JPS6385630A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To prevent reduction of cyan coloring density, even in case of processing the titled material with a bleaching or a bleach-fixing solution which is exhausted or is weakened oxidizing force, by incorporating a specific naphthol type cyan coupler and carboxylic acids having a non-coloring and an anti- diffusion properties in the same layer of the titled material. CONSTITUTION:The titled material contains the naphthol type cyan coupler shown by formula I and the carboxylic acids having the non-coloring and anti- diffusion properties in the same layer of the titled material. In formula I, R1 is -CONR4R5, etc., R2 is a group capable of substituting in a naphthalene ring, (l) is an integer of 0-3, R3 is a monovalent org. group, X is hydrogen atom, etc., R4 and R5 are each hydrogen atom etc. The concrete example of the compd. shown by formula I is preferably the compd. shown by formula I-1. Thus, the color developing property of the cyan coupler is improved, and the titled material having the high sensitivity is obtd.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention exhibits high sensitivity and high color development, and furthermore, even when a bleach bath or a bleach-fix bath is used, which is fatigued due to running during development processing, the color density decreases and the color density does not decrease. This invention relates to a silver halide color photographic material that provides cyan images with little variation.

(Prior art) When a silver halide photographic light-sensitive material is exposed to light and then subjected to color development, an oxidized aromatic primary amine developer and a dye-forming coupler (hereinafter referred to as coupler) react to form a color image. It is formed.

Various requirements are imposed on couplers used in recent silver halide color photographic materials. For example, it has excellent stability, excellent processing suitability, 1. excellent color development, excellent hue of color images, 1. robustness of color images, low cost, and excellent manufacturing suitability. There is such a thing as being there.

Conventionally, phenolic couplers and naphthol couplers have been used as cyan couplers.

In particular, /-naphthol couplers have a long wavelength absorption maximum (Cλmax) of the coloring dye produced, have little side absorption in the edge region, and are excellent in color reproduction, and many couplers with excellent coloring properties have been found. Moreover, it is inexpensive and has excellent manufacturing suitability, and has been widely put into practical use as a color negative photosensitive material.

However, phenolic couplers and naphthol couplers, especially co-alkylcarpamoyl-l-naphthol couplers, which have been widely used in the past, cannot be used in the bleaching or bleach-fixing process of color development processing due to oxidation or fatigue in the bleaching or bleach-fixing solution. If the power is weak, a sufficient color image cannot be obtained. This development is thought to be due to reduction fading of the cyan dye due to gr and i iron ions generated during the bleaching or bleach-fixing process. Furthermore, the cyan images formed by these couplers have a drawback of low fastness.

The disadvantage of the former in naphthol couplers is that the substituent of the carbamoyl group at the 2-position is changed from an alkyl group to an aryl group, resulting in a co-arylcarbamoyl/-naphthol coupler (for example, as described in U.S. Pat. However, the latter drawback is still insufficient even when using this coupler, and using this coupler as a cyan coupler is not necessarily preferable in terms of image preservation. It wasn't.

On the other hand, in order to improve these drawbacks, a phenolic cyan coupler having a phenylureido group at the U position and a carbonamide foundation at the VC7 position was proposed. These couplers are used, for example, in Japanese Patent Application Publication No. Sho Jt-6j/J≠ No.
7-Ko O Hiroj Hiro No. 3.

Same 17-2044.1≠ issue, same 17-20 Hiro! Hiroj issue,
It is disclosed in J-r-332 Kode No. 1, No. 11-33 Ko No. 10, etc. It is true that the 2-position phenylureido substituent couplers are superior to the conventionally known phenolic cyan couplers and naphthol cyan couplers in the above points, but these couplers are difficult to couple with the oxidized product of the current active ingredient. It has become clear that there is a problem in that the activity is low and a sufficient color density cannot be obtained.

European Patent Publication /l, /, A2 No. 2, Japanese Patent Publication No. 1 Sho 1sO
-237μar, t/-/7944J7, and A/-/7ri≠3 have proposed l-7toll couplers with a specific substituent at the j1 position.These drawbacks have been largely eliminated. It was done. However, these couplers also often have the problem of producing brown coloring, so-called staining, when exposed to light for a long time after development, and that they have insufficient color development and are not suitable for use in recent high-sensitivity photosensitive materials.

On the other hand, Japanese Patent Publication No. Sho tit-4co4c2 claims the use of an alkyl-substituted phenoxyalkylcarboxylic acid as a solvent component of a coupler having an alkyl-substituted phenoxyalkanamide group as a diffusion-resistant group. However, the patent does not make any description of the cyan coupler of the present invention, and the present patent does not describe the cyan coupler of the present invention, as does the patent.

There is no need for the coupler to have an alkyl-substituted phenoxyalkanamide group, nor does the carboxylic acid need to be an alkyl-substituted phenoxyalkylcarboxylic acid, for incorporation to be obvious.

Further, European Patent Publications No. 7/ and /J disclose the color development improving effect and grain size improving effect of a carboxylic acid compound having an ester group. However, the effect of the present invention can be exhibited only by the cyan coupler within the present invention, and the effect can also be exhibited by carboxylic acids other than those included in the patent.

Differences from these conventional techniques will be shown in Section 1.

(Objects of the Invention) The first object of the present invention is to provide a silver halide color photographic material that does not cause a decrease in cyan color density even when processed using a bleach or bleach-fix solution that is tired or has weak oxidizing power. The second object of the present invention is to provide a silver halide color photographic light-sensitive material which improves the coloring properties of a cyan coupler and is suitable for increasing sensitivity.

A third object of the present invention is to provide a silver halide color photographic light-sensitive material in which the occurrence of staining due to long-term exposure of the light-sensitive material after processing is suppressed.

(Structure of the Invention) These objects of the present invention are characterized by containing a naphthol cyan coupler represented by the following general formula [I] and a non-color-forming and diffusion-resistant carboxylic acid in the same layer. This can be achieved using silver oxide color photographic materials.

In 3NHX (general formula CI), R1 is -CONR, R5--N
HCOR4--NHCOOR6, NH302R6--N
HCONR4R5'' or -NH8O2NR4R5, R2 represents a group that can be substituted on the naphthalene ring, and L
represents an integer from O to 3, R3 represents a monovalent organic group, and X represents a hydrogen atom or a group capable of being separated by a coupling reaction with an oxidized aromatic primary amine developer. However, R4 and R5 may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group, and R6 represents an aliphatic group, an aromatic group or a heterocyclic group.

When t is plural, R2 may be the same or different, or may be bonded to each other to form a ring. R2 and R3, or R3 and X may be bonded to each other to form a ring.

Further, R1, R2, R3, or X may each form a λ-mer or a multimer of more than λ-mer which is bonded to each other via a divalent or divalent or more-valent group.

Here, the aliphatic group is i [chained pentabranched or cyclic,
Indicates an alkyl group, alkenyl group or alkynyl group.
It may be either substituted or unsubstituted. The aromatic group refers to a substituted or unsubstituted aryl group, and may be a condensed ring. The term "heterocycle" refers to a substituted or unsubstituted single PJ or fused ring heterocyclic group.

The substituents in general formula [I] will be described in detail below.

R1 is -CONR4R5--NHCOR, --NHCO
OR6--NH8O2Ra-NHCONR4Rs- or -NH8O2NR4R5. R4, and R5 and R6 are carbon number / - aliphatic group of JO - carbon number 6
Examples thereof include an aromatic group having ~30 carbon atoms and a heterocyclic group having ~30 carbon atoms.

