JPS63127242A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To realize the titled material having excellent sharpness, without reducing graininess by combining a yellow coupler which has a low molecular weight type and is shown by a specific formula, and a compd. capable of releas ing a development restrainer. CONSTITUTION:The titled material having the excellent sharpness as well as graininess is obtd. by combining at least one kind of the lipophilic diequivalent yellow coupler which is shown by formula II and has an equivalent molecular weight of 250-680 or said yellow coupler which is shown by formula II and has the equivalent molecular weight of 250-700, and at least one kind of the compd. shown by formula I. The equivalent molecular weight is shown by the formula M/N wherein N is a number of coupling position contd. in the 1mol of the yellow coupler, and M is the molecular weight of the 1mol. The yellow coupler shown by formulas II and III does not contain the water soluble groups such as a sulfonic acid and a carboxylic acid residue, etc. In formula I, A is a group capable of forming the development restrainer by reacting with an oxidant of a developing agent.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a silver halide color photographic light-sensitive material having excellent sharpness and graininess. (Prior art) Using exposed silver halide as an oxidizing agent, the oxidized aromatic 7th class amine color developing agent and coupler react to form indophenol, indoaniline, indamine, azomethine, phenoxazine, phenazine and It is well known that similar pigments can be produced and color images can be formed. Among these, in order to form a yellow image, α
-Benzoylacetanilide couplers and α-piparoylacetanilide couplers are used, but α-benzoylacetanilide couplers are more efficient in forming yellow azomethine dyes through coupling reaction with oxidized color developing agents; In addition, because the azomethine dye has a high molecular extinction coefficient, it exhibits extremely high coloring performance.
The coupler itself had a large molecular weight and the storage stability of yellow images was poor. On the other hand, although α-piparoylacetanilide couplers have good storage stability for yellow images, they are inefficient in forming azomethine dyes during color development, and the molecular extinction coefficient of the formed dyes is low, so some color development is required. When trying to obtain density, coupler application amount and /-! However, the coating amount of silver halide must be increased, resulting in deterioration of sharpness due to an increase in emulsion film thickness and an increase in cost. From the point of view of thinning the emulsion film, the method of using a polymer coupler instead of an oil-protected coupler was proposed in the
4t-/JJ7J' issue, Tokukai Sho! Although it is described in Co/JrOtj/No. and U.S. Pat.
It has become clear that it is necessary to make the emulsion film thicker. In addition, for the purpose of reducing the molecular weight of each coloring unit,
2, same jj-ko 30θ and same! A yellow coupler such as 2339 has been proposed, which has a number of color forming units in one molecule. However, since these couplers have low solubility, it is necessary to use a large amount of a high-boiling point organic solvent, resulting in the problem that the emulsion film cannot be made very thin. The yellow coupler of the present invention solves these problems. In general, in the emulsion of a silver halide color photographic light-sensitive material, in addition to a dye-forming coupler such as the yellow coupler of the present invention, in order to improve color reproducibility, sharpness, and graininess,
Many functional couplers are used. For example, JP-A-6
0-/23.34t1, J-/-, 24,034
Colored couplers with color correction functions as shown in issues such as those shown in JP-A-Sho! 2-♂ko, 4tλgu, Tokuko Akira! /-/
J, /ri No. 7 and U.S. Patent No. 3.2J7, jj4
There are couplers such as those shown in No. 1 that release a development inhibitor upon development (so-called DIR cazolers). In particular, DIR couplers have been shown to have various improvements because their use allows for significant improvements in color reproducibility, sharpness, and graininess. For example, the timing type DIR coupler shown in JP-A No. 77-/141.2341 and U.S. Pat.
Examples include the diffusive DIR coupler shown in No. t4. The compound represented by the general formula [C] of the present invention has the above-mentioned DI
It was found that the R coupler also improved both color reproducibility and sharpness. However, the above improvements are still incomplete, and further improvements are desired. (Problem to be Solved by the Invention) The above-mentioned functional coupler can be caused to coexist with the dye-forming coupler in the same or adjacent emulsion layer, and to react competitively with the dye-forming coupler with the oxidized developing agent. This function can be fully expressed. However, the yellow coupler of the present invention is
It has been found that the reaction between other couplers present in the same layer and adjacent layers, especially the DIR coupler, and the oxidized developing agent tends to be suppressed. Therefore, it has been found that when the present yellow coupler and the DIR coupler are used, the sharpness is improved compared to the conventional ones, but the graininess is reduced. Therefore, the problem to be solved by the present invention is how to achieve both sharpness and graininess. (Means for solving the problem) The above problem is that the equivalent molecular weight represented by the following general formula (A) is 2 to 610, or the equivalent molecular weight represented by the following general formula [B] is 250 to 700. At least one type of lipophilic two-equivalent yellow kazoler and the following general formula [!
The problem was solved by a silver halide color photographic light-sensitive material containing at least one of the compounds represented by the following. General formula [A] In general formula [A], R1 is an aliphatic group, R2 is a hydrogen atom, a halogen atom, or an aliphatic oxy group, R3 is a group (including atoms) that can be substituted for a benzene ring, and l is a An integer from θ to da, and Xl represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, when l is plural, (R3) l may be the same or different. In addition, R1, R2, R3''!! or Xl may serve as a co-valent to g-valent linking group to form a 1-4tflr form of a yellow coupler represented by the general formula [Al. General formula CB) In the formula CB+, R4 and R6 are groups (including atoms) that can be substituted on the benzene ring, R5 is a hydrogen atom, a halogen atom, or an aliphatic oxy group, m is an integer of θ ~!,
n represents an integer of o - g, and X2 represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, when m is plural, (R4)m may be the same or different; similarly, when n is plural, (R6)n
may be the same or different. Also R4, R5, R6
, or X2 becomes a co-valent to trivalent linking group to form the general formula [B
] It may be a polymer of a yellow coupler represented by the following formula. In the present invention, the equivalent molecular weight of a yellow coupler is defined as the number of coupling positions in seven molecules of the yellow coupler represented by general formula [A] or [B], where N is the molecular weight of the seven molecules, and M is the molecular weight of the seven molecules. It is defined by the following formula. (Equivalent molecular weight)=− When the equivalent molecular weight defined above for the yellow coupler of the present invention is represented by the general formula (A), It is a coequivalent coupler of Q~6♂0, but preferably the equivalent molecular weight is 4t! θ〜≦1
0, preferably! 00～Otsu! It is 0. Further, in the case of general formula [B], it is a monoequivalent coupler with an equivalent molecular weight of θ~700, but preferably an equivalent molecular weight of 4
T! θ~200, more preferably 100~700
It is. The yellow couplers represented by formulas (A) and [B) of the present invention do not contain water-soluble groups such as sulfonic acid and carboxylic acid. General formula CI) -PD I In the general formula [I], A represents a group that cleaves PDI by reacting with an oxidized developing agent, and after PDI is cleaved by A, it reacts with an oxidized developing agent. Represents a group that forms a development inhibitor. This K makes it possible to improve color reproducibility and sharpness compared to the case where the conventional DIR coupler is used. As the seven constituent elements of the present invention, general formulas [A] and [
A yellow coupler represented by B] is used. This coupler not only reduces the volume of the coupler in the emulsion layer, but also reduces the amount of gelatin and high-boiling organic solvent used, making it possible to improve sharpness by making the layer thinner. However, it has become clear that the yellow coupler of the present invention has a disadvantage in that it is inferior in graininess compared to conventional yellow couplers. This problem can be solved by using the compound represented by the general formula CI) in accordance with the present invention in the form that the sharpness is further improved and the graininess is also improved due to the synergistic effect of both. Ta. Furthermore, this improvement in sharpness was not only evident in the layer containing the yellow coupler, but was also effective in the photosensitive layer closer to the support. This is because the thinning of the layer containing the yellow coupler suppressed color fringing development caused by optical factors. As a result, a silver halogenide photographic material with good color reproducibility, sharpness and graininess was obtained. Next, each substituent in the yellow coupler represented by the general formula [A] will be described in detail. General formula [A] R1 is an aliphatic group having up to 30 carbon atoms; , an aliphatic sulfonyl group, an aromatic sulfonyl group, etc. R2 is a hydrogen atom, a halogen atom (fluorine atom, chlorine atom, bromine atom), or an aliphatic oxy group having a carbon number of 24t. Examples of R3 include a fluorine atom (fluorine atom, chlorine atom, bromine atom), an aliphatic group having 20 carbon atoms, and 6 to 20 carbon atoms.
20 aromatic groups, carbon number/~, 2O aliphatic oxy groups,
Aromatic oxy group having 6 to 20 carbon atoms, carbonamide group having 2 to 2 carbon atoms, sulfonamide group having 20 carbon atoms,
Carbamoyl group having carbon number 0-S-24t, carbon t, t1.
Sulfamoyl group having 0 to 20 carbon atoms, acyloxy group having 2 to 20 carbon atoms, 2 to 20 carbon atoms. 2g substituted amine group, carbon number/
~λda aliphatic thio group, ureido group having 0-20 carbon atoms,
a sulf7 amoylamino group having O-10 carbon atoms, a cyan group,
Aliphatic oxycarbonyl group with ~2Q carbon atoms, aliphatic oxycarbonylamino group with ~20 carbon atoms, 9-carbon atoms
Imide group of 10, imide group of carbon number q to coθ, carbon number /
Examples include an aliphatic sulfonyl group having ˜2θ, an aromatic sulfonyl group having 6 to 2θ carbon atoms, and a heterocyclic group having ˜0 carbon atoms. Xl is a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer).
