JPS6370251A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To eliminate inferior color developing characteristic and to improve the sharpness and light stain of a silver halide color photographic sensitive material by constituting the photosensitive material of a coupler expressed by the general formula I and >=one kind of cyan coupler expressed by the general formula II or III. CONSTITUTION:A photosensitive material is constituted of a coupler expressed by the general formula I having a dye moiety contg. a max. absorption wavelength shifted toward the short wavelength side, which is splitted by a coupling reaction with an oxidized body of a developing agent, and >=one kind of cyan coupler expressed by the general formula II or III. Cp in the formula I is a coupler residue; (TIME)n is a timing group; Dye is a dye residue; and X is an auxochromic residue. R1 in II and III are aromatic group; R2 is a group which can be substituted by a naphthol ring; and R3 is an aliphatic group. The inferior color developing characteristic is eliminated and the sharpness and the light stain are improved by using a sample prepd. by a combination of a yellow coupler and a cyan coupler in the above described manner.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic material. In particular, the present invention relates to a silver halide color photographic light-sensitive material that has excellent sharpness and color image storage stability, and has little change in hue due to the density of a cyan image. (Prior art) When a silver halide photographic light-sensitive material is exposed to light and then subjected to color development, a color developing agent such as an oxidized aromatic primary amine reacts with a dye-forming coupler.
Indophenol, indoaniline-inda-yone-azomethine-phenoxazine, phenazine, and similar pigments have been produced and utilized for the formation of one stroke. in general,
In this method, a subtractive color reproduction method is used,
In order to reproduce blue, green, and red, images of yellow, magenta, and cyan, which are complementary colors, are formed. In this case, phenols or naphthols are often used as cyan dye-forming couplers. However, there have been several problems with the storage stability of color images obtained from these cyan couplers. For example, U.S. Patent No. 2゜3b7,131 and US Pat.
The color images obtained with the 2-acylaminophenolic cyan couplers described in the JO specification generally have poor heat fastness;
772. /λ described in the specification of No. Color images obtained from j-diacylaminophenol cyan couplers generally have poor light fastness, and sil-hydroxy-1-naphthamide cyan couplers are generally unsatisfactory in both light fastness and heat fastness. Couplers that improve this point include U.S. Pat.
No. 1,233 - No. 3,711,301 - No. 3,1
10. t4/issue and % Kaisho jA-6! A phenolic cyan coupler having a ureido group at the 2-position is known, which is described in the specification of No. 3 IIL, etc., and has a higher light resistance than the other general cyan couplers mentioned above. Significant improvements in heat fastness. however,
A phenolic cyan coupler having a ureido group at the 2-position is, for example, published by JP-A-Sho! ? -≠6, as described in the Komu issue, had a serious drawback in that the spectral absorption of the developed color image varied greatly depending on the color density. As described in European Patent No. 17J, No. 302! Positionally substituted naphthol cyan couplers and their polymer couplers have excellent light and heat fastness and are excellent in that the spectral absorption of their developed color images does not depend on X7 on the color density. However, these 5-substituted naphthol cyan couplers and their polymer couplers. It has the disadvantage that stain (yellow stain) occurs more when exposed to light than conventional cyan couplers.

[Problems to be Solved by the Invention] The problem to be solved by the present invention is how to realize a silver halide color photographic light-sensitive material that is excellent in both sharpness and cyan image storage stability. (c) Means for solving the problem) The above problem is caused by the dye moiety whose maximum absorption wavelength is shifted to the short wavelength side due to a bond that is cleaved directly or via a timing group due to the coupling reaction with the oxidized developing agent. and at least one coupler represented by the following general formula (I), which is characterized in that the reaction produces a compound having a dye moiety having a maximum absorption wavelength before shifting. The problem was solved by a silver halide color photographic material containing at least one cyan coupler represented by the following general formula (III) and (m): General formula (II Cp-(T I ME 1n- X-Dye (I
) In the formula, -Cp represents a coupler residue capable of releasing -(TIME)n-X-Dye through a coupling reaction with an oxidized product of an aromatic primary amine developing agent. TIME represents a timing group, and n represents an o-4 positive integer. Dy
e is a dye residue, and X represents an auxochrome residue of the dye. In the formula, R1 represents an aromatic group or a heterocyclic group, -R2 represents a group that can be substituted on a naphthol ring, -13 represents an aliphatic group, a represents an integer from O to ≠, and -b represents an integer from O to 3. represents an integer of -Z1 represents a hydrogen atom or a coupling-off group, general formula (It) and general formula C■)
Zl in may be different from each other. Z2tt-
0---s-. Or represents R4-N-. However, R4 represents a hydrogen atom or an organic substituent, and when a and b are plural, and R2 in general formula +II) and general formula (III)
may be the same or different, and may be bonded to each other to form a ring. In general formula (II[), R2 and z2- or Zi and Z2 may be bonded to each other to form a ring. may be formed. Also + R1, R2-R
A multimer of λ-mer or higher may be formed by a-R4-Zl or Z2. Moreover, Zl is -l-TIME-)-X-Dye in the general formula (I), and is Ruko and Hanai. In the present invention, one of the constituent elements includes a dye moiety whose maximum absorption wavelength is shifted to the short wavelength side by a bond that is cleaved by a coupling reaction with an oxidized aromatic primary amine developing agent, and the reaction results in a compound having a dye moiety with a 4j large absorption wavelength before shifting, such as European Patent No. 173,302.
A coupler represented by the general formula (I) described in No. A is used. In this coupler, when a dye is formed by the bond between the coupler core and the oxidized product of the aromatic primary amine developing agent, the dye is released from the new coupler core to form an image. The dye newly released from this coupler core can solve various problems that could not be satisfied with only the dye formed by the coupling reaction between the conventional coupler and the oxidized developing agent. It became. That is, the color image density, that is, the color density is increased, the color reproducibility is improved by adjusting the hue of a single color image, and the color image fastness is improved. As a result, it has become possible to reduce the amount of coupler used and further reduce the amount of silver halide used to compensate for the increase in color density, thereby making it possible to improve sharpness by thinning the layer. This improvement in sharpness was effective not only in the layer containing the coupler but also in the photosensitive layer on the support side. This is because - due to the thinning of the layer containing the coupler, the color bleeding phenomenon caused by optical factors is suppressed. Furthermore, due to its color-forming principle, the coupler has the characteristic that, in a state where it does not perform a coupling reaction with an oxidized developing agent, it has an absorption on the shorter wavelength side than the hue of the dye restored by the reaction. Cyan couplers represented by general formulas (II) and (m) are used as another component of the present invention. Such couplers are disclosed in U.S. Patent No. μ, μJ'/. A cyan image that is fast to light and heat can be obtained without using the method of coordinating a transition metal after one color development as described in No. 261. Another feature is the use of a diffusion-resistant cyan coupler built into the photosensitive material. It has become clear that the cyan coupler of the present invention has a drawback in that it causes more light stain (yellow stain) due to light irradiation than conventional cyan couplers. As a means to solve this problem, the patent application 1986-/7
As described in No. 1,31-, there is a method of using the cyan coupler and an ultraviolet absorber together. but,
It is unavoidable that the film thickness increases due to the use of ultraviolet absorbers and that the sharpness deteriorates accordingly. On the other hand, when a coupler represented by the general formula (I) is used in combination according to the present invention - the sharpness is improved, light staining is effectively prevented, and excellent color image storage properties are obtained. In addition to the characteristic that the cyan coupler used in the invention inherently has of little change in hue due to one concentration, the color image storage stability is also improved, so that a very good silver halide photographic light-sensitive material can be obtained.Furthermore, the present invention The composition of the dye used in the present invention will be described in detail. and, as a result of the reaction, produces a compound or a precursor thereof having a dye moiety having a maximum absorption wavelength before shifting" includes those represented by the first-order general formula (I). Cp-(TIME)-X-Dye (I) where,
cp represents a coupler residue capable of releasing -(TIME)-X-Dye through a coupling reaction with an oxidized form of an aromatic primary amine developing agent. TIME represents a timing group, and n represents O or a positive integer. Dye is a dye residue and X represents an auxochrome residue of the dye. Here, the coupler residue represented by Cp forms a dye through a coupling reaction with an oxidized product of an aromatic primary amine developing agent. In some cases, it forms a colorless substance (so-called colorless coupler residue). When Cp has a diffusion-resistant group,
It may have a diffusion-resistant group or an alkali solubilizing group. When n≧/, 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. The mechanism for releasing -X-Dye when it has TIME is, for example, -photographically useful group C or less. Mention may be made of those disclosed as release timing type couplers (abbreviated as PUG). A method for releasing PUG by an intramolecular nucleophilic substitution reaction after elimination, described in U.S. Pat. 7-7, μ234L, and j7-/1103! A method for releasing PUG by electron movement along a conjugated system after detachment, described in JP-A-1-7-! No. 6137- and same sr-ko 7I
A method of releasing PUG by causing an intramolecular nucleophilic substitution reaction with a newly generated nucleophilic group by electron transfer along a conjugated system after one separation described in No. AO 1% Ganshoj Day 7! lA
7! Same issue! Examples include a method of releasing PUG by cleavage of hemiacetal after detachment, as described in Patent No. 71. The coupler of the present invention includes not only the case where the coupler has a timing group represented by the general formula (I) but also the case where the coupler has a trivalent timing group such as a primary one. For example, as described in 1% Kaisho J-R-20R No. 7AO, -Cp and TIME have a bond also in the non-coupling site of cp, and the coupling reaction with the oxidized form of the developing agent and There are cases where Cp and TIME remain bonded even after the subsequent reaction. Also, special request Akira! 19-1
97/ri issue, same! Tata Ohiro 37-same j9-taco 11
+ issue, and the same! 9-? 2! As described in No. J7, the case 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 the subsequent reaction is 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 subsequent reactions. Alternatively, in the structure of general formula (I), such an uncleavable bond is replaced by Cp and T.
