JPS63202745A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having the excellent sharpness by incorporating a coupler which has more than a specific pKa value of a conjugate acid contd. in a colored part which cleaves by a coupling reaction with an oxidant of an aromatic primary amine developing agent, in the emulsion layer of the titled material. CONSTITUTION:The emulsion layer of the titled material contains the coupler shown by the formula wherein Cp is a coupler residual group capable of releasing -(Time)n-X-Dye group by a coupling reaction with an oxidant of an aromatic primary amine developing agent. (Time ) is a timing group, (n) is an integer of 0 or an positive integer, Dye is a dye residual group having low pKa, X is an auxochrome residual group of the dye. The pKa of the conjugate acid (H-X-Dye) to the dye residual group having low pKa of the dye is adjusted <=0.5. As the pKa of the conjugate acid (H-X-Dye) in the auxochrome residual group X of the dye is <=0.5, thereby controlling the change of the hue of the image dye. Thus, as the pKa of the conjugate acid (H-X-Dye) is controlled to <=0.5, the sharpness of the titled material is improved.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic material with excellent sharpness. (Prior art) When a silver halide color photographic material is color-developed, an oxidized aromatic-amine color developing agent and a coupler react with K to form indophenol, indoaniline, etc.
It is known that indamine, azomethine, phenoxazine, 7enazine and similar dyes are produced and color images are formed. In this method, subtractive color method is usually used for color reproduction.
A silver halide emulsion selectively sensitive to back, green, and red colors and yellow, magenta, and cyan color image-forming agents (couplers), which are complementary colors, respectively, are used. Many studies have been conducted to improve the performance of color formers (couplers) for forming image dyes, and many patents and technical documents have disclosed this. This is because the performance of the coupler used has a large impact on overall photographic performance, such as image quality performance such as sensitivity, color reproducibility, sharpness, or graininess, and color image preservation performance against heat, light, humidity, etc. This is because there is nothing else. For example, if the spectral absorption width of the dye formed by the coupling reaction between the coupler and the oxidized developing agent is broad, or if there is unnecessary side absorption, constant temperature 9 will occur, impairing color reproducibility. become. Also, unit type i
-The larger the amount of dye that can be produced from the coupler, the smaller the amount of cazoler added to the emulsion layer, which reduces the emulsion film thickness, suppresses color distortion caused by optical factors, and improves sharpness. is improved. Furthermore, it is resistant to the heat, light, and humidity of the dye produced by the coupler, as well as to the material components contained in color photographs.

[7] The higher the stability of the dye, the better the storage stability of the image dye. Furthermore, the faster the coupler undergoes a coupling reaction with the oxidized developing agent, the more efficiently development occurs and the sensitivity of the photosensitive material increases. As specific examples of couplers proposed for the purpose of improving photographic performance as described above, the following are known. Journal of the Chemical Society
al of Chemical 5ociety
) +, R-Kin (Perkin) Ig /277, 20 Hiroshi 7 pages! - A coupler has been reported in which the secondary absorption on the short wavelength side of the azomethine dye produced by the pyrazolone type coupler is reduced. U.S. Patent No. 2
μr, YTI discloses a bis-type yellow coupler for the purpose of reducing the molecular weight of the coupler required to form a certain amount of dye concentration. Additionally, U.S. Patent No.
, J//, ≠ 7 and Dohiro, 12, 3ri No. 6 propose couplers with improved color image fastness. Also,
U.S. Pat.
, Ko3! No. 1 discloses a highly color-forming coupler that is advantageous for increasing sensitivity. In recent years, there have been advances in performance in the molecular design of couplers, but this is not necessarily sufficient.In fact, due to the limitations that inevitably arise as long as conventional couplers are used, even more dramatic advances have been made. It can be said that it is now difficult to improve performance. The inevitable limitation of conventional couplers is that the coupler itself has the function of ``receiving the image information accumulated in silver halide via the oxidized developing agent, and itself becoming a chromophore component of the image dye.'' The point is that it has. For this reason, the properties of the image dye produced are determined by the molecular structure of the coupler.
This results in various molecular design contradictions. For example, even if a coupler with a high coupling rate is designed, the spectral absorption of the resulting image dye may be in an undesirable wavelength range or the secondary absorption may be large. Furthermore, even if the coupler forms a robust dye, if the coupling rate is low, and even if the coupler forms a dye with a sharp spectral absorption width and no side absorption, there are problems with the stability of the coupler. An example of this is the case. In other words, the guidelines for selecting a coupler to achieve an efficient coloring function and the guidelines for selecting a coupler to achieve a desired function as an image dye were not necessarily compatible. Under these circumstances, Tokukai Sho! Da l da! /3
1, 4/-/II1. Eye l, same otsu/-/J'tOμ7
, 4/-26! J4/-7, 61-λ/WO4c
J discloses dye-releasing couplers. The couplers disclosed in these patents are an excellent solution to the above-mentioned contradictions and also represent a new direction for photographic color formers. One of the advantages of color forming agents based on the new concept described above is that the volume of coupler required to form a certain amount of dye concentration (reduction in molecular weight) can be reduced, and furthermore, by reducing the amount of dispersion medium. This makes it possible to reduce the overall oil-soluble content.However, there is also a practical concern.That is, the hue of the cleaved dye changes after development. , especially H
There are concerns when selecting dyes that utilize alochromism (the heteroatoms of the auxochrome act as image-forming dyes in a dissociated state). For this reason, Tokukai Showa J4! −／
≠! In the IJJ issue, a method was used in which the dye was immersed in a special mordant bath after treatment, and in JP-A-4/-/140≠7, a method was adopted in which a tertiary amine or μ-class ammonium salt derivative was incorporated to fix one hue. I'm thinking about it. Although these methods are certainly effective, from a practical standpoint, there remain problems such as complicating the development process and reducing the effect of thinning the layer, that is, the effect of improving sharpness. -ing (Problems to be Solved by the Invention) Accordingly, an object of the present invention is to provide a silver 10 genide color photographic light-sensitive material having excellent sharpness. (Means for Solving the Problem) The above object of the present invention is to provide a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support. A dye having a dye moiety whose maximum absorption wavelength is shifted to the shorter wavelength side by a bond that is cleaved directly or through a timing group due to a coupling reaction with an oxidized form of In couplers that produce compounds with moieties, the p
Ka! This was achieved by a silver halide photographic light-sensitive material containing a coupler having a content of 0 or less. It has a dye moiety whose maximum absorption wavelength is shifted to the short wavelength side by a bond that is cleaved directly or through a timing group by the coupling reaction with the oxidized developing agent used in the present invention, and as a result of the reaction, the maximum absorption wavelength is shifted to the shorter wavelength side. A coupler that produces a compound or a precursor thereof having a dye moiety having a maximum absorption wavelength of is represented by the following general formula (I). Cp-(Time)-=, (-I)ye
(I) In the formula, Cp is (Time)-
Represents a coupler residue capable of releasing X-Dye. Time represents a timing group, and n represents O or a positive integer. l) ye is a dye residue with low DK, and the pKa of its conjugate acid (H-X-Dye) is 5.0 or less. X represents an auxochrome residue of the dye. When the coupler of the general formula (I) is subjected to imagewise exposure and color development in a color photographic material, it undergoes a coupling reaction with the oxidized developing agent produced in an imagewise manner to form an imagewise color image. . This color image is composed of two different molecules of dye produced from one molecule of coupler.
