplers, the ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to the above-mentioned pattern (■) depends on the physical properties of the copolymer to be formed and/or Characteristic properties, targets include solubility, compatibility with gelatin as a binder for photographic colloid compositions, its flexibility,
The thermal stability etc. can be selected so as to be affected by the light*'i.

The yellow polymer cover 2- used in the present invention is the above-mentioned -
A lipophilic polymer coupler obtained by polymerization of a vinyl-based monomer to give a coupler unit that appears in the pattern (IV) is dissolved in a solvent and emulsified and dispersed in the form of latex in an aqueous solution of whole gelatin. It may be made by a direct emulsion polymerization method.

Next, the yellow coupler represented by the general formula (IF) will be explained in more detail.

For Y, the group used in -monana (1) can be similarly used. In addition, Zo is -Momonana (II
The non-metal groups used in Z2 of I) can be used in the same way.

Specific sequences of the leaving groups, 几, and Y of the couplers of general formulas (1) and -Momona (II) are shown below, but the present invention is not limited thereto.

ll11! Specific examples of the groups are shown below.

(1) (2) (5) (6) 1 (11) (12) (13) (14) Cal.

(18) (20) (21) (15) (17) (22) (23) (24) (25) Specific examples of R3 and Y are shown below.

C, Hlko (36) (CHx)xCHCRzC*H*-t (37) CH2 CIJ! ? -NIICOCR1C)lcOOcH34HSOzC1
Jms-11 (38) (39) -COOC+Jii CH寞空-COOCHCOOC+511m5 -CONHC+#lltw (42) (43) (44) -CONH(CHt) sOc+ Jzs-NflCO
Specific examples of the yellow dye-forming coupler represented by the general formula [1] are shown below.

In this case, the numbers in parentheses are the numbers assigned to the specific groups of X and R3, and the numbers in brackets are the substituent positions on the anilide group.

The coupler of the present invention can be synthesized by conventionally known synthesis methods. As a specific example, %opening≦j-1
230≠7 according to the synthesis method described in the specification.

Specific examples of the yellow coupler represented by -mona CI) are shown below, but the present invention is not limited to these.

(A-/) α (A-2) (A-J) (A-≠) α α α (A-j) α (A-r) α (A-/J) α (A-/a) (A-/6) α α (A-/7) α (A-/I) α less than, Although specific examples of high-boiling point solvents are shown, this book The invention is not limited to these.

(B-/) (B-2) (B-J) (B-da) (B-z) C2) 15 2h5 (B-4) (B-7) (B-/ko) (B-/J ) (B-/ri) (B-ko0) (B-21) 0=)’+0C4H,-n)3 (B--ko) (B-23) 0=P+0C6I(,3-li.

(B-λ reference (B-koj) o=P+OC, Hl, -li.

(B-24) (B-27) (B-Kota) o=Ptuc, Hl, -〇) 3 (B-30) (B-J/) 0=P e-QCl, H21-it) 3 (B -32
) (13-JJ) (B-34/L) (B-j!r) (B-36) (B-37) CB-31) (B-3ri) 2H5 (B-3) (B- ≠1) (B-4I-ko) (H-44J) 2H5 2H5 (B-4CA) (B-4L7) (B-≠1) (B-data) - 2Hs (B-jO) (B-!t /) (B-!J) (B-z≠) (B-ss) (B-s4) (B-67) (B-jtr) C)i (:0C)C4H0 ch oco-c-cooc4i-i .

C)i CUOC41-1゜(BiO) (B-47) (B-62) CHCO(JCH2(CF2CF2)2)11 C)ICOC)CH2(CF2(,F2) 2)1(B
-43) (B-j4/l) CB-j j ) (B-67) CB-tr) 018H370H (B-AP) C□. H210(CH2) 50(C)12) 20H
(B-70) C, H C2) 15 CH, CH2C00CH, C) IC4H.

■ (B-74) 2H1s ? CUOC)I2CI(C,)l.

algae (CH2).

C00CR2C)ic4H0 C2H.

(B-77) 2I-15 CI　C00C)12C)IC,)].

(B-71) (B-72) A high-boiling point single solvent or other oil having a solubility in water of less than or equal to 100 ml, which is used in coexistence with the uninvented oil bathing substance and the yellow coupler of the present invention. It is a soluble four-purpose additive (for example, an ultraviolet absorber).

General formula (1) of the yellow coupler of general formula (n) of the present invention
) with respect to the yellow coupler is preferably o, i~/, 0 in terms of ]I1 ratio, and more preferably IL < is 0.
It is 2-00S.

The amount of oil-soluble additives such as high boiling point organic solvents that coexist with the yellow couplers of the general formula (1) and -Momonana [...] of the present invention is 0.0000000000000000 with respect to the total weight of the yellow coupler.
It is preferably 0j0 or less, more preferably 0. +0 or less.

Yellow coupler #! The coating amount is preferably 0.1097 m2 or more and 2.00 f/m2 or less, preferably 097 m2 or more and 100 m2 or more.

It is preferably less than j　Ot　/　m　l.

High boiling point 1 used in the present invention! As a modest solvent, if you keep it, WO1007 Ko3, vs4! tra4o4, JP-A-6
3-ko172$j, JP-A-62-/J/ko! the law of nature,! Kaisho 4J-/J/Kojri, JP Kaisho 62-Jr 6J j J
, JP-A-61-λ4774 (7, JP-A-61-TYZ7
4Ar149N flat/-! The IL described in t004AP is preferably used. Although it is particularly preferable, JP-A-H/-! D
Epoxy-based materials described in Otari et al. are preferred.

The color photographic light-sensitive material of the present invention can be constructed by coating at least one blue-sensitive silver halide emulsion layer, one R-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support. In general color photographic paper, the layers are usually coated on the support in the above order, but they may be applied in a different order. Furthermore, an infrared-sensitive silver halide emulsion layer can be used in place of at least one of the above-mentioned emulsion layers. These photosensitive emulsion layers contain a silver halide emulsion sensitive to each wavelength range, and dyes that are complementary colors to the sensitizing light - yellow for blue, magenta for green, and cyan for red.
By containing a so-called color coupler that forms a color, subtractive color reproduction can be performed. However, the coloring hues of the photosensitive layer and the coupler may not correspond as described above.

As the silver halide emulsion used in the present invention, one consisting of silver chlorobromide or silver chloride that does not substantially contain silver iodide can be preferably used. Here, "substantially free of silver iodide" means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. The halogen composition of the emulsion may be different or the same among the grains, but if an emulsion having the same halogen composition among the grains is used, it is easy to make the properties of each grain uniform. In addition, regarding the halogen composition distribution inside silver halide emulsion grains, there are grains with a so-called uniform structure in which the composition is the same in every part of the silver halide grain, and grains with a core inside the silver halide grain and a shell surrounding it. (shell) [-layer or multiple layers] Particles with a so-called layered structure in which the halogen composition is different, or
Particles with a structure that has parts with different halogen compositions in a non-layered manner inside or on the particle surface (if on the particle surface, parts with different compositions are joined on the edge, corner, or surface of the particle) are appropriately selected and used. be able to. In order to obtain high sensitivity, it is more advantageous to use one of the latter than particles with a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the above structure, the boundaries between the parts that differ in halogen composition are
The boundaries may be clear, or may be unclear due to the formation of mixed crystals due to compositional differences, or may have continuous structural changes.

Regarding the halogen composition of these silver chlorobromide emulsions, any silver bromide/silver chloride ratio can be used. Although this ratio can vary widely depending on the purpose, a silver chloride ratio of 2% or more is preferably used.

Also, so-called high-silver chloride emulsions having a high silver chloride content are preferably used in light-sensitive materials suitable for rapid processing. The silver chloride content of these high silver chloride emulsions is preferably 90 mol% or more, more preferably 95 mol% or more.

Such a high silver chloride emulsion preferably has a structure in which the silver bromide is localized in a layered or non-layered manner inside and/or on the surface of the silver halide grains as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, and more preferably exceeds 20 mol%. These localization boxes can be located inside the grain, on the edge, corner, or surface of the grain surface, but one preferred example is one in which epitaxial growth is made on a part of the corner of the grain.