It is also possible to have IME and between TIME and Dye. 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 short wavelength side due to the auxochrome group being blocked by Cpt or TIME. These pigments are described, for example, by J. Fabian, H. Hartmann, @Light Absorption.
Of Organic Calaransi (LightAbso)
rption of Organic Co1ora
ntsl'. (Springer-
Verlag), but is not limited to these. The most desirable dyes are those which have the appropriate hue in the dissociated state of the auxiliary chromophore. Preferred dyes include substituted aromatic azo dyes and substituted heterocyclic aromatic azo dyes represented by the following general formula ([). General formula (IV) -X-y1-N=N-Y2 In the formula, X has the same meaning as defined in general formula (I) and represents 110-1-S-1 or L-N- . However, L represents a hydrogen atom, an aliphatic group, an aromatic group or an acyl group. Yl represents an atomic group that contains at least one unsaturated bond that is in a conjugate relationship with an azo group and connects to X through an atom that constitutes the unsaturated bond; Represents an atomic group containing one. The total number of carbon atoms contained in yl> and Yl is 10 or more. In the general formula (Yl), Yl and Yl 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 mononitrogen A 4! to 7-membered ring heterocyclic group having one atom sulfur atom or a petro atom selected from an oxygen atom is preferable and may be a benzene-fused ring. Examples of the heterocyclic group include pyrrole, thiophene-furan, imidazole, etc. -/, 2.4<- A group having a ring structure such as triazole-oxazole, thiadiazole, pyridine, indole, benzothiophene-benzimidazole, or benzoxazole. Yl has a substituent in addition to X and an azo group. may have,
Substituents include aliphatic groups, aromatic groups - acyl groups, alkoxycarbonyl groups - aryloxycarbonyl groups, acylamino groups, alkylthio groups, arylthio groups, heterocyclic groups, sulfonyl groups - halogen atoms - nitro groups, nitroso groups, Cyano group. Carboxyl group - Hydroxyl group - Sulponamide group -
These include an alkoxy group, an aryloxy group, an acyloxy group, and a carbamoyl group-amine group, a ureido group, a sulfamoyl group, a carbamoylsulfonyl group, or a hydrazinyl group. These groups may be further substituted. When Yl represents a substituted aromatic group or a substituted unsaturated heterocyclic group, the substituents include those listed above for Y1. When Yl and Yl contain an aliphatic group moiety as a substituent, it may be substituted or unsubstituted, saturated or unsaturated, linear or branched, linear or cyclic, with 7 to 3λ carbon atoms, preferably / -20. There may be. When Yl and Yl contain an aromatic group moiety as a substituent, the number of carbon atoms is a-io, and it is preferably a substituted or unsubstituted phenyl group. Among the groups represented by general formula (IV), preferred examples are as follows. (D-2) (D-3) (D-≠) (D-A) In the formula, X' is 10-1-8-1 or. -N- and -L1 represents a hydrogen atom-aliphatic group, aromatic group, or group. W represents a substituent selected from those listed as substituents for Yl and Y2 in the general formula (I't7), n represents θ-/or λ, -q represents O1/-2 or 3, and - r represents O- or an integer from 7 to 7; Preferably W represents -8O2L2 or -C(B3)3. B2 represents an aliphatic group, an aromatic group, a heterocyclic group, or an amino group, each of which may be unsubstituted or have a substituent, and B3 represents a norogen atom. B1- B2 and B3-B4 each represent a hydrogen atom or a substituent explained for W, or B1
, B2-B5 and B4 may be connected to each other to represent a benzene condensed ring. When a benzene condensed ring is not represented, at least one of B1 and B2 is preferably an electron-absorbing group. When representing a benzene condensed ring, the moiety may be substituted with a substituent represented by W. In the formula, when p-q or r represents a number of 2 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. (2) When 2 represents an aliphatic hydrocarbon residue, it may be either saturated or unsaturated, and may be linear or branched-cyclic. Preferred are alkyl groups having 1 to 22 carbon atoms (such as methyl, ethyl, isopropyl, butyl, dodecyl, octadecyl, cyclohexyl, etc.) - alkenyl groups (for example, allyl, octenyl, etc.) . The aryl group is preferably a phenyl group. Examples of naphthyl groups and heterocyclic groups include -pyridinyl, quinolyl, chenyl-piperidyl, and imidazolyl. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic groups include Y in the general formula (I()).
The following are listed for l. v3 is a carbon atom/~32. Preference 1. < is/~λλ linear or branched argyl, alkenyl - cyclic alkyl, aralkyl, cyclic alkenyl group - aryl group and heterocyclic group - alkoxycarbonyl group (methoxycarbonyl group, stearyloxycarbonyl group, etc.) −
-ruoxy carbonyl group (e.g. phenoxycarbonyl group, naphthoxycarbonyl group, etc.) -aralkyloxycarbonyl group (e.g. benzyloxycarbonyl group, etc.)