General formula [XI[) -0-R4 General formula (Xnl
) -8-R5 In the general formula (Xll), R4
is an aromatic group having 2 to 30 carbon atoms, carbon number/~co? heterocyclic group, an acyl group having -2/carbon atoms, an aliphatic sulfonyl group having 7 to 24 carbon atoms, or a C6 to . 24t aromatic sulfonyl group. General formula (X1ll "1, R5 is the number of carbon atoms) ~ 30
The aliphatic group has 1 carbon number! , represents an aromatic group having ~30 carbon atoms or a heterocyclic group having 7 to 2 carbon atoms. In the general formula [X■], 2 represents a nonmetallic atomic group necessary to form a monocyclic or condensed j to 2-membered heterocycle together with N. Examples of heterocycles formed by N and 2 include pyrrole, pyrazole, imidazole, /,! , 4
One triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, tetraazaindene, succinimide, phthalimide,
Saccharin, oxazolidine-2,4t-dione, imidazolidine-2,4t-dione, thiazolidine. 11-dione, urazole, parabanic acid, maleimide, corpyridone, na-pyridone, 6-pyridazone, 6
-Pyrimidone, Corvilazone, /,! . ! -triazine-kone, /, co+”) riazin-6-one, /, 3. cootriazin-6-one, kochizolone, kochizolone, kochizazolone, 3-isoxacilone, !-tetrazolone, /, 2. &-triacy These may be substituted, and examples of substituents include halogen atoms, hydroxyl groups,
Nitro group, cyan group, hydroxy group, aliphatic group, aromatic group, heterocyclic group, aliphatic oxy group, aromatic oxy group, aliphatic thio group, aromatic thio group, aliphatic oxycarbonyl group,
Examples include carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, sulfamoylamino group, aliphatic oxycarbonylamino group, substituted amino group, and the like. In the present invention, the aliphatic group refers to a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group, which may be substituted. Examples of aliphatic groups include methyl group, ethyl group, isopropyl group, n-butyl group, t-
Butyl group, t-amyl group, n-hexyl group, cyclohexyl group, n-octyl group, coethylhexyl group, n-
Decyl group, n-dodecyl group, n-tetradecyl group, n
-hexadecyl group, cohexyldecyl group, n-, t-
Phtadecyl group, allyl group, benzyl group, phenethyl group,
Examples include undecenyl group, octadecenyl group, trifluoromethyl group, chloroethyl group, cyanethyl group, /-(ethoxycarbonyl)ethyl group, methoxyethyl group, butoxyethyl group, 3-dodecyloxypropyl group, and phenoxyethyl group. In the present invention, the term "heterocyclic group" refers to a substituted or unsubstituted monocyclic or condensed ring heterocyclic group, including, for example, a caufuryl group, a cochenyl group, a copyridyl group, a 3-pyridyl group, a y-pyridyl group, Coquinolyl group, oxazole-coyl group, thiazole-coyl group, penzoxazole-coyl group, penzothiazole-coyl L/. 3. Couthiadiazol-2-yl group, /, 3°guoxadiazol-λ-yl group, etc. In the present invention, the aromatic group refers to a substituted or unsubstituted monocyclic or condensed ring aryl group, examples include phenyl group, tolyl group, cuchlorophenyl group, goomethoxyphenyl group, /-naphthyl group, and 2-naphthyl group. group, at-butylphenoxy group, etc. Next, examples of preferred substituents in the coupler represented by the general formula (A) used in the present invention will be described. R1 is preferably a substituted or unsubstituted tertiary alkyl group (t-butyl group, /, /-dimethylpropyl group, /, /-dimethylbutyl group, /-methyl-/-ethylpropyl Li, /-
dimethyl-cochloroethyl group, /,/-dimethyl-2
-phenoxyethyl group, /, /-dimethyl-cophenyltheoethyl group, /-adamantyl group, etc.), and more preferably t-butyl group. R2 is preferably a chlorine atom or an aliphatic oxy group (methoxy group, ethoxy group, methoxyethoxy group, n-octyloxy group, coethylhexyloxy group, n-tetradecyloxy group, etc.)
It is. R3 is preferably an aliphatic group (methyl group, ethyl group, n-propyl group, t-butyl group, etc.), an aliphatic oxy group (methoxy group, ethoxy group, n-butoxy group, n-
dodecyloxy group, etc.), halogen atom (fluorine atom, chlorine atom, bromine atom), carbonamide group (acetamide group, n-butanamide group, n-tetradecanamide group, benzamide group, etc.) or sulfonamide group (methylsulfonamide group) group, n-butylsulfonamide group, n-
octylsulfonamide group, n-dodecylsulfonamide group, toluenesulfonamide group, etc.). R2 is preferably a chlorine atom or an aliphatic oxy group (methoxy group,
ethoxy group, methoxyethoxy group, n-octyloxy group, coethylhexyloxy group, n-tetradecyloxy group, etc.), aliphatic oxycarbonyl group (methoxycarbonyl group, ethoxycarbonyl group, n-butoxycarbonyl group, n- xyloxycarbonyl group, coethylhexyloxycarbonyl group, / (ethoxycarbonyl)ethyloxycarbonyl group, -1-butoxyethyloxycarbonyl group, 3-dodecyloxypropyloxycarbonyl group, n-decyloxycarbonyl group, n-
(dodecyloxycarbonyl group, phenethyloxycarbonyl group, etc.) or carbamoyl group (dimethylcarbamoyl group, diptylcarbamoyl group, diptylcarbamoyl group, di-ethylhexylcarbamoyl group, n-dodecylcarbamoyl group, etc.). E is preferably O-1. Xl is preferably a group of the general formula (,
cyanophenoxy group, q-dimethylsulfamoylphenoxy group, coacetamido-monoethoxycarbonylphenoxy group, q-ethoxycarbonylcomethylsulfonamidophenoxy group) or the general formula (XIV
), and among the latter, the following general formula CXV
) is more preferable. In the general formula [X■], a substituted or unsubstituted methylene group or a substituted or unsubstituted imino group is represented, and W represents an oxygen atom, a sulfur atom, a substituted or unsubstituted methylene group, or a substituted or unsubstituted imino group. However, when V is an imino group, W is neither an oxygen atom nor a sulfur atom. Examples of the group represented by general formula (XV) include succinimide group, phthalimide group, /-methyl-imidazolidine--, 4t-dione-3-yl group, /-be/di-imidazolidine-2.4t -dione-3-yl group,!
-Ethokicou/-methylimidazolidine-2,kudione-3-yl group,! -methoxy/-methylimidazolidine-λ, 4t-dione-3-yl group,! ,! -dimethyloxasilysia J, 4t-dione-3-yl group, thiazolidine-J, 4t-dione-3-yl group, /-penzylcophenyltriazolidine-3,j-dione-kuyl group, /-n- Propylucophenyldria/
Ricin-3. ! -dione-q-yl group, etc. In the yellow coupler represented by the general formula (A), any of the substituents R1, R2, R3, or mer or monomer is preferable.Here, the yellow coupler represented by the general formula (A) has 1 to q
mer, R1. serves as a linking group. R2, R3 or Xl
The carbon number range listed above is not limited to that. Next, each substituent in the yellow coupler represented by the general formula CB used in the present invention will be described in detail. General formula [B] R4 and R6 in general formula [:B]K are general formula (A)
This is equivalent to the example of R3 in . m and n are preferably 0-2. R5 in the general formula CB) is the general formula [
A], and Xl is equivalent to the example of xl. In the yellow coupler represented by the general formula CBI, any of its substituents R4, R5, R6, or or λ-mer is preferred. Here, when the yellow coupler represented by the general formula CB) is a - to 4-mer, the range of carbon numbers listed for R4, R5, R6 or Xl serving as a linking group is not limited thereto. General formula [A] and general formula [
Specific examples of the yellow coupler represented by B] are shown below, but the couplers used in the present invention are not limited to these. The equivalent molecular weight of each coupler is shown in parentheses. 'l'-/ Y -4t C2H5 station Y -t CH3Y-
♂ Y-wa α Y-//cH3 Y-/7! Y-/3 Y-/4t -ij (a3g) (+27) Y-/♂ Y-/riY-co0 Y-co/Y-,2e (4t37) 2H5 Y-3= H3 2H5 Y-j da (6 pieces/) Y-3I CH3 Y-3/ LshiY-3de2H5 Y-<t. CH3 Y-<tl (jjJ) Y-4,2 Y-<t3 -4t4t Y-g! Y-<tt -4t2 Y-e♂ Y-<triY-! 0 Y-! /Y-! 3 Y-z g Y-jj (j4tr) α to Y-z (j colo) Y-! 7 α Y-jj Y-triY-t. (2 (3 OZ 0) Y-bu / -t2 (4tOZ) -44t Y-6! The yellow coupler used in the present invention is synthesized by a conventionally known method. For example, U.S. Pat. No. 3,
227, jJ-41, No. 3, 4t07. No. 799, 3. <tit, tt2, samej, 4t4t
7, Ri2! No. 4t4tO/7! Co No., British Patent/. 04tO, No. 710, Tokukai Showa 4t? -215733,
Same 4t? -3773 issue, same gu♂-7jj/4t7 issue,
Same group♂-94t4t32, same tit, r-t/e3<
No. 4t/-67736, &/-47134.