The dyes are dyes conventionally used in conventional color photographic materials, such as indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine, etc., which are produced by coupling with an oxidized product of an aromatic primary amine developing agent. Similar pigments,
The first dye molecule is a new dye that is simultaneously released from the coupler of the present invention during the coupling reaction, and the properties imparted to this dye increase color image density, improve hue,
It is possible to bring about great effects on color photographic materials, such as improving color image fastness, and among them, the effect on increasing color image density is great. When the concentrations are simultaneous, the couplers of the invention have 7
The molecular coupler provides approximately twice the color image density. Therefore, by increasing the color image density, it is possible to reduce the amount of silver halide or coupler used in Kaji photographic materials, and to improve sharpness by reducing the film thickness of color photographic materials. is huge. However, although the sharpness is improved by thinning the layer, it has been found that the hue of the dye in one image changes after development. Therefore, the present inventors. As a result of intensive research, it was found that if the pKa of the conjugate acid of the auxochrome, which is cleaved directly from the coupler or via a timing group, is lower than S or O, the hue of the image dye is expected to change due to K. It has become clear that this can be improved further. As a result, the object of the present invention has been achieved, and it has become possible to maximize the function of a dye-releasing coupler that shows a new direction as a color former. Furthermore, the configuration of the present invention will be described in detail. The coupler residue represented by Cp in general formula (1) may form a dye through a coupling reaction with an oxidized product of an aromatic primary amine developing agent, or may form a colorless substance. In some cases (so-called colorless coupler residues). Cp may have a diffusion-resistant group, may not have a diffusion-resistant group, or may have an alkali solubilizing group. When n≧l, the timing group represented by TIME is C
It represents a divalent or trivalent organic group that connects the coupling part of p and -X-Dye. When n=O, -X-D
ye will be directly coupled to the coupling part of Cp. Examples of the mechanism for releasing -X-Dye when TIME is present include those disclosed as photographically useful group (hereinafter abbreviated as PUG) release timing couplers. A method for releasing PUG by an intramolecular nucleophilic substitution reaction after elimination, as described in U.S. Pat. 7-/j4'JJ4C, O and J7-/rlrOJ! A method for releasing PUG by electron movement along a conjugated system after detachment, described in JP-A-7
7-46137, and the same sr-coO described in 74AOK.
How to release G, special application Shoj Turf J'μ77, same! Examples include a method of releasing PUG by cleavage of hemiacetal after detachment, as described in Section 71. The coupler of the present invention includes not only cases in which the coupler has a timing group represented by general formula (I) but also cases in which it has a trivalent timing group as shown below. For example, Tokukai Akira! As described in No. r-20P74cO, Cp and TIME also have a bond at the non-coupling site of Cp, even after the coupling reaction with the oxidized form of the developing agent and subsequent reactions. There are cases where Cp and TIME have a bond. Also, special request Akira! Tarjri No. 71, Tatata 04c37
Same issue! Tata ajjt issue, and the same ry-ta 2! to 7
As described in the above issue, cases where TIME and Dye further have a bond that is not cleaved even after the coupling reaction with the oxidized form of the developing agent and subsequent reactions are also included. In each of the above cases, Cp and Dye may further have a bond that does not cleave even after the coupling reaction with the oxidized form of the developing agent and the subsequent reaction. Alternatively, in the structure of general formula (I), such non-cleavable bonds can be formed between Cp and TIME and TIM E])
You may further have it between ye and e. Examples of the auxochrome residue represented by X include an oxygen atom, a nitrogen atom, or a heteroatom such as a sulfur atom. The dye residue represented by Dye has its maximum absorption wavelength shifted to the shorter wavelength side due to the auxochrome group being diblocked by Cpt or TIME. The most desirable dyes are those that have an appropriate hue when the auxochrome is dissociated, and the pK of the dye is 1. is preferably 5.0 or less. In the present invention. The concept of rpKaJ, that is, the reciprocal of the logarithm of the acid dissociation constant, is described in ``Acids and Bases'' by Michinori Oki, Baifukan (l.
7 years)'l! According to the concept described on pages 2o to 2o. Further, all pK values described in the present invention are values obtained by the following measurement method unless otherwise specified. The aromatic/azo compounds of the present invention having a pKa of 4.0 or less include all aromatic/azo compounds whose values obtained by the following measurement method are t, o or less. As a solvent, water/ethanol = λ//, Rirui,
Using water/tetrahydrofuran = 2/1, the target compound was prepared as follows: ■/X10-2 mol, ■/X/O-'
Adjust to three concentrations: mol, tX10-6 mol. Measurement is performed using a GT-or type automatic titrator manufactured by Mitsubishi Kasei using O0λNHCl and NaOH. ■～■3
Find the pKa value at a point, extrapolate the value at concentration O, and find pK
Let be the value of a. This method is described in detail in "Acids and Bases" above. These pigments are described, for example, in ``Light Absorption,'' by J. Fabian, H. Hartmann.