, alkoxy groups (e.g., methoxy-ethoxy, heptadecyloxy, etc.); -amylphenoxy)acetamido]benzamide group, etc.) -diacyl amino group, N-alkyl acylamino group (e.g. N-, methylpropionamide group)
, N-arylamylamino group (C e.g. N-phenylacetamide group), ureido group (e.g. ureido, N-
aryl ureido, N-alkylureido groups, etc.), alkylamino groups (e.g. (alkylsulfonic acid group, arylsulfonic acid group, etc.). These groups may have the substituents listed for Yl in the general formula (III). v3 also represents a halogen atom (for example, a chlorine atom, a bromine atom, etc.), a cyano group. Ua, Ub, and Uc is methine, substituted methine-=N-
1 or -NH-, -Ua-Ut+ bond and Ub-
One of the Uc bonds is a double bond. The other is a single bond. However, Ua-Ub. Uc is never N at the same time. Ub-Uc is 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 ¥1 above. Further, either Ua-Ub or Uc is combined with -X' to take the form -X/-(:=. In general formula (I), -Cp-+Time-74 or
It may be a bis-type coupler or a polymer coupler in which two or more molecules are connected at the -Dye portion. Furthermore, the present invention is particularly effective for the general formula (I
), cp is represented by the following general formula IV), (■). (■)-(■)-(■i (X), (ML, (■), α
TII)-(X!V[or (xv). These couplers have a high coupling rate and are preferable. P2 General formula (MI General formula (■) General formula (IX) General formula (X) Ps General formula ('M) General formula (X[[) General formula rxm+ General 2〇 (IV) 〇General formula (x■) PIOCHpH In the above formula, the free bond derived from the coupling position represents the bonding position of one coupling-off group.In the above formula, Pi, P2-Ps, P4゜P5.Ps-P7,
When Ps, P9, PIG or pH contains a diffusion-resistant group,
It is selected such that the total number of carbons is r~3, preferably 10-λ, otherwise the total number of carbons is preferably less than /o. Next K, P1 to P1□ of the general formulas (v) to CX■). k, t, and m will be explained. In the formula, -Pl represents an aliphatic group, aromatic group, alkoxy group or heterocyclic group, and P2 and Ps each represent an aromatic group or a heterocyclic group. In the formula, the aliphatic group represented by PI preferably has a carbon number/
-22, which may be e-substituted or unsubstituted, linear or cyclic. Preferred substituents for the alkyl group include an alkoxy group, an aryloxy group, an amine group-acylamino group, and a halogen atom, which may themselves have further substituents. Specific examples of aliphatic groups useful as Pl are: isopropyl, isobutyl, tart-butyl, isoamyl. tert-amyl group, l,/-dimethylbutyl group. /, l-dimethylhexyl group, /, /-diethylhexyl group, dodecyl group, hexadecyl group-octadecyl group,
Cyclohexyl group, 2-methoxyisopropyl group, 2-
Phenoxyisoprobyl group. 'p-tert--/tylphenoxyisopropyl group, α-aminoisopropyl group, α-(diethylamino)isopropyl group-α-(axinimido)isopropyl group, α-Cphthalimido)isopropyl group, α-(benzenesulfonamide) Examples include inpropyl group. If Pl, P2 or Ps represents an aromatic group, in particular a phenyl group - the aromatic group may be substituted. Aromatic groups such as phenyl groups include alkyl groups having 32 or less carbon atoms, alkenyl groups, alkoxy groups-alkoxycarbonyl groups,
It may be substituted with an alkoxycarbonylamino group, a fatty acid amide group, an alkylsulfazoyl group, an alkylsulfonamide group, an alkylureido group, an alkyl-substituted succinimide group, etc. In this case, the alkyl group is an aromatic group such as phenylene in the middle. may intervene. The phenyl group may also be substituted with an aryloxy group, an aryloxycarbonyl group, an arylcarbamoyl group, an arylamido-arylsulfamoyl group, an arylsulfonamide group, an arylureido group, etc. The Ryl group moiety may be further substituted with one or more alkyl groups having a total number of carbon atoms of / to 2-. The phenyl group represented by Pl-P2 or Ps further includes an amino group, including one substituted with a lower alkyl group having 7 to 2 carbon atoms, a hydroxy group, a carboxy group, a sulfo group-nitro group, a cyan group, a thiocyano group. Alternatively, it may be substituted with a halogen atom. Pl-p2t or P3 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 coumaranyl group, or a tetrahydronaphthyl group. These substituents may themselves have further substituents. When Pl represents an alkoxy group, the alkyl moiety has carbon atoms ranging from 1 to 32. Preferably, it represents a linear or branched alkyl group, alkenyl group, cyclic alkyl group, or cyclic alkenyl group of 1 to λ, and these are a halogen atom or a ring group. It may be substituted with an alkoxy group or the like. When Pl, P2 or P3 represents a heterocyclic group, the heterocyclic group is connected to the carbon atom of the carbonyl group of the acyl group in alpha acylacetamide or 9 of the amide group via one of the carbon atoms forming the ring, respectively. Combines with elementary atoms. Such heterocycles include thiophene-furan, pyran, and virol. Examples include pyrazole, pyridine, virazine-pyrimidine-pyritazine/, indolizine, imidazole, thiazole, oxazole, triazine, thiadiazine, and oxazine. These may further have a substituent on the ring. In the general formula (■), P5 is a linear or branched alkyl group having 1 to 32 carbon atoms, preferably 1 to 2.2 carbon atoms (for example, methyl, isopropyl-tert-butyl, hexyl, dodecyl group, etc.), alkenyl Group C (e.g. allyl group, etc.), cyclic alkyl group (e.g. cycloantyl group, cyclohexyl group, norbornyl group, etc.), aralkyl group (e.g. benzyl, β-phenylethyl group, etc.), aralkyl group (e.g. benzyl, β-phenylethyl group, etc.)
For example, cyclopentenyl, cyclohexenyl group, etc.), and these are halogen atoms. Nitro group, cyan group, aryl group, alkoxy group. Aryloxy group, carboxy group, alkylthiocarbonyl group, arylthiocarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, sulfo group-sulfamoyl group-carbamoyl group, acylamino group, cyanuramino group-ureido group, urethane group-thiourethane group, Sulfonamide group, hetero 1] group, arylsulfonyl group, alkylsulfonyl group, arylthio group, alkylthio group, alkylamino group, dialkylamino group-anilino group, N-arylanilino group, N-argylanilino group, N-acylanilino group , a hydroxyl group, a 2-mercapto group, etc. may be substituted. Furthermore, P5 may represent an aryl group (for example, a phenyl group -α- to β-naphthyl group). The aryl group may have one or more substituents, such as an alkyl group, an alkenyl group, a cyclic alkyl group, an aralkyl group, a cyclic alkenyl group, a halogen atom, a nitro group, a cyano group, an aryl group, and an alkyl group. group, aryloxy group. Carboxy 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, A+7-ruthio group-furkylthio group, alkylamino group, dialkylamino group. Anilino group-N-alkylanilino group, N-arylanilino group, N-acylanilino group, hydronashi group, mercapto group, etc. may be included. More preferred as P5 is phenyl in which at least 7 of the mono-ortho positions are substituted with an alkyl group, an alkoxy group, or a halogen atom. It is small and useful. Furthermore, P5 contains a monoheterocyclic group C, for example, a nitrogen atom-oxygen atom or a sulfur atom as a petro atom! a negative or JJj ring heterocycle-fused heterocyclic group (pyridyl, quinolyl, furyl, benzothiazolyl, oxasilyl, imidazolyl, naphthoxacylyl, etc.), substituted with the substituents listed for the aryl group above. heterocyclic group, aliphatic or aromatic acyl group, alkylsulfonyl group. Arylsulfonyl group, alkylcarbamoyl group. Arylcarbamoyl group - may represent an alkylthiocarbamoyl group or an arylthiocarbamoyl group. In the formula, -P4 is a hydrogen atom, a straight chain or branched alkyl, alkenyl, cyclic alkyl, or aralkyl having from / to 32 carbon atoms, preferably from / to one. Cyclic alkenyl groups (these groups may have the substituents listed for P5 above), aryl groups and heterocyclic groups may have the substituents listed for P5 above), alkoxycarbonyl groups (e.g., methoxycarbonyl group - ethoxycarbonyl group, stearyloxycarbonyl group, etc.), aryloxycarbonyl group (e.g., phenoxycarbonyl group, naphthoxycarbonyl group, etc.) - aralkyloxycarbonyl group (e.g., benzyloxycarbonyl group, etc.), alkoxy Group C (eg, methoxy group-ethoxy group-heptadecyloquine group, etc.), aryloxy group (eg, phenoxy group, tolyluoquine group, etc.), alkylthio group (eg, ethylthio group, dodecylthio group, etc.). Arylthio group (e.g. phenylthio group, α-naphthylthio group, etc.), carboxy group, acylamino group (e.g. acetylamino group-3-[Cλ, l-di-tert-amylphenoxy)acetamide] benzamide group, etc.),
Diacylamino group + N-alkyl acylamino group (e.g. N-methylpropionamide group, etc.) -N-arylacylamino group C (e.g. N-phenylacetamide group, etc.) -ureido group C e.g. ureido, N-arylureido, N-alkylureido group, etc.), urethane group-thiourethane group, arylamino group C, e.g. phenylamino-N-methylanilino group-diphenylamino group-N-
Acetylanilino group, 2-chloro-! -tetradecanamidoanilino group, etc.) -alkylamino group (e.g. n
-butylamino group. (methylamino group, cyclohexylamino group, etc.), cycloamino group C (e.g. piperidino group, pyrrolidino group, etc.)
, a heterocyclic amino group (e.g. ≠-bilidylnamino group 1.2
-benzoxasilylamino groups, etc.), alkylcarbonyl groups (e.g., methylcarbonyl groups, etc.), arylcarbonyl groups (e.g., phenylcarbonyl groups, etc.), sulfonamide groups (e.g., alkylsulfonamide groups, arylsulfonamide groups, etc.), Carbamoyl group (e.g. ethylcarbamoyl group, dimethylcarbamoyl group -N-
methyl-phenylcarbamoyl-N-phenylcarbamoyl, etc.), sulfamoyl group r example, tHN-alkylsulfamoyl, N,N-dialkylsulfamoyl group, N-arylsulfamoyl g-N-alkyl-N-
arylsulfamoyl M, N, N-diarylsulfamoyl group, etc.), cyano group, hydroxy group, mercapto group. Represents either a halogen atom or a sulfo group. In the formula, P6 represents a hydrogen atom or a linear or branched alkyl group having carbon atoms of / to 32°, preferably / to 22, an alkenyl group, a cyclic alkyl group, an aralkyl group, or a cyclic alkenyl group. may have the substituents listed above. Further, P6 may represent an aryl group or a 7I ring group, and these may have the substituents listed for P5 above. ) Also, P6 is a cyano group, an alkoxy group-aryloxy group, a halogen atom, a carboxy group-alkoxycarbonyl group-aryloxycarbonyl group-acyloxy group,
Sulfo group, sulfamoyl group, carbamoyl group, acylamino group, diacylamino group - ureido group - urethane group, sulfonami) group, arylsulfonyl group - alkylsulfonyl group, arylthio group, alkylthio group - alkylamino group, dialkylamino group, anilino group Group-N
-Arylanilino group, N-alkylanilino group%N-
It may also represent an acymu anilino group, a hydroxy group or a mercapto group. P7. P8 and P9 each represent a group used in a typical μ-equivalent type phenol or α-naphthol coupler, and specifically, P7 is a hydrogen atom, a halogen atom-alkoxycarpho'dyl amino group, or an aliphatic hydrocarbon residue. , N-7 aryl ureido group, acylamino group --
o-p12 or -8-PI3 (where PI3 is an aliphatic hydrocarbon residue), and if there are 1/(u or more P7s in one molecule, two or more P7s are different groups). The aliphatic hydrocarbon residues include those having substituents. Also, when these substituents include an aryl group, the aryl group may have the substituents listed for P5 above. P8 and P9 are aliphatic hydrocarbon residues. Mention may be made of groups selected from aryl groups and heterocyclic residues - or one of these may be a hydrogen atom; Including those with substituents, P8 and P9 may jointly form a nitrogen-containing heterocyclic nucleus.The aliphatic hydrocarbon residue may be either saturated or unsaturated. It may be straight-chain or straight-chain. It may be any branched tortoise chain, and preferably contains an alkyl group (e.g. methyl, ethylpropyl, isopropyl, butyl, t-butyl-inbutyl, dodecyl-octadecyl, cyclobutyl, cyclohexyl, etc.) ), alkenyl groups (C such as allyl, octenyl, etc.). Aryl groups include phenyl group, naphthyl group, etc.