Same issue! 0-3 Guco No. 32, same j/-307 J4,
same! /-10 Colo No. 36, same! ! -! Wa? Same issue! ! −
/ Core / Ko3ri issue, same! 6-ta! No. 232, same! Otsu-／≦
/Yoq3, same! T-/! 3J4t3, same! Tar/7
No. 4t73, No. tO-3!730 and special application Akigo/-
It can be synthesized by the synthesis method described in the specification of Hat4t2.27. Among the compounds represented by the general formula (N), a preferable compound is represented by the following general formula (II). In the general formula (n) A-(Ll), -B-(Ll)w-DI, A is (Ll)v-B (L
l) represents a group that cleaves W-DI, Ll represents a group that cleaves B-(Ll)w-DI after cleavage from A, and B represents a group that cleaves B-(Ll)w-DI after cleavage from A-(Ll)v, Represents a group that reacts with the oxidized crude drug to cleave (L 2 ) w-DI, Ll represents a group that cleaves DI after being cleaved from B,
l) I represents a phenomenon inhibitor. V and W represent O or /. The reaction process in which the compound represented by the general formula (II) releases 0 when it occurs is represented by the following reaction formula. (Ll)v-B-(Ll)w-DI-B-(Ll)
In the W-DI formula, A, Ll, B, Ll, Dl, , v and W represent the same meaning as explained in the general formula (III), and To represents an oxidized developing agent. In the above reaction formula, From B-(Ll)w-DI (Ll
) The reaction producing w-DI characterizes the excellent effects of the present invention. That is, this reaction involves To and T3-(Ll)w-
This is a secondary reaction with DT. In other words, the reaction rate depends on the concentration of each. Therefore, where TO is generated, B - (Ll), -DI is (Ll)
Generate w-DI immediately. In contrast, in places where only a small amount of TO is generated, B − (Ll) W D
T slowly produces (Ll)w-DI. This reaction process, in combination with the above reaction process, effectively exhibits the effect of l)I. Next, the compound represented by the general formula (II) will be explained in detail. In general formula (I[), A specifically represents a coupler residue or a redox group. When A represents a coupler residue, known ones can be used. For example, yellow coupler residues (side-light open-chain ketomethylene type coupler residues), magenta coupler residues (e.g., pyrazolone type, pyrazoloimidazole type, pyrazolotriazole type coupler residues, etc.), cyan coupler residues (e.g. phenolic type, naphthol type, etc.), and colorless coupler residues (e.g. indanone type, acetophenone type, etc. coupler residues) or US Pat. No. 1I-, 3/! , No. 070, same g, /13
. 7j No. 2, u, /7/, 2.23, IA, 226
Examples include coupler residues described in , Rihiro No. 3, etc. When A represents a redox group, in detail, the following general formula (i
ll). General formula (It[) Al-P-(X=Y)n Q A2 In the formula, P and Q each independently represent an oxygen atom or a substituted or unsubstituted imino group, and One of each represents a methine group having -(Ll) -B+R2)WDT as a substituent, the other X and Y represent a substituted or unsubstituted methine group or a nitrogen atom, and n is /
Represents an integer from 3 to 3, X of n1fi, Y of n + a
represent the same or different "'rλ人!" and A2 each represent a hydrogen atom or a group that can be removed by an alkali. Here, any two substituents of P, X, Y, Q, AI and A2 Also includes combinations in which two groups are connected to form a cyclic structure. For example, (X=Y)
n is a benzene ring. This is the case when a pyridine ring is formed. In the general formula (n), the groups represented by Ll and R2 may or may not be used in the present invention. They are appropriately selected depending on the purpose. The groups represented by Ll and R2 are, for example, the following known Examples include linking groups. (1) Groups that utilize the cleavage reaction of hemiacetal. For example, U.S. Pat.
It is a group represented by the following general formula and is described in the -, 2μr lvr number, and the same 60-2μr/μr number. Here, the red stamp represents the position where it is bonded to the left side in general formula (1), and the rice red stamp represents the position where it is bonded to the right side in general formula (1). represents a group (R3 represents an organic substituent), R1 and R2 represent a hydrogen atom or a substituent,

[ represents 1 or C, and when t is 2, λ R. and R2 may be the same or different (,
Also included is a case where any two of R1, R2 and R3 are linked to form a cyclic structure. Specifically, the following groups may be mentioned. *-0CH2-half rice coming-〇C)i-shu coming rice-8
CH-hanmai (2) A group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction. For example, the timing group described in US Pat. It can be expressed by the following general formula. Rice-Nu-L ink-E-Ithalf (T
--2) In the formula, the red stamp represents the bonding position on the left side in general formula (1), the American red stamp represents the bonding position on the right side in general formula (1), Nu represents a nucleophilic group, and the oxygen atom , or a sulfur atom is an example, E represents an electrophilic group and is a group that can cleave the bond with U.S. by receiving a nucleophilic attack from Nu, and Link is an intramolecular nucleophilic substitution reaction between Nu and E. Represents a linking group that allows for steric relationship. Specific examples of the group represented by (T-2) are as follows. NO□ 000C4H002CH3 +-〇 Rice-8COOCH
3N02 N (3) A group that causes a cleavage reaction using an electron transfer reaction along a conjugated system. For example, U.S. Pat. It is a group described in No. 1 and represented by the following general formula. R, R2 where red seal, rice red seal, R1, R2 and t are (T-/)
It has the same meaning as explained above. Specifically, the following groups may be mentioned. COOCH3COOC4H9 COOH5O2CH3 α (4) A group that utilizes a cleavage reaction due to ester hydrolysis. For example, West German Published Patent No. 2. ax+ is a linking group described in Jir No., and includes the following groups. The red seal and rice red seal in the formula have the same meaning as explained for (T-/). In general formula (II), the group represented by B is specifically A
-(Ll) A group or A that becomes a coupler after being cleaved from v
(Ll) A group that becomes a redox group after being cleaved from v. For example, in the case of a phenol type coupler, the group serving as a coupler is a group that is bonded to A-(Ll) at an oxygen atom other than a hydrogen atom of a hydroxyl group. Again - in the case of pyrazolone type couplers! - A tautomerized type of hydroxyl group in -hydroquinpyrazole is bonded to A(Ll)v at the oxygen atom with the hydrogen atom removed. In these examples, A−(Ll)v
It becomes a phenol-type coupler or a pyrazolone-type coupler only after separation. They have (L2Lw-DI) at the coupling position. When B represents a group serving as a redox group, it is preferably represented by the general formula (B-/). The general formula (B-/ ) US-p-(x'=y').-Q-A2 In the formula, the red stamp represents the bonding position with A (Ll), and A
2, P s Q and n represent the same meaning as explained in general formula (1), and X' and Y' of n4ra
(Tomo/1[!I represents a methine group having (L 2 )WD I as a substituent, and the other X' and Y' represent a substituted or unsubstituted methine group or a nitrogen atom. A2 s P s Q, X' and Y'
A case where any one of the λ substituents becomes a divalent group to form a cyclic structure is also included. In general formula (If), DI is specifically a tetrazolylthio group, a benzimidazolylthio group, a benzothiadiazolylthio group, a benzoxazolylthio group, a quinzotriazolyl group, a penzoindazolyl group, a triazolylthio group,
imidazolylthio group, thiadiazolylthio group, thioether-substituted triazolyl group (for example, the expression-inhibiting chiron or Φthadiazolyl group described in U.S. Pat. Typical substituents include the following examples. In the following examples, the total number of carbon atoms is preferably 20 or less.)