of Organic Colorants (LightAbso)
rption of Organic Co1o
rants)” (Springer Förlag (Sp
(Ringer-Verlag), but is not limited to these. Preferred dyes include hydroxy group-substituted aromatic azo dyes and hydroxy group-substituted heterocyclic aromatic azo dyes represented by the first-order general formula (I[). General formula (I[) -X-Y-N=N-Z In the formula, X represents the same meaning as defined in general formula (1), and Y represents an unsaturated bond in a conjugated relationship with the azo group. In an atom containing at least one unsaturated bond, X
Z represents an atomic group containing at least one unsaturated bond that can be conjugated with an azo group, and the total number of carbon atoms contained in Y and Z is 70 or more. In general formula (II), X is preferably an oxygen atom or a sulfur atom. In general formula (II), Y and Z are preferably aromatic groups or unsaturated heterocyclic groups. The aromatic group is preferably a substituted or unsubstituted phenyl group or naphthyl group. The unsaturated heterocyclic group is preferably a 4- to 7-membered heterocyclic group having a hetero atom selected from a nitrogen atom, a sulfur atom, or an oxygen atom, and may be a benzene-fused ring. Heterocyclic groups include, for example, pyrrole, thiophene, furan, imidazole, ' , ' * "t"J
Azole, oxazole, thiadiazole, pyridine,
indole, benzothiophene, k-benzimidazole,
Or it is a group with a ring structure such as benziosol. Y may have a substituent in addition to X and the azo group (substituents include an aliphatic group, an aromatic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acylamino group, Alkylthio groups, arylthio groups, heterocyclic groups, sulfonyl groups, halogen atoms, nitro groups, nitrone groups, cyano groups, carbamoyl groups, hydroxyl groups, sulfonamide groups, alkoxy groups, aryloxy groups, acyloxy groups, and carbamoyl groups. , an amino group, a ureido group, a sulfamoyl group, a carbamoylsulfonyl group, or a hydrazyl group.These groups may be further substituted.Z is a substituted aromatic group or a substituted unsaturated heterocyclic group When it represents, the substituents include those listed above for Y. When Y and Z contain an aliphatic group moiety as a substituent,
It may be substituted or unsubstituted, saturated or unsaturated, linear or branched, chained or cyclic, and has 1 to 3 carbon atoms, preferably /-20 carbon atoms. When Y and Z contain an aromatic group moiety as a substituent,
It has 6 to 10 carbon atoms, preferably a substituted or unsubstituted phenyl group. Among the groups represented by general formula (n), preferred examples are as follows. (D-/) BI B2 B3 84 I B2 (D-3 (D-Hirono83 B4 (D-!) 3 B4 (D-6) In the formula, X' represents an oxygen atom or a sulfur atom, and W
represents a substituent selected from those listed as substituents for Y and Z in general formula (II), and n is O1
/ or ko, q represents 017%2 or 3, and r represents 0 or an integer from / to hi. Bl, B2
, B3 and B4 each represent a hydrogen atom or a substituent as explained for W, or B1 and B2,
B3 and B4 may be connected to represent a benzene condensed ring. When representing a benzene condensed ring, that portion may be substituted with a substituent represented by W. In the formula, when n, Q or r represents a number of 4 or more, W
may be the same or different. vl represents an oxygen atom, a sulfur atom, or an imino group which may have a substituent. v2 represents an aliphatic hydrocarbon residue, an aryl group, and a heterocyclic residue. When v2 represents an aliphatic hydrocarbon residue, it may be either saturated or unsaturated, and may be linear, branched, or cyclic. Preferred are aryl groups (for example, methyl, ethyl, isopropyl, butyl, dodecyl, octadecyl, cyclohexyl, etc. groups) and alkenyl groups (for example, allyl, octenyl, etc. groups) having 22 carbon atoms. Aryl group Preferably, phenyl group, naphthyl group, and heterocyclic group include pyridinyl, quinolyl,
These include chenyl, piperidyl, imidazolyl, etc. Examples of the substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic groups include those listed for Y in the general formula (■) above. v3 is a linear or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl group, aryl group and heterocyclic group, alkoxycarinyl group (e.g. methoxycarbonyl) having /~32 carbon atoms, preferably /~22 carbon atoms; groups, stearyloxycarbonyl groups, etc.), aryloxycarbonyl groups (e.g., phenoxycarzenyl groups, naphthoxycarbonyl groups, etc.), aralkyloxycarbonyl groups (e.g., benzyloxycarbonyl groups, etc.), alkoxy groups (e.g., ethoxy groups, ethoxycarbonyl groups, etc.), 71J-ruoxy group (e.g., phenoxy group, tolyloxy group, etc.), acylamino group (e.g., acetylamino group, 3-[λ,
4cm di-tert-amylphenokidinoacetamide] benzamide group], diacylamino group,
N-alkyl acylamino groups (e.g. N-methylpropionamide group), N-arylamylamino groups (e.g. N-phenylacetamido group), ureido groups (e.g. ureido, N-arylureido, N-arylureido groups, etc.) ], arulamino group in alkali (e.g., n-butylamino group, methylamino group, cycloheΦsylamino group, etc.), tocroamino group (e.g., pyridino group, pyridino group, etc.), sulfonic acid group (e.g., alkylsulfonic acid group, aryl sulfonic acid group, etc.]. These groups may have the substituents listed for Y in the general formula! (■). , bromine atom, etc.), represents a cyano group. Z a s Z b s and Zc represent methine, substituted methine, =N-1 or -NH-, and one of the Za-Zb bond and the Zb-Zc bond is One bond is a double bond, and the other is a single bond.However, ZaSZb.Zc cannot be N at the same time.Zb-Zc is a carbon-
In the case of a carbon double bond, it may form part of an aromatic ring, and this aromatic ring may have the substituents listed for Y above. Further, either Za%zb or Zc is bonded to X' to form -X/-C+. Furthermore, the present invention is particularly effective in the general formula (I
), Cp is the following general formula (1), (IV), (V)
, (Vl), (Vll), (VI), (DOl(X),
(X[), (XII) Mataha (X11I) is an interesting coupler residue. These couplers have a high coupling speed (preferably. General formula (IV) General formula (V) ■ General formula (Vl) General formula (■) μ General formula (■) General formula (IX) General formula (X) General formula (XI) General formula (■) 〇 General formula (XI [) RIOCH-Rtl In the above formula, the free bond derived from the force and the tsubbling position represents the bonding position of the coupling-off group.In the above formula, , Rls R2, R3, R4, R5・R6, R
7, R8, R9, Ftto or R11 contains a diffusion-resistant group, it is selected such that the total number of carbon atoms is r ~ 3.2, preferably 10-22, otherwise the total number of carbon numbers is preferably lj or less. Next, R1-R11 of the general formulas ([1) to (Xlll)
, 1, m and b will be explained. In the formula, R represents an aliphatic group, an aromatic group, an alkyl group, or a heterocyclic group, and R2 and R3 each represent an aromatic substituent or a heterocyclic group. In the formula, the aliphatic group represented by R preferably has 1 carbon number.