Representative heterocyclic residues include pyridinyl-quinolyl, chenyl, bilysyl, imidazolyl, and the like. Substituents introduced into these aliphatic hydrocarbon residues, aryl groups, and heterocyclic residues include halogen atoms, nitro, hydroxy, carboxyl, amino, substituted amino, and sulfo. Examples include groups such as alkyl, alkenyl, aryl, heterocycle, alkoxy-aryloxy, arylthioarylaso, acylamino, carbamoyl, ester, acyl, acyloxy, sulfonamide, sulfamoyl, sulfonyl, and morpholino. L is an integer of /~μ, 1m is an integer of 1 to 3, and k is an integer of /~. PIO is an arylcarbonyl group, preferably an alkanoyl group having 2 to 3 carbon atoms, preferably 2 to 2 carbon atoms, an arylcarbamoyl group, an alkanecarbamoyl group having 2 to 3 carbon atoms, preferably 1 to 2 carbon atoms, preferably 1 to 3 carbon atoms. represents an arylcarbonyl group or an aryloxycarbonyl group of /~2.2, which may have a substituent, such as an alkoxy group, an alkoxycarbonyl group, an acylamino group, an alkylsulfamoyl group, an alkyl Examples include a sulfonamide group, an alkylsuccinimide group, a halogen atom, a nitro group, a carboxyl group, a nitrile group, an alkyl group, and an aryl group. The pH is a carbonyl group, preferably λ to 32 carbon atoms, a 2-alkanoyl group, an arylcarbamoyl group, an alkanecarbamoyl group having 3 carbon atoms, preferably λ to 2 carbon atoms, 1 to 3 carbon atoms. Preferably! -22 alkoxycarbonyl groups or aryloxycarbonyl groups, la/~31 preferably 1 to 2 alkanesulfonyl groups -arylsulfonyl groups -aryl groups,! Negative or t-membered heterocyclic group (heteroatoms include nitrogen atom,
Selected from oxygen atom-sulfur atom, for example triazolyl group, imidazolyl group, phthalimide group. a succinimide group, a furyl group, a pyridyl group or a benzotriazolyl group;
It may have the substituents mentioned above. As mentioned above, in m 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 campling reaction has diffusivity depending on the non-diffusion resistant group that Cp has. Furthermore, when Cp has an alkali solubilizing group. The compounds formed by the coupling reaction will be eluted from the film. The coupler represented by the general formula (I) of the present invention may also be a monopolymer. That is, it is derived from a monomeric coupler represented by the following general formula CX), and the general formula C
A polymer having repeating units represented by - or
It is a copolymer with seven or more types of non-chromogenic monomers containing at least one ethylene group that do not have the ability to couple with the oxidized product of an aromatic primary amine active ingredient. Here, two or more types of monomer strength pullers may be simultaneously polymerized. General formula (X) CH2=C+A2+r+A3+T+A1 Q General formula (X
■) +CH2-C-)- ■ (A2ga→A3force→A1hoQ In the formula, P is a hydrogen atom, a lower alkyl group having carbon number/~μ,
or represents a chlorine atom, and AI is -CONH-, -NH
CONH-1-NHCOO-. -COO-1-so2-1-〇〇-1-NHCO-. -8O2NH-, -NH8O2-, -0CO-. -0CONH---NH-1-8- or -0-, and A2 represents -CONH- or -COO-. A3 represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 7 to 10 carbon atoms, and the alkylene group may be linear or branched. (Examples of alkylene groups include methylene, methylmethylene-dimethylmethylene, dimethylene, trimethylene-tetramethylene, intamethylene-hexamethylene,
(Tesylmethylene-aralkylene group, for example, benzylidene, arylene group, for example, phenylene, naphthylene, etc.) Q represents a compound residue represented by m general formula (I),
It may be bound at any of the Cp, TIME- and Dye sites. Lj, and h#'i-O or l, but i, j
, and h cannot be O at the same time. Here, the substituents of the alkylene group-aralkylene group or arylene group represented by A3 include an aryl group (e.g. phenyl group)-nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group. (e.g. phenoxy group)-acyloxy group (e.g. acetoxy group). Acylamino group (e.g. acetylamino group) - Sulfonamide group (e.g. methanesulfonamide group) - Sulfamoyl group (e.g. methylsulfamoyl group), Halogen atom (e.g. fluorine, chlorine, bromine, etc.) - Carboxy group, carbamoyl group (e.g. methylcarbamoyl group), alkoxycarbonyl group (eg, methoxycarbonyl group), and sulfol group (eg, methylsulfonyl group). When there are λ or more substituents, they may be the same or different. Next, non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid, and derivatives of these acrylic acids. Examples include esters or amides, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds-maleic acid conductors, and vinylpyridines. The non-color-forming ethylenically unsaturated monomer used here can also be used in combinations of 2s or more. The compound represented by the general formula (I) of the present invention is
9-/77t70-same rq-a71rto, same AD
-60//≠ issue, same to tough 119, same j /-4
It can be synthesized by the method described in tJ≦jj. Next, the compounds represented by the general formulas rII) and rIII) will be described in detail below. Examples of the aromatic group represented by R1 include substituted or unsubstituted aromatic groups in which the aromatic residue has t to 30 carbon atoms. Examples of the aliphatic group represented by R3 include substituted or unsubstituted aliphatic groups in which the aliphatic residue has 7 to 30 carbon atoms. Examples of the heterocyclic group represented by R1 include substituted or unsubstituted heterocyclic groups in which the heterocyclic residue has 2 to 30 carbon atoms. R2 represents a group (including a W atom, the same applies hereinafter) that can be substituted on the naphthol ring, and typical examples include a halogen atom, a hydroxy group, an amino group, a carboxyl group, a sulfonic acid group, a cyano group, an aromatic group, and a heterocyclic group. - Carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic sulfonyl group - aromatic Examples include a group sulfonyl group, a sulfamoylamino group, a nitro group, an imide group, and the number of carbon atoms contained in R2 is θ to 30. 2 R2
Examples of cyclic R2 include a dioxymethylene group. Z2 represents >0, >S or R4N, and -R4 represents hydrogen or a heptavalent group. The monovalent group is preferably represented by the following general formula (■). RIO(Z a )T(■) Here, Z3 represents 7CO or S02, -d represents zero or /, and -RIO is a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, and t to 30 carbon atoms. aromatic group, carbon 11-J
In oo hetero'fM group, -0H--ORII, .R11 and R12 represent an aliphatic group, aromatic group, heterocyclic group or hydrogen atom, and in NRII R12, R11 and R12
12 may be the same or different. R11 and R1 of -NRII R12 in RIO
2 may be bonded to each other to form a nitrogen-containing heterocycle (morpholine ring-pi is a lysine ring-pyrrolidine ring, etc.). zl represents a hydrogen atom or a coupling-off group (including a separation thickness; the same applies hereinafter). Typical examples of coupling-off groups include halogen atoms -0R13-0CR13, NH
302R13-10C-OR13--0CNHR1a-
Examples include heterocyclic groups having 1 to 30 carbon atoms and connected to the coupling active position of the coupler via a nitrogen atom (succinimide group, phthalimide group, hydantoinyl group, pyrazolyl group, cobenzotriazolyl group, etc.). can. Here, R13 is an aliphatic group having a carbon number/~30, and a carbon number 6~
30 aromatic group or a heterocyclic group having λ to 30 carbon atoms. D represents an aromatic group having 6 to λO carbon atoms or a heterocyclic group having 2 to λ0 carbon atoms. In the present invention, aliphatic groups are monosaturated and unsaturated. They may be substituted or unsubstituted, linear, branched, or cyclic; typical examples include methyl group, ethyl group, hydroxyethyl group, butyl group, cyclohexyl group, allyl group, and pro/cergyl group. , methoxyethyl group, n-7" yl group - n-dodecyl group, n-hexatecyl group,) Q fluoromethyl group - hebutafluoropropyl group, dodecyloxypropyl group, co-, tert-amylphenoxypropyl group, λ,≠-di-tert-amylphenoxybutyl group, etc.Aromatic groups may also be substituted or unsubstituted, and typical examples include -phenyl group, naphthyl group, tolyl group, -1 Tetradecyloxyphenylene A4, -'?ntafluorophenyl group-≠-tert-octylphenyl group-