R2 contains a group C atom which can be substituted on the naphthalene ring. The same applies hereinafter). 1 representative example and [7] halogen atom, hydroxy group, amino group, carboxy group, sulfonic acid group-cyan group, aromatic group, heterocyclic group, carbonamide group, sulfonamide group-carbamoyl group, Threfamoyl group, ureido group, acyl group.

Examples include acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl a, aromatic sulfonyl group, sulfamoylamino group, nitro group, imide group, etc. , the number of carbon atoms contained in R2 is 0 to 30. When t=x, an example of cyclic R2 is a dioxymethylene group.

R3 represents a monovalent organic group, preferably represented by the following general formula [''In.

General formula CI[] R7CY)m- Here, Y represents NH,, Co or so2, and 1m
represents zero or /, and R8 is a hydrogen atom.

Aliphatic group with carbon number/~30, aromatic group with carbon number t~3Q, heterocyclic group with carbon number 2~30 --OR8゜-P 0-(
-ORIO12, -PQ+R1(1)2- or -8O
20R1, where R8, R9 and RIO are the same as defined above for R4, R5 and R7, respectively.

may be bonded to form a nitrogen-containing heterocycle (morpholine y1-piperidine ring, pyrrolidine ring, etc.).

X represents a hydrogen atom or a coupling-off group (including a leaving atom; the same applies hereinafter). A typical example of a coupling-off group is a halogen atom.

-0R11, -8R11--OCRHl-NHCORl
l-Aromatic azo group with t to 3Q carbon atoms, heterocyclic group with carbon number/~3° and connected to the coupling active position of the coupler with a nitrogen atom (succinimide group, phthalimide group, hydantoinyl group, pyrazolyl group) , copenzotriazolyl group, etc.). Here, R11 represents an aliphatic group having 3 to 3 carbon atoms, an aromatic group having t to 30 carbon atoms, or a heterocyclic group having 30 carbon atoms.

In the present invention, the aliphatic group may be saturated or unsaturated, substituted or unsubstituted, linear, branched, or cyclic,
Typical examples include methyl group, ethyl group, butyl group, cyclohexyl group, allyl group-propargyl group, methoxyethyl group, n-decyl group, n-dodecyl group, n-hexadecyl group, trifluoromethyl group, heptafluoro Propyl group, dodecyloxypropyl group - 29 μm dite
rt-amylphenoxypropyl group, co, French-te
Includes rt-amylphenoxybutyl group and the like.

Also, it may be aromatic basic substituted or unsubstituted.
Typical examples are - phenyl group, tolyl group, cochtradecyloxyphenyl group - interfluorophenyl group,
Cochlorophenyl group, cyanophenyl group, μ
m-hydroxyphenyl group, etc. are included.

The X1 group may also be substituted or unsubstituted, and typical examples include a 2-pyridyl group-≠-pyridyl group and a 2-furyl group-≠-chenyl group.

Includes quinolinyl group, etc.

Examples of preferable substituents in the present invention are explained below.
1 is preferably -CONR4R, and one specific example is a carbamoyl group, an ethylcarbamoyl group, a morpholinocarbonyl group, a dodecylcarbamoyl group, a hexadecylcarbamoyl group, a decyloxypropyl group, a dodecyloxypropyl group, -co, ≠-ditert- Examples include amylphenoxypropyl group and 1.2°hiro-di-tert-amylphenoxybutyl group.

Regarding R2, tVc, t=o, that is, unsubstituted is most preferable.Next, R2 is a halogen atom, an aliphatic group -
Carbonamide groups, sulfonamide groups, and the like are acceptable substituents.

A preferable R3 is one in which m is zero in the general formula [■], and R3 is
-COR8 (formyl group, acetyl group, trifluoroacetyl group - chloroacetyl group, benzoyl group, pentafluorobenzoyl group, p-chlorobenzoyl group, etc.) 1. -COORI as 7;

C methoxycarbonyl group, ethoxycarbonyl group.

Phthoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group - phenoxycarbonyl group ft) -So2R10 (methanesulfonyl group,
Ethanesulfonyl group, phthanesulfonyl group, hexatecanesulfonyl group, benzenesulfonyl M,) luenesulfonyl group, p-chlorobenzenesulfonyl group, etc. L -
CONR8R9 (N.

N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group-N,N-dibutylcarbamoyl group, morpholinocarbonyl group, Pi is lysinocarbonyl group-μmdianophenylcarbonyl group, J.

≠-dichlorophenylcarbamoyl group + Hiro-methanesulfonylphenylcarbamoyl group)--3O2NR8
R9 (N, N-dimethylsulfamoyl group, N, N-diethylsulfamoyl group, N.

N-dipropylsulfamoyl group, etc.).

Particularly preferred R3s are -COOR1o, -COR8 and -
8O2R1o, and among these, -000R1o is more preferable.

X is preferably a hydrogen atom, a chlorine atom, an aliphatic oxy group C
For example, cohydroxyethoxy group, 2-chloroethoxy group, carboxymethyloxy group.

/-carboxyethoxy group, 2-methanesulfonylethoxy group, 3-carboxypropyloxy group.

Comethoxyethoxycarbamoylmethyloxy group, /
-carboxytridecyl group, co(/-carboxytridecylthio)ethyloxy group -cocarboxymethylthioethyloxy group -λ-methanesulfonamidoethyloxy group, etc.], aromatic oxy group [e.g. μm acetamidophenoxy group -2-acetamido Phenoxy group, ≠-(
j-carboxypropanamide) phenoxy group, etc.] and carbamoyloxy groups (eg, ethylcarbamoyloxy group, phenylcarbamoyloxy group, etc.).

The coupler represented by the general formula [I] has substituents R1, R2
, R3 or X may form a λ-mer or a multimer of more than λ-mer, each of which is bonded to each other via a divalent or divalent or more-valent group.

In this case, the number of carbon atoms in each substituent group may be outside the range indicated above.

When the coupler represented by the general formula [I] forms a multimer, a typical example is a homopolymer or a copolymer of an addition-polymerizable ethylene mechanically saturated compound (f cyan color-forming monomer) having a cyan dye-forming coupler residue. In this case - the multimer contains repeating units of the general formula [■] and of the general formula (III)
The cyan color-forming repeating unit represented by may be contained in a multimer or more, and may be a copolymer containing a non-color-forming ethylene-like monomer or two or more types as one copolymer component. .

General formula [■] In the formula, R represents a hydrogen atom, an alkyl group having -4 carbon atoms, or a chlorine atom, and -CONH-.

-COO- or a substituted or unsubstituted phenylene group, and B represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group.

L is -CONH---NHCONH-, -NHCOO-
1-NHCO---OCONH-1-NH-, -Coo
−.

-0CO-1-Co-, -0---802.

-NH8O2- or -8O2NH-. a.

b and c represent O or /. Q represents a cyan coupler residue in which a hydrogen atom other than the hydrogen atom of the 7-position hydroxyl group is removed from the compound represented by the general formula [I].

As the multimer, a copolymer of a cyan color-forming monomer that provides a coupler unit of the general formula [■] and a non-color-forming ethylene-like monomer shown below is preferred.