-22, which may be substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amino group, an acylamino group, and a halogen atom, which may themselves have further substituents. Typical examples of aliphatic groups useful as R1 are: isoprobyl, isobutyl, tert-butyl, isoamyl, te.
rt-amyl group, /, l-dimethylbutyl group, /, /-
Dimethylhexyl group, /, l-diethyl group, dodecyl group, decyl group, octadecyl group, cyclohexyl group, 2-methoxyisopropyl group, cophenol diisopropyl group, 2-p-tert-butylphenoxyisopropyl group , α-aminoisopropyl group, α-(
These include diethylamitsunoisopropyl group, α-(succinimide)isopropyl group, α-(phthalimitocaisopropyl group, α-(benzenesulfonamido)inpropyl group, etc.) R1s R2 or R3 is an aromatic group (especially phenyl basis)
The aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 3 or less carbon atoms, alkenyl groups, alkoxy groups, alkoxycarbonyl groups, alkoxycarbonylamino groups, aliphatic amide groups,
Arylcarbamoyl group, alkylsulfonamide group,
Substituted with an alkylureido group, an alkyl-substituted succinimide group, etc. (in this case, the alkyl group is in the chain)1
An aromatic group such as dishin may be present. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido group, an arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc., and the aryl group of these substituents The moiety may be further substituted with one or more alkyl groups having a total number of carbon atoms of / to 22. The phenyl group represented by R, %R2 or R3 further includes an amino group, a hydroxy group, a carboxyl group, a sulfo group, a nitro group, a cyano group, including those substituted with a lower alkyl group having carbon number/-j. , a thiocyano group or...Rogge/atom. R, , R2 or R3 may also represent a substituent in which a phenyl group is fused with another ring, such as a naphthyl group, a quinolyl group, an isoquinolyl group, a chromanyl group, a yma5nyl group, a tetrahydronaphthyl group, etc. These substituents may themselves have further substituents. R1 represents an alkoxy group, the alkyl moiety represents a straight or branched alkyl group, alkenyl group, cyclic alkyl group or cyclic alkenyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms; These may be substituted with an I.logen atom, an aryl group, an alkoxy group, or the like. When R1%R2 or R3 represents a heterocyclic group (respectively, a heterocyclic group is a carbon atom of the carbonyl group of an acyl group in alpha acylacetamide or a nitrogen atom of an amide group via one of the carbon atoms forming the ring). Examples of such heterocycles include thiophene, furan, pyran, pyrrole, pyrazole, pyridine, pyrazine, and pyrimidine. These may further have a substituent on the ring. In the general formula (V), R5 is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 7 carbon atoms (for example, methyl , isopropyl, tert-butyl, hexyl, dodecyl, etc.), alkenyl groups (e.g. allyl group, etc.), cyclic alkyl groups (e.g. cycloantyl group, cyclohexyl group, norbornyl group, etc.), aralkyl groups (e.g. benzyl, β-phenylethyl group, etc.], cyclic alkenyl group (e.g., cyclo-enthenyl, cyclohexenyl group, etc.), and these represent halogen atoms, nitro groups, cyano groups, aryl groups, alkoxy groups, aryloxy groups, -ip syl group, alkylthiocarzenyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, thiourethane group, sulfone Amido group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-alkylanilino group, N-acylanilino group , a hydroxy group, a mercapto group, etc. Furthermore, R5 may represent an aryl group (for example, a phenyl group, an α- or β-naphthyl group, etc.).The aryl group may be substituted with one or more substituents. It may have a group (as a substituent, for example, an alumyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group), a 10-gen atom, a nitro group, a cyano group, an aryl group, an alkoxy group, an aryloxy group. , carboxyl group, alkoxycarbonyl group,
Aryloxycarbonyl group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group, sulfonamide group, heterocyclic group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkyl It may have an amino group, dialkylamino group, anilino group, N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydroxy group, mercapto group, etc. More preferred as R5 is phenyl in which at least one of the ortho-positions is substituted with an alkyl group, alkoxy group, rogen atom, etc., and this is because the coupler remaining in the film is less sensitive to light and heat. Furthermore, R5 is a heterocyclic group (for example, a J- or T-membered heterocyclic ring containing a nitrogen atom, an oxygen atom, or a sulfur atom as a petro atom, a fused heterocyclic group, a pyridyl group, a quinolyl group, etc.). group, furyl group, benzothiazolyl group, oxasilyl group, imidazolyl group, naphthoxacylyl group, etc.], a heterocyclic group substituted with the substituents listed for the above-mentioned aryl group, an aliphatic or aromatic acyl group, an alkylsulfonyl group, It may also represent an arylsulfonyl group, an alkylcarbamoyl group, an arylcarbamoyl group, an arylsulfonyl group, or an arylthiocarbamoyl group. In the formula, R4 is a hydrogen atom, with a carbon number of 1 to 32, preferably /
Straight-chain or branched alkyl, alkenyl, cyclic alkyl, aralkyl, cyclic alkenyl groups (these groups may have substituents listed for R5 above), aryl groups and heterocyclic groups (these groups include Regarding R5, an alkoxycarbonyl group (for example, a methoxycarbonyl group, an ethoxycarbonyl group, a stearyloxycarbonyl group, etc.), an aryloxycarbonyl group (for example, a phenoxycarbonyl group, a nutoxycarbonyl group, etc.) Φ dicarbonyl group, etc.), aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy group (e.g., methoxy group, ethoxy group, heptadecyloxy group, etc.), aryloxy group (e.g., phenoxy group, tolyloxy group, etc.) ), argylthio groups (e.g. ethylthio, dodecylthio, etc.), arylthio groups (e.g. phenylthio, α-naphthylthio), carboxyl groups, acylamino groups (e.g. acetylamino, j-((J, IA-tert),
-amylphenol)acetamide]benzamide group, etc.), diacylamino group, N-furkylacylamino group (
For example, N-methylpropionamide group, etc.), N-arylicylamino group (for example, N-phenylacetamide group, etc.), ureido group (for example, ureido, N-arylureido, N-arylureido group, etc.), urethane group. ,
Thiourethane group, arylamino group (e.g. phenylamino, N-methylanilino group, diphenylamino group, N
-acetylanilino group, 2-chloro-! -tetradecanamide anilino group], alkylamino group (e.g. n
-butylamino group, methylamino group, cyclohinocylamino group, etc.), cycloamino group (e.g. lysino group,
pyrrolidino group, etc.], heterocyclic amino group (e.g., μm pyridylamino group, λ-benzoxasilylamino group, etc.)