Included are m2-chloro-1-)'f syloxycarzenylphenyl group, μm chlorophenyl group, ≠-methoxyphenyl group, ≠-hydroxyphenyl group, and the like. In addition, the heterocyclic group may be substituted or unsubstituted,
Typical examples are 11-pyridyl group-≠-pyridyl group,
- monofuryl group - μm chenyl group. Includes quinolinyl group, 1 μm pyrazolyl group, etc. Preferred examples of substituents are explained below. R1 is preferably an aromatic group, with 1% preferably a phenyl group and a naphthyl group. Preferred substituents for aromatic groups include alkoxy groups (e.g., tetradecyloxy, methoxy), alkoxycarbonyl (e.g., dodecyloxycarbonyl, methoxycarbonyl), acylamino groups (e.g., ≠-(co, 4L-tert), -amylphenoxy)butanamide group, tetradecanamide group), sulfonamide group (e.g. hexadecylsulfonamide, do group), sulfamoyl group (C e.g. J-(,2,
≠-di-tert-amylphenoxypropylsulfamoyl group + N,N-diethylsulfamoyl group. hexatecylsulfamoyl group) -carbamoyl group (e.g. dodecylcarbamoyl group -≠-[2゜≠-dite
rt-amylphenoxy)butylcarbamoyl group), imide groups (e.g. dodecylsuccinimide group-octadecenylsuccinimide group). Examples of sulfonyl group r, t is dodecylsulfonyl group - furo,
R sulfonyl group, methanesulfonyl group), m-aliphatic thio group (for example, dodecylthio group-ethylthio group), halogen atom-cyano group, aliphatic group (eg, methyl group, t-butyl group), and the like. Regarding R2, a and bK, a=b=0 (most preferably when D, then a=i or b=/ and R2 is a halogen atom, an aliphatic group f such as a methyl group, an ethyl group, a t-octyl group)-acylamino group C such as acetamido group, butanamide group), sulfonamide group C such as benzenesulfonamide group. Preferred examples include a methanesulfonamide group), an alkoxyacylamino group (eg, an ethoxycarbonylamino group, an isobutoxycarbonylamino group), and the like. The aliphatic group represented by R3 is 1, for example, a methyl group. Examples include propyl group, butyl group + tart-butyl group-bentyl group, tridecyl group, and cases where these have a substituent. Preferred substituents for aliphatic groups include aromatic oxy groups such as 1 μm di-tert-amylphenoxy group, 21 μm di-tert-hexylphenoxy group, 2. μm sheet tert-octylphenoxy group-2-chlorophenoxy group, μ-(≠-hydroxyphenylsulfonyl)phenoxy group)-aliphatic oxy group (e.g. evamethoxy group, ethoxy group, dodecyloxy group, hexadecyloxy group)-sulfone Examples include amide groups (eg, methanesulfonamide group, μm methylbenzenesulfonamide group), and the like. Preferable Z2 is R2H, , where R4 is 100R1o C formyl group - acetyl group - trifluoroacetyl group - chloroacetyl group, hensoyl group, interfluorobenzoyl group - p-chlorobenzoyl group, etc.), - COOR1, (methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, decyloxycarbonyl group, methoxyethoxycarbonyl group, phenoxycarbonyl group) -S 02 RIO (methanesulfonyl group - ethanesulfonyl group, phthanesulfonyl group, hexadecanesulfonyl group, benzenesulfonyl group, toluenesulfonyl group-p-chlorobenzenesulfonyl group, etc.), -CONR11R□2 (N,N-dimethylcarbamoyl group, N,N-diethylcarbamoyl group, N,
N-dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group -≠-cyanophenylcarbonyl group, 31≠-dichlorophenylcarbamoyl group, Hiro-methanesulfonylphenylcarbamoyl group Nato1- -8O2NR11R12 (N,N-dimethylsulfur group) moyl group, N,N-diethylsulfamoyl group, N-dipropylsulfamoyl group, etc.). Particularly preferred Z2 are -coR1o--COOR□ and -8O2R1. Here, R11-R12 have the same meanings as before. Preferred examples of zl include a hydrogen atom-halogen atom, an aliphatic oxy group, and an aromatic oxy group. The couplers represented by general formulas (II) and (m) are mutually 〈
A λ-mer or more multimers may be formed to bind. In this case, the carbon number range shown above for each substituent may be outside the specified range. When the coupler represented by the above general formula forms a multimer, a typical example is a single or copolymer of an addition-polymerizable ethylenically unsaturated compound (cyan color-forming additive) having a cyan dye-forming coupler residue. In this case, the multimer contains repeating units of the general formula (XK), and seven or more types of cyan color-forming repeating units represented by the general formula (XK) may be contained in the multimer, which is non-conforming as a co-electrochemical synthesis. It may also be a copolymer containing one or more color-forming ethylene-like monomers. In the formula, R13 represents a hydrogen atom, an alkyl group having 1-μ carbon atoms, or a chlorine atom, and E represents 100NH-. -C00- or a substituted or unsubstituted phenylene group, G represents a substituted or unsubstituted alkylene group -phenylene group or an aralkylene group -T is -CONH-
--NHCONH-, -NHCOO--NHCO-1-
0CONH-1-NH-, -COO-. -oco, -co-1-o-, -5o2-1-NH8O
Represents 2- or -8O2NH-. f. g and t represent O or l. QQ represents a cyan coupler residue from which a hydrogen atom other than the hydrogen atom of the hydroxyl group at the 1-position of synapthol has been removed from the compounds represented by the general formulas (TI) and (m). As the multimer, a copolymer of a cyan color-forming polymer giving a coupler unit of the general formula (XK) and a non-color-forming ethylene-like monomer described below is preferred. As a non-color-forming ethylene-like monomer that does not couple with the oxidation product of an aromatic-grade amine developer. Acrylic acid - α-chloroacrylic acid, α-alacrylic acid [e.g. methacrylic acid, etc.] Esters or amides derived from these acrylic acids (e.g. acrylamide, methacrylamide, n-butylacrylamide, t-dutylacrylamide) , diacetone acrylamide, methylene bisacrylamide, methyl acrylate, ethyl acrylate, n-
Propyl acrylate, n-butyl acrylate, t
-butyl acrylate -1so-7'' thyl acrylate, coethylhexyl acrylate, n-octyl acrylate, lauryl acrylate - methyl methacrylate - ethyl methacrylate - n-butyl methacrylate (beta-hydroxy methacrylate), vinyl ester f e.g. vinyl acetate, vinyl zolobionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds such as styrene and its derivatives - such as vinyltoluene, divinylbenzene, vinylacetophenone and sulphostyrene), itaconic acid. Citraconic acid-crotonic acid, vinylidene Chloride, vinyl alkyl ether (e.g. vinyl ethyl ether)
, maleic acid ester, N-vinyl-2-pyrrolidone,
Examples include N-vinylpyridine and Co and 1 μm vinylpyridine. Particularly preferred are acrylic esters, methacrylic esters, and maleic esters. The non-color-forming ethylene-like monomer used here can also be used together with 27f or more. 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. Polymer Cub 2 - When containing repeating units represented by the above general formula (2) as well known in the art. In order to form this, the non-chromogenic ethylene-like monomer copolymerized with the ethylene-like monomer having cyan dye-forming residues of the present invention is determined by the physical and/or chemical properties of the copolymer formed, e.g. Solubility, compatibility of the photographic colloidal composition with binders such as gelatin - its readability,
It can be selected so that thermal stability etc. are favorably affected. The cyan polymer coupler C used in the present invention (a lipophilic polymer coupler obtained by polymerization of a vinyl monomer that provides a coupler unit represented by the general formula (XK)) is dissolved in an organic solvent and added to an aqueous gelatin solution. It may be made by emulsifying and dispersing it in the form of latex, 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. three! /, t20, and U.S. Patent No. tt for emulsion polymerization.