Non-chromogenic ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine derivatives include monoacrylic acid,
α-chloroacrylic acid, α-alkylacrylic acid (e.g. methacrylic acid, etc.) Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-
Butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 1so-butyl acrylate, coethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate , ethyl methacrylate, n-butyl methacrylate and β
-hydroxy methacrylate), vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile-aromatic vinyl compounds (e.g. styrene and its derivatives, e.g. vinyltoluene, divinyl hazene, vinyl acetophenone and sulfostyrene), itaconic acid-citraconic acid-crotonic acid, vinylidene chloride,
Examples include vinyl alkyl ether (911 is vinyl ethyl ether), maleic acid ester, N-vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and -guvinylpyridine.

Particularly preferred are acrylic esters, methacrylic esters, and mannic esters. One or more of the non-color-forming ethylene-like monomers used here can also be used together. For example, methyl acrylate and butyl acrylate, butyl acrylate and styrene, butyl methacrylate and methacrylic acid, methyl acrylate and diacetone acrylamide, etc. can be used.

As is well known in the polymer coupler art, the general formula CIII
) The ethylenically unsaturated monomer to be copolymerized with the vinyl monomer corresponding to For example, it can be selected so that its compatibility with gelatin, its flexibility, thermal stability, etc. are favorably influenced.

Original F! Cyan polymer coupler used in AK A lipophilic polymer coupler obtained by polymerizing a vinyl monomer to give a coupler unit represented by the above general formula CIII) is dissolved in an organic solvent. It may be made by emulsifying and dispersing it in the form of latex in an aqueous gelatin solution, or it may be made directly by emulsion polymerization.

A method of emulsifying and dispersing a lipophilic polymer coupler in an aqueous gelatin solution in the form of latex is described in US Patent No. 3. ≠
! /, in U.S. Pat. No. 20, and emulsion polymerization in U.S. Pat.
The method described in Oro, Co//No. 3, 370, P12 can be used.

The non-color-forming and diffusion-resistant carmenic acids used in the present invention are represented by the following general formula [■].

General formula [■] (Itiz -coo)nM'' R12 represents a substituent that imparts diffusion resistance to the compound of general formula [IV'), 1Mn+ represents a hydrogen ion-metal ion or ammonium ion, and n/ ~Hiro represents an integer.

The group represented by R12 that imparts diffusion resistance to the compound of general formula [■] has a carbon number from r to 32, preferably from / to 32, and has a linear or branched alkyl group (for example, methyl group, ethyl group, n-propyl group, n-butyl group,
1so-butyl group, n-pentyl group-n-heptyl group,
n-nonylM-n-undecyl group, n-)I7decyl group, etc.), alkenyl groups (e.g. allyl group, decenyl group, dodecenyl group).

oleyl group, etc.), cycloalkyl group (e.g., cyclopropyl group, cyclointyl group, cyclohexyl group, norbornyl group, etc.), alkynyl group (e.g., pro, e-ergyl group, etc.), aralkyl group (e.g., benzyl group-7enethyl group, etc.), A cycloalkenyl group (for example, cyclo is a nthenyl group, a cyclohexenyl group, etc.), an aryl group (for example, a phenyl group, an α-naphthyl group, a β-naphthyl group, etc.) or a heterocyclic group C, i.e., a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom. Make at least one of the atoms a constituent element of the ring! to 7-membered monocyclic or condensed ring heterocyclic group 1, such as copyridyl group, ≠-pyridyl group 1.2-
Quinolyl group - Caufuryl group.

Cochenyl group (1 μm pyrazolyl group -≠-imidazolyl group, etc.), these are substituted so that the total number of carbon atoms is in the range of r to tio, and the number of substituents may be 7 or more. (However, the number of carbon atoms in these groups!
The above items may not be replaced. ) Examples of substituents for these groups include halogen atoms (e.g. fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc.), nitro groups,
Cyano group - hydroxy group, carboxy group, sulfo group, mercapto group, alkoxy group, such as methoxy group.

ethoxy group, dodecyloxy group, etc.), aryloxy group (e.g. phenoxy group - 2-tert-intylphenoxy group, J-tert-butyl-μm hydroxyphenoxy group, 3-tert-decylphenoxy group - cochlorophenol group) Hiro-tert-pentylphenoxy group, cocyanophenoxy group, ≠-1ert-octylphenoxy group, ≠-dodecyloxyphenoxy group, etc.), alkylthio group (e.g. methylthio group, ethylthio group, dodecylthio group, etc.), arylthio group C For example, phenylthio group, Hiro-dodecyl phenylthio group, l-octyloxyphenylthio group, etc.), alkylsulfonyl group (methylsulfonyl group, benzylsulfonyl group, dodecylsulfonyl group, etc.), arylsulfonyl group, group, p-)lylsulfonyl group (1 μm dotecylphenylsulfonyl group, v-dodecyloxyphenylsulfonyl group, etc.), carbonamide group C (e.g., acetamide group-benzamide group, N-phenylacetamide group, tetradecaneamide group, etc.)-sulfonamide groups (e.g. methylsulfonamide group, phenylsulfonamide group).

p-)lylsulfonamide group, hexadecylsulfonamide group, etc.), amino group C, for example, amine group.

dimethyl group, pyrrolidyl group, Pi is lysyl group, dodecylamino group-anilino group, etc.), carbamoyl group (eg, carbamoyl group, N,N-dimethylcarbamoyl group, N-dodecylcarbamoyl group, etc.).

Alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group-dodecyloxycarbonyl group, etc.).

Aryloxycarbonyl group (e.g., phenoxycarbonyl group, p-tert-i tylphenoxycarbonyl group, etc.), acyloxy group (e.g., acetoxy group, etc.),
Sulfamoyl fi (e.g., tif sulfamoyl group, dimethylsulfamoyl group, dimethylcarbamoyl group, etc.)
, acyl group (e.g., acetyl group, benzoyl group, etc.) - imide group (e.g., succinimide group, etc.), ureido group (e.g., 3,3-dimethylureido group, etc.), alkoxycarbonylamino group (e.g., ethoxycarbonylamino group, etc.) , aryl group (e.g. phenyl group -p-)1l group, p
-methoxyphenyl group -α-naphthyl group.

β-naphthyl group, etc.) and heterocyclic groups (e.g. /-imidazolyl group, /-pyrazolyl group, copyridyl group, 4cm pyridyl group, coquinolyl group-cofuryl group, cochenyl group, /-benzotriazolyl group, phthalimide group, etc.)
etc.

When R12 is an aryl group, a heterocyclic group or an aralkyl group, substituents for these groups include, in addition to the above substituents, an alkyl group (for example, methyl group - ethyl group + 1so-propyl group - tert-butyl group - tert- is a methyl group-tert-hexyl group-/, /, j.

3-tetramethylbutyl group, etc.), alkenyl groups (e.g., allyl group, hexenyl group, oleyl group, etc.).

Examples include alkynyl groups (e.g., propargyl group, etc.) and cycloalkyl groups (e.g., cyclopropyl group, cyclo-ethyl group, cyclohexyl group, etc.).

Mn+ is an ion of Group 1 of the periodic table (for example, H+-Na
, Ni-Cs, etc.), group II ions (such as Mg
"-Ca"-Ba etc.), Group 1 ions C such as p c2+, p e3+ -Co2+, Co",
(Ni, etc.), and ammonium, but preferably ions of Group 1, Group 2, and ammonium ions of the periodic table. Particularly preferred are H+, Na+, K+- and NH4+, and most preferred is H+.