, alkylcarbonyl groups (e.g., methylcarbonyl group, etc.), arylsulfonyl groups (e.g., phenylcarbonyl group, etc.), sulfonamide groups (e.g., alkylsulfonamide groups, arylsulfonamide groups, etc.), carbamoyl groups (e.g., ethylcarbamoyl group, Dimethylcarbamoyl group. yl group, N-alkyl-N-arylsulfamoyl group, N,N-diarylsulfamoyl group, etc.), cyano group, hydroxy group,
Represents any one of a mercapto group, a halogen atom, and a sulfo group. In the formula, R6 represents a hydrogen atom or a linear or branched argyl group, alkenyl group, or cyclic alkyl group having 1 to 32 carbon atoms, preferably 1 to 22 carbon atoms; an aralkyl group, or a cyclic alkenyl group; may have the substituents listed above. R6 may also represent an aryl group or a heterocyclic group (which may have the substituents listed for R5 above). R6 may also represent a cyano group, an alkoxy group, an aryloxy group, a halogen atom, a carboxy group, alkoxycarbonyl group, aryloxycarbonyl group, alkoxy group, sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group, ureido group, urethane group,
Sulfonamide group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group, anilino group, N-arylanilino group, N-argylanilino group, N-acylanilino group, hydroxy group or mercapto May also represent a group. R7, R8, and R9 each represent a group used in a conventional high-equivalent phenol or an α-naphthol coupler, and specifically, R7 is a hydrogen atom, a rogen atom, an alkoxycarbonylamino group, an aliphatic hydrocarbon residue, N-IJ-luureido group, acylamino group, -0R12 or -8R12 (wherein R12 is an aliphatic hydrocarbon residue, and two or more R7 groups are present in the same molecule)
is present, two or more R7s may be different groups (including those having a substituent as an aliphatic hydrocarbon residue. Also, if these substituents contain an aryl group) In the case of One of these may be a hydrogen atom,
These groups also include those having substituents. Further, R8 and R9 may jointly form a nitrogen-containing heterogeneous source. The aliphatic hydrocarbon residues can be either saturated or unsaturated (also straight-chain, branched,
Any ring-shaped one may be used. and preferably alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, dodecyl, octadecyl, cyclobutyl,
These include groups such as cyclosil, alkenyl groups (for example, allyl groups, octenyl groups, etc.). Aryl groups include phenyl groups, naphthyl groups, etc.
Representative heterocyclic residues include pyridinyl, quinolyl, chenyl, pyridyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups and heterocyclic residues include halogen atoms,
Nitro, hydroxy, carboxy group, amino, substituted amino, sulfo, alkyl, alkenyl, aryl, heterocycle, alkoxy, aryloxy, arylthio, arylthio, acylamino, carbamoyl, ester, acyl, acylamino, sulfonamide, sulfamoyl, sulfonyl, Examples include various groups such as morpholino. l is an integer of /-4, m is an integer of 1 to 3, and p is 1 to ! represents an integer. RIO is an arylcarbonyl group, an alkanoyl group having 2 to 32 carbon atoms, preferably Co to 2 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 3 to 3 carbon atoms, preferably λ to 2 carbon atoms, carbon! /~3 represents an alkoxycarbonyl group or an aryloxycarbonyl group, preferably /-22, which may have a substituent (substituents include an alkoxycarbonyl group, an alkoxycarbonyl group, an acylamino group, an alkyl Examples include sulfamoyl group, alkylsulfonamide group, alkylsuccinimide group, haloken atom, nitro group, carboxyl group, nitrile group, alkyl group, or aryl group. R11 is an arylcarbonyl group, preferably having 2 to 32 carbon atoms. Co-2-2 alkanoyl group, arylcarbamoyl group, alkanecarbamoyl group having 2 to 32 carbon atoms, preferably λ to 12 carbon atoms, preferably l-coco alkoxycarbonyl group or aryloxycarbonyl group having 1 to 32 carbon atoms, carbon number/~!-2 preferably /~12 flucansulfonyl group, arylsulfonyl group, aryl group, j
or t-membered heterocyclic group (the hetero atom is selected from a nitrogen atom, an oxygen atom, a sulfur atom, such as a triazolyl group, an imidazolyl group, a phthalimide group, a succinimide group, a furyl group, a pyridyl group, or a benzotriazolyl group) ), which may have the substituents mentioned above for RIO. As stated above, in general formula (I), C
When p has a diffusion-resistant group, a diffusion-resistant colored or colorless compound is formed after a coupling reaction with the oxidized product of an aromatic primary amine developing agent, and Cp has a non-diffusion-resistant group. When it has, the compound formed by the coupling reaction has diffusivity depending on the non-diffusion resistant group that Cp has. Furthermore, when Cp has an alkali solubilizing group, the compound formed by the coupling reaction will be eluted from the film. The coupler represented by the general formula (1) of the present invention also includes cases where it is a polymer. That is, the following general formula (XIV)
It is derived from a monomeric coupler represented by the general formula (X
A polymer having a repeating unit represented by V) or a non-color-forming monomer containing at least one ethylene group that does not have the ability to couple with an oxidized product of an aromatic primary amine active ingredient. It is a copolymer with seven or more types of. Here, two or more types of monomer couplers may be simultaneously polymerized. General formula (xIv) CH2=C+A27-rtA3A1fiQ General formula (X
V) ■ (-CH2-Cs(A2←A3←A sq Q l ”) In the formula, R is a hydrogen atom, a lower alkyl group having carbon number/~μ,
or represents a chlorine atom and %A1 is -CONH-1-NH
CONH-1-NHCOO-1-COO-1-SO2-
1-〇〇-1-NHCO-1-8o 2NH-1-NH
8O2-1-OCO-1-OCONH-1-NH- or -〇-, A2 is -CONH'- or -COO-
and A3 represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having -70 carbon atoms, and the alkylene group may be linear or branched. (Examples of alkylene groups include methylene, methylmethylene, dimethylmethylene, dimethylene, trimethylene, tetramethylene, hantamethylene, hexamethylene, and decylmethylene; examples of aralkylene groups include benzylidene; examples of arylene groups include phenylene and naphthylene) Q is Represents a compound residue represented by general formula (1), and may be bonded at any site of CI) x TIME or Dye. 1% j and k represent O or /, but 1%
J and k cannot be O at the same time. Examples of substituents for the alkylene group, aralkylene group, or arylene group represented by A3 include aryl group (e.g., phenyl group), nitro group, hydrogen group, cyano group, sulfo group, cy group in alkyl group (e.g., methoxy group, Aryloxy groups (e.g. phenolic groups), acyloxy groups (e.g. acetoxy groups), acylamino groups (e.g. acetylamino groups, sulfonamide groups (e.g. methanesulfonamide groups), sulfamoyl groups (e.g. methylsulfamoyl groups), ...Rogen atoms (e.g. fluorine, chlorine, bromine, etc.), carboxy groups, carbamoyl groups (e.g. methylcarbamoyl group), alkoxycarbonyl groups (e.g. methoxycarbonyl group), sulfonyl groups (e.g. methylsulfonyl group), etc. When there are two or more of these substituents, they may be the same or different.Next, as a non-color-forming earth tyrene-like monomer that does not couple with the oxidation product of an aromatic-grade amine developer. is acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and esters or amides derived from these acrylic acids, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinylodopyridine The non-color-forming ethylenically unsaturated monomers used here can also be used in combination of two or more.The amount of the above-mentioned coupler of the present invention added is determined by When adding the coupler to a photosensitive silver halide containing layer, the amount of the coupler added is based on 1 mole of silver halide contained in that layer, and the amount added to the adjacent layer. In this case, it is contained in the adjacent layer...0.00j per mol of silver halide
~1 mol is preferred. Particularly preferably 0.00j to 0.