, oro, 2// issue, same 3゜J 70. Ta! The method described in No. λ can be used. The coupler represented by the general formula (It) is disclosed in the U.S. patent μ,
Coj μ, +27 Co., same μ, +2ri No. 6,199, Same J
, 4Ll#, /93, English
,. ! It can be synthesized by the method described in Japanese Patent Publication No. 07, Japanese Patent Publication No. Shoyo ψ-37122, etc. The coupler represented by the general formula (I[) is the patented Shoj Tata 360! Same issue! 9-, 2J≠277 and the same! Tar 2
6♂/3! P-synthesis is performed by the method described in No. The compounds of general formulas (I) and (II) or (U) of the present invention can be used in multilayer, multicolor photographic materials having at least three different spectral sensitivities on a support, mainly for improving sharpness and improving sensitivity. It can be applied for the purpose of improving properties.Multilayer natural color photographic materials usually consist of a red-sensitive emulsion layer, a green-sensitive emulsion layer,
and at least one blue-sensitive emulsion layer. Headnotes for these layers can be selected arbitrarily as necessary. The compound of the present invention can be used in any layer such as a high-speed layer, a low-speed layer or a medium-speed layer, and can also be used in any light-sensitive silver halide emulsion layer or a layer adjacent thereto. The amount of the compound of general formula (I) to be added varies depending on the structure of the compound, but is preferably 0.00/-1 mol of F) per mol of silver present in the same layer or an adjacent layer. Particularly preferred is a range of o, ooz to 0.2 mol. The amount of the compound of general formula (It) or (III) to be added varies depending on the structure of the compound, but is preferably from F)/×10-5 to 7 mol of silver present in the same layer or an adjacent layer.
mol, particularly preferably from /x10-' to 0.2 mol. Compounds of general formula (II) and general formula (IF) or (III
) may be used in the same layer or in different layers of the sensitive material. (Compound Examples) Specific examples of the compounds of the present invention are listed below, but the invention is not limited thereto. In general formula (I), the bond between TIME (when n≧/) or Cp (when n=0) and X is cleaved to restore the yellow dye Example S (J21NHu12M25 C02C12H25 Y-2 / 1-C3HH O2 In general formula (I), TIME (when n/) or Cp (when the bond between n=O and X is cleaved,
Example of a coupler that restores magenta dye M-/H3-J M-≠ α In general formula (I), the bond between TIME (when n≧/) or Cp (when n=o) and X is Examples of cazolers that are cleaved to restore cyan dyes Examples of compounds represented by general formula (n) and general formula (III) (!O) (jl) (j2) 02H (!3) (j≠) (!riO2H (!6) (!7) CH2COOC1□H25 (!r) (!ri) (aO) eH2cH2s02t-H3 (t/) (t2) (tj) (tj) (tj) (tbu) ( i) (-'4 on i9U to U 14u (t7) (ar) (Otori) CI (3eoN) 1 0CH2CO2Hx:y=70:
30 (molar ratio) (7 co) ) (:y=60:≠0 (molar ratio) When the new dye-releasing coupler of the present invention is used in a silver halide photographic light-sensitive material, the photosensitive material on the support The dye formed by the coupling reaction between the coupler core of the coupler of the present invention and the oxidized developing agent, or the new dye released during the reaction, can be contained in the photosensitive layer group or the non-photosensitive layer group. If any of the dyes is a yellow dye, it can be contained in the blue-sensitive emulsion layer, if it is a magenta dye, it can be contained in the green-sensitive emulsion layer, and if it is a cyan dye, it can be contained in the red-sensitive emulsion layer. The present invention is not limited to this, and other combinations may also be used.
It is also possible to contain a secondary amine, a tertiary amine compound, or a secondary ammonium salt as described in O, and a polymer mordant containing these as repeating units. The silver halide photographic material used in the present invention may be a monochromatic color photographic material having one light-sensitive silver halide emulsion layer on a support, or a multilayer color photographic material having at least λ different spectral sensitivities on a support. It can also be applied to materials. Further, the present invention can also be applied to photographic materials that use developed silver as an image in addition to the dye produced from the coupler of the present invention. Multilayer color photographic materials usually have at least one each of a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected as necessary. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the green-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. 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 about 2 molts to about 2 molts! It is silver iodobromide containing silver iodide up to molti. Silver halide grains in photographic emulsions include those with regular crystal shapes such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical 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 less than about 1/2 micron or large grains with a projected area diameter of up to about 70 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), Al76≠J(
/27g/72), pp. 22-3, “Engineering, emulsion manufacturing (
Emulsion preparation and
types )' and the same, A/17/1 (I2
7 years//month), 44 cf pages, "Physics and Chemistry of Photography" by Grafkides, published by Beaumontel (P. G1afkides+ Chimie et P.
hysiquePhotographique Pau
``Photographic Emulsion Chemistry'' by Duffin, published by Focal Press (G, F, D
uf f in + PhotographicEmu
lsion Chemistry (Focal P
ressp15'AA), "Manufacture and Coating of Photographic Emulsions" by Zelikman et al., published by 7 Ocal Press (V, L,
Ze 1 ikmanet al+ Making
and CoatingPhotography
c Emulsions Focal Pressy
It can be prepared using the method described in, for example, 6. U.S. Patent No. 3. j74L, No. 1.21,
Same 3rd. T! ! r, 3ri≠ and British Patent No. 1. 'l
Monodisperse emulsions described in -/J, 7tA♂, etc. are also preferred. Also, Asu's kuto ratio is about! Tabular grains such as those described above can also be used in the present invention. Tabular grains are described by Guto 7, Photographic Science and Engineering.
5science and engineering)
+Volume 11-, +2pr~, page 2!7 (70 years ago);
U.S. Patent No. V, ≠3≠. 221, No., same≠,≠/Hiroshi, 310, same Hiro,≠33,
Oμ can be easily prepared by methods such as those described in U.S. Pat. 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. Additives used in such processes are subject to Research Disclosure A/7.
6≠3 and IR'YI6 of the same Constitution, the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also listed in the above two Research Disclosures and are listed in the table below. Additive type RD/7A44J RD/Ir71
tl Chemical sensitizer page 23 Bu 4t, page r right column Sensitivity increasing agent Same as above 3
Spectral sensitizer, 23-24! Page ≠ r Page right column ~
Super sensitizer 2 pages right column μ Brightener λ ≠ page! Anti-fogging agent Pages 27-25 t μ page right column and stabilizer 2 Light absorber, page 2-26 t ≠ right column ~ Ilter dye t y O left column Ultraviolet absorber 7 Stain inhibitor 2 page right Column Page 120 left to right column r Dye image stabilizer Ko! page hardener ko page tri page left column 10 binder λ page same as above/l
Plasticizers, lubricants Core page 120 Right column 12
Coating aids, Table 2t-Page 47 Same as above Surface activator 13 Static prevention Page 27 Same as above Stop agent Various color couplers can be used in the present invention, and specific examples thereof include the above-mentioned Research °Dinuclosion (
RD) A/74≠3, described in the patents described in ■-C to G. As a yellow coupler, for example, U.S. Patent No. 3. Ri3! , No. 101, Hiroshi No. 0.22, A, No. 20,
Same No. μ, j, 2A, 021It No. ≠, ≠O/,
7! No. 2, Tokko Akira! 1r-1073P, British Patent No. 1
,! No. 721.0.20, No. 1. Hiro 7A. Those described in No. 71.0 etc. are preferred. As a magenta coupler! -Pyrazolone and pyrazoloazole compounds are preferred, US Pat.
10. T/ri issue, same issue μ, 3! ! . No. 7, European Patent No. 73, AjA, U.S. Patent No. 3
．． oti, Hiroshi No. 3.2, same No. J, 72! , No. 067, Research Disclosure No. 5 ≠ 220 (/June 27), JP-A-1.0-33j! Co No., Research Disclosure A-2≠230 (lPrlI-June), JP-A No. 4' J Aj, U.S. Patent No.≠, zoo, t3o, same No.≠, tpo, tzti
Particularly preferred are those described in No. Cyan couplers include phenolic and naphthol couplers, and are described in U.S. Pat. 012.2/2, same No. μ, /lft, No. 326, same No. ≠,, 221,233, same No. 1.2 A, 200, same No. 1,3t, Takota No., same No. -2tO/, 171
No. 2, 77, /1, 2, No. 2. rij,
No. 124, No. 3, No. 772, No. 002, No. 3.7
61.3C# issue, same number t, 33≠, 0// issue, same number ≠,
No. 327.173, West German Patent Publication No. 3,327,722
European Patent No. 12/, 31. ! A, U.S. Patent No. 3,
1 bow, No. 6λλ, No. ≠, 333. Tatata issue, same number≠,
≠! /,! ! Preferred are those described in No. 27.7t7, No. 27.7t7, etc. Colored couplers for correcting unnecessary absorption of coloring dyes are disclosed in Research Disclosure-ya/76413, ■-G section, US Pat.