Here R□3. R14, R15, R16 are hydrogen atoms -
Alkyl groups (e.g. methyl group, ethyl group + 1-butyl group, etc.), substituted alkyl groups, aralkyl groups (e.g. benzyl group, phenethyl group, etc.), converted aralkyl groups, aryl groups (e.g. phenyl group, naphthyl group, etc.)
and represents a lightning group, R13 to R16i
The number of carbon atoms in and does not include O and may form a ring between R13 and R16, and may be the same or different in size.

Examples of substituents for alkyl groups, aralkyl groups, and aryl groups include monotro group, hydroxyl group, cyan group-sulfo group, alkoxy group (e.g., methoxy group)-aryloxy group (e.g., phenoxy group), and acyloxy group (e.g., acetoxy group). group), carzenamide group (e.g. acetamide group), sulfonamide group (e.g. methylsulfonamide group).

Sulfasoyl group (e.g. methylsulfamoyl group)
, a halogen atom (eg, fluorine-chlorine-bromine), a carboxy group, a carbamoyl group (eg, methylcarbamoyl group, etc.), an alkoxycarbonyl group (eg, methoxycarbonyl group, etc.).

Examples include sulfonyl groups (eg, methylsulfonyl groups). When there are two or more of these substituents, they may be the same or different.

Next, among the compounds represented by the general formula [I].

Preferred specific examples will be shown, but the invention is not limited thereto.

CF30ONH H3CNH) i3s (to J2 H α F (I-71 C3F7CONHα rr-r> H (I-//”1 (knee/co) OH (iso)C4HgOCONH (I-/7) 0OH (knee 0) t OH (I-/ 7 ) (i-/1) OH CH3SO2NH0CH2CH20H (I-/ri) (nee 201 (I-2/) 12H25 C1zH2s(n) (I-2≠) Sign 0OH (1-2z) rI- 26) (Knee Core) H (I-J/1 (I-J Ko) (1-″” OH (Knee 3≠) (I-3j1 (I-jj) (Knee 37) (Knee 31) x:y= rO: 20 (mole ratio) (I-32) (Nie San〇) (Nie pzl OH C knee ≠ 1) (Nee μ3) CF3SO2NH0 H2 (I-μhiro) (l-4tt) (I-Hiro7) x :yx70:J0 (I-at) A I-4-Otsu La-1) The coupler represented by the general formula CII is
No. 71, same A/-/≠! ! ! No. 7 and same j/-/! 3
It is synthesized by the method described in No. 6≠O.

Preferred specific examples of the compounds represented by the general formula [■] will be shown below, but the invention is not limited thereto.

(t)C5H1l (t)C5H1l (t)C6H13 (A-μ) −+ C17H35COONH4 (A-11 1 person-t) α (A-7) (A-r) C1sH31COOH (A-//) (A-/ko) C18H35CH-COOH ■ (A-/≠) HssClg-CH-COOH CH2-C00H (A-/!'1 (n)H25C12-CH-COOH CH2-C00H C5H11(t) 12H25 (A-/Pl (A-20) A-z71 (t)CsH.

N (k-Kohiro) (A-Jj) (人-2j) (A-27) (t)C5H11 (A-Kor) (A-Kota) (t)CsHly (A-J/) (A- 32) (A-731 (A-3μ) 1 person-Jj) OOH The cyan coupler of the present invention is added to the same layer as the carboxylic acids of the present invention, but the amount of the cyan coupler added is 0.
0/~/97m2, preferably 0°0j~0.
! f7m2, more preferably O17~0.3f/m2
It is. The carboxylic acids of the present invention are contained in the same layer in a weight ratio of 0.0/~i to the cyan coupler of the present invention.
oo times, preferably 0.101 to 20 times, more preferably 0.7 to 1 times.

The cyan coupler of the present invention and the carboxylic acid of the present invention may be used in any layer in the light-sensitive material as long as they are used in the same layer, but preferably in the red-sensitive silver halide emulsion layer or its adjacent layer. is a red-sensitive emulsion layer.

The cyan coupler of the present invention can be dispersed and mixed with the carboxylic acids of the present invention alone or in combination with one or more thereof, and can also be used in combination with a conventionally known high-boiling organic solvent as described below.

The preferred silver halide contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention is silver iodobromide-silver iodochloride or silver iodochlorobromide containing about 30 moles or less of silver iodide. Particularly preferred is about λ mol to about ko! It is silver iodobromide containing up to a mole of silver iodide.

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

The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of about io microns, and may be a polydisperse emulsion or a monodisperse emulsion. Silver Fide photographic emulsions - e.g. Research Disclosure (RD).

＆/76 Ko 3 (/ri 7 December 2013), here~23 pages, 1
．． Emulsion preparation
onand types)' and same 1611
7/l (/7/17), t4cr page, "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimle et Phy
siquePhotographique Paul
Montel, / 5'≦7), Duffin, "
'Photographic Emulsion Chemistry', published by Focal Press (G, F, Du
ffin, PhotographicEmulsiOn
Chemistry (Focal Press.

/ri66), “Production and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelikma
Net al, Making and Ccatin
gPhotographic Emulsion, Fo
It can be prepared using the round method described in CalPress, /Pj4t), etc.

U.S. Patent No. 3. ! 7μ, 6ko r issue, same number 3.6! ! ,3
2μ and British Patent No. 1. Monodisperse emulsions described in ≠73, 7≠r and the like are also preferred.

Tabular grains having an asquid ratio of about 3 or more can also be used in the present invention. Tabular grains are.

Gutoff 7M, 7 Otographic Science and Engineering (Gutoff.

Photographic 5science an
dEngineering I-Volume 144, 24Lr
A7217 pages (17th layer year); US Patent No. ≠, Ko 34c
, Koichi No., Same Da, ≠/Hiroshi, No. 310, Dohiro, ≠33゜oar No., Same Gu, Gu JP, J-2θ and British Patent No. Ko, // Ko, l! It can be easily prepared by the method described in No. 7, etc.

The crystal structure may be --like, the inside and outside may have different halogen compositions, and the crystal structure may be a single layer structure. Furthermore, silver halides having different compositions may be bonded by epitaxial bonding, or compounds other than silver halide such as silver rhodan or lead oxide may be bonded.

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

The silver halide emulsion used is one that has been subjected to physical ripening, chemical ripening and spectral sensitization. Additives used in such products are subject to Research Disclosure A/7.
j≠3 and MU/17/jK, and the relevant parts are summarized in Table K below.

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

/Chemical sensitizers, page 23 - Sensitivity enhancers Same as above 3 Spectral sensitizers, 23~. ! /Page 7 Page 6jr right column ~ Super sensitizer Bu4'? Right column of page≠ Brightener
Ko≠page! Antifoggant - Guru 2! Page tμ right side of page and stabilizer B Light absorber, fuco Page J-27 6j Page 2 right column ~
Ilter dye page 410 left column ultraviolet absorber 7 stain inhibitor page 21 right f4 page 410 left to right column l dye image stabilizer page 21
Plasticizer, lubricant Core page 2 to O page Right Kiri lko
Coating aids Table 1 - Page 27 Same as above Surface activator 13 Static prevention Core page Same as above Agent Various color couplers can be used in the present invention, and specific examples thereof can be found in the above-mentioned Research Disclosure (
RD) Black/71. ≠3, ■-c-G and is described in the following patent.