It is in the range of 5 moles. In the present invention, preferred specific examples of couplers represented by formula (I) are shown below, but the invention is not limited thereto. In general formula (1), an example of a coupler in which the bond between TIME (when n≧l) or Cp (when n = 0) between Time and X is cleaved to restore the yellow dye. -4AI- - J Y-da C8H17-≠t- Y-t 12 Y-/ Koy-i 3 Y-74t Y-/ E12H25 Y-/7 -tr In general formula (1), Time (when n≧l) Alternatively, an example of a coupler in which the bond between Cp (when n=0) and X is cleaved to form a magenta dye as γ element. M-/M-Co-J α M-Reference-a M-7 503NtlL: An example of a coupler that restores the cyan dye by cleaving the bond between Time (when n≧7) or Cp (when n=O) and X in the I2M part general formula (1).C-Reference NL)z Ntli>U2L; 121125 The following is the pKa value of the conjugate acid of the dye moiety cleaved from the coupler described as a compound example in this specification. The coupler capable of releasing the new dye according to the present invention is disclosed in JP-A-61-/rllj'fl, JP-A/-/! t04L7
, 4/-2/90≠3, 61-ko! 3 μl and the method described in Japanese Patent Application No. Shoj/-4'j & 4A. 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 mole or less silver iodide. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 2 j mole percent silver iodide. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. may have crystal defects, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 microns or less, or large grains with a projected area diameter of up to about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Al76μJ (/
7, December 2007), pp. 22-23. @1. Emulsion preparation
tionand typeB)”, and the same &/1
716 (/7/I), 6th page, graphic "Physics and Chemistry of Photography", published by Paul Montell (P. G1afkides+ Chemic et P.
hisiquePhotographique Pau
``Photographic Emulsion Chemistry'' by Duffin, published by Focal Press (G, F, Du
ff in, Photographic Emulsio
n Chemistry (Focal Press
sl AA)), “Manufacturing and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L. Zelikman et al+ Making
andCoating Photographic
Emulsion Focal Press+ /
It can be prepared using the method described in A4A). U.S. Patent No. 3. j7≠, No. 62r, same 3. T! , 32
No. Reference British Patent No. 1. Monodisperse emulsions in which ≠13, 7≠ are also preferred. Tabular grains having aspect ratios of about 5 or more can also be used in the present invention. Tabular grains are described in Gutoff, Photographic Science and Engineering (Gutoff + Photographic 5).
science and 'Engineer in
g), Volume 1+, J4'r N217 page (L70
); U.S. Pat.
μ, No. 310, Dohiro, ≠33゜oar No., Same≠, μ32
, No. 120 and British Patent No. CO,/12,117. The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered 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 usually one that has been subjected to physical ripening, chemical ripening, and spectral sensitization. The additives used in such processes are manufactured by Research Disclosure Shop/7.
It is described in A Ko 3 and A Ko 16/17/l, and the relevant locations are summarized in the table below. Known photographic additives that can be used in the present invention are also described in one of the above research disclosures, and the relevant descriptions are shown in the table below. Additive type RD/76≠J RD/ryit
l Chemical sensitizers page 23, page 2, right column 2
Sensitivity increasing agent Same as above 3 Spectral sensitizer, page 23 - ≠ Page t4 cr page right column - Super sensitizer 6th page right column ≠ Brightening agent
Page 24A! Kabushi prevention agent 24A-2! Page t Data page right column ~ and stabilizer 6 Light absorber, F λ! ~, page 27, right column on page 2 - Ilter dye, left column on page 7, ultraviolet absorber 7, anti-stain agent, right column on page 2, right column on page 2, left to right column on page t, dye image stabilizer 2! page hardener page ko page tri page left column 10 ζ inder page 26 same as above// hardening agent, lubricant page 27 tzo right column/, 2 coating aid, surface page 26 ~ core page same as above activator 13 static prevention Agent Page 27 Same as above Various Cassie couplers can be used in the present invention.
, a17+Hiro3. ■It is described in the patent described in -〇-G. As a yellow coupler, for example, U.S. Pat.
J, No. 10.1, No. 02, No. 620, No. ≠,
3 Kot, oλ No. Reference No. ≠01゜732, Special Publication No. 11-107J, British Patent No. 1. Part 2! T, 02
No. 0, No. 1. ≠76.71°0, etc. are preferred. As a magenta coupler! - Pyrazolone and pyrazoloazole compounds are preferred, US Pat.
0. La/ri issue, same No. 3/. No. 7, European Patent No. 73.4JA, US Patent No. J,
O4l, No. 4!32, No. 3,725, No. 0!7, Research Disclosure Shop 2≠2koO
month), JP-A-60-33! ! No. 2, Research Disclosure & 2445. IO (June 19117), Unexamined Japanese Patent Publication No. 1911-4' JAj No. 9, U.S.A.
Particularly preferred are those described in No. 30, No. ≠, TPO, tz≠, and the like. Cyan couplers include phenolic and naphthol couplers, as disclosed in U.S. Pat. 0!2, 2/2 issue, 4', /4'j, JPA issue, 1st hiro, λ21r, , ZJJ issue, 2nd issue ≠, -tat, Joo
No. 2, 36, Takota No. 2, 10/. 17/No. 2, 77.5. /4.2, same No.2゜r
yr, rλ No. 6, same No. J, 775.002, same No. J
, 7! I, No. 301, No. JJ4A, 0
// issue, same number ≠ +327. /7J, West German Patent Publication No. 3
, 322, 7 Kota, European Patent No. i2i. JtjA, U.S. Patent No. 3.1 et al., 622, ≠,
333, Tatata issue, same number φ, thing! l,! No. j, No. 4c27,747, European Patent No. 1A/, jJjA
Preferably, those described in No. Colored couplers for correcting unnecessary absorption of coloring dyes are research disclosure A/76≠3
■-G term, U.S. Patent No. t/t J tl, 70
No., Special Publication No. 7-32≠13, U.S. Patent No. 3, ooμ
, Takota No. DA, /31,2!2, British Patent No. 1
, /4!4.3t1 is preferred. Couplers whose coloring dyes have appropriate diffusivity include U.S. Pat. l coj
, No. 170, European Patent No. 24,770, West German Patent (
Those described in Publication No. J, 234A, 133 are preferred. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. /-! /, No. 120, same No. a, orO, co//
No. 347,212, British Patent No. λ*, /
0λ, No. 173, etc. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD/744c3.
, the patents described in sections ■ to F, JP-A No. 7-IZI Risan No. 1, same! July-July-34L issue, 60-/r4A24
fir, U.S. Patent No.≠. , 2≠! , those described in No. 6λ are preferred. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 5.0-7, 1110
No. 2, /Jl, No. 111, JP-A-69-1
Preferred are those described in No. 17631 and Tatar/701rlAO. In addition, examples of couplers that can be used in the photosensitive material of the present invention include viewing couplers described in U.S. Pat. Jrj, 4t7J, 1st fi, 331.3! PJ No., No. 310. Multi-double coupler described in t/r issue etc., JP-A-60-/Irj? ! DIR redox compound releasing couplers described in European Patent No. 17J, JO2A, etc.