7-32 Hiroj No., U.S. Patent No. ≠, oo≠, Takota No.
μ, /31.2yo2, British Patent No. 1. /≠6.3
Those described in No. ty are preferred. Examples of couplers in which coloring dyes have appropriate diffusivity include U.S. Patent No.≠, JjA, No. 237, and British Patent No. 12!
, Ir70, European Patent No. 570, West German Patent (Publication) No. 3, 23ILt,! The one described in No. 33 is preferred. Typical examples of polymerized dye-forming couplers are described in U.S. Patent No. 3. ≠Yo/, Ir20, Hiromu Dodai, Q♂O, Ko//
No. 367.212, British Patent No. 2,102
, 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 above-mentioned R:()/7A≠3
, Patents described in sections ■ to F, JP-A-37-/! /ri4
L≠, same! 7-1f≠23hiro, same Otsu 0-/I≠ko≠♂,
US Patent No. ≠, Ko Hiro! , No. 262 is preferred. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. S, OP7.1410
No. 2. /J/, No. 111, Tokukai Shojter/! 76
31, those described in t5'-/70r'tO are preferred. Other couplers that can be used in the photosensitive material of the present invention include U.S. Pat. Competitive couplers described in Ko 27 et al., U.S. Pat.
Same number! ,! ,! r, No. 323, same No. ≠, sio, t
Long equivalent coupler described in No. iIr etc., JP-A-Sho tO-/r
! ? ! Examples include DIR redox compound releasing couplers described in No. 0 and the like. The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. Examples of high-boiling organic solvents used in oil-in-water dispersion methods are U.S. Patent No. λ, 322.027.
It is written in the number etc. The steps and effects of latex dispersion methods and specific examples of latex for impregnation are described in U.S. Pat. , No. 31, 3, West German Patent Application (OLS”) No. 2.j4L
/. No. 27μ and No. 2. ! ≠/, No. 230, etc. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D, A/711Aj (7) 2! page r and same, 5117
It is written from the right column on page 6≠7 of 1t to the left column of page 2hiro. The color photographic light-sensitive material according to the present invention has the above-mentioned RD, reduction/71. ≠2 of 3! - Development processing can be carried out by the usual method described in the left column to the right column of page 1 and 17/1 of the same page. The color photographic material of the present invention is usually subjected to a water washing treatment or a stabilization treatment after development, whitening 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 multi-stage countercurrent stabilization treatment as described in JP-A-7-1RJ-Hiroshi No. 3 in the water washing step. (Example) The content of the present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. Example 1 In order to evaluate the effectiveness of the compound of the present invention, a sample was prepared in which a photosensitive layer having the composition shown below was coated in a multilayer structure on a cellulose triacetate film provided with an undercoat multilayer.
I made it oi. (Preparation of sample 10/) Coating amounts are expressed in g/m2 of silver for silver halide and colloidal silver, and in g/m2 for couplers, additives and gelatin. The sensitizing dyes are expressed in moles per mole of silver halide in the same layer. 1st layer (antihalation layer) Black colloidal silver...0.2 gelatin
...7.3 Ultraviolet absorber UV-/
...0. /Same as above UV-2...O8λ Dispersion oil 0il-/...0,0/Same as above
Oil --2...0,0/First layer (intermediate layer) Fine grain silver bromide (average grain size 0.07μ)...0. /! gelatin
...1.0 colored coupler Cp-
/ ... o, i same as above Cp-ko ...
0,0/Dispersion oil Oil/...0. /
No. JFJ (1st red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide molar ratio, average grain size O0≠μ)...silver/, tazelatin.../,! Sensitizing dye I
--・t, 1xlo 'sensitizing dye ■
..., r×1o-5 sensitizing dye■
...J, J'X10' sensitizing dye■
... Ko, Ko Xio 'Coupler C Rouj
-・-0,10 coupler Cp-≠ ・・・0
．． 0 Coupler Cp-Co...0,003
Dispersion oil OiOil/...0.03 Same as above
0i1-J...0.012 μth layer (first
Red-sensitive emulsion layer) Silver iodobromide emulsion (7 moles of silver iodide, average grain size o, Aμ)...silver 1.3 gelatin...i. Sensitizing dye ■ ...t, z x 1o-5 sensitizing dye ■ ... Ko, oxio-5 sensitizing dye ■
···Ko,! X10-'sensitizing dye■...
・Co, jXlo"-5 Casoler Cp-1...0.0
! Coupler cp-+ ・--0,016 Coupler Cp-2...o, oi Dispersion oil 0il-/ ---o, o/Same as above
0il-ko...o, orth! Layer (middle layer) Gelatin...1.0 compound Cp d
-A...0.03 Dispersion oil Oil
-/ -・-0,01 Same as above 0i1-1
...0. Oj second skin (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide μmolti, average grain size O0vμ)...O3 sensitizing dye ■...2. /X10' Sensitizing dye ■...44, j X, / 0-
'Gelatin...i. Coupler cp-7...o, p Coupler Cp-μ...o, ot coupler C
p-/...o, iz dispersion oil 0il-
/ ... o, z 7th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide z morch, average grain size 0.7 μ) ... silver □, tazelatin ... /, 0 increase Sensitive dye V
...-1, oxlo-' sensitizing dye■
...λ, o×i o−'force゛Shiller Cp−ta
・ ・ ・o, o≠Cazolar Cp-7o
...0.0! Coupler cp-/・・
・0.02 coupler Cp-r ・・-o, o
Co-dispersion oil 0il-/ =・0.10 Same as above
Oil -2...-0,0! Layer 1 (Yellow filter single layer) Gelatin °°-/, 2 yellow colloidal silver...o, or compound) 1-j
...0. /Dispersion oil 0il-/・
...Q,! Second layer (first blue-sensitive emulsion layer) Monodisperse silver iodobromide emulsion (silver iodide≠malt, average grain size o, t
iμ)...Silver o, r Gelatin...1. ≠Sensitizing dye■
...jXlo-'coupler cp-//
...0.7 coupler Cp-p ...
...0.07 dispersion oil 0il-/ ...O8
λj io layer (second blue-sensitive emulsion layer) Silver iodobromide (silver iodide iomolti, average grain size i, oμ)...silver o, t gelatin.../, 0 sensitizing dye ■
...-,! ×10' coupler Cp-ii
...0.2! Dispersion oil 0il-/
...0.07 1st/Skin (1st protective layer) Gelatin ...O1! Ultraviolet absorber UV-/ ・・・o, i Same as above UV-2・
・・Q, co-dispersed oil 0 il-/ ...o, oi-dispersed oil 0 il-co ・--0・0/12th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ) ・--0,! Gelatin...O0 Hiro3 Polymethyl methacrylate particles (diameter i, zμ)...0.2 Hardener -i...O,4A formaldehyde scavenger S-/.../, 0 For each layer In addition to the above ingredients, a surfactant was added as a coating aid. The chemical structural formulas or chemical names of the compounds used in the above examples are shown below. Cp-≠ ("p-t (tJU4H9 Cp-x Cp-7 Molecular weight approximately 20.000 α Cp-ta cp-10 α cp-// V-2 Oil-/ Tricresyl phosphate 0il-λ Dibutyl phthalate 0i1- J His (2-ethylhexyl) phthalate pa A -J Sensitizing dye I (UH2) 45 (J 3 N:a Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ 2H5 Sensitizing dye■ Sensitizing dye■ Sensitizing Dye ■ Sensitizing dye ■ - / H The development process used here was conducted under the following conditions with Jr' (: -
It was. (Development processing A) /, color development λ minutes≠j seconds,
Bleach ・・・・・・・・・ 6 minutes 30 seconds 3, water
Washing ・・・・・・ 3 minutes l seconds ≠, fixation ・
・・・・・・・・・ 2 minutes 30 seconds, wash with water ・・・・
・・・・・・ 3 minutes, 1 seconds, stable ・・・・・・・
... 3 minutes/j seconds The composition of the treatment liquid used in each step is as follows. Color developer Sodium nitrilotriacetate 7.01 Sodium sulfite Hiroshi, oy Sodium carbonate 3O, oy Potassium bromide
/, ≠1 hydroxylamine sulfate Ko, Hiro! Hiro-(N-ether-N-βhydroxyethylamino)-2-methyl-aniline sulfate ≠,! Add water /1 Bleach Liquid ammonium bromide /1O, (#ammonia water (-r)), oyethylenediamine-sodium iron salt of tetraacetic acid /309 Glacial acetic acid
l≠d add water
/1 Fixer sodium tetrapolyphosphate λ, OF sodium sulfite ≠, OP ammonium thiosulfate (';#7%) / 7 j, 0vt1 sodium bisulfite μ, Ajl Add water
/1 stabilized formalin r, add 0ml water /1 (sample 10
A sample was prepared in which the coupler cp-// of the second layer of sample 10/ was replaced with the coupler Y-/ of the present invention. c.