As a yellow coupler, for example, U.S. Patent No. 3. Ri3! , No. 10, Hiroshi No. 02, No. 62Q, No. ≠
, 3ko1,0=≠ No., same No.≠, ≠O/, 7jko No., Special Publication Showjl-1073F, British Patent No. 1. Hiro, 2j, 0λO
No. 1. Preferred are those described in H.76.760 and the like.

As the magenta coupler, terpyrazolone-based and pyrazoloazole-based compounds are preferred, and U.S. Pat.
10, 6/ri issue, same No. 1, 3 ri l.

No. 227, European Patent No. 73,636, U.S. Patent No. j
, 04. / , Hiroshi No. 32, same No. 3,721,067,
Research Disclosure & λ≠220 (/9II
≠June 2013), JP-A-Sho AO-3jjtλ, Research Disclosure A2 Hiro-30 (15) J'j June 2013)
, Japanese Patent Publication No. 36-36-2, US Patent No. 00.
No. 630, same No. ≠, Tahiro Q, 6! Particularly preferred are those described in Hiroshi et al.

Cyan couplers that can be used in combination with the cyan coupler of the present invention include phenolic and naphthol couplers, and U.S. Pat.
A, J Riwo issue, same number ≠, 221.233, same number 1t,
No. 294,200, No. ko, jAri, No. 2, No. 2
, 10/, No. 171, No. 2,77, /Jλ No., No. ryr, No. 124, No. J, No. 772.002,
Same No. J, 7jr, No. 307, Same No. Hiroshi, JJ4t, 0
// issue, Hiroshi No. 327,773, West German Patent Publication No. 3
．． 3 Kota, 7 Kota No. 1, European Patent No. 12/,! ttA,
U.S. Patent No. J, 1llfit, t22, ≠, 33
3. ? ! Puri issue, same issue≠, Hiro! l, Evening No. 2, Same No. 1I
Those described in tl≠27,767, etc. are preferred.

Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure i%/76μ3 ■-G section, U.S. Patent No. μ,/lJ, t7.0, Special Publication Shoyo 7-324L/3, U.S. Patent No. V.

Preference is given to those described in oohiro, Takota No., oohiro, i3r, Kota No. 1, British Patent No. 1,7≠t, 361.

Couplers whose coloring dyes have appropriate diffusivity include U.S. Pat. /2ta,! No. 70, European Patent No. 26. ri No. 70, West German Patent (Publication) No. 3, 23≠,! The one described in No. 33 is preferred.

A typical example of a polymerized subpigment-forming puller is disclosed in U.S. Patent No. 3. μri/, 1rko O issue, same Daihiro, orO, co//
No. 367.212, British Patent No. 2,102
, No. 173, etc.

Couplers that release all photographically useful residues upon coupling can also be preferably used in the present invention. The DIR coupler that releases the development inhibitor is the above-mentioned RD/76 Hiro 3.1.
Patent listed in ~1, JP-A-Sho Tough/Yu/Ri≠Hiroshi,
Same Tahu/Yu≠23≠, Same t O-/llll-217
1, U.S. Patent Nos. 2, 2 and 6 are preferred.

As a coupler that releases all of the image-forming nucleating agent or development accelerator during development, British Patent No. 2. o5P7.1140
No. 2, /J/, No. 111, JP-A-1972-/!
7631. same! ? -/70rllO is preferred.

Other couplers that can be used in the light-sensitive material of the present invention include competitive couplers described in U.S. Pat. , Hiro 72
No., same No.≠,! 31. J23, Hiroshi, 3io, ti
Multi-equivalent coupler described in No. e etc., JP-A-Shoto-irry
DIR redox compound releasing couplers described in ro et al.
Examples include couplers that emit a color 'X which is recolored after separation, as described in European Patent No. 773.30 CoA.

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

Examples of high boiling point organic solvents used in the oil-in-water dispersion method are described in US Pat.

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

jAJ No., West German Percent Ala (OLS) If, re/
.

No. 27≠ and No. 2 of the same. rlIi, No. 230, etc.

Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/7A≠3, page 21 and same, ya 117/6-6
≠ written in the right column of page 7 to t≠ left column of page r.

The color photographic light-sensitive material according to the present invention includes the above-mentioned RD% M/76 Ko 3, pages 2r to λ, and 6/17/L of the same.
The materials are described in the left column to the right column and can be developed by a conventional method.

The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, bleach-fixing or fixing treatment.

In the washing process, it is common to use countercurrent washing in tanks of λ class or higher to conserve water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A-57-4 Yuhiro No. 3 instead of the water washing step.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color par, color positive film, and color reversal paper. The present invention can also be applied to black-and-white light-sensitive materials using a mixture of three color couplers as described in Research Disclosure 17123 (published July 1999).

〔Example〕

The present invention will be described in detail below with reference to Examples, but the manner in which the present invention may be carried out is not limited.

Example-1 On a cellulose nine triacetate film support with a lower slope,
A multilayer color photosensitive material 10/f was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) What is the number corresponding to each component? / m 2 unit indicates the total coating amount, and for silver halogenide, it indicates the silver equivalent t'. However, for sensitizing dyes and couplers, the amount coated per mole of silver saponide in the same layer is shown in moles.

(Sample 101) 1st layer; antihalation layer black colloidal silver ・・・・・・・・・ Silver 0, / a' gelatin
/, μOth λ layer; middle layer, ! -G-t-pentadecylhydroquinone ・・・・・・・・・・・・
0. l? C-／・・・・・・・・・・・・
・0,07C-J・・・・・・
・・・・・・ 0.02U-10,01 U-2・・・・・・・・・ 0.0IHB
S-／・・・・・・・・・・・・ 0
,10HBS-λ ・・・・・・・・・・・・
0. O Cogelatin /
, 017 3rd layer; 1st red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide A molar ratio, average grain size o, rμ) ...... Silver 1.00 Sensitizing dye ■ ...・・・・・・・・・6. ri×l
0-5 sensitizing dye■ ・・・・・・・・・・・・t
,rxio 'sensitizing dye■ ・・・・・・・・・
...3. /×10' Sensitizing dye■...
・・・・・・・・・≠、0×1O-5C-co
・・・・・・・・・・・・ 0,2
Evening OHB S-t・・・・・・・・・
...0. l0C-IO・・・・・・
・・・・・・ 0.020 gelatin
・・・・・・・・・・・・ /, 20th layer; 2nd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide molar ratio, average grain size o, rri μ)... Silver 1. /! Sensitized color sensitization ・・・・・・・・・・・・! , /×10
'Sensitizing dye■ ・・・・・・・・・・・・／、
Hiro X/I! 7-5 Sensitizing dye ■・・・・・・・・・
...2.3x10 sensitizing dye■ ...
...J, O x 1O-5C-2...
... o, ox.