On the other hand, in order to minimize the decrease in sensitivity when a photosensitive material is subjected to pressure, even in high silver chloride emulsions with a silver chloride content of 90 mol% or more, grains with a uniform structure with a small distribution of halogen composition within the grains are used. It is also preferable to use

Furthermore, it is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the amount of replenishment of the development processing solution.

In such cases, the silver chloride content is 98 mol% to 10
Emulsions of almost pure silver chloride, such as 0 mol %, are also preferably used.

Average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is taken)
is preferably 0.1μ to 2μ.

In addition, their particle size distribution has a coefficient of variation (standard deviation of particle size distribution divided by average particle size) of 20%.
Hereinafter, a so-called monodisperse material having a content of 15% or less is preferable. At this time, it is preferable to blend the above-mentioned monodispersed emulsions in the same layer or to apply multilayer coating in order to obtain a vague latitude.

The shape of silver halide grains contained in photographic emulsions is regular (cubic, tetradecahedral, or hemispherical).
lar) those with crystal shapes, those with irregular crystal shapes such as spherical, plate-like, etc.
Alternatively, a composite form of these can be used. Moreover, it may be made of a mixture of crystals having various crystal forms. In the present invention, among these particles, it is preferable to contain particles having the above-mentioned regular crystal shape in an amount of 50% or more, preferably 70% or more, and more preferably 90% or more.

In addition to these, the average aspect ratio (yen equivalent diameter/
Emulsions in which the projected area of tabular grains having a thickness of 5 or more, preferably 8 or more, exceeds 50% of the total grains can also be preferably used.

The silver chlorobromide emulsion used in the present invention is P, Glafkid
Chimia et Ph1sique Pho by es
togriphique (Pau1Monte1, 1967), Photo by G. F. Uffin
o-graphic Emulsion Chemises
try (Focal Press, 1966)
, V. L., Zelik++ an at al Ma.
kircg and Coating Photogra
phic Emulsion (Focal Pres.
It can be prepared using the method described in J.S. Publishing, 1964). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt includes the one-sided mixing method,
Any method such as a simultaneous mixing method or a combination thereof may be used. A method in which particles are formed in an atmosphere containing excess silver ions (so-called back mixing method) can also be used. As one type of simultaneous mixing method, a method in which PAg in a liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Various polyvalent metal ion impurities can be introduced into the silver halide emulsion used in the present invention during the process of emulsion grain formation or physical ripening.

Examples of compounds used include cadmium, zinc, lead,
Salts such as copper and thallium, or iron, which is a group II element,
Examples include salts or complex salts of ruthenium, rhodium, palladium, osmium, iridium, platinum, and the like. In particular, the above-mentioned Group Ⅰ elements can be preferably used. The amount of these compounds added varies widely depending on the purpose, but is preferably from 10@-1 to 10@-' mol based on the silver halide.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization and spectral sensitization.

Regarding the chemical sensitization method, sulfur sensitization typified by the addition of unstable sulfur compounds, noble metal sensitization typified by gold sensitization, or reduction sensitization can be used alone or in combination. Regarding compounds used for chemical sensitization, see the lower right column on page 18 of the specification of JP-A-62-215272.
Those described in the upper right column of page 22 are preferably used.

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a folded light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention. In the present invention, it is preferable to add a dye-spectral sensitizing dye that absorbs light in a wavelength range corresponding to the desired spectral sensitivity. Spectral sensitizing dyes used at this time include, for example, FoM, Heter
ocyclic compounds-Cyanine
dies and related compounds
ds (Johnlliley & 5ons I:N
aw York, London], 1964)
Examples include those listed in . Specific examples of compounds and spectral sensitization methods are described in the above-mentioned JP-A-62-
Those described in the upper right column of page 22 to page 38 of the specification of JP 215272 are preferably used.

The silver halide emulsion used in the present invention has the following properties:
Alternatively, various compounds or their precursors can be added for the purpose of stabilizing photographic performance. As specific examples of these compounds, those described on pages 39 to 72 of the specification of JP-A-62-215272 mentioned above are preferably used.

The emulsion used in the present invention may be either a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface or a so-called internal latent image type emulsion in which a latent image is mainly formed inside the grain. Also good.

When the present invention is applied to a color photosensitive material, the color photosensitive material includes a yellow coupler, a magenta coupler, and a cyan coupler that form yellow, magenta, and cyan colors respectively by coupling with an oxidized product of an aromatic amine color developer. is usually used.

Cyan couplers and magenta couplers preferably used in the present invention have the following formats (C-I), (C-I[n, (M-I)
and "(M-II)".

General formula (C-I) H - Monka (C-I[) H Y.

General formula (M-I) R9 General formula% Formula%) In general formula (C>-1) and (C-IF), RR
and R4 is a substituted or unsubstituted aliphatic, aromatic or compound ring group, and R3 is a compound.

R3 represents a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, and R3 represents a group of nonmetallic atoms that together with R2 form a J-membered ring or a 6-membered ring. Even = good. Y□ and Y2 are hydrogen atoms or groups that can be separated during the coupling reaction with the oxidized form of the developing agent. n is O or /l' R5 in Rokuchoujishikomonana (C-11) is preferably an aliphatic group, and examples include methyl group, ethyl group, propyl group, butyl group, interdecyl group, tert-7'thyl group, cyclohexynyl group,
Examples include cyclohexylmethyl group, phenylthiomethyl group, dodecyloxyphenylthiomethyl group, butanamidomethyl group, and methoxymethyl group.

The preferred sequence of 7 Ankapuku, where the above-mentioned - Monka (C-I) x Nen is (C-1f), is as follows.

In general formula (C-I), preferred R1 is an aryl group,
Heterocyclic groups, halogen atoms, alkyl groups, alkoxy groups, aryloxy groups, acylamino groups, acyl groups,
More preferably, it is a carbamoyl group, a sulfonamide group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group, or an aryl group substituted with a 77 group.

In the general formula (C-1, 1, when and FL2 do not form a ring, R2 is preferably a substituted or unsubstituted alkyl group or aryl group, particularly preferably hr!IL
is a substituted arylaryloxy substituent group, and R3
1. < is a hydrogen atom.

- Preferred R4 in C-n is a substituted or unsubstituted alkyl group, an aryl group, and particularly preferably a substituted aryloxy alkyl group.

In general formula (C-11), R5 preferably has a carbon number λ~
It is a methyl group in which M is an alkyl group and a substituent having 1 or more carbon atoms, and is a vIL substituent, or an arylthio group,
Alkylthio group, annylamino group, aryloxy group,
Alkylthio groups are preferred.

- In the pattern hole (C-11), R5 is more preferably an alkyl group having carbon number λ to 15, particularly preferably an alkyl group having 1 to 1 carbon atoms.

Preferred R6 line hydrogen atom in general formula (C-I),
It is a halogen atom, and chlorine atoms and heptad atoms are particularly preferred. - Monnament (C-I) Machining (In C-IN, each of Y and Y2 is preferably a hydrogen atom, a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, or a sulfonamide group.

In the general formula (M-I), and R8 represent an aryl group, R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, an aliphatic or aromatic sulfonyl group,
Y3 has 19 hydrogen atoms and 6 leaving groups. The substituent line allowed for the aryl group (preferably phenyl group) of R7 and Ro is the same as the substituent line allowed for the substituent R, and when more than one ms group is included, the same But they can be different. I:L8 is preferably a hydrogen atom, and the aliphatic afur group 19 is a sulfonyl group, and more preferably a hydrogen atom. Preferably, Y3 is of the type that is released by any of sulfur, oxygen, or nitrogen atoms.
10 Hiro 7F! The sulfur atom dissociative type described in the above is particularly preferred.