Since the coloring density of Y-/ is three times that of p-1/, the amount added was reduced to 77 ml. Needless to say, the amount of gelatin in the photosensitive material affects the film properties of the photosensitive material, but in order to keep the gelatin film properties (film strength in %) constant, the amount of gelatin in the photosensitive material is determined by the total amount of coupler and high boiling point organic solvent. The ratio of the amount of seratin to the amount of a certain oil-soluble component was adjusted to a constant value. As a result, by using Y-/, the amount of coupler and high-boiling organic solvent were reduced, so the amount of gelatin in the second layer was reduced to 7 m2 compared to / and Or. (Creation of sample 103) Third layer coupler Cp-J''Ir of sample 10/: Replaced with the coupler (j3) of the present invention, coupler Cp of the μth layer
Sample 103 was prepared in the same manner as Sample 10/, except that -1 was replaced with the coupler of the present invention (!≠). (Creation of sample IO≠) The coupler Cp-j of the third layer of sample 102 was replaced with the coupler of the present invention (!3), and the coupler Cp-6 of the first layer was replaced with the coupler of the present invention (!≠) Sample 70 except
．． Sample No. 10 was prepared in the same manner as No. 2. (Experiment/) Samples 10/ to IO Hiro were exposed to white light using an imagewise wedge and then subjected to the following processing to give similar gradations to the samples. Next, it was exposed to green light and the MTF value was measured. The method for measuring the MTF value is the method used by T.H.
, H. James), “The Theory of the Photographic Process” (rheTheor
y of the Photographic P
rocess) 1st Hong Kong Edition” (Mac MiI
Published by FAN) Co., Ltd., 1977), pages to≠-607. The MTF value of the obtained magenta color image is
Shown in the table. (Experiment 2) Development processing B was the same as development processing A, except that the composition of the bleaching solution was changed as described below. Development process B The development process (temperature and time) is the same as development process A. Bleach solution ammonium bromide ito, oy ammonia water (2g%) 2! ml ethylenediamine-tetraacetic acid /27F thorium iron (I[
[) Salt ethylenediamine-tetraacetic acid 3y Thorium/iron (n) Salt glacial acetic acid 1 Hiroshi - Add water /1 Other processing liquids are the same as development processing A. Development process B is inferior to A in its oxidative bleaching ability, and there is a high possibility that the oxidized color developing agent reacts with the coupler to produce a reduced product (leuco dye), which is a stage before becoming a dye. It is prepared so that its performance does not deteriorate. Development processing B compared to the color density when processing
If the color density decreases when the dye is applied, then the color development defect is due to insufficient oxidation process from the leuco dye to the dye. Through the above experiments, it is possible to compare the dependence of each coupler on the oxidation ability of the processing solution in the dye formation process. It can be said that the less the dependence on the oxidation ability of the processing solution, the more stable the dye is produced, and the less likely the coupler is to cause poor color development. Samples 10/1 to 1 ott are exposed to white light using an imagewise wedge, and then subjected to the development treatments A and B. Color density of cyan image when sample 10/ is subjected to development treatment A: 1. ! Table 1 shows the results of comparing the color density after processing B at the same exposure amount and the exposure amount giving the same amount of light. (Experiment 3) Samples IO1 to ioμ are exposed to white light using an imagewise wedge, and then development treatment A is performed. Using the obtained sample, test it in a fluorescent lamp fading tester (approximately 10°o Lux
), the emulsion side was irradiated with light for 7 days, and light staining, which is a component of color image preservation, was investigated. The results are summarized in Table 1. (Effect of the invention) According to the results in Table 1, in sample IO≠, which is a combination of the yellow coupler of the present invention and the cyan coupler of the present invention,
It has been revealed that the photosensitive material has improved sharpness, no defective color development occurs, and has improved light staining, which is a drawback of the cyan coupler of the present invention. Patent applicant: Fuji Photo Film Co., Ltd., Showa 6λ, month, day 1, case indication: Showa≦7, patent application No. 2/Da♂10
No. 2, Title of the invention Silver halide color photographic light-sensitive material 3, Relationship with the case of the person making the amendment Patent applicant 4, Subject of the amendment Akira, Column 5 of "Detailed description of the invention" in letter M, Contents of the amendment The statement in the "Detailed Description of the Invention" section of the specification is amended as follows. (I) The structural formula of compound Y-/7 on page 70 is corrected as "". (2) After the structural formula of compound Y-26 on page 72, 1'-
Insert "Y-27". (3) Page 11.2, line 3 to page 1/3/! Correct the description up to line 1 as shown in the attached sheet -/. (4) Attachment page IIT/line 2 to 2 is attached.
Correct as in 2. Attachment-1: Exposed samples should be developed at 3♂0C according to the following processing steps.Color development 3 minutes/! seconds Bleaching 6 minutes 30 seconds Washing - minutes 10 seconds Fixation Participation 0 seconds Washing with water 3 minutes/! seconds Stability 1 minute 0! seconds The specific processing solution composition used in each step was as follows: Color developer diethylenetriaminepentaacetic acid /, Of/-hydroxyethylidene- /, /-diphosphone Acid 2.0? Sodium sulfite Hiroshi, ot potassium carbonate
30.0? potassium bromide
/, lA? potassium iodide
/, 31n9 hydroxylamine sulfate
λ,≠2μm (N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate Hiro,! ? Add water /, 01 pH 10,0 Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt ioo, θ2 Ethylenediamine acetate disodium salt 10. O? Ammonium bromide lyoo,oy ammonium nitrate 10. O? add water
i, ot pH4,0 Fixer ethylenediaminetetraacetic acid disodium trilam salt i, oy Sodium sulfite ≠, o7 Ammonium theosulfate aqueous solution (70%) 77! , 0ml sodium bisulfite ≠, A? add water
/, otpH, g, J Stabilizing liquid formalin (≠O%) 2. O-polyoxyethylene-p-7nononylphenyl ether (average density of about IO) Add 0.3 fl water /, O1J Attachment - Bleach solution ferric ethylenediaminetetraacetic acid Tough, Of ammonium salt ethylenediaminetetraacetic acid Ferrous 3.0?Ammonium salt ethylenediaminetetraacetic acid disu) 10.Otlium ammonium chlorobromide /jO,0?Ammonium nitrate io,oy Add water
/,01pHbu,0''

Claims (1)

[Scope of Claims] A dye moiety whose maximum absorption wavelength is shifted to a shorter wavelength side due to a bond that is cleaved directly or via a timing group by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. and at least one coupler represented by the following general formula (I), which is characterized by producing a compound having a dye moiety having a maximum absorption wavelength before shifting as a result of the reaction, and the following general formula: (II) and (III)
A silver halide color photographic material comprising at least one cyan coupler represented by: General formula (I) Cp-(TIME)_n-X-Dye In the formula, Cp releases -(TIME)_n-X-Dye through a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Represents a coupler residue that can be used. (TIME)_n represents a timing group, and n represents 0 or a positive integer. Dye is a dye residue and X represents an auxochrome residue of the dye. General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 represents an aromatic group or a heterocyclic group, and R_
2 represents a group that can be substituted on the naphthol ring, R_3 represents an aliphatic group, a represents an integer from 0 to 4, b represents an integer from 0 to 3, and Z_1 represents a hydrogen atom or a coupling-off group. Z_1 in general formula (II) and general formula (III) may be different from each other. Z_2 represents -O-, -S-, or R_4-N-. However, R_4 represents a hydrogen atom or an organic substituent, and when a and b are plural, R_2 in general formula (II) and general formula (III) may be the same or different, and may be bonded to each other. may form a ring. In addition, in general formula (III), R_2 and Z_2,
Alternatively, Z_2 and Z_1 may be combined with each other to form a ring. Also, R_1, R_2, R_3, R_4
, Z_2 or Z_1 may form a dimer or more multimer. Also, Z_1 is − in general formula (I)
It does not represent (TIME)-_nX-Dye.