rogene atom, aliphatic group, nitro group, 7syl amino group, aliphatic oxycarbonyl group, aromatic oxycarbonyl group,
imide group, sulfonamide group, aliphatic oxy group, aromatic oxy group, amino group, imino group, cyano group, aromatic group,
Acyloxy group, sulfonyloxy group, aliphatic thio group,
Aromatic thio group, aromatic oxysulfonyl group, aliphatic oxysulfonyl group, aliphatic oxycarzenylamino group, aromatic oxycarbonylamino group, aromatic oxycarponyl oxycarbonyl group , heterocyclic group, sulfonyl group, acyl group, ureido group, heterocyclic group,
Examples include hydroxyl group. In the general formula (II), the present application also covers cases where any two of the groups represented by A, Ll, B%L2 and DT have a bond in addition to the bond represented by the general formula (II) and are connected. . Even if this second bond is not broken at the time of the phenomenon, the effect of the present invention can be obtained. Examples of such a bond are as follows. In the general formula (n) of the present invention, The represented compound also includes cases where it is a polymer.That is, it is derived from a monomer compound represented by the following general formula (P-I),
), or a non-chromogenic monomer containing at least one ethylene group that does not have the ability to couple with the oxidized product of aromatic primary amine derivatives. It is a copolymer with one or more types. Here, two or more types of monomers may be simultaneously polymerized. General formula (P-I) CH2 = C + A2 1 + A3 CH dimension A1 7 Q1
” General formula (P-2) ■ +CH2-Csu (A2su → A 3+T+A I+g QIn the formula, R represents a hydrogen atom, a lower alkyl group having carbon number/~μ, or a chlorine atom, and %AI is -CONH- 1-N)iCONH-1
-N) ICOO-1-COO-1-8O2-1-CO-
1-Nt-1CO-1-3O2NH-1-N)ISO2
-1-0CO-1-〇C0NH-1-S-1-Nt-1
- or -〇-, A2 represents -CONH- or -〇〇〇-, A3 represents an unsubstituted or substituted alkylene group, an aralkylene group, or an unsubstituted or substituted arylene group having 7 to 10 carbon atoms, The alkylene group may be a straight chain or a branched chain. Q represents a residue of a compound represented by general formula (II), and may be bonded at any site of A% "1, B and L2. i, j, and k represent O or /; Ding is i, 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, hydroxyl group, cyano group, sulfo group, alkoxy group (e.g. methoxy group), aryloxy group ( For example, a phenolic group), an acyloxy group (for example, an acetoxy group, an acylamino group (for example, an acetylamino group), a sulfonamide group (for example, a methanesulfonamide group), a sulfamoyl group (for example, a methylsulfamoyl group), a rogen atom (for example, fluorine, chlorine, sodium bromine), carboxy group, carbamoyl group (for example, methylcarbamoyl group), alkoxycarbonyl group (for example, methoxycarbonyl group, etc.), and sulfonyl group (for example, methylsulfonyl group). When there are two or more, they may be the same or different.Next, examples of non-color-forming ethylene-like monomers that do not couple with the oxidation products of aromatic-grade amine developers include acrylic acid, α-chloroacrylic Examples include acids, α-alkylacrylic acids and esters or amides derived from these acrylic acids, methylenebisacrylamide, vinyl esters, acrylonitrile, aromatic vinyl compounds, maleic acid derivatives, vinylpyridines, etc. One or more color-forming ethylenically unsaturated monomers can be used simultaneously.Next, more preferred ranges among the compounds of the present invention will be explained.In the general formula (1) or ((I) Preferred examples of A are the following general formulas (Cp-/), (Cp-2), (Cp-j)
, (Cp-Hiroshi), (Cp-yo), (Cp-A), (Cp
-7), (Cp-J') is a coupler residue represented by (Cp-ta). These couplers are preferred because of their high coupling speed. General formula (Cp-/) General formula (Cp-2) General formula (Cp-j) General formula (Cp-≠) General formula (Cp
-41 General formula (Cp-B) General formula (Cp-7) OH General formula (Cp-f) General formula (Cp-ta) In the above formula, the free bond derived from the coupling position is Indicates the bonding position of the group. In the above formula, R51, R52% Rss, R54, R5
5s Rss, R5? , Rss R591R
601Ra1% If R62 or R63 contains a diffusion-resistant group, what is the total number of carbon atoms? ˜ψO1 is preferably selected to be 10 to 30, and in other cases, the total number of carbon atoms is preferably lj or less. In the case of bis-type, telomer-type or polymer-type couplers, any of the above-mentioned substituents represents a divalent group and connects repeating units and the like. In this case, the range of carbon numbers may be outside the specified range. R51""R63, d and e will be explained in detail below. In the following, R41 represents an aliphatic group, an aromatic group, or a heterocyclic group, R42 represents an aromatic group or a heterocyclic group, and R43, R44, and R45 represent a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group. represents. 1'tst represents the same meaning as R41. R52 and 几53 each have the same meaning as R42. R54 represents a group having the same meaning as R41, l'(41C0N- group, ■43R44 represents a group having the same meaning as It41, R56 and R57 each have the same meaning as R43 group, R41S-R3
8 represents a group having the same meaning as R41. R59 is a group having the same meaning as R41, R4IC0N- group, Gen atom or R4
Represents a 1N- group. d represents O to 3. When d is plural, the plural 159's represent the same substituent or different substituents. Further, each R59 may become a divalent group and connect to form a cyclic structure. Examples of two radicals for forming a cyclic structure are an integer from 43 to μ, and g is an integer from O to C, respectively. R60 represents a group having the same meaning as R41. R61 represents a group having the same meaning as R41. R62 is 14
A group having the same meaning as 1, R4IC0Nt-1-4. 44R45 R44R45 0R63 representing a halogen atom or R41N-4 has the same meaning as It41, R43NSO2- group, R41SO2- group/R430C0
- group/R430-8O2-'Ts, halogen atom, nitro group, cyano group or R43CO- group. e is O
Represents an integer between or ≠. Multiple R62 or R63
When there are, they each represent the same or different things. In the above, the aliphatic group is a saturated or unsaturated, chain or cyclic, straight chain or branched, substituted or unsubstituted aliphatic hydrocarbon group having 3 to 3 carbon atoms, preferably 1 to 22 carbon atoms. Typical examples include methyl group, ethyl group, propyl group, inpropyl group, butyl group, (1)-butyl group,
(i)-butyl group, (1)-amyl group, hexyl group, cyclohexyl group, 2-ethylhexyl group, octyl group,
／、／、! , J-tetramethylbutyl group, decyl group, dodecyl group, hexadecyl group, or octadecyl group. The aromatic group is a phenyl group having A-, 20 carbon atoms, preferably substituted or unsubstituted, or a substituted or unsubstituted naphthyl group. A heterocyclic group is a substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms, preferably 7 to 7 carbon atoms, preferably a 3- to r-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom. It is. Typical examples of heterocyclic groups are! -Pyridyl group, ≠-pyridyl group, Nietzschenyl group, Niefuryl group, λ-imidazolyl group, pyrazinyl group, 2-pyrimidinyl group, /-imidazolyl group, /-indolyl group, phthalimide group, /
, 3. ≠-thiadiazole-coyl group, (nzoxazol-1-yl group, 2-Φnoryl group, 2.≠-dioquine-7,3-imidazolidine-yolyl group 1.2.tA
-dioquine-1,3-imidazolidin-3-yl group, scunnimide group, phthalimide group, /l'l''
Examples include -triazolenyyl group and/-pyrazolyl group. When the aliphatic hydrocarbon group, aromatic group and heterocyclic group have a substituent, typical examples of the substituent include -.logen atom, R470- group, R46S- group, R47R48 R470802- group, cyano group, or Examples include nitro group. Here, R46 represents an aliphatic group, an aromatic group, or a heterocyclic group, and R47s R4B and R49 each represent an aliphatic group, an aromatic group, a heterocyclic group, or a hydrogen atom. Aliphatic, aromatic or heterocyclic have the same meanings as defined above. Next, the preferred range of 1.1 for R51 to R63, d and e will be explained. R51 is preferably an aliphatic group or an aromatic group. R52, R53 and R55 are preferably aromatic groups. R
54 is preferably R41CONH- group or R41"- group. R56 and R57 are aliphatic group, R410- group,
or R41S- group is preferred. Rss is preferably an aliphatic group or an aromatic group. In general formula (Cp-6), R
59 is a chlorine atom, an aliphatic group, or R4I C0N)
The i-group is preferred. d is preferably 1 or 0. R60
is preferably an aromatic group. In general formula (Cp-7), R
59 is preferably an R4IC0NH- group. General formula (Cp-
7) In smell, d is preferably /. R61 is preferably an aromatic group spanning an aliphatic group. In the general formula (Cp-J'), eI/'i, O or l is preferred. R62 is R
410CON) i- group, R41CO to 1(- group, or R41So 2Nl-1- group are preferable, and the substitution position thereof is preferably the 5-position of the naphthol ring. As R63, R
4IC0N) L- group, R41So 2NH- group, R41
NSO2- group, I't41SO2-1, R41NC〇-
A nitro group or a cyano group are preferred. Next, a typical example of Rsl=Rs3 will be explained. Examples of R51 include (1)-butyl group, Hiro-methoxyphenyl group, phenyl group, J-(-2-(λ1 μm di-t-amylphenol)butanamido) phenyl group, ≠-octadecyloxyphenyl group, or methyl group. It will be done. R52 and R53 are the 2-chloro-dodenyloxy group, λ-chloro! -hexadecylsulfonamidophenyl group, Cochrolow! −
Tetradecanamidophenyl L J-chloro-2-(≠
-(U,Hiro-di-t-amylphenoxy)butanamido)phenyl group, Cochlororoyo-(Co(2,a-di-
t-amylphenoxy)butanamido)phenyl group, 2
-methoxyphenyl group, 2-methoxy-yo-tetradecyloxycarbonylphenyl group, λ-chloroj-(/
-ethoxycarbonyl(ethoxycarbonyl)phenyl%
, 2-pyridyl group, cochloroj-octyloxycarbonylphenyl L 2. tA-dichlorophenyl L
Examples thereof include a 2-10-(/-dodenyloxycarbonyl)phenyl group, a cochlorophenyl group, and a coethoxyphenyl group. R54 is a 3-(-1(co.≠-di-t-amylphenoxy)butanamide)benzamide group, a 3-(gu(2, goo-di-t-amylphenoxy)butanamide)benzamide group, a 2-10ro-benzamide group, Tetradecanamidoanilino Lj-(λ, 44-di-t-amylphenoxyacetamide)benzamide group,
-1chloro-dodecenylsuccinimideanilino group, 2-chloro-5-(λ-(3-1-duty-ψ-hydroxyphenoxy)tetradecanamide)anilino group,
Examples thereof include a 2,2-dimethylpropanimide group, a λ-(J-A-antadecylphenol)butanamide group, a pyrrolidino group, and an N,N-dibutylamino group. R55 is co, ≠, J-1 dichlorophenyl group, cochlorophenyl group, +2゜j-dichlorophenyl Iss J
, 3-'#diphenyl group λ, J-dichloro≠-diphenyl group m (co(2, hiro-di-t
-amylphenoxy)butanamido)phenyl group or 2,6-cyclohiro-methanesulfonylphenyl group,
is a preferred example. R56 is a methyl group, an ethyl group, an inpropyl group, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a 3-phenylureido group, a 3-
Butylureido group, also ll13-(2, μm di-t-
Examples include amylphenoxy)propyl group. R57 is J-(2,#-di(-amylphenoxy)propyl group, 3-(u-(x-(g-(IA-hydroxyphenylsulfonyl)phenoxy)tetradecanamide)