Examples include couplers that release a dye that recovers color after separation, as described in the above issue. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high boiling point solvents used in the oil-in-water dispersion method are described in US Pat. The steps and effects of latex dispersion methods, and specific examples of latex for impregnation, are described in U.S. Pat. Jrj, first West German patent application (OLS)! 4A/. -27μ issue and the same issue,! ≠It is described in No. 11.230, etc. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/74μ3 page, and the same Airyit page 4
It is written from the right column on page 4C7 to the left column on page t≠r. The color photographic material according to the present invention includes the above-mentioned RD,
A/74 $ jt7) J r -page 29, tzt left column to right column of Ait'ytt, Oyohi, can be used for development processing. 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 larger than one to conserve water. A representative example of the stabilization treatment is a multistage countercurrent stabilization treatment as described in JP-A No. 7-4JllJ, which is applied to the water washing step. (Examples) The present invention will be described in detail below using Examples, but the present invention is not limited thereto. The structural formulas of the nine compounds other than the present invention used in the examples are described at the end of the examples. Example 1 A multilayer color photosensitive material 10 was prepared on a cellulose triacetate film support provided with a multilayer undercoat and each layer having the composition shown below. The numbers corresponding to each component indicate the coating weight expressed in P/m2, and for silver halide. The coating amount is shown in terms of silver. However, for sensitizing dyes, the coating amount is expressed in moles per mole of the same silver halide. (Sample 1Ol) 7th layer (antihalation layer) Black colloidal silver...0.2 gelatin
...1.3 Ultraviolet absorber UV-/
... o, i Same as above UV-J ...
0.2 Dispersion oil 0il-/-Tera・0.0/Same as above 0il-co...o, oi 2nd layer (intermediate layer) Fine grain silver bromide (average particle size 0.07μ)...0. /! gelatin
.../, 0 colored coupler C-t
...o, i same as above C-co...
・0.0/Dispersion oil Oi l-/...o,
i 3rd layer (7th red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 3 molar ratio, average grain size 0.3μ)...silver 1. r gelatin
.../, J sensitizing dye I --
-/, /X/7-'I ■ ...ko, J
'pCIO-51III-・J,Z
×10-5'IV...λ, coxio-
'Cub5-C-J ---0, IrO coupler C-see...0.02 Coupler C-co...0.003 Dispersion oil 0il-/
...0. OJ ditto 0i1-j
...0.0/λ 1st layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (6 moles of silver iodide, average grain size 0.7μ) ...Silver 10.2 gelatin ... /, 0 sensitizing dye I
...t,! X1O-5t 11 ---
5. Ox10-5-m... Ko! ×io
-'t ■ ---J, jXlo-5 coupler C-t...o, or coupler C-
j ---0, O1t coupler C-2...
・o, oi Dispersion oil 0il-/ ...0.0/'
Same as above 0il-2...0.01 No.! Layer (middle layer) Gelatin.../, 0 compound cpc
t-A...0.03 Dispersion oil 0i
l-/...0. Oj same as above 0i1-2
...o, or 6th layer (7th green-sensitive emulsion #) Silver iodobromide emulsion (silver iodide ginseng morch, average grain size 0.Jμ) ...0.1! Sensitizing dye V
...λ, /X10"-'I ■
... Da! ×10−'gelatin ・
...i,. Coupler C-7...O0 reference coupler C-≠...0.06 coupler C
-/...o, is dispersion oil Oil
/ ...0.3 7th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 mol ratio, average grain size 0.7μ) ...Silver O, tazelatin
e-Fist 1.0 Sensitizing Dye V...
・/, 0X10-'# M ---2,
0x10-' Coupler C-2...0.0 Coupler C-70..., o, or Coupler C-/...0.02 Coupler cr...0.02 Dispersion oil 0il
-/...0.10 darkness 1-n roll ・
・・o-or rth layer (yellow filter single layer) gelatin -・2 yellow colloidal silver ・・o, or compound H-J
...0. /Dispersed oil 0il-/ ・・
・0. ! Second layer (seventh blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide≠molar ratio, average grain size 0.3
μ) ...Gin O0 Hiromu! gelatin
...1. O sensitizing dye■...z×1
o-4 coupler C-/λ...O, coupler C-≠...0.07 Dispersion oil 0il
-/...0.2 10th layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide lO molar ratio, average grain size 1.jμ)...Silver 0. ! j gelatin
...o, is a sensitizing dye■ ・
...Co, zxio-' coupler C-/λ ・φ
-0.2! Dispersion oil Qil-/...0.0
7 Eleventh layer (first protective layer) Gelatin...o, r Ultraviolet absorber UV-/...0. / Same as above UV-2・
...Q, -2 Dispersion oil 0il-/ ...o,oi Dispersion oil 0il-λ ...0.0/12th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ)・ ・ ・ O,! Gelatin...Q, daj Polymethyl methacrylate particles (diameter 1.3μ)...0. Co-hardening agent/
...O1≠formaldehyde scavenger 8-/.--i,. In addition to the above components, a surfactant was added to each layer as a coating aid. The chemical structural formulas or chemical names of the compounds used in the above examples are shown below. UV-/ UV-2 0il-/ Tricresyl phosphate 0il-λ Dibutyl phthalate 0i1-j His (λ-ethylhexyl) phthalate sensitizing dye I Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye Sensitizing dye ■ Sensitizing dye ■ -/ -1ti C-/ α t) -j Q-7 Molecular weight approximately -20,000 -r -2 α c-i. C-// pd A-s H cp-/J (Sample 102) Except that coupler C-// in the second and tenth layers of sample ioi was replaced with coupler C-/J so that the moles were equimolar. Sample 102 was prepared in the same manner as sample toi. (Sample 103) Sample 1 except that the coupler C-// in the second and tenth layers of Sample 10/ was replaced with the present compound Y-10 in equimolar amounts.
Sample 10J was prepared in the same manner as 0/. (Sample ioμ) Sample 1 except that the coupler C-// in the second layer and the tenth layer of Sample 10/ was replaced with the compound y-s of the present invention in an equimolar amount.
Sample IO'l was prepared in the same manner as 0/. (Sample 10) The coupler C-/I in the second layer and the first O layer of sample IO/ was replaced with the coupler cp-/λ so that the coloring units were equimolar, and accordingly, 0.00% of the dispersion oil-7 was added. J7f/WL
2 to 0. u6P/m”, add 7.4 ml of gelatin/Island 2
From 1. Sample 10 except that the weight was reduced to 1/m2.