C-J・・・・・・・・・・・・
・ o, oorC-10・・・・・・・・・
・・ 0.00≠HBS−/ ・・・・・
・・・・・・・・・ 0, JO gelatin ・
・・・・・・・・・・・・ 1. 3rd red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 molar ratio, average grain size/, rμ) ・・・・・・ Silver/, RiO sensitizing dye ■ ・・・・・・・・・・・・j, Hiroshi X1
0' Sensitizing dye■ ・・・・・・・・・・・・
/, lt×10-5 sensitizing dye■ ・・・・・・・
・・・・・・ko, ≠X10' sensitizing dye■ ・・
・・・・・・・・・・・・1. /X1O-5C-j
・・・・・・・・・・・・ o
, oi λC−J ・・・・・・
・・・・・・ 0,003C-Hiroshi
・・・・・・・・・・・・ 0.
321-IBs-/
0.32 Gelatin ・・・・・・・・・
・・・ l, 62 4th layer; middle layer gelatin ・・・・・・・・・・・・
/ , 06 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 molar ratio, average grain size o, rμ) ・・・・・・ Silver 0.3 sensitizing dye ■ ・・・・・・・・・・・3.0X1
0 5 Sensitizing dye ■ ・・・・・・・・・・・・／
, 0x10' sensitizing dye■ ・・・・・・・・・
...3. ton/Q-4C-bu
・・・・・・・・・・・・ 0. /10U-/
・・・・・・・・・・・・
O, θ 10C-7・・・・・・・・・・・・
O, O≠kocr...
・・・・・・・・・ 0,02! H8B-/
・・・・・・・・・・・・ 0.
20 Gelatin ・・・・・・・・・・・・
0.70 rth layer; 2nd green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide molar ratio, average grain size 0.1 jμ)... Silver 0.7! Sensitizing dye■ ・・・・・・・・・・・・Co, 1xio-
5 Sensitizing dye■ ・・・・・・・・・・・・7.0
x10-5 sensitizing dye ■・・・・・・・・・・・・
・ko, tx10'shi-6・・・・・・・・・・・・
0,03 taCt...
・・・・・・・・・ 0.00≠C-/
・・・・・・・・・・・・ 0,00
2C-7・・・・・・・・・・・・ o, oir)
JSB-／・・・・・・・・・・・・
o, ir gelatin...fist...0...
0.10 2nd layer; 3rd green-sensitive emulsion layer Silver iodobromide (iodide@lO molar average grain size 1.μ) ・・・・・・ Silver/, l'0
Sensitizing dye■ ・・・・・・・・・・・・3. ! ×
10 5 Sensitizing dye■ ・・・・・・・・・・・・
r, ox1o-5 sensitizing dye ■・・・・・・・・・
...J, 0X10 'C-// ・-
------Old-o, ot2C-/...
...Mountain... o, ooi) IBS-ko
・・・・・・Old-0, Otase gelatin ・・・
...... /, 7μ 1st O layer; yellow filter layer yellow colloidal silver ... river ... silver o,
o Octopus, Tarji t- Tadecylhydroquinone ・・・・・・・・・・・・ 0
．． 0! Gelatin ・・・・・・・・・・・・
0. Tata 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 molt, average grain size o, tμ) ・・・・・・ Silver 0.2 sensitizing dye■ ・・・・・・・・・・・・・・・3. jX
10'C-2... old and old... O, core cmr
...Kawa・dan・O0θQriHBS
-/ ・・・・・・・・・・・・ 0.
21 Gelatin ・・・・・・・・・・・・
/, Cor 1st layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mole, average grain size /, 0 μ) ... Silver o, xi-
r sensitizing dye■ ・・・・・・・・・・・・・・・・・・1
X10 'C-ta...
・・・ OoOri rHBS-/ ・・・・
・・・・・・・・・ 0. OJ gelatin
O1≠6 73rd layer; Jxfr sensitized emulsion layer Silver iodobromide emulsion (silver iodide lO mole, average grain size i, rμ) ...... Silver 0.77 sensitized color scheme ■ ...・・・・・・・・・ko,,2X
/θ-4C-2・・・・・・・・・・・・ 0.0
341-IBS-/・・・・・・・・・・・・
・ 0.07 gelatin ・・・・・・・
...0.62 1st layer; 1st protective layer silver iodobromide (silver iodide 1 molti, average grain size 0.07μ) ... Silver O5ri U-/
・・・・・・・・・・・・ 0. /
/U-co ……………… 0. /
Butyl 7p-hydroxybenzoate 0.0/2HBS
-/ ・・・・・・・・・・・・ o,
y.

Gelatin ・・・・・・・・・・・・
/, O 1st j layer; Co-retention layer polymethyl methacrylate particles (diameter approx. /, ! μm) ・φ・・・・・・・・・ 0 ,! ≠S
-/ ・・・・・・・・・・・・
o, 1zS-2・・・・・・・・・・・・ o,
i.

Gelatin ・・・・・・・・・・・・
0.72 In addition to the above composition, each layer contains a gelatin hardening agent H-
7 and surfactant are added.

(Sample 102 to 1ot) 0.0% to the third layer of sample 10/. Oj? /7 In the same manner as sample ioi, except that 0,1017 m2 of the compounds of the present invention A-/, A-yu, A-no2, A-/6, and A-/r5 were added to FL2 and the first Hiro layer. Sample 102~1ot
2 each made a friend.

(Samples 107-72≠) The couplers of the third layer and the second layer of Samples 10/-10t were C-//, couplers of the present invention (1-3) and (1-/
Samples 10/~101.2) were replaced with equimolar amounts except for 9.
Samples 107 to 12≠ were prepared in the same manner as above.

For these samples, use light source A and set the color temperature to ≠I using a filter.
After adjusting the temperature to 00'K and applying imagewise exposure so that the maximum exposure amount is /QCMS, color development processing is performed using the following bleach-A solution at 2.yroc.

These results are shown in Table 1.

Color development λ minutes≠! seconds Bleach-A 4 minutes 30 seconds (or bleach-B) Water Wash 2 minutes 10 seconds Fixed Arrival: Kobunko O seconds Water Wash 3 minutes 1 second Stable / minute O seconds The composition of the treatment liquid used in each step was as follows.

Color developer diethylenetriaminepentaacetic acid /, 02/-hydroxyethythelene-/.

/-Diphosphonic acid, Q2 Sodium sulfite ≠, oq Potassium carbonate
30.09 Potassium Bromide
1. ≠1 potassium iodide
/, 3m9 Hydroxylamine sulfate Ko, Hirot≠-(N-ethyl-N-β-hydroxyethylamine)-11 methylaniline sulfate Hiro, evening? Add water / 01 pH / 0, 0 bleaching solution Ethylenediaminetetraacetic acid ferric ammonium salt / 00.0? Ethylenediaminetetraacetic acid disodium salt io,ot ammonium bromide /jO,0? Ammonium nitrate 10.0? add water
/, 01 pH 4,0 Foot dressing ethylenediaminetetraacetic acid disodium salt /, O1 sodium sulfite ≠, ot ammonium thiosulfate aqueous solution (70%) /7, Omi sodium bisulfite ≠, tf water added
/, olpHA, Omt stabilized formalin (≠Ochi) 2, Omt
Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10) 0.3? Adding water /, 01 Next, the bleaching during the development process was changed to the following processing solution formulation, and the development process was carried out in the same manner except for the solution. This Bleach-B solution is prepared as a forced deterioration solution as a model for the condition in which a large amount of photosensitive material is processed and becomes fatigued.

Bleach-BiH (B-/) liquid 00rnl and (B-2)/
It is a mixture of θO-.

Bleach solution composition (B-λ') Pour steel cool into (B-λ'), seal it tightly, and leave it to stand until Fe (m)-EDTA'! kFe(II)
- After carrying out EDTA, this solution is referred to as solution 't(B-2).

Density when developed with fresh Shohaku-A solution.

Table 1 shows the percentage decrease in concentration of Bleach-B solution, which is a forced fatigue solution, at an exposure dose of Oo.