Phenyl]propyl group, methoxy group, ethoxy group, methylthio group, ethylthio group, methyl group, l-methyl-2-
[2-octyloxy]
-(/, /, J, J-tetramethylbutyl) phenylsulfonamide] phenylsulfonamido) ethyl Lj
-(μm(Hiro-do. tecyloxyphenylsulfonamido)phenyl)propyl group, /, I-dimethyl-2-(co-octyloxy-(/, /, 3.3-tetramethylbutyl) phenylsulfone 7 groups) )-)ethyl group or dodecylthio group. R5B is a 2-chlorophenyl group,
Heptafluorophenyl group, heptafluoropropyl L
/-(2゜μm di-t-amylphenoxy)propyl group, 3-(2,μm di-t-amylphenoxy)propyl group, 2.4! -di-t-amylmethyl group or furyl group. R59 is a chloro atom, a methyl group, an ethyl group, a propyl group, a butyl group, an inpropyl group,
λ-(2,≠-di-t-amylphenoxy)butanamide group, 2-(2,IA-1-amylphenoxy)hexanamide group, λ-(J, ψ-di-t-octylphenoxy)octanamide group group, co(2-chlorophenyl group)tetradecanamide group, co,, 2-dimethylpropanamide group, 2-(≠-(μm hydroxyphenylsulfonyl)phenox7) tetradecaneamide group, or λ-(co(2, Examples include A-di-t-amylphenol diacetamide)phenoquine)butanamide group. R60 is a cyanophenyl group, cocyanophenyl L ta-butylsulfonylphenyl L a--P
Examples thereof include a lopylsulfonylphenyl group, a tt-ethyldicarbonylphenyl group, a N,N-diefylsulfamoylphenyl group, and a 3-methoxybenzenylphenyl group spanning a 3-dichlorophenyl group. R61 is a dodecyl group, hexadecyl group, ncrohexyl group,
Butyl group, 3-(2, Hiro-di [-amylphenoxy)]
Propyl group, "(', ≠-di-t-amylphenoxy)butyl group, 3-dodecyloxypropyl group, λ-
Tetradecyloxox7phenylX, t-butyl group, 2-(
Examples thereof include a 2-hexyldecyloxy)phenyl group, a 2-methoxy-yododecyloxycarbonylphenyl group, an x-butoxyphenyl group, and a /-naphthyl group. R62 is an inbutyroquine group,
Ethodicarbonylamino group, phenylsulfonylamino group, methanesulfonamide group, butanesulfonamide group, Hiro-methylbenzenesulfonamide group, benzamide group, trifluoroacetamide group, 3-phenylureido group, butoxycarbonylamino group, or An acetamide group is added. R63 is λ, tA-di-1-amylphenoxyacetamide group 1.2-(j, ≠
-di-t-amylphenoxy)butanamide group, hexadecylsulfonamide M, N-methyl-N-octadecylsulfamoyl group, N,N-dioctylsulfamoyl group, dodecyl oxene carbonyl group, chlorine atom,
Furan atom, nitro group, cyano group, N-3-(2,41
-di-t-amylphenoquine) flobylsulfamoyl group, methanesulfonyl group or hexadecylsulfonyl group. Preferred ranges will be explained below when A in general formula (If) is represented by general formula (III). When P and Q represent a substituted or unsubstituted imino group, it is preferably an imino group substituted with a sulfonyl group or an acyl group. At this time, P and Q are expressed as follows. General formula (N-/) General formula (N-2) Here, the half mark represents the bonding position with A or A2, and the rice red seal represents the bonding position with one of the free bonds of -(X=Y In the formula, the group represented by G is a straight chain or branched, chain or cyclic, saturated or unsaturated, substituted or unsubstituted fatty acid group having 32 carbon atoms, preferably 22 carbon atoms (for example, a methyl group). , ethyl group, benzyl group, phenoxybutyl group, inpropyl group), #-substituted or non-substituted aromatic group having 6 to 10 carbon atoms (for example, phenyl group, μm methylphenyl group, /-naphthyl group, Hiroshi) -dodecyloxyphenyl group, etc.), or a ≠- to 7-membered heterocyclic group selected from a nitrogen atom, a sulfur atom, or an oxygen atom as a hetero atom (e.g., a 2-pyridyl group, a /-phenyl-Hiro-imidazolyl group, Caufuryl group, benzochenyl group, etc.) are preferred examples. When A and A2 represent a group that can be removed by an alkali (hereinafter referred to as a precursor group), preferably an acyl group or an alkoxycarbonyl group. An aryloxycarbonyl group, Hydrolyzable groups such as carbamoyl, imidoyl, oxacyl, and sulfonyl groups, U.S. Pat. tix, a type of precursor group that utilizes the anion generated after the ring cleavage reaction as an intramolecular nucleophilic group, U.S. Patent Nos. J, J7IA,
! 7. No. 1', same j, m. Kou No. 10 or Kou 3. Tata 3. Precursor group in which the anion described in tti transfers electrons through a conjugated system and thereby causes a cleavage reaction, US Patent Ko, 33! ,
200, or a precursor group that causes a cleavage reaction by electron transfer of the reacted anion after ring cleavage, or U.S. Pat. IAt No., IAtA, It10. t/r
In the general formula (III), preferably P represents an oxygen atom and A2 represents a hydrogen atom.General formula More preferably in (I[), X and Y
is a methine group having −(LlgaB+Lz+gDI) as a substituent, except when X and Y are substituted or unsubstituted methine groups. Among them, particularly preferred ones are represented by the following general formula (IV) or (V): General formula (IV) -A2 In the formula, the red stamp is +L l+;q B+L 2 ) w-D
Represents the bonding position of I, Ps Q, Al and A2
represents the same meaning as explained in the general formula (In), R represents a substituent, and q represents 0. Represents an integer from / to 3. When q is co or more, two or more R's may be the same or different, and when λ R's are substituents on adjacent carbon atoms, it also includes the case where they are connected as 2IITli groups to form a cyclic structure. At that time, it becomes a benzene condensed ring, such as naphthalene,
Benzonorbornenes, chromanes, indoles, benzothiophenes, quinolines, benzofurans, 2.
It has a ring structure such as 3-dihydrobenzofurans, indenes, or indenes, which may further have one or more substituents. Preferred examples of It substituents when these fused rings have substituents, and preferred examples of R when R does not form a fused ring V! These are listed below. That is, aliphatic groups (e.g. methyl group, ethyl group, allyl group, benzyl group, dodecyl group), aromatic groups (e.g. phenyl group, naphthyl group, Hirofuenogyu dicarbonylphenyl group), norogen atoms (e.g. Chloro atom, bromo atom, alkoxy group (e.g. methoxy group, hexadecyloxy group), alkylthio group (e.g. methylthio group, dodecylthio group, benzylthio group), aryloxy group (lf'll, t phenoxy group, hi-''
t-octylphenoxy, Z, Carbamoyl group, hehexadecyl group,
N-t-butylcarbamoyl LN-J-(2,≠-di-t-amylphenol)propylcarbamoyl group, ~-
methyl-N-octadecylcarbamoyl group), alkoxycarbonyl group (e.g. methoxycarbonyl group, --cyanoethoxycarbonyl group, etoxycarbonyl group, dodecyloxycarbonyl group, 3-<2.lC-di-
(t-amylphenoxy)propoquine carbonyl group), aryl dicarbonyl group (e.g. phenoxycarbonyl group, μm nonylphenoxycarbonyl group), sulfonyl group (e.g. methanesulfonyl group, benzenesulfonyl group, p-toluenesulfonyl group), Sulfamoyl group (
For example, N-propylsulfamoyl L N-methyl-N
-octadecylsulfamoyl L N-phenylsulfamoyl group, N-dodecylsulfamoyl group], acylamino group (e.g. acetamido group, benzamide group, tetradecaneamide group, e-(2,II-di-t-amylphenoxy ) Butanamide group 1.2-(2,ψ-di-amylphenoxy)butanamide group, λ-(2,μm
di-t-amylphenoquine)tetradecanamide group),
Sulfonamide groups (e.g. methanesulfonamide group, benzenesulfonamide group, hexadecylsulfonamide group), acyl groups (e.g. acetyl group, benzoyl group, myristoyl group, lumitoyl group), nitrone group, alkoxy group (e.g. acetyloxy group, benzoyloxy group,
lauryloxy group), ureido group (e.g. 3-phenylureido)'LJ-(≠-cyanophenylureido group j,
Nido-a group, cyano group, heterocyclic group (heterocyclic group with a ≠-membered or inter-membered ring selected from a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom. For example, a 2-furyl group, a copyridyl group, a /-imidazolyl group, /-morpholino group), hydroquinl group, carboxyl group, alkoxycarbonyl 7
/ group (e.g. methoxycarbonylamino group, phenoxycarbonylamino group, dodenruoquinylamino group), sulfo group, amine group, arylamino group (e.g. anilino group, hiro-methkine group), aliphatic amino group (e.g. N, N-diethylamino group, dodecylamino group), sulfinyl group (e.g. group), thiourido group (e.g. 3-phenylthioureido group), heterocyclic thio group (e.g. thiadiazolylthio group),
Imide groups (e.g. succinimide group, phthalimide group,
octadecenyl imide group) or heterocyclic amino group (e.g. gooimidazolylamino group, ≠-pyridylamino group)
Examples include. When there is an aliphatic group in the partial structure of the above substituent, the number of carbon atoms is /~3.2, preferably /~20, chain or cyclic, linear or branched, saturated or unsaturated, or substituted. It is a substituted or unsubstituted aliphatic group. When there is an aromatic group in the substituent structure listed above, the number of carbon atoms is t to 10, and preferably a substituted or unsubstituted phenyl group. The h group represented by B in the general formula (11) is preferably one represented by the general formula (B-/). In the general formula FB-/), P preferably represents an oxygen atom, and Q preferably represents an oxygen atom or one represented below. The red seal here is (X'=Y'). It represents the joining hand that joins with A2, and the rice red stamp represents the joining hand that joins A2. Rice-To-Future Rice-N- Rice S02-
GCO-G In the formula, G has the same meaning as explained in the general formula (N-/) and (N--21. Furthermore, the group represented by B in the general formula ([) can be represented by the following general formula (B- 2) Also, when it is represented by f-i (B-3), it is particularly preferable in terms of the effects of the present invention.General formula (B-1) Yonekaoru-A2 General formula (B-j) In the Yonemi-shiki, red seal A -(represents the bond bonding to LIJv-, the American red seal represents the bond bonding to -(LzJw-DI, R, q, Q and A2 are general formula U) or (V
) has the same meaning as explained in . Preferred examples of R in general formulas (B--2) and CB-J) include the following examples. In the following example, the total number of carbon atoms is preferably /j or less. Aliphatic groups (e.g. methyl, ethyl), alkoxy groups (
(e.g. methoxy group, ethoxycarbonyl group), alkylthio group (e.g. methylthio group, ethylthio group), alkoxycarbonyl group (e.g. methoxycarbonyl group, propoquine carbonyl group), aryloxycarbonyl group (e.g. phenoxycarbonyl group), carbamoyl group (e.g. N-propylcarbamoyl group, ~-1-butylcarbamoyl group,
H-ethyl Rubamoyl M1. Examples include sulfonamide groups (eg, methanesulfonamide groups), acylamino groups (eg, acetamido groups), heterocyclic thio groups (eg, tetrazolylthio groups), hydroquinyl groups, or aromatic groups. A preferred example is when V and W are both O in general formula (II). The group represented by human in general formula (II) is particularly preferably a coupler residue. Further preferred embodiments of the present invention will be described below. Particularly preferred DI in general formula (n) is a compound that has development inhibiting properties when cleaved as ])I,
It is a development inhibitor that has the property of decomposing (or changing) into a compound that does not substantially affect photographic properties after flowing out into the color developing solution. For example, U.S. Pat.
2/♂, A4'ψ, to--λ/, 7jO, A
O-, 23J, tJ-0, or 6/-//, 71
Examples of the phenomenon inhibitors described in No.
D-Hiroshi), (D-j), (D-4), (D-7),
(D-f), (D-9), (1)-70) or (]
)−//). 3-Y 3-Y , -NyN outside N -N In the formula, Shin-U is the position ii bonded to A+L 1) v-B-(L2) w- in the general formula (■)
v table bt, X represents a substituent containing a hydrogen atom, d represents a substituent containing a hydrogen atom, L3 represents a group containing a chemical bond that is cleaved in a developer, and Y expresses an event-suppressing effect. It is an aliphatic group, an aromatic group, or a heterocyclic group. The above phenomenon suppressor is A (Ll)V B (L2)
After being cleaved by W-, it diffuses through the photographic layer while showing an effect of inhibiting the development process, and a portion of it flows out into the color development processing solution. The development inhibitor that has leaked into the processing solution reacts with hydroxyl ions or hydroxylamine commonly contained in the processing solution, and rapidly decomposes at the chemical bonding part contained in L3 (for example, by decomposition of the ester bonds). That is, the group represented by Y is cleaved, and the highly water-soluble compound becomes a compound with low inhibitory properties, and eventually the development inhibiting effect is substantially eliminated. A preferred example of X is a hydrogen atom, but it may also represent a substituent such as an aliphatic group (e.g. methyl group, ethyl group), an acylamino group (e.g. acetamido group, propionamide group), an alkogine group (e.g. metgyushi group,
Typical examples include nitogishi group, ... rogone atom (e.g., chloro atom, bromo atom, nitro group, or sulfonamide group (e.g., methanesulfonamide group). This includes chemical bonds that are cleaved in the color developer solution. Examples of such chemical bonds include the examples listed in the table below. It is cleaved by a nucleophilic reagent such as nucleophilic reagents such as Directly connects to Y. When connecting via an alkylene group or phenylene group, an ether bond, amide bond, carbonyl group, thioether bond, sulfone group, sulfonamide bond, or urea bond is added to the two intervening groups. When Y represents an aliphatic group, it is a saturated or unsaturated, linear or branched, chain or cyclic, substituted or unsubstituted hydrocarbon group having 20 carbon atoms, preferably 10 carbon atoms. , particularly preferably a hydrocarbon group having a substituent. When Y represents an aromatic group, it is a substituted or unsubstituted phenyl group or a substituted or unsubstituted naphthyl group. When Y represents a heterocyclic group, it is a substituted or unsubstituted naphthyl group. It is a ψ- to ♂-membered heterocyclic group containing a sulfur atom, an oxygen atom, or a nitrogen atom. Examples of the heterocyclic group include a pyridyl group, an imidazolyl group, a furyl group, a pyrazolyl group, an oxacylyl group, a thiazolyl group, and a thiadiazolyl group. , triazolyl group, diazolidinyl group, diazinyl group, etc. When the aliphatic hydrocarbon group, aromatic group, and heterocyclic group has a substituent, examples of the substituent include a rogen atom, a nitro group, and a carbon number. l~10 alkoxy group, carbon number 2~10
Arylthio group, alkanesulfonyl group having 7 to σ carbon atoms, arylsulfonyl group having carbon number A to 10, alkanamide group having 10 carbon atoms, anilino group, (nzuide group, 10 carbon atoms) Alkylcarbamoyl group of carbamoyl L carbon@6 to 10 arylcarbamoyl Is, carbon MTI / -/ 0 alkylsulfonamide group, arylsulfonamide group of carbon number t to 10, alkylthio group of carbon number / ~ IQ, Arylthio group, phthalimide group, succinimide group, imidazolyl group with carbon number z to IO, /,, 2.g = nitriazolyl, pyrazolyl group, benztriazolyl group, furyl group, × ndthiazolyl group, alkyl with carbon number /~IO Amino group, alkanoyl group with carbon number/~10, benzoyl group, carbon number/~
10 alkanoyloxy groups, 7 benzoyloxy groups, perfluoroalkyl groups with a carbon number of ~10, an ano group, a tetrazolyl group, a hydroxy group, a mercapto group, an amine group,
Sulfamoyl group with carbon number/~10, arylsulfamoyl group with carbon number t~10, morpholino group, carbon number t~
10 aryl groups, pyrrolidinyl groups, ureido groups, urethane groups, alkyl dicarbonyl groups having 1 to 10 carbon atoms, aryloxycarbonyl groups having 1 to 10 carbon atoms, imidazolidinyl groups, or alkylidene amino groups having 1 to 10 carbon atoms, etc. Can be mentioned. Specific examples of the compound represented by the general formula (C) used in the present invention are shown below, but the compound used in the present invention is
It is not limited to these. -i t, ut12M5 Z-λ -J 2-Rike H2 -t Z-Go Z-7 Z-♂ 2-Wharf 0 Z-// Shirisushi 2F15 Z-74t Z-/! z-/6 Z-/7 z-/9 2-λ/ Z-2= Z-, 24t Z-2! Z-, 27 Z-=? Z-Kota Z-3゜z-3/ Z-3,2 -j4t Z-3! Z-j/z2H5-G0Z-G/ The compound of the present invention can be synthesized by a known synthesis method. For example, the compound represented by the general formula (A) is
No. 33.999, same g, j ko 2゜723, JP-A No. 7
-2041j4t3, j7-204t61741, same! 7--θ da! Da! No. ♂-332jI, U.S. Patent No. G, Kotata Ris/Su No. 3.73-r, 3
No. 01, same 3. Tata 6゜2/3 or Tata 6゜2/3,
It can be synthesized by the method described in No. 00j or similar methods. For example, the compound represented by the general formula (B) is
/♂! ri No. 30, ri 40-ko 03 ri 4/3, Tokuhan Sho ≦
0-7604tO, jO-72379, 40-
7.277/issue, same Otsu 0-/ko/ko♂j issue, same, 40-
No. 710/J, No. 40-710/λ or No. 60-
/4141227 or a similar method. Two or more kinds of the yellow couplers of the present invention may be used, or they may be used in combination with yellow couplers other than those of the present invention. The compound of general formula (1) of the present invention and the yellow coupler are contained in the light-sensitive silver halide emulsion layer and its adjacent layer. The total amount of the couplers of the present invention added is 0.0.2 to 3.
og/m2, preferably θ, /~/,! g/m2, more preferably 0.2 to 0 g/m2. Further, the amount of the compound of general formula (1) of the present invention to be added varies depending on the structure and use of the compound, but is preferably from 1 mol of silver (F)/×10-7 to 0 .1 mol, particularly preferably from /x10-6 to /x/
θ-1 mole. The usage ratio of the yellow coupler of the present invention and the compound represented by general formula (1) is the molar ratio ((A) or (B)/(
1)) is 99.910. /~10/9θ. Preferably it is Tata//~40/410. In addition to the couplers of the present invention, useful couplers that can be used in combination with the present invention include cyan, magenta, and yellow-colored couplers other than those of the present invention, typical examples of which include naphthol or phenolic compounds, pyrazolone, Alternatively, there are pyrazoloazole compounds and open-chain or heterocyclic ketomethylene compounds. Specific examples of these cyan, magenta and yellow couplers that may be used in the present invention are provided in Research Disclosure.
arch Disclosure) / 7 t < t
3 (/ri2♂/ko month)■-D term and same/♂7/7
It is described in the patent cited in (July, 2007). The coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a pallast group or being polymerized. A two-pixel coupler substituted with a leaving group can reduce the amount of coated silver and provide higher sensitivity than a four-pixel coupler in which the coupling active position is a hydrogen atom. A coupler in which the coloring dye has appropriate diffusivity, a non-coloring coupler, or a D that releases a development inhibitor along with the coupling reaction.
IR couplers or couplers that release development accelerators can also be used. A representative example of the yellow coupler that can be used in conjunction with the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 4tθ2. Ko/θ No. 2, 17j-, Oj No. 7 and No. 3. λ≦! . It is described in No. 303, etc. Two-pixel yellow couplers include U.S. Pat. ri3
3.Oxygen atom separation type yellow couplers described in jO1 and <t, O, 2λ, and 20, etc., or Tokukosho! ♂-10739, U.S. Patent No. 4t, 4tO
/, 7 Jr. No. 4t% 326,02q, RD/
♂oz3 (/? 2nd month), UK patent No. 1, 4tJ
J, No. 020, West German Application Publication Tube 2゜2/Ri, Ri No. 77, No. -9λ6/, 3 Otsu/No. 2, 3.29, 62
No. 2 and No. 2, 4tJ! . A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 27.2. The magenta coupler that can be used in the present invention is preferably an oil-protected indacylon or cyanoacetyl coupler! - Pyrazoloazole couplers such as pyrazolone and pyrazolotriazoles are mentioned. ! -Pyrazolone couplers are preferably those in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and coloring density of the coloring dye, and representative examples thereof include U.S. Pat. , No. 2,
Same 2nd degree! 'lJ, No. 703, No. λ, t00.77
No. 7, No. 2,90♂! No. 73, same No. 3,062. Bu No. 13, No. 3 I/! Ko, No. 296 and No. 3゜? 3
Otsu, θ/! It is written in the number etc. Two equivalents! - As a leaving group for pyrazolone couplers, U.S. Patent No. 41,3
10,6/9 or US Pat. No. 41.3! The arylthio groups described in /, rri No. 7 are particularly preferred. Also European Patent No. 73.631. There is a pallast group described in the issue! - Pyrazolone couplers provide high color density. As a pyrazoloazole coupler, US Patent No. 3.
Pyrazolobenzimidazoles as described in US Pat. No. 3,79/79, preferably US Pat. No. 3,72! Pyrazolo[j,/-c][/,2.41] triazoles described in , No. 047, Research Disclosure, 24t22
Pyrazolotetrazoles and Research Disclosure 24t230 described in 0 (/Waza 9 Year 2 Month)
Examples include pyrazolopyrazoles described in (June 1991). The imidazo C/, 2-b) pyrazoles described in European Patent No. 1/9.2g/ are preferred from the viewpoint of low yellow side absorption of coloring dyes and light fastness. , /Pyrazolo [/. ! -b](/, J, 4t':) triazole is particularly preferred. Cyan couplers that can be used in the present invention include oil-protected naphthol couplers and phenolic couplers, preferably the naphthol couplers described in U.S. Pat. No. J, 4t71°293, and preferably U.S. Pat.
! Ko, 2/, No. 2, Same No. G. Typical examples include two-equivalent naphthol couplers of the oxygen atom dissociative type described in No. 233 and No. 9.2, No. 200. It will be done. Specific examples of phenolic couplers include U.S. Patent Nos. 369,929 and 2,10/1.
No. 71, No. 2, No. 77.2, No. 2, No. 2, No. 7, /ri! , ♂2 Otsu No. etc. Cyan couplers that are robust to humidity and temperature are preferably used in the present invention, exemplified by U.S. Pat.
72.00.2, a phenolic cyan coupler having an alkyl group greater than or equal to ethyl group at the meta-position of the phenol nucleus, U.S. Pat.
Same number 3.7! t, No. 307, same No. 4t, /, 24.3
No. 96, No. 33, No. 077, No. 327°723, West German Patent Publication No. 3.329.722 and Patent Application Sho! ♂-Octopus described in '4247/ issue, etc. −
Diacylamino-substituted phenolic turnip 2- and U.S. Pat.
, No. 9 Tade, No. G, 4t6/, J'Tawa No. and <j, No. 4427.747, etc., which have a phenylureido group at the 11th position and! A phenolic coupler having an acylamino group at the -position, and a patent application! Taawa 36θ! Same issue! 9-2 Otogu No. 277, same! Day, 2
6♂/3! It was listed in the issue! - It is an amidnaphthol coupler. In order to correct unnecessary absorption in the short wavelength range of dyes generated from magenta and cyan couplers, it is preferable to use colored couplers in combination with color sensitive materials for photographing. U.S. Patent No. 3,670 and Japanese Patent No. J2
-3 Yellow-colored magenta coupler described in Tag No. 73, etc. or U.S. Pat. ? No. O: and British Patent No. 1, /4tt
Typical examples include the magenta-colored cyan coupler described in , No. 347, etc. Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Examples of such blur couplers are shown in U.S. Pat. No. 41.3tt.237 and British Patent No. 1/2J. Jj4t, No. 633 describes specific examples of yellow, magenta or cyan couplers. The dye-forming couplers and the special couplers described above may form dimers or more polymers. Typical examples of polymerized dye-forming couplers are U.S. Patent No. J, 41! /
, No. 220 and Da, o, ro. It is described in No. 277. Specific examples of polymerized magenta couplers are described in British Patent No. 10, 723 and U.S. Pat.
．． Examples include monoequivalent cassillar described in J/, No. 2. These couplers may be either q-equivalent or mono-equivalent to silver ions. It may also be a colored coupler that has a color correction effect. In order to satisfy the characteristics required for a photosensitive material, two or more of the above-mentioned couplers can be used in the same layer of the photosensitive layer, or the same compound can be introduced into two or more different layers. I go to school with Kotomo. The couplers of the present invention and the couplers that can be used in combination can be introduced into the silver halide emulsion layer using known methods, such as those described in US Pat. No. 2,3.2λ,027. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate), phosphoric esters (
Diphenyl 7 phosphate, triphenyl 7 phosphate, tricresyl 7 phosphate, dioctyl butyl phosphate), citric acid esters (e.g. acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauryl amide), fatty acids esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc., or organic solvents with a boiling point of about 3°C to /zo0c, such as lower alkyl acetates such as ethyl acetate, butyl acetate. , ethyl zolopionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate,
After being dissolved in methyl cellosol heptatate, etc., it is dispersed in a hydrophilic colloid. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination. Also, Tokko Akira! /-39♂33, Tokukai Akira! /-! ri94
The dispersion method using polymers described in No. t3 can also be used. When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline aqueous solution. As the binder or protective colloid that can be used in the emulsion layer or intermediate layer of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can also be used alone or together with gelatin. In the present invention, the gelatin may be either lime-treated or acid-treated. Details of the method for producing gelatin are described in The Macromolecular Chemistry of Gelatin, written by Arthur Weiss (Academic Press, published in 2006). Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is /! It is silver iodobromide containing silver iodide under Momoru. Particularly preferred is silver iodobromide containing silver iodide at 2 to 72 moles. The average grain size of silver halide grains in photographic emulsions (the grain size is expressed as the grain diameter for spherical or approximately spherical grains, and the wavelength for cubic grains, and is expressed as an average calculated by the projected area) is particularly important. Although it does not matter, it is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains in the photographic emulsion may have regular crystal bodies such as cubic or octahedral, or may have spherical,
It may have an irregular crystalline shape such as a plate shape, or it may have a composite shape of these crystalline shapes. It may also consist of a mixture of particles of various crystalline forms. stomach. Also, the diameter of the particle is the same as its thickness! An emulsion may be used in which ultratabular silver halide grains occupy 10% or more of the total projected area. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which a latent image is mainly formed on the surface, or may be particles in which a latent image is mainly formed inside the particle. The photographic emulsion used in the present invention is B. graccides (
'Chimie etPhy Photographic' (P. Glafkides)
sique Photographique)'
(Published by Paul Montel,
/ 1966), FF E-x Roots
otographic Emulsion)” (The
The Focal Press
It can be adjusted using the method described in, for example, published by Shasha, 1994). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method). As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist. Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, an etch fuser (H
, Fieser), eds.
der Photographischen Proze
sse mit 5ilber Halogeni
den)” (Akademisch Verlag)
Published by sgesellschaft), /9 Otori, No. 67!
The method described on pages 734 to 734 can be used. That is, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, pt, I
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as r, Pd, etc. can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing capri during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. such as benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (in particular /-phenyl-mercaptotetrazole); mercaptopyrimidines; mercaptotriazines: thioketo compounds, such as oxadorinthion; azaindenes, such as triazoles; Zaindenes, tetraazaindenes (especially g-hydroxy-substituted (/, 3.3a, 7) tetraazaindenes), hantaazaindenes: benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. A number of compounds known as anti-capri agents or stabilizers can be added. The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be contained for purposes such as development acceleration, contrast enhancement, and sensitization. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, urethane derivatives,
It may also contain urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in the photographic emulsion layer or other hydrophilic colloid layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (vinyl acetate with side light), acrylonitrile, olefin styrene, etc. alone or in combination, or these and acrylic acid. , methacrylic acid, α, β-unsaturated dicarboxylic acid,
A polymer containing a combination of hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus,
Selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.: a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and a nucleus in which an aromatic hydrocarbon ring is fused to these nuclei, i.e., indolenine nucleus, Benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole nucleus, quinoline nucleus, etc. are applicable. These nuclei may be substituted on carbon atoms. Merocyanine dyes or composite merocyanine dyes contain pyrazoline-! as a core having a ketomethylene structure. -one nucleus, thiohydantoin nucleus, cochoxazolidine-λ
,<t-dione nucleus, thiazolidine-2,4t-dione nucleus, rhodanine nucleus, thiobarbital acid group, etc.! ~6-membered heteroartic ring nuclei can be applied. These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
λ/), aromatic organic acid formaldehyde condensates (for example, those described in US Patent J, 74t3.j10), cadmium salts, azaindene compounds, and the like. The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium alum, chromium acetate, etc.)