Sample lor was prepared in the same manner as /. (Sample 106) The coupler C-// in the second layer and the tenth layer of sample 10/ was replaced with K so that the coloring units of the coupler Y-IOVC of the present invention were equimolar, and accordingly, 1 dispersion oil 0. j7ri/
From Sendai 2 to 0.7797m2. Gelatin from 7.4P/m2/,,2F/Fl! Sample 10 was prepared in the same manner as Sample 10/, except that the weight was reduced to 2. These samples 10/% 10co and 103.10hi were subjected to back exposure and color development as shown below, and the yellow density of the resulting processed samples was measured. The results of photographic properties are shown in Table 1. Development was carried out at sr 0c as described below. The color development process used here is as follows. (Development treatment) The exposed sample was developed at 3rC according to the following processing steps. Color development 3 minutes/! Bleach for 6 minutes and 30 seconds Wash with water
λ minutes IO seconds Fixation μ minutes λO seconds Water washing 3 minutes lj seconds Stability 7 minutes 03 seconds The composition of the processing liquid used in each step was as follows. Color developer diethylenetriaminepentaacetic acid H/, 0g 1-hydroxyethylidene- /I/-diphosphonic acid x, og sodium sulfite Hiroshi, 0g potassium carbonate
30.0g potassium bromide
/, 4'g potassium iodide /, J
Dahydroxylamine sulfate 5.44g≠-(
N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Hiroshi, add 1g water
/, 01 pH 10,0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 1jO1Og Ammonium nitrate
io, add 0g water
/, 01pH≦, 0 Fixer ethylenediaminetetraacetic acid disodium salt /, 0g sodium sulfite ≠, og ammonium thiosulfate aqueous solution (70%) t 7 z , oWL
t Sodium bisulfite, ag Add water /, 01 pH 4,4 Stable liquid formalin (4 cO%) , ornl Polyoxyethylene-P-monononylphenyl ether (average degree of polymerization about 10) Add 0.3 g water / , O1 Table Sample Coupler Capri Relative sensitivity Maximum concentration 10/
cp-// 0.07 100 /,,! T
O102Cp-/J O, Or Tar
2,20VOJ Y-100,07tat, 5
．． ri r104A Y-J O,0ta tat ko, 2≠From the table, the sample of the present invention 703%io
u is the existing coupler C-//-? It is clear that the color development is extremely high compared to the coupler Cp-12 having a dye with pK a of 5 or more (dye part pK, t, o). This makes it possible to reduce the amount of coupler and silver halide used. Next, samples 10/10 were subjected to white exposure for cytometry at -t=y to iot, and the above-mentioned color development process was performed, resulting in substantially the same sensitivity and gradation. Next, sample lOj and 101. The MTF value was measured by exposing the sample to blue light. The method for measuring MTF is T. A. James (T.
The Theory of the Photographic Process, edited by James H.
of the PhotographicProc
ess) 1st Edition (Macmillan Publishing Co., Ltd., 1277) No. 407, top page. The results are shown in Table 2. The above results show that sample 104 of the present invention has superior sharpness compared to the comparative sample. Combining the results in Tables 1 and 2, it is clear that the present invention provides a silver halide color photographic light-sensitive material that has a high maximum density, can achieve thin layers, and has excellent sharpness as a result. is clear. Patent applicant: Fuji Photo Film Co., Ltd. Procedural amendment 1, case description: 1988 Patent Application No. 74.2Lt
No. 2, Name of the invention Silver halide color photographic light-sensitive material 3. Relationship with the person making the amendment Patent applicant Address: 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Contact address: 2-26-30 Nishiazabu, Minato-ku, Tokyo 106 4. Subject of amendment Column 5 of the "Detailed Description of the Invention" of the specification and contents of the amendment The entry wX of the "Detailed Description of the Invention" section of the specification will be amended as follows. 2) Page 57 Corrected as M-t. 3) Correct at No. Jrl*MP. The structural formula of compound M-t on page 17 is corrected as " , n
~ "The silver halide color photographic light-sensitive material of the present invention is generally washed with water and/or stabilized after fixing or step-down processing such as bleach-fixing. The amount of water for one wash is as follows: It can be set over a wide range of conditions depending on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. , the relationship between the number of flushing tanks and the amount of water in the multi-stage countercurrent method is described in the Journal of the Society of Motion Picture and Telegraphy Engineers (Jo
urnalof the 5ociety of
Motion Picture and Te1ev
ion Engineers) Volume 4II. It can also be stopped by the method described in p, J dat, -ko 13 (/ri! J month issue) k. According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be greatly reduced, but due to the increase in the residence time of the effluent in the tank, bacteria will multiply and the generated suspended matter will be transferred to the photosensitive material. Problems such as adhesion may occur. In the processing of the color light-sensitive material of the present invention, as a solution to such problems, the method for reducing calcium and magnesium described in Japanese Patent Application No. 131132/1988 can be used very effectively. 9, isothiasolone compounds and thiabendazoles, chlorinated disinfectants such as chlorinated sodium incyanurate, and other benzotriazoles, as described in JP-A No. 7-11-1983, and other chlorine-based disinfectants such as benzotriazole, etc. It is also possible to use the fungicides described in "Microbial Sterilization, Disinfection, and Anti-Mold Technology" edited by Japan Sanitation Technology Society, "Encyclopedia of Antibacterial and Antifungal Agents" edited by Japan Society of Anti-Bacterial and Antifungal Agents.゛How to use washing water in the processing of the photosensitive material of the present invention? and preferably j-1. The washing water temperature and washing time can be set in various ways depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds at %/J0C.
10 minutes, preferably tiJj-4406(:TEJO seconds-j
A range of minutes is selected. Furthermore, the photosensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 17-114AJ, 5r-te
rs4c issue, jter/rllJuJ issue, 60-2201
Da! No., 4O-2JII No. 32, No. 40-23271, to-2J? 74C5', A/-00ju, t/
All known methods described in Japanese Patent No.-1117179 and the like can be used. In particular, l-hydroxyethylidene-
/, /-diphosphonic acid,! -ri-a-roko-methyl-l-
Stabilizing baths containing inthiazolin-3-one, bismuth compounds, ammonium compounds, etc. are preferably used.

Claims (1)

[Claims] In a silver halide color photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, a timing group can be formed directly or by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. In a coupler that has a dye moiety whose maximum absorption wavelength is shifted to the short wavelength side due to a bond that is cleaved through the reaction, as a result of the reaction, a compound having a dye moiety having a maximum absorption wavelength before the shift is produced, directly, Alternatively, a silver halide color photographic light-sensitive material containing a coupler characterized in that the conjugate acid of the dye moiety connected to the coupler mother nucleus via a timing group has a pKa of 5.0 or less.