- In formation (M-11), 几□. is a hydrogen atom or a parishioner of the Substitution Fund. Y4 represents a hydrogen atom or a leaving group, and a halogen atom or an arylthio group is particularly preferred. Za, Z
b and Zc are methine, substituted methy/, =N- or F'L-
NH-1-&, 10,000 of the Za-Zb bonds and Zb-ZcNj bonds are 21m groups, and the other is a single bond. Zb
The case where the -Zc introduction is a carbon-charcoal 2XtS combination includes the case where the seven strands are part of an aromatic ring. Ordinary. This includes the case where a dimer or more multimer is formed with l or Y4, and the case where a λ-mer or more multimer is formed with the substituted methine when l or Za, Zb or Zc is a substituted methine.

Among the pyrazoloazole couplers represented by the formula (M-n), imidazo ('t) described in U.S. Pat. Cob] pyrazoles are preferred, and Virazo o[t
, 5-b) (/.

Triazole is particularly preferred.

In addition, a branched alkyl group as described in JP-A No. 7/-AI2-H6 is directly connected to the 2.3 or 4-position of the pyrazolotriazole ring to form a pyrazolotriazole coupler, as described in JP-A-1989/-AI2-H6. A pyrazoloazole coupler containing a sulfonamide group in the molecule is described in NFC technology, and a pyrazoloazole coupler with an alkoxyphenylnulfonamide paranut group as described in JP-A-4/-/4A72J4' and European Patent (Publication) No. 221. R-tei issue, same number Kota-tei, 7r! It is preferable to use a pyrazolotriazole coupler having an alkoxy group or an aryloxy group at the 6-position as described in No.

-Formation (C-1), (C-11), (M-1,) and (
Specific examples of the coupler represented by M-11) are listed below.

(C-1) α (C-4) α (C-7) (C-9,) (C-12) (C-13) (C-14) (C-15) (C-17) (C -18) (C-19) (C-20) (C-21) (C-22) Lll (M-L) (M-2) (M-3) Koro (M-4) (M-6 ) Co(M-7') (M-8) The couplers represented by -formation (C-1) to CM-1) are usually contained in silver halide emulsion layers constituting the photosensitive layer. It is contained in an amount of 0.1 to 1.0 mol, preferably 0.1 to 0.5 mol per mol.

In the present invention, various known techniques can be applied to add the front rudder coupler to the photosensitive layer. Usually, it can be added by the oil-in-water dispersion method known as the oil protection method, and after being dissolved in a solvent, it is emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution may be added to a coupler solution containing a surfactant to form an oil-in-water droplet dispersion with phase inversion.

Alkali-soluble couplers can also be dispersed by the so-called Fischer dispersion method. From the coupler dispersion,
The low-boiling organic solvent may be removed by distillation, noodle washing, ultrafiltration, or the like, and then mixed with the photographic emulsion.

As a dispersion medium for such a coupler, the dielectric constant (25℃)
It is preferable to use a high boiling point organic solvent and/or a water-insoluble polymer compound having a refractive index (25°C) of 1.5 to 1.7.

As a high boiling point organic solvent, preferably the following general formula () () A high boiling point organic solvent represented by It will be done.

General formula () General formula CB) Balance - -CDOL General formula () %Formula% (In the formula, s 111% wt and 1 are each substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocycle group, I14 is LS
represents oL or 5-11 +, n is an integer from 5 to 5, and when n is 2 or more, , and may be the same or different from each other, and in - formation (E), L and L are condensation grooves may be formed).

The high boiling point organic solvent used in the present invention has a melting point of 100°C or less and a boiling point of 140°C, even in cases other than -formation (A) or E).
Any of the above water-immiscible compounds can be used as long as they are good solvents for couplers. The melting point of the high boiling point organic solvent is preferably 8
The temperature is below 0°C. The boiling point of the high boiling point organic solvent is preferably 160°C or higher, more preferably 170°C or higher.

For details on these high boiling point organic solvents, please refer to JP-A-62
It is described in the lower right column on page 137 to the upper right column on page 144 of jlE of the published specification No. 215272.

These couplers can also be synthesized with rhodapul latex polymers (
For example, it can be emulsified and dispersed in an aqueous hydrophilic colloid solution by impregnating it with a water-insoluble but organic solvent-soluble polymer.

Homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088100723 are preferably used, and acrylamide polymers are particularly preferred from the viewpoint of color image stabilization.

The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant.

Various anti-fading agents can be used in the photosensitive material of the present invention. That is, hydroquinones, 6
-Hydroxychromans, 5-hydroxycoumarans,
Spirochromans, p-alkoxyphenols, hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines, and silylation and alkylation of the phenolic hydroxyl groups of these compounds. Typical examples include ether or ester derivatives. Furthermore, gold complexes such as (bissalicylaldoxyshift)nickel complexes and (bis-N,N-dialkyldithiorubamato)nickel complexes can also be used.

Specific examples of organic antifade agents are described in the following patent specifications:

Hyde 0 quinones are disclosed in U.S. Patent No. 2.360.290,
Same No. 2.418.613, Same No. 2. TOo, 45
3, 2.701, 197, 2.728.6
No. 59, No. 2.732.300, No. 2.735.
No. 765, jlE3.982.944, jK4,
430, 425, British Patent II El, 363.92
No. 1, U.S. Patent No. 2, 710.8 (No. 1, U.S. Pat.
816.028 etc., 6-hydroxychromans,
5-Hydroxycoumarans and spirochromans are disclosed in U.S. Pat.
No. 9, No. 3.764.337, JP-A-52-152
No. 225, etc., and spiroindanes are disclosed in U.S. Patent No. 4.3.
60.589, p-alkoxyphenols are disclosed in U.S. Patent No. 2.735.765, British Patent No. 2.066,
No. 975, JP-A-59-10539, JP-A-57-1
No. 9765, etc., and hindered phenols are disclosed in U.S. Patent No. 3.700.455, JP-A-52-72224,
U.S. Patent No. 4.228.235, Japanese Patent Publication No. 52-6623
Gallic acid derivatives, methylenedioxybenzenes, and aminophenols are disclosed in U.S. Patent No. 3.45, respectively.
No. 7.079, No. 4.332.886, Special Publication No. 1983
．． No. 21144, etc., and hindered amines are disclosed in U.S. Patent No. 3.336.135, U.S. Pat.
British Patent No. 11.326.889, British Patent No. 1.354.3
No. 13, No. 1, 410.846, Special Publication No. 1983-14
No. 20, JP-A-58-114036, JP-A No. 59-53
No. 846, US Pat. No. 59-78344, etc.; metal complexes are described in US Pat. No. 4.050.938, US Pat.
No. 55, British Patent No. 2.027.731 (A), etc., respectively. The purpose of these compounds can be achieved by co-emulsifying them with the couplers and adding them to the photosensitive layer, usually in an amount of 5 to 100% by weight based on the corresponding color coupler. In order to prevent the cyan dye image from deteriorating due to heat and especially light, it is more effective to introduce an ultraviolet ray acid into the cyan coloring layer and the layers on both sides adjacent thereto.

As ultraviolet absorbers, benzotriazole compounds substituted with aryl groups (for example, U.S. Pat. No. 3,533.7
94), 4-thiazolidone compounds (e.g., U.S. Pat. No. 3.314.794, U.S. Pat. No. 3.352;
681), benzophenone compounds (e.g., those described in JP-A No. 46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Pat. ), butadiene compounds (as described in U.S. Pat. No. 4,045,229), or benzoxidole compounds (e.g., U.S. Pat. No. 3,406,070, U.S. Pat. 271.307) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers.

Among these, benzotriazole compounds substituted with the aforementioned aryl group are preferred.

In addition to the above-mentioned couplers, it is particularly preferable to use the following compounds. Particularly preferred is the combination with a pyrazoloazole coupler.

That is, a compound CF) which chemically combines with the aromatic amine developing agent remaining after color development processing to produce a chemically inert and substantially colorless compound and/or an aroma remaining after color development processing. For example, in storage after processing, the compound (G) that chemically bonds with the oxidized form of a group amine color developing agent to produce a chemically inert and substantially colorless compound may be used simultaneously or singly. This is preferable in order to prevent staining and other side effects caused by the formation of coloring dyes due to the reaction between the color developing agent or its oxidized product remaining in the film and the coupler.

A preferred compound (F) has a second-order reaction rate constant ki (in trioctyl phosphate at 80°C) with p-anisidine of 1. OA/a+ol ・sec ~l
It is a compound that reacts in the range of xlo-' 1 /mol-sac.

Incidentally, the second-order reaction rate constant can be measured by the method described in JP-A-63-158545.

When k is larger than this range, the compound itself becomes unstable and may react with gelatin or water and decompose. On the other hand, if k is smaller than this range, the reaction with the remaining aromatic amine developing agent will be slow, and as a result, side effects of the remaining aromatic amine developing agent may not be prevented.

A more preferable compound (F) can be represented by the general formula (FI) or (Fn).

General formula (FI) R, -(^). -X General formula (FIG) R, -C=Y In the formula, R1 and R3 each represent an aliphatic group, an aromatic group, or a hetero serial number. n represents 1 or 0.

A represents a group that reacts with the aromatic amine developer to form a chemical bond, and X represents a group that reacts with the aromatic amine developer and leaves. B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterogeneous group, a sulfonyl group, or a sulfonyl group,
Y is an aromatic amine developing agent added to the compound of general formula (FII). represents a group that promotes Here R
3 and X, Y and R1 or B may be bonded to each other to form a cyclic structure.

Among the methods of chemically bonding with the residual aromatic amine developing agent, the typical ones are substitution reaction and addition reaction.

For specific examples of compounds represented by general formulas (Fl) and (FII), please refer to Japanese Patent Application No. 158545/1983,
283338, European Patent Publication No. 298321, European Patent Publication No. 27
Those described in specifications such as No. 7589 are preferred.

On the other hand, more preferable compounds (G) that chemically bond with the oxidized aromatic amine developing agent remaining after color development processing to produce a chemically inert and colorless compound are shown below. ).

General formula (Gl) -Z In the formula, R represents an aliphatic group, an aromatic group or a heterocyclic group. Zlt represents a nucleophilic group or a group that decomposes in a photosensitive material to release a nucleophilic group. -Formation (Gl) is a compound where Z is Pearson's nucleophilicity "CLI value (
R.G., Pearson, et al., J.A.
rn.

Chem, Sac, 90.319 (1968)
) is preferably 5 or more, or a group derived therefrom.

- For specific examples of compounds represented by the formation (Gl), see European Patent Publication No. 255722, W.
No. 48, No. 62-229145, patent application No. 63-136
No. 724, No. 62-214681, European Patent Publication 29
Those described in No. 8321, No. 277589, etc. are preferred.

Further, details of the combination of the above-mentioned compound (G) and compound (F) are described in European Patent Publication No. IH277589.

The photosensitive material produced using the present invention contains a water-soluble dye or a dye that becomes water-soluble through photographic processing as a filter dye in the hydrophilic colloid layer or for various purposes such as preventing irradiation or halation. You can leave it there. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes, hemioxonol dyes and merocyanine dyes are useful.

As the binder or protective colloid that can be used in the emulsion layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin.

In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry Office of Gelatin, written by Arthur Weiss (Academic Press, published in 1964).

As the support used in the present invention, transparent films such as cellulose nitrate film and polyethylene terephthalate, which are usually used in photographic materials, and reflective supports can be used. For purposes of the present invention, the use of reflective supports is more preferred.

The "reflective support" used in the present invention is one that enhances the reflectivity and makes the dye image formed in the silver halide emulsion layer clearer. Includes those coated with a hydrophobic resin containing a dispersed light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, and calcium sulfate, and those using a hydrophobic resin containing a dispersed light-reflecting substance as a support. . For example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer or a reflective material, such as glass plates, polyester films such as polyethylene terephthalate, cellulose triacetate or cellulose nitrate, Examples include polyamide film, polycarbonate film, polystyrene film, and vinyl chloride resin.

As other reflective supports, supports having a specular reflective or second type diffuse reflective metal surface can be used. The metal surface has a spectral reflectance of 0.5 in the visible wavelength range.
The above is preferable, and it is also preferable to roughen the metal surface or use a total bending powder to make it diffusely reflective. The metal may be aluminum, tin, silver, magnesium, or an alloy thereof, and the surface may be a surface of a metal plate, metal foil, or thin metal layer obtained by rolling, vapor deposition, plating, or the like.

Among these, it is preferable to obtain the metal by vapor-depositing the metal onto another substrate. It is preferable to provide a water-resistant resin layer, particularly a thermoplastic resin layer, on the metal surface.An antistatic layer is preferably provided on the opposite side of the support of the present invention from the side having the metal surface. For details of such a support, see, for example, JP-A-61-210
No. 346, No. 63-24247, No. 63-24251
No. 63-24255, etc.

These supports can be appropriately selected depending on the purpose of use.

As a light-reflecting substance, it is best to thoroughly knead a white pigment in the presence of a surfactant, and also coat the surface of the pigment particles with
It is preferable to use one treated with tetravalent T alcohol.

Area ratio (%) - is the area per defined unit area of white pigment fine particles - most typically the observed area is 6uInx61! The occupied area ratio (%) of fine particles divided into unit areas of Ln and projected onto the unit area (Ri
) can be determined by measuring. Occupied area ratio (%)
The coefficient of variation can be determined by the ratio s/R of the standard deviation S of Ri to the average value (R) of Ri. The number (n) of target unit areas is preferably 6 or more. Therefore, the coefficient of variation S/π can be found as follows.

In the present invention, the coefficient of variation of the occupied area ratio (%) of the pigment fine particles is preferably 0.15 or less, particularly 0.12 or less. If it is 0.08 or less, the dispersibility of the particles can be said to be "substantially uniform."

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-phinidine diamine compounds are preferably used, and a typical example is 3-methyl-4-amino-N,N-diethylaniline. , 3-methyl-4-amino-N-ethyl-N
-β-hydroxyethyla, niline, 3-methyl-4-
Amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-
N-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride or p-)luenesulfonate. Two or more of these compounds can be used in combination depending on the purpose.

The color developing solution contains a pH buffering agent such as carbonate or phosphate of alkali goldite, a development inhibitor or antifoggant such as bromide salt, iodide salt, benzimidazole, benzothiazole or mercapto compound. It is common to include In addition, if necessary, hydroxylamine, diethylhydroxylamine, sulfite, N, N
- hydrazines such as biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine,
Various preservatives such as catechol sulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, and amines, dye-forming couplers, and competitive couplers 1-7 enyl Auxiliary developing agents such as 3-pyrazolidone, viscosity imparting agents, various calcinates such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids;
For example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroquinethylidene-1,1-diphosphonic acid, nitrilo-N,N
, N-)rimethylenephosphonic acid, ethylenediamine-N
, N,N'N'-tetramethylenephosphonic acid, ethylenediamine-di(0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, color development is usually performed after black and white development and reversal processing. This black and white developer contains known black and white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidone compounds 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 developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic light-sensitive material being processed, but in general it is 31 or less per square meter of light-sensitive material, and by reducing the bromide ion concentration in the replenisher, it can be increased to 500 or less.
mj! You can also do the following: When reducing the replenishment m, it is preferable to reduce the contact surface 1 with the air in the processing tank to prevent evaporation of the solution and air oxidation.The contact area between the photographic processing solution and the air in the processing tank is , can be expressed by the aperture ratio defined below: aperture ratio=contact area of treatment liquid and air (cm2)/capacity of treatment liquid (cm2)
') The aperture ratio is preferably 0.1 or less, more preferably 0.001-0.05.

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, methods using a movable lid as described in Japanese Patent Application No. 62-241342, Examples include the slit development method described in Japanese Patent No. 63-216050.

It is preferable to reduce the aperture ratio not only in both color development and black-and-white development, but also in 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. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, depending on the purpose, treatment may be carried out in two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment. As the bleaching agent, for example, a compound of a polyvalent metal such as iron (I[[) is used. Typical bleaching agents include organic complex salts of iron (II[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropanetetraacetic acid, glycol etherdiaminetetraacetic acid, etc. Aminopolycarboxylic acids or citric acid, tartaric acid,
Complex salts such as malic acid can be used. Among these, aminopolycarboxylic acid iron (III) complex salts such as ethylenediTminetetraacetic acid iron (III) complex salts are preferred from the viewpoint of rapid processing and prevention of trench boundary pollution. Additionally, aminopolycarboxylic acid iron (nl) complexes are particularly useful in both bleach and bleach-fix solutions. The pH of bleaching solutions or bleach-fixing solutions using these aminopolycarboxylic acid iron (I [ You can also.

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, JP-A-53-! 156ac No.1,
Research Disclosure Nα No. 17.129 (1
Compounds having a mercapto group or a disulfide bond described in JP 50-140129 (July 1978) and others;
Thiazolidine derivatives described in US Pat. No. 3,706
．． Thiourea derivatives described in No. 561; JP-A-58-16
Iodide salts described in No. 235; West German Patent No. 2.748.4
Polyoxyethylene compounds described in No. 30;
Polyamine compounds described in No. 5-8836; bromide ions, etc. can be used. Among these, compounds having a mercapto group are preferred from the viewpoint of a large promoting effect, and are particularly preferred as disclosed in US Pat. No. 3,893,858 and West German Patent No. 1,290. No. 812, JP-A-53-95630
The compounds described in No. 1 are preferred. Additionally, U.S. Pat.
Also preferred are the compounds described in No. 552,834. These bleach accelerators may be added to the light-sensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

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 Preservatives for bleach-fix solutions include sulfites, bisulfites, and p-
) Sulfinic acids such as luenesulfinic acid or carbonyl bisulfite 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 Society of Mo
tion Picture and Tele-vis
ion Bngineers Volume 64, p. 248
-253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in JP-A-62-288838 can be used very effectively. Also, JP-A-57-8542
Chlorinated disinfectants such as isothiazolone compounds, thiabendazole, chlorinated sodium isoneurate, and other benzenes described in the issue, IJ Azole, etc., Hiroshi Horiguchi, Chemistry of Bacteria and Mildew Prevention (1986) Sankyo Publishing, 14j “Microbial Sterilization, Disinfection, and Mildew Prevention Technology J” edited by Biotechnology Society (198
2) It is also possible to use the fungicides described in "Encyclopedia of Antibacterial and Antifungal Agents" (1986) edited by the Society of Industrial Science and Technology and the Japan Society of Antibacterial and Antifungal Research.

The pl of 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 20 minutes.
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 carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

It is also possible to add various botanical agents and antifungal agents to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3. 342.
Indoaniline compounds described in No. 597, No. 3, 3
42. No. 599, Research Disclosure 14
, No. 850 and No. 15, No. 159; T-rudol compounds described in US Pat. No. 3.924, US Pat. 719. Examples thereof include metal complexes described in No. 492 and urethane compounds described in JP-A-53-135628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are described in JP-A Nos. 56-64339, 57144547, and 58-115438.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to.

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

The Kalani photographic material of the present invention is preferably subjected to color development, bleach-fixing, and water washing treatment (or stabilization treatment). Bleaching and fixing may be carried out separately instead of in one bath as described above.

The color developer used in the present invention contains a known aromatic primary amine color developing agent.

Preferred examples are p-phenylenediamine derivatives, representative examples of which are shown below, but are not limited thereto.

D-IN, N-diethyl-p-phenylenediamine D-22-amino-5-diethylaminotriene D-32-amino-5-(N-ethyl-N-laurylamino)toluene D-44-[N-ethyl- N-(β-hydroxyethyl)amino]Tniline D-52-methyl-4-[N-ethyl-N(β-hydroxyethyl)aminocoaniline D-64-7 minnow 3-methyl-N-ethyl -N16-
(methanesulfonamide)ethyltwoaniline D-7N-(2-amino-5-diethylaminophenylethyl)methanesulfonamide D-8N, N-dimethyl-p-phenylenediamine D-94-amino-3-methyl-N- Ethyl-N-methoxyethylaniline D-104-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-114-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Among the above p-7 22 diamine derivatives, 4-amino-3-methyl-N-ethyl-N-[β-(
methanesulfonamido)ethyl]-aniline (exemplified compound D-6).

In addition, salts of these p-phenylenediamine derivatives such as sulfates, hydrochlorides, sulfites, and p-)luenesulfonates may be used. The amount of the aromatic primary amine developing agent used is preferably about 0.1 g to about 20 g per developer solution 11.
, more preferably at a concentration of about 0.5 g to about 10 g.

In practicing the present invention, it is preferred to use a developer solution that is substantially free of benzyl alcohol. Here, "substantially free" means preferably 2-/1 or less,
More preferably, the concentration of benzyl alcohol is 0.5 ml/i or less, and most preferably, it contains no benzyl alcohol at all.

It is more preferable that the developer used in the present invention does not substantially contain sulfite ions. The sulfite ion functions as a preservative for the developing agent, and at the same time has the effect of dissolving silver halide and reacting with the oxidized product of the developing agent to reduce the dye formation efficiency.

Such an effect is presumed to be one of the causes of increased fluctuations in photographic characteristics due to continuous processing. Here, "substantially not containing" means preferably having a sulfite ion concentration of 3.0 x 10-' mol/1 or less, and most preferably not containing any sulfite ions.

However, in the present invention, a very small amount of sulfite ion used to prevent oxidation in a processing agent kit in which the developing agent is concentrated before being mixed into a solution for use is excluded.

The developer used in the present invention preferably does not substantially contain sulfite ions, and more preferably does not substantially contain hydroxylamine. This is because hydroxylamine functions as a preservative for the developing solution and also has silver developing activity itself, and it is believed that fluctuations in the concentration of hydroxylamine greatly affect photographic properties.

The expression "substantially not containing hydroxylamine" as used herein means preferably a hydroxylamine concentration of 5.0 x 10-' mol/1 or less, and most preferably no hydroxylamine at all.

It is more preferable that the developer used in the present invention contains an organic preservative instead of the hydroxylamine or sulfite ion.

The organic preservative herein refers to any organic compound that reduces the deterioration rate of the aromatic primary T-mine color developing agent when added to the processing solution for color photographic materials. In other words, they are organic compounds that have the function of preventing color developing agents from being oxidized by air, among others, hydroxylamine derivatives (excluding hydroxylamine; the same applies hereinafter), hydroxamic acids, hydrazines, hydrazides, and phenols. , α-hydroxyketones, α-aminoketones, sugars, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds, fused cyclic amines, etc. It is a particularly effective organic preservative. These are JP-A-63
-4235, 63-30845, 63-216
No. 47, No. 63-44655, No. 63-53551, No. 63-43140, No. 63-56654, No. 6
No. 3-58346, No. 63-43138, No. 63-1
No. 46041, No. 63-44657, No. 63-446
No. 56, U.S. Patent No. 3.615.503, 2, 49
No. 4.903, JP-A No. 52-143020, Special Publication No. 4
No. 8-30496 and the like.

Other preservatives include various metals described in JP-A-57-44148 and JP-A-57-53749;
Salicylic acids described in No. 180588, JP-A-54-35
Alkanolamines described in No. 32, JP-A-56-94
No. 349, the polyethyleneimines described in U.S. Patent No. 3.
If necessary, aromatic polyhydroxy compounds described in No. 746.544 and the like may be contained. In particular, alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine,
Preferably, a hydrazine derivative or an aromatic polyhydroxy compound is added.

Among the above-mentioned organic preservatives, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred.
It is described in No. 5270, No. 63-9713, No. 63-9714, No. 63-11300, etc.

Further, it is more preferable to use the above-mentioned hydroxylamine derivative or hydrazine derivative in combination with amines from the viewpoint of improving the stability of the color developer and further improving the stability during continuous processing.

Examples of the above-mentioned amines include cyclic amines as described in JP-A-63-239447 and JP-A-63-128.
Amines such as those described in No. 340 and other patent applications filed in 1983
Examples include amines such as those described in No. 3-9713 and No. 63-11300.

In the present invention, 3.5% of chloride ions are added to the color developer.
It is preferable to contain Xl0-' to 1.5 Xl0-' mol/i. Particularly preferably 4×10−2 to lXl0
−'mol/i. Chlorine ion concentration is 1.5X10-
If the amount is more than 10-1 mole/1, it has the disadvantage of delaying development, which is not preferable in achieving the object of the present invention of rapid development and high maximum density. Also, 3.5×101
If it is less than mol/1, it is not preferable in terms of preventing fog.

In the present invention, 3. bromine ions are added to the color developer.
Ox 10-'+-ru/1-1. It is preferable that the bromide ion concentration is greater than 1X10-' mole/Il. More preferably, it is 5.0×10-s to 5X10-' mole/Il.
3. Delays development, reduces maximum density and sensitivity; 3. OX
If it is less than 10-' mole/1, fog cannot be sufficiently prevented.

The chlorine ions and bromine ions may be added directly to the developer, or may be eluted from the light-sensitive material into the developer during the development process.

When added directly to a color developer, examples of the chloride ion supplying substance include sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride, and cadmium chloride, among which preferred ones are preferred. are sodium chloride and potassium chloride.

Alternatively, it may be supplied from an optical brightener added to the developer.

As a supply material for bromide ions, sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide, thallium bromide Among these, preferred are potassium bromide and sodium bromide.

When eluted from the light-sensitive material during the development process, both chloride ions and bromine ions may be supplied from the emulsion, or may be supplied from a source other than the emulsion.

The color developer used in the present invention is preferably p11
9 to 12, more preferably 9 to 11.0, and the color developer may contain other known developer component compounds.

In order to maintain the above pH, various methods are required! Preferably, a balancing agent is used. Buffers include carbonate, phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N,N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3゜4- Dihydroxyphenylalanine salt, alanine salt, T-minobutyrate, 2-amino-2
-Methyl-1°3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt, etc. can be used. In particular, carbonates, phosphates, tetraborates, and hydroxybenzoates are soluble at pH 9,
These &l buffering agents have excellent buffering ability in the high pH range of 0 or higher, have no adverse effects on photographic performance (fogging, etc.) even when added to color developers, and are inexpensive. It is particularly preferable.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. Potassium, sodium tetraborate (borax), potassium tetraborate, sodium 0-hydroxybenzoate (sodium salicylate), potassium ○-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) ), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is 0.1 mol/1
It is preferably at least 0.1 mol/l-0, particularly 0.1 mol/l-0,
Particularly preferred is 4 mol/l.

In addition, various caloric acid agents can be used in the color developer as agents for preventing precipitation of calcium and magnesium, or for improving the stability of the color developer. For example, nitrilotriacetic acid, diethylenetriaminepentaacetic acid,
Ethylenediaminetetraacetic acid, N,N,N-trimethylenephosphonic acid, ethylenediamine-N,N,N',N'-
Tetramethylene sulfonic acid, transsiloxane diaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediamine orthohydroxyphenylacetic acid, 2-phosphonobutane-1,2
,4-)licarboxylic acid, 1-hydroxyethylidene-1
, 1-diphosphonic acid, N.

Examples include N'-bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination, if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer. For example 11
It is about 0.1g to 10g per serving.

Any development accelerator can be added to the color developer if necessary.

As a development accelerator, Japanese Patent Publication No. 37-16088 and No. 3
No. 7-5987, No. 38-7826, No. 44-123
No. 80, No. 45-9019 and U.S. Patent No. 3.813
．． thioether compounds shown in JP-A No. 247, p-phinidine diamine compounds shown in JP-A-52-49829 and JP-A-50-15554;
No. 137726, Japanese Patent Publication No. 44-30074, Japanese Patent Publication No. 1977
Quaternary ammonium salts shown in No. 6-156826 and No. 52-43429, etc., U.S. Patent No. 2゜494,
No. 903, No. 3.128.182, No. 4.230.7
No. 96, No. 3.253.919, Special Publication No. 41-114
No. 31, U.S. Pat. No. 2,482.546, U.S. Pat.
Amine compounds described in 6.926 and 3.582.346, etc., Japanese Patent Publication No. 37-16088, 42-2
5201, U.S. Patent No. 3.128.183, Japanese Patent Publication No. 41-11431, Japanese Patent Publication No. 42-23883, and U.S. Patent No. 3.532゜501, etc. - Pyrazolidones, imidazole, etc. can be added as necessary.

In the present invention, any antifoggant can be added if necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and organic antifoggants can be used. Examples of organic antifoggants include benzotriazole, 6-nidropenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-benzotriazole, and 2-thiTzolylupenz. Typical examples include nitrogen-containing heterocyclic compounds such as imidazobe 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine, and adenine.

The bright color developer used in the present invention preferably contains an optical brightener. As an optical brightener, 4.4'
-Diamino-2,2'-disulfostilbene compounds are preferred. The amount added is 0 to 5g/1. Preferably 0.1g
~4/j7.

Furthermore, various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids, and aromatic carboxylic acids may be added as necessary.

The processing temperature of the vine color phenomenon liquid applied to the present invention is 20~
The temperature is 50°C, preferably 30 to 40°C. Processing time is 20
The time is from seconds to 5 minutes, preferably from 30 seconds to 2 minutes. It is preferable that the amount of replenishment is small, but it is 20 to 600 per m'' of photosensitive material.
- is appropriate, preferably 50 to 300. More preferably 60rnl~200m! ! , most preferably from 60 to 150.

Next, a desilvering process that can be applied to the present invention will be explained.

The desilvering step may generally include any process such as a bleaching step-fixing step, a fixing step-bleach-fixing step, a bleaching step-bleach-fixing step, or a bleach-fixing step.

The bleaching solution, bleach-fixing solution and fixing solution applicable to the present invention will be explained below.

As the bleaching agent used in the bleaching solution or bleach-fixing solution, any bleaching agent can be used, but in particular, scissors (
I[I] organic complex salts (e.g. ethylenediaminetetraacetic acid,
T-minopolycarboxylic acids such as diethylenetriamine pentacholic acid, complex salts of aminopolyphosphonic acid, central sulfonocarboxylic acid, and organic phosphonic acid) or organic acids such as citric acid, tartaric acid, and phosphoric acid; persulfates; hydrogen peroxide, etc. preferable.

Among these, organic complex salts of iron (I[I) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution. Aminopolycarboxylic acids useful for forming organic complex salts of iron(II[),
Aminopolyphosphonic acids, organic phosphonic acids, or salts thereof include ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, 1. 3-diaminopropanetetraacetic acid, propylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, iminodiacetic acid, glycol ether diaminetetraacetic acid,
etc. can be mentioned. These compounds may be sodium, potassium, thium or ammonium salts. Among these compounds, iron(II[) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1.3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

These ferric ion complex salts may be used in the form of complex salts, or ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, and ferric phosphate. A ferric ion complex salt may be formed in a solution using a chelating agent such as aminopolycarboxylic acid, aminopolybosphonic acid, or phosphonocarboxylic acid. In addition, a chelating agent can be used as a second
It may be used in excess to form an iron ion complex salt. Among the iron complexes, aminopolycarboxylic acid iron complexes are preferred, and the amount added is 0.01 to 1.0 mol/1, preferably 0.05 to 0.50 mol/1.

Various compounds can be used as bleach accelerators in the bleach solution, bleach-fix solution and/or their pre-bath. For example, U.S. Pat.
Publication No. 630, Research Disclosure No. 1712
No. 9 (July 1978 issue), compounds with mercapto groups or disulfide bonds, and Japanese Patent Publication No. 45-85
No. 06, JP-A-52-20832, JP-A No. 53-3273
Thiourea compounds described in No. 5 and US Pat. No. 3,706,561, or 10-genides such as iodine and bromide ions are preferred because they have excellent bleaching properties.

In addition, the bleaching solution or bleach-fixing solution that can be applied to the present invention contains bromides (for example, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg, potassium chloride, sodium chloride, ammonium chloride) or iodides (eg, ammonium iodide) can be included. If necessary, use one or more types of borax, sodium boronate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, citric acid, etc. with pH/Wt balance, such as IJum, tartaric acid, etc. Inorganic acids, organic acids, alkali metal or ammonium salts thereof, or corrosion inhibitors such as ammonium nitrate and guanidine can be added.

The fixing agents used in the bleach-fix solution or fixing solution are known fixing agents, namely thiosulfates, such as ammonium thiosulfate, ammonium thiosulfate; thioneanates,
Thiocyanate salts such as ammonium thionate; ethylene bisthioglycolic acid, 3.6-cythia 1.8-
These are water-soluble silver halide dissolving agents such as thioether compounds such as octanediol and thioureas, and these can be used alone or in combination of two or more.

It is also possible to use a special bleach-fix solution made of a combination of a fixing agent and a large amount of a halide such as potassium iodide as described in JP-A-55-155354. In the present invention, the use of thiosulfates, particularly ammonium thiosulfates, is preferred. The amount of fixing agent per 11 is
Preferably 0.3 to 2 mol, more preferably 0.5 to 1 mol
．． It is in the range of 0 mol. The pH range of the bleach-fixing solution or fixing solution is preferably 3-10, more preferably 5-9.

Further, the bleach-fix solution may contain various other optical brighteners, antifoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol.

Bleach-fix solutions and fixing solutions contain sulfites (e.g., sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (e.g., ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc.) as preservatives.
, metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.).

These compounds are approximately 0.02 to 0.02 in terms of sulfite ion.
The content is preferably 0.05 mol/l, more preferably 0.04 to 0.40 mol/l.

Sulfites are commonly added as preservatives, but other preservatives include ascorbic acid, carbonyl bisulfite adducts,
Alternatively, a carbonyl compound or the like may be added.

Furthermore, buffering agents, optical brighteners, chelating agents, antifoaming agents, antifungal agents, etc. may be added as necessary.

After desilvering treatment such as fixing or bleach-fixing, washing with water and/or stabilization treatment is generally performed.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, using a coupler, etc.), the use, the temperature of the washing water, the number of washing tanks (the 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 flush tanks and the amount of water in a multistage countercurrent method is described in the Journal of the Society of Motion Picture and Television Engineers.
rnalof the 5ociety of Mot
ion Picture and Te1evi-si
on Bngineers) Volume 64, p. 248~
253 (May 1955 issue).

Generally, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, particularly preferably 2 to 4; according to the multistage countercurrent system, the amount of washing water can be greatly reduced, for example, 0.51 to 11 or less per 1 m'' of photosensitive material. is possible, and the effect of the present invention is remarkable, but problems such as bacteria propagation and floating matter adhering to the photosensitive material arise due to the increased residence time of water in the tank.Such problems arise. As a solution to the problem, the method of reducing calcium and magnesium described in JP-A No. 62-288838 can be used very effectively.
542, chlorine-based disinfectants such as isothiazolone compounds and cyryobendazole, chlorinated sodium isocyanurate described in JP-A No. 61-120145,
Benzotriazole, copper ion, etc. described in No. 267761, Hiroshi Horiguchi, “Chemistry of antibacterial and antifungal J (1986)
Sankyo Publishing, Hygiene Technology complete volume "Sterilization, sterilization, and anti-mold technology of microorganisms" (1982) Edited by Society of Industrial Engineers, Japan Society of Antibacterial and Anti-Mold "
The fungicides described in Dictionary of Antibacterial and Antifungal Agents J (1986) can also be used.

Further, in the washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softener can be used.

The above-mentioned water washing step can be followed or the stabilizing solution can be directly treated without going through the water washing step. A compound having an image stabilizing function is added to the stabilizing liquid, such as an aldehyde compound such as formalin, or a film suitable for stabilizing the dye.
Examples include buffers for preparing H and ammonium compounds. Further, in order to prevent the proliferation of bacteria in the liquid and to impart anti-mold properties to the photographic material after processing, the various disinfectants and anti-mold agents described above can be used.

Furthermore, surfactants, optical brighteners, and hardeners can also be added. In the processing of the photosensitive material of the present invention, when stabilization is performed directly without passing through a water washing step,
No. 8543, No. 58-14834, No. 60-2203
All known methods described in No. 45 and the like can be used.

In addition, it is also a preferable embodiment to use chelating agents such as 1-hydroxyethylidene-1,1-diphosphonic acid and ethylenediaminetemethylenephosphonic acid, and magnesium and bismuth compounds.

A so-called rinsing solution is also used as a washing solution or stabilizing solution used after desilvering treatment.

Preferable 1) 11 in the water washing step or stabilization step is 4 to 10
and more preferably from 5 to 8. The temperature can be set variously depending on the use and characteristics of the photosensitive material, but generally it is between 15 and 4
The temperature is 5°C, preferably 20 to 40°C. Although the time can be set arbitrarily, a shorter time is preferable from the viewpoint of reducing processing time. Preferably it is 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds. The smaller the amount of replenishment, the better from the viewpoints of running costs, reduced emissions, ease of handling, and the like.

A specific preferable replenishment amount is 0.5 to 50 times, preferably 3 to 40 times, the amount brought in from the previous bath per unit area of the photosensitive material. Or it is 11 or less per m' of photosensitive material, preferably 500rn1 or less. Further, replenishment may be performed continuously or intermittently.

The liquid used in the water washing and/or stabilization step can also be used in the previous step. An example of this is reducing the amount of waste liquid by using a multi-throw countercurrent system to allow the overflow of the washing water to flow into the bleach-fixing bath, which is a pre-bath, and replenishing the bleach-fixing bath with concentrated liquid.

Example 2 Multilayer color photographic paper A (for comparison) having the layer structure shown below was prepared on a support laminated on both sides with polyethylene. Coating wL was prepared as follows.

1st layer coating 1fl preparation example yellow coupler (Y-tco)/7. jIF and color image stabilizer (cpct-/) 4L, 4AP and color image stabilizer (Cpd-7)/, acetic acid ether core in da2.

2CC and solvent (8o1v-7)1. λft710 Esoru M L, this melt 1F! L't'' IO% dodecylbenzene sulfo/sodium acid lcc% - containing IO% gelatin aqueous solution/rjtcc to emulsify and disperse. Things and 0.
3-nia mixture (silver molar ratio) with 70 μm.

The coefficient of variation of the grain size distribution was 0.01 and 0.10, and each emulsion contained 0.2 mol % of silver bromide localized on the grain surface. For dog-sized emulsions, γtJ, 0x10 molar n0,
For small size emulsions, no need to worry! X10
After adding 4 mol, sulfur sensitization was carried out to prepare the sample.

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

The second to seventh calendar month coating solutions were prepared in the same manner as the first layer coating solution. l-oxy-3,5-dichloro-5-) riazine sodium salt was used as the gelatin hardening agent for each layer.

The following spectral sensitizing dyes were used in each layer.

Blue sensitive emulsion layer SO, θ SO, NIl (C, ll5).

(2.OX 10-mol each for large size emulsions and 2.5X10-' mol each for small size emulsions per mole of silver halide) green sensitive emulsion layer (per mole of silver halide , 4.0XIO-' moles for large size emulsions and 5.6 for small size emulsions.
(per mole of silver halide, 7.OX 10-' mol for large size emulsions and 1.OX 10-' mol for small size emulsions) Red-sensitive emulsion layer C , H8 (e C9■ (per mole of silver halide, 0.9X10-' mole for large emulsions and 1 mole for small emulsions)
．． I x 10-' mol) The following compound was added to the red-sensitive emulsion layer in an amount of 2.6 x 10-' mol per mol of silver halide.

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 per mol of silver halide.
8.5 X 10-'-T-Jl/? , 7xlO-'
mol, 2.5 x 10-' moles were added.

Furthermore, for the blue-sensitive emulsion layer and the edge-sensitive emulsion layer, 4-hydroxy-6-methyl-1,3,3a,? -tetrazaindene per mole of silver halide, respectively, lXl0-'
mol and 2X10-' mol were added.

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

and (Layer structure) The composition of each layer is shown below. The number is the coating amount (g/m') represents. The silver halide emulsion represents the coated amount in terms of silver.

Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (T+Oz) and a bluish dye (ulmarine)] -th layer (sensitive layer) The above silver chlorobromide emulsion 0.30 Gelatin 1.86 Yellow Turnip 5- <Y-140,'75 color image stabilizer (Cpd-1)
0.19 solvent (+-,-1)
045 color image stabilizer (Cpd
-7) o, 06 Fifth layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.
16 solvent (Solv-4)
0.08 Fifth layer (green sensitive layer) Silver chlorobromide emulsion (cubic, 1:3 mixture (^g molar ratio) of one with an average grain size of 0.55- and one with an average grain size of 0.39 t!M. The coefficient of variation of particle size distribution is 0.10 and 0.0
8. Each emulsion contained 0.8 mol% of HegBr locally on the grain surface) 0.12 Gelatin
1.24 magenta coupler (BX
M) 0.20 color image stabilizer (['pd
-2) 0.03 color image stabilizer (C
pd-3) 0.15 color image stabilizer (Cpd-4) 0.02 color image stabilizer (Cpd-9) 0.02 solvent (Solv-2) 0.
40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixing prevention agent (Cpd-5) 0.05
Solvent (SoIv-5)
0.24 Fifth layer (red-sensitive layer) Silver chlorobromide emulsion (cubic, 1:4 mixture of one with an average grain size of 0.58 m and one with an average grain size of 0.45 I!IO (heg
molar ratio). The coefficient of variation of particle size distribution is 0.09 and 0.09.
11. Each emulsion contained 0.6 mol% of AgBr locally on a part of the grain surface) 0.23 Gelatin
1.34 cyan coupler (Bx
C) 0.32 color image stabilizer (Cp
d-6) 0.17 color image stabilizer (
Cpd-7) 0.40 Color image stabilizer (Cpd-8) 0.04 Solvent (Solv-6) 0.1
5 Sixth layer (ultraviolet absorption layer) Gelatin 0.53 Ultraviolet absorber (UV-1) 0.16 Color mixing prevention agent (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%)
) 0.17 Liquid paraffin 0.03 (BxM) 1:1 mixture (molar ratio) of magenta coupler (BxC) Cyan coupler I R=C2L and C,H.

(Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer (Cpd-3) Color image stabilizer (Cpd-4) -5) Color mixture inhibitor n■ (2:4:4 mixture (weight ratio) of Cpct-6 color image stabilizer (Cpcl-7) Color image stabilizer -(C)1.-CH)-= C0NI( Cdb (t) Average molecular weight 60,000 (Cpd-8) Color image stabilizer <Cpd-9) Color image stabilizer (UV-1) 4::4 mixture (weight ratio) of ultraviolet absorber (Solv-1) Solvent (Solv-2) 2:1 mixture (volume ratio) of solvent (Solv-4) Solvent (Solv-z) Solvent C00C8H□7 (CH2) 8 C00C8)117 (5olv-4) Solvent Then sample A and Similarly, Samples B to X, which were the same as the sample except for the factors shown in Table 6 and Table 1, were prepared.

1 photosensitive needle for each sample (Fuji Photo Film Co., Ltd. table,
FWH type, light source color temperature jJOO''K) was used, and a gradation exposure tube of a three-color separation filter for sensitometry was provided.The exposure at this time was 2!rOcM8 with an exposure time of o and i seconds.
The exposure amount was set to .

After the exposure, the exposed sample was subjected to continuous processing (two-time processing) in the next processing step using Evar processing fIAt-1, which was refilled twice the capacity of the tank.

Color development Jz”C4cs seconds /4/d /71
Bleach fixing 30~J! r ”C4C7 seconds ko/!Id
17g Linne■ 30~J0C20 seconds -10
1 rinse ■ 30~jj'c 20 seconds -104
Rinse ■ 30～3r”Cλ0ffp JjOd
101 Drying at 70.40° C. for 4 o seconds The amount of blue light supplementation is photosensitive material/m Akuri (3 tank countercurrent blade type from rinsing ■ to ■). The composition lines of each processing solution are as shown below.

Color developer tank liquid water
100m ethylenediamine-
N.

N,N,N-tetrame replenisher 00ml Terenephosphone Potassium dibromide Triethanolamine Sodium chloride Potassium carbonate N-Ether-N-(β-Methanesulfonamidoethyl)-3-Methyl≠-Aminoaniline sulfate N,N - Bis(carboxymethyl)hydrazine fluorescent whitening agent (WHITEX /,!? 2. Of O, 0/ j f - r, oy ix, oy /, Hiroshi? - λjf cosy s, oy 7, Of 1,! t 7.0? Add water 1000J pH (2z 0C) lo, oj bleach-fix solution (tank solution and replenisher are the same) water ammonium thiosulfate (70%) sodium sulfite 1ooo, 1 10.4c! ≠00x1 00yd / 7f Ethylenediaminetetraacetate iron (III) Ammonium je?Ethylenediamine/tetraacetic acid disodium jf Add water to 1000slpH (Kozo
c) O rinse solution (tank solution and replenishment solution are the same) Ion exchange water (calcium 9m and magnesium are each jppp
m or less) Next, using the above-mentioned treated sample, evaluation of color reproducibility (based on visual judgment and chromaticity diagram), light fastness and dark fastness were all tested. Each sample was stored for 1 day at 70% relative humidity at 0°C, and for 7 days using a xenon weight meter with an illuminance of 10,000 lux.
For the case of zon, the initial density of yellow FIt/,
# degree reduction from 0 at- was measured. 6l of these results
and shown in Mr. 2.

1. From the results in Table 1, the general formula (1) has superior color reproducibility.
The coupler has poor dye fastness, but - Monna (II)
The color image fastness of the coupler increases by about 30% from f to about 30%, and an image with excellent color reproducibility and color image fastness can be obtained. In addition, it can be seen from Mr./and 6-2 that the coating amount of the coupler according to the present invention and the ratio of the total oil-soluble component to the total yellow coupler are significantly improved, and the color image fastness is further improved. Therefore, the present invention can greatly improve both color reproducibility and color image storage stability compared to conventional yellow dye images.

Epoxy-based solvents are advantageous as high-boiling solvents.

〔Effect of the invention〕

As is clear from the above implementation, the unexploded BA can improve color reproducibility and color 651 by combining the yellow coupler represented by the pattern hole (1) and the yellow coupler represented by the general formula (It). The sex has improved as well, and moreover, surprisingly,
The color image fastness can be greatly improved by the combination of the ratio and coating amount of the oil-soluble substance coexisting with the yellow coupler and the yellow coupler.

Claims (2)

[Claims] (1) In a silver halide photographic material having at least one blue-sensitive silver halide emulsion layer, one green-sensitive silver halide emulsion layer, and one red-sensitive silver halide emulsion layer on a support, the green-sensitive emulsion layer is as follows: A silver halide photographic material containing at least one yellow coupler represented by the general formula [I] and at least one yellow coupler represented by the following general formula [II]. General formula [I] ▲Mathematical formulas, chemical formulas, tables, etc. are available▼ [In the formula, R_1 is an aryl group or a tertiary alkyl group,
R_2 is a fluorine atom, alkyl group, aryl group, alkoxy group, aryloxy group, dialkylamino group, alkylthio group, or arylthio group, R_3 is a group that can be substituted on the benzene ring, and X is a hydrogen atom or an aromatic group. l represents a group that can be separated by a coupling reaction with an oxidized product of a primary amine developer, and l represents an integer of 0 to 4, respectively. However, when l is plural, the plural R_3 may be the same or different. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Y represents a group that can be substituted on the benzene ring, and m
represents an integer from 0 to 4. However, when m is plural, the plural R_4 may be the same or different. Z_1 represents a group of nonmetallic atoms necessary to form a ring] (2) The oil-soluble substance coexisting and dispersed with the yellow couplers of the above general formulas [I] and the above general formulas [II] is equal to the total weight of the yellow couplers of the above general formulas [I] and the above general formulas [II]. On the other hand, a patent characterized in that the weight ratio is 0.55 or less, and the total coating amount of the yellow coupler of the general formula [I] and the general formula [II] is 0.80 g/m^2 or more. A silver halide photographic material according to claim 1.