From Table 1, it is clear that the samples of the present invention have high sensitivity and high contrast, and also show little decrease in density under forced deterioration conditions. In addition, carboxylic acids other than carboxylic acid A-1λ included in Yorotsu, R Publication Patent No. 7/122 are also effective, Akihiro Tokuko! It is clear that the 10 samples of the combinations included in -≠θμ No. 22 do not have these effects, and the samples //Yu~/lr and /2/~/2'l that are not included have these effects.

Example 2 The following multilayer color photosensitive material was prepared in the same manner as in Example 1.

The numbers corresponding to each component are shown using the same notation method as shown in Example 1.

(Sample 20/) 1st layer (antihalation layer) Black colloidal silver ・・・・・・・・・・・・
0.2 gelatin /, 0
C-10,ob UV-10,o3 U'V-2・・・・・・・・・・・・ O0O
HiroHBS-/ ・・・・・・・・・・・・
0.0/1-IBS-2・・・・・・・・・・
・・o, otth layer (intermediate layer) Gelatin /, 0C-J
・・・・・・・・・－・・・ 0.0
2HBS-10, / 3rd layer (first red-sensitive emulsion WI) Silver iodobromide emulsion (silver iodide λ molar ratio, average grain size O, Jμ) ・・・・・・ 0. ≠Gelatin ・・・・・・・・・・・・
0.6 Sensitizing dye I ・・・・・・・・・・・・／
, 0X10' sensitizing dye ■・・・・・・・・・
・・・3.0×10′ sensitizing dye m ・・・
・・・・・・・・・ /×1O-5C-/J
・・・・・・・・・・・・ o, ot
.

C-/3 ・・・・・・・・・・・・
0,07 TaC-/Evening
・・・・・・・・・・・・ 0.010 coupler C-j ・・・・・・・・・・・・ 0.
03) IBS-/・・・・・・・・・・・・
・・0.031-IBS-J
・・・・・・・・・・・・ 0.0/Co 1st layer (2nd red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide! molar ratio, average grain size Q, μ) ・・・・・・・ 0.7 sensitizing dye l ・・・・・・・・・・・・ /×1
0' Sensitizing dye■ ・・・・・・・・・・・・
,? X/(7' sensitizing dye■ ・・・・・・・
・・・・・・／×10'Coupler of the present invention (1-
/J)... 0.2≠C-10...
・・・・・・ 0.0 Ta coupler C-2・・・・・・
・・・・・・ 0.0μHBS-co
・・・・・・・・・・・・ o,orHBS
-3・・・・・・・・・・・・ 0th and 10th layers (3rd red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide/Q momol, average grain size 0.7μ)... ...i,.

Gelatin /, 0 sensitizing dye!・・・・・・・・・・・・／×10
'Sensitizing dye■ ・・・・・・・・・・・・
JXlo 'sensitizing dye■ ・・・・・・・・・
・・・／×IQ-5C-J ・・・・
...... o, ooz coupler of the present invention (
1-2r)・0, Oj 0HBS-J...
・・・・・・・・・・・・ 0.10HBS-ko
・・・・・・・・・・・・ 0. Ota 6th layer (middle layer) Gelatin 1.0(n)-
Sodium octadecylhydroquinone sulfonate 0. Q3HBS-/
・・・・・・・・・・・・ o, or 7th
Layer (first edge-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide emulsion, average grain size 0.3μ) - Old... 0.30 sensitizing dye ■ ・・・・・・・・・・・・・ Evening x 10
'Sensitizing dye■ ・・・・・・・・・・・・
2 x 10' gelatin
/, OC-/μ ・・・・・・・・・・・・
0,01C-/4 ・・・・・・・・・
・・・ 0.07cmr ・・・
・・・・・・・・・ o, orC-7・・・・・・
・・・・・・・ OoOri) IBS-i
・・・・・・・・・・・・ O1! Layer (
(1st f-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide t morch, average grain size Q, ri μ) ・・・・・・ O0≠sensitizing dye■ ・・・・・・・・・・・・Taxi
o 'Sensitizing dye■ ・・・・・・・・・・・・
KOX10'C-/ ≠ ・・
・・・・・・・・・・ o, i.

C-/4 ・・・・・・・・・・・・
o, orC-/ ・・・・・・
・・・・・・ 0.0/2C-7・・・・・・
・・・・・・ 0.037C-t
・・・・・・・・・・・・ 0.
03HBS-/・・・・・・・・・・・・
・ 0.2 second layer (third green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 molti, average grain size 0.7 μ) ・・・・・・ o, tr
r gelatin /, 0 sensitizing dye■ ・・・・・・・・・・・・3. riX10
'Sensitizing dye■ ・・・・・・・・・・・・／、
≠×io 'C-／≠ ・・・・・・・・・
... 0. l0C-7・・・・・・・・・・・・
・0.0IC-/・・・・・・
・・・・・・ O0Oko HBS-ko ・・
・・・・・・・・・・・・ 0,101(B S −
J ・・・・・・・・・・・・ o, o
r10th layer (yellow filter layer) Gelatin, 1.2 C-/7 ・・・・・・・・・・・・
0.03 pieces! -G-t-octylhydroquinone ・・・・・・・・・・・・
O0/HBS-10,/ 1st/layer (1f sensitive emulsion layer) Silver iodobromide emulsion (Silver iodide Hiromorchi, average grain size 0.3μ) ・・・・・・ 0. ≠Gelatin ・・・・・・・・・・・・
/, 0 sensitizing dye■ ・・・・・・・・・・・・
KO
・・ o, orHBS-2・Old...Old...
0.2 First co-layer (first f-sensitive emulsion layer) Silver iodobromide (silver iodide 10 moles, average grain size/μ) ・・・・・・ 0. Tagelatin... Old... 0.
6 Sensitizing dye V ・・・・・・・・・・・・／
×10'C-ta・・・・・・・・・
・・0,2 evening C-/!・・Dan・・Old・・ 0. Q Evening HBS-J...
... Mountain... 0.07 13th layer (1st protective layer) Gelatin ......
o, Ultraviolet absorber UV-/・・・・・・
o, i Same as above UV-2... River... 0
．． 2HBS-/ ・・・・・・・・・・・・
o,oiHB S-J
・・・・・・・・・・・・
o, oi 1st Hiro layer (λth a layer) Gelatin ・・・・・・・・・・・・
O0≠Polymethyl methacrylate particles (A diameter 1.jμ) ・・・・・・ 0.2 Hardener I-1-/ ・・・・・・・・・・・・
O0 Hiro Formaldehyde Scavenger S-/ ・・・・・・・・・・・・
0. Taformaldehyde Scavenger S-Co O, I In addition to the above-mentioned components, a gelatin hardener H-2 and a surfactant were added as coating aids to each layer.

(Sample 202, λ03) Sample 20/5th layer coupler of the present invention (I-2r) t?
(1-, zr), Oyo Uc 1-30”) TK, replaced with equimolar amount Sample 201 except for the following.
Create ko, and 203 as follows.

(Sample Koda~2/2) 0.109/m2 in the μth layer of sample Ko0/~203 and 0.0 in the first layer! ? /@2, compound of the present invention (A-t
o), (A-,2J) >Lbi(A-2!r)
were added respectively, and sample 20≠～204.207～ko0
Created by RiP Yohiko 10-272.