, aldehydes, (formaldehyde, glyoxal, geltaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.), activated vinyl compounds (i, 3.z) -) Liacryloyl-hexahydro-S-triazine, /, 3
-vinylsulfonyl-2-furono-nor, etc.), active halogen compounds (,z,4t-dichloro-g-hydroxy-S-)riazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.), etc. Can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an amine phenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color anti-capri agent. The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. For example, benzotriazole compounds substituted with aryl groups (e.g. those described in U.S. Pat. No. 3.3j, 794), q-thiazolidone compounds (e.g. U.S. Pat. 3!λ.327), benzophenone compounds (e.g., those described in JP-A No. 4-271'1), cinnamate ester compounds (e.g., U.S. Pat. No. 3,20!, ♂0!, U.S. Pat. 3.707.37J-), butadiene compounds (such as those described in U.S. Pat. No. 3.707.37J-), butadiene compounds (such as those described in U.S. Pat.
tittt issue) can be used. An ultraviolet absorbing coupler (for example, an α-naphthol cyan dye-forming coupler) or an ultraviolet absorbing polymer may be used. These ultraviolet absorbers may be mordanted in specific layers. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes; hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and hibisphenols. For photographic processing of the layer consisting of the photographic emulsion produced using the present invention, any of the known methods and known processing solutions, such as those described in Research Disclosure No. 726, pages ♂ to 30, may be applied. be able to. The processing temperature is usually chosen between /♂0C and 40°C, but /!
Temperatures below 0C or! The temperature may exceed θ0C. Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenediamines (e.g., guamino-N, N-diethylaniline, 3-methyl-guamino-N, N-diethylaniline, guamino-N-
Ethyl-N-β-hydroxyethylaniline, 3-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-amino-N-x
f-N-β-methanesulfamide ethylaniline, teramino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used. In addition, F.A. Mason, 'Photographic Processing Chemistry =
ssing Chemistry)' (published by Focal Press, 7966)
, No. 26 to Kokota, U.S. Patent No. 21/3. θ/
! No., same co,! Octopus, 3 Zagu, Tokukai Akira♂-Bukuri 3
Those described in No. 3 may also be used. Color developers may also contain pH buffering agents such as alkali metal sulfites, carbonates, borates, and phosphates, development inhibitors or anticapri agents such as bromides, iodides, and organic anticapri agents. can include. Also, if necessary, water softeners, preservatives such as hydroxylamine,
Organic solvents such as pendyl alcohol, diethylene glycol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride, auxiliary developers such as /-phenyl-3-pyrazolidone, viscosity-imparting agents, polycarboxylic acid chelating agents, antioxidants. It may also contain agents. After color development, the photographic emulsion layer is usually bleached. The bleaching process may be performed simultaneously with the fixing process, or may be performed separately. As a bleaching agent, for example, iron (DI)
, compounds of polyvalent metals such as cobalt (III), chromium (■), and copper (U), peracids, quinones, and nitroso compounds. For example, 7 erythyanide, dichromate, iron (Ill
) or organic complex salts of cobalt (III), such as aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, and 7゜3-diamino-2-propatoltetraacetic acid, or complex salts of organic acids such as citric acid, tartaric acid, and malic acid. ; persulfate, permanganate; nitrosophenol, etc. can be used. Of these, potassium ferricyanide, sodium iron(In) ethylenediaminetetraacetate, and ammonium iron(III) ethylenediaminetetraacetate are particularly useful. Iron(II) ethylenediaminetetraacetate
I) Complex salts are useful both in stand-alone bleach solutions and in -bath bleach-fix solutions. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. Here, after the fixing step or bleach-fixing step, washing with water,
Although it is common practice to perform a treatment process such as stabilization, it is also possible to perform only a water washing process or, conversely, to perform only a stabilization process without providing a substantial water washing process (Japanese Patent Application Laid-open No. 7
-I! A simple processing method such as 4t3 Publication) may also be used. The rinsing water used in the rinsing step can contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid,
Bactericidal agents and antifungal agents to prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, and surfactants to prevent drying load and unevenness can be used. Or, L.E. West (L.E. West), “Water Quality Flying Territory 7”
(Water Quality Cr1teria)
'7 Photo, Sci, and Eng.
,),VOl,? At page j 4t4t~3!
It is also possible to use the compounds described in 79g. In addition, the washing step may be carried out using more than one tank if necessary, and the washing water may be washed in multiple stages (e.g. As the stabilizing solution used in the stabilization step, a processing solution that stabilizes the dye image is used. For example, 1) a solution having a buffering capacity of HJ ~, an aldehyde (for example, formalin) A liquid containing such a substance can be used. The stabilizer may contain fluorescent brighteners, chelating agents, fungicides, fungicides, etc. as necessary.
A hardening agent, a surfactant, etc. can be used. In addition, the stabilization process may be carried out using more tanks than necessary, and the stabilizing liquid can be saved by performing multi-stage countercurrent stabilization (for example, - to three stages), and furthermore, the water washing process can be omitted. can. (Examples) The present invention will be described in detail below using Examples, but the present invention is not limited thereto. Example: 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 layer.
It was set to 0/. (Preparation of Sample 10/) Coating amounts are expressed in g/m2 of silver for silver halide and colloidal silver, and g/m2 for couplers, additives, and gelatin. The sensitizing dye is expressed in moles per mole of silver halide in the same layer. @7 layers (antihalation layer) Black colloidal silver ・・・ 0.2 gelatin ・・・ /, UV absorber UV
-/ ・・・ 0.7 Same as above UV-λ ・・・
・O, θ dispersion oil 0 il-/ ・・・θ, θ same as above 0
i1-2...θ, 0.2th 0. (Intermediate layer) Fine grain silver bromide (average particle size θ, 07 μ) ...0.0♂ gelatin
... /, θ colored coupler C
Lou / ... θ, / same as above Cp-ko ... θ
, 0/Dispersed oil 0il-/ 0.Co Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (iodide steel q morch, average grain size θ, 4tμ) ・・・Silver 7.4t gelatin...K, O sensitizing dye■
.../ , /X10-4 sensitizing dye■ ・
...λ, jX10-5 sensitizing dye■ ...3
．． 3 x 70-5 sensitizing dye ■...2.2 x 7
0-4 Coupler Cp-3...θ,♂O Coupler Cp-na...0.02 Coupler Cp-co...0.003 Dispersion oil 0il
-/...0.03 Same as above Oi 1-3 ・
-0,072 qth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 7 molt, average grain size O, Sμ) ... 7.4t silver gelatin ... /, j Sensitizing dye■
...B, j×10-5 sensitizing dye■ ...
・λ, O×70-5 sensitizing dye ■ ・・・・λ,!
X10-4 sensitizing dye ■...λ,! ×10-
5 coupler Cp-, t...θ, Oj coupler Cp-t...0.0//. Coupler Cp-co ... θ, 0/Dispersion oil 0il-/ ...0.0/Dispersion oil 0i
l-ko...o, orth! Layer (middle layer) Gelatin ・・・ Ha θ compound Cpd
-A...0.0.3 dispersion oil 0il
−/ ・・・θ, Of same as above Oil −, z
・-・-o, or 6th layer (first green-sensitive emulsion layer) Silver iodobromide emulsifier (silver iodide qmolti, average grain size o, <tμ) ・・・・7.0 Sensitizing dye■ ・...λ, /×10-4 sensitizing dye■
...Q, 3x10-4 gelatin
...7.4t coupler Cp-7...
0.4t Coupler Cp-<t...θ, Q coupler Cp-/...θ,/! Dispersion oil 0
il-/... θ,! 7th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (silver iodide 6 molt, average grain size 0.7μ)...Sen 7.2 gelatin
・・・／、! Sensitizing dye V
.../, 0X10-4 sensitizing dye■ ...
λ, θX10-4 coupler Cp-ta...
・θ, o4t coupler Cp-/θ ・・・θ,
θ? Coupler Cp-/...0.0 Co-coupler Cp-, r...0.02 Dispersion oil 0il-/...0.70 Same as above Oil
-,l! ...θ, O! Female layer (yellow filter single layer) Gelatin... /, yellow colloidal silver...o, o, r compound H-3
...0.7 Dispersion oil 0il-/ ...0.3 9th layer (first blue-sensitive emulsion layer) Monodispersed silver iodobromide emulsion (silver iodide q morch, average grain size o, <
tμ) ・・・Silver 0.7 gelatin
... /, /sensitizing dye■ ...
j'pL:, 10-4 coupler Cp-// ・
...0.2 Coupler Cp-ri ...0
．． 07 Dispersion oil 0il-/...o, 2!
1st O layer (1st blue-sensitive emulsion layer) Silver iodobromide (silver iodide 10 molti, average grain size/, Qμ) ...Silver o, tr gelatin ...0.1 sensitizing dye■
····Ko,! ×10-4 coupler Cp-//
...θ, 2! Dispersion oil 0il-/
...0.07 1st/layer (first protective layer) Gelatin ... o, r Ultraviolet absorber UV-/ ...0.7 Same as above UV-co ...0. Co-dispersion oil 0il-/...0.0/Dispersion oil 0il-2...0.0/12th layer (second protective layer) Fine grain silver bromide (average particle size 0.07μ)...・ ・ θ,! Gelatin...O, aZ polymethyl methacrylate particles (diameter/, jμ)...0.2 hardener to 1/...O,4t formaldehyde scavenger S-/... ・ ・ ・ / ,
θ In addition to the above-mentioned components, a surfactant was added as a coating aid to each layer. The chemical structural formulas or chemical names of the compounds used in the above examples are shown below. UV-/UV-co0il-/tricresyl phosphate0il-λ Diptyl phthalate0i1-j Bis(-monoethylhexyl) phthalate C
p-/ Cp-J R Cp-1 (Z) Cp-3 Cp-7 m/m'=/(weight ratio) Molecular weight approximately 20. θQθ Cp-/α Cp-taCp-/. α Cp-// Cp-/λ Cp-/J Cpd A H-3 Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ Sensitizing dye■ 2H5 Sensitizing dye V Sensitizing dye■ Sensitizing dye■ Ni-/ '1F1 in S-/ (Preparation of sample/θ, 103) In place of coupler Cp-// in the 9th layer of sample/θ/, equimolar replacement was made with comparative couplers Cp-/co and Cp-/3. Sample 10.2.103 was prepared in the same manner as Sample 10/ except for this. (Preparation of sample 7041% 10B) Instead of the coupler Cp