Multilayer color photosensitive materials that exploded in this way 20/~, 2/
2 was subjected to wedge exposure (color temperature aroo 0KvccsoCMSI), and then the following processing was performed at 31r0C using an automatic bright image method.

Color development 3 minutes! Second bleaching 7 minutes bleach-fixing 3 minutes/evening second water washing■ HiroQ second water washing■ 1 minute stable ≠0 second drying (evening 0'C) / minute second In the above processing steps, water washing ■ and ■ A countercurrent water washing method was used from to ■. Next, the composition of each treatment liquid will be described.

The supplementary light amount of each processing solution is /200rrLl for color photosensitive material 7, color development per 2, and 200m for all others including washing with water.
It was set to 1. In addition, the pre-bath brought into the washing process is a color light material/2.

(Color developer) Mother solution Replenisher diethylenetriamine /, Of /, /? Pentaacetic acid/-hydroxyethylidene! , I-diphosphonic acid, 0? 2.2? Sodium sulfite Il, Of μ, ≠1 potassium carbonate 30. Of 32.0? Potassium bromide /, ≠1 0.77 Potassium iodide /, 3m9 -Hydroxylamine sulfate 2β Lico, Ar≠-(N
-ethyl-N-β-hydroxyethylamino)-comethylaniline sulfate Hiroshi, j? Evening, O
Add water /, Ol /, 01
pH 10,010,0 (bleaching solution) Common to mother liquor and replenisher ethylenediaminetetraacetic acid ferric ammonium salt / coo,oy ethylenediaminetetraacetic acid disodium salt 10.0? Ammonium nitrate 10. Of ammonium bromide / 00.0? bleach accelerator
! ×／Q Add mole ammonia water
pH 4, J Add water /
, Ol (bleaching solution) Ethylenediaminetetraacetic acid ferric ammonium salt common to mother liquor and replenisher solution! 0.0? Ethylenediaminetetraacetic acid disodium salt or sodium sulfite /2.0? Ammonium thiosulfate water bath solution (70%) Add λti, O edition ammonia water pF (7,3 Add water
/73 (washing water) Calcium ion 32m9/1. magnesium ion 7
．． Tap water containing 3m9/l'i of kHz-type strongly acidic cation exchange resin and OH-type strongly basic anion exchange resin was completely filled and passed through nine columns, and calcium ion/,comm9/l,
Magnesium IyF70. Processed to um9/1 to nine pieces,
Sodium insialylate dichloride 20Tn9 per tel
It was added and used.

(Stabilizing solution) Common to mother solution and replenisher solution
,0rrtl polyoxyethylene-p-monononylphenyl ether 0. ! ? (Average degree of polymerization IO) Ethylenediaminetetraacetic acid di-sodium salt o, o tr
.

(113p with water)
] r,! (Drying) Drying temperature is ro 0c.

The concentration of the resulting treated strips was measured. Photographic performance is shown in Table 2.

After irradiating the above-treated strips from the support side with a fluorescent lamp Columx for 7 days, all measurements were taken again, and the increase in yellow density is shown in Table 2.

It is clear from Table 2 that the samples of the present invention have high sensitivity and little staining (increase in yellow density) due to light irradiation6.

Structure of the compound used in Example/C-/3 (t) CsHxt C-/ ≠ U -tr CH2 HBS-/) Liclesyl phosphate HBS-λ Dibutyl phthalate HBS-J) Li n-hexyl phosphate H-/
CH2=CH-SO2-CH2CONH-CH2C
H2=CH-802-CH2CONH-CH2 Sensitizing dye (CHz) asOaNa 2Hi5 2H5 ■ % Applicant Fuji Photo Film Co., Ltd. Procedural amendment 1, case description Showa t/year patent application No. -231!0
No. 2, No. 2, Title of the invention Silver halide color photographic X-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment ``Detailed description of the invention'' column 5 of the specification, Contents of the amendment The statement in the "Detailed Description of the Invention" section of the specification is amended as follows.

1) Page j, line 7 "Development" "phenomenon" and correct it.

2) It line of page j gi rank” "5th place" and correct it.

3) Page 10/line 1 rUV-/J rU-/j and correct it.

4) Toth page/co-th row “UV-λ” "U-2" and correct it.

5) No. J! page 77th line rUV-/J rU-/J and correct it.

6) @rr page line II rUV-2” "U-2" and correct it.

1. Indication of the case 1986 Patent Application No. 2315C) 2 2. Name of the invention Silver halide color photographic abrasive material 3. Person making the amendment Relationship with the case Patent application Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Name (
520) Fuji Photo Film Co., Ltd. Contact information: 2-26-30 Nishiazabu, Minato-ku, Tokyo Fuji Photo Film Co., Ltd.
Insert the following statement before the first line from the bottom of page 102 of the Tokyo Head Office Specification Example 3 Coupler (I-28) in the fifth layer of sample 210 of Example 2
Replace (I-23) with equimolar amount and further? l511
C-18 and C-1 respectively for C-9 of WJ and 12th layer
9, C-20, C-21, C-22, C-23, C-2
Samples 301 to 309 were prepared in the same manner as sample 210, except that equimolar amounts of C-4, C-25, and C-26 were substituted.

Multilayer color photosensitive materials 301 to 309 prepared in this way
was exposed and developed in the same manner as in Example 2, and then the same fluorescent lamp irradiation experiment as in Example 2 was conducted.

As a result of the experiment, Samples 301 to 309 of the present invention had high sensitivity and less occurrence of staining (increase in yellow density) due to light irradiation.

Coupler C-18, C-19 used in this example,
C-20, C-21, C-22, C-23, C-24,
The structures of C-25 and C-26 are shown below.

Example 4 Coupler C-14 in the 17th layer, 8th JVi, and 9th layer of sample 305 of Example 3 was replaced with C-27, C-28, and C, respectively.
Sample 3 except that -29 and C-30 were replaced in equal molar amounts.
Samples 401 to 404 were prepared in the same manner as 05. The multilayer color photosensitive materials 401 to 404 thus prepared were exposed and developed in the same manner as in Example 2, and then
A fluorescent lamp irradiation experiment similar to that in Example 2 was conducted.

As a result of the experiment, samples 401 to 404 of the present invention have high sensitivity and do not cause staining (increase in yellow density) due to light irradiation.
There were also few.

Coupler C-27, C-28 used in this example,
The grooves of C-29 and C-30 are shown below.

Claims (1)

[Scope of Claims] A silver halide color photographic light-sensitive material characterized by containing a naphthol-based cyan coupler represented by the following general formula [I] and a non-color-forming and diffusion-resistant carboxylic acid in the same layer. . General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the general formula [I], R_1 is -CONR_4R_
5--NHCOR_4, -NHCOOR_6, -NHS
O_2R_6-NHCONR_4R_5 or -NHS
O_2NR_4R_5, R_2 represents a group that can be substituted on the naphthalene ring, l represents an integer from 0 to 3, R_3 represents a monovalent organic group, and X represents a hydrogen atom or aromatic primary amine developer oxidation. Represents a group that can be separated by a coupling reaction with a body. However, R_4 and R_5 may be the same or different and independently represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group, and R_6 represents an aliphatic group, an aromatic group, or a heterocyclic group. When l is plural, R_2 may be the same or different, or may be bonded to each other to form a ring. R_
2 and R_3, or R_3 and X may be bonded to each other to form a ring. In addition, R_1, R_2, R_3 or
mer or more multimers may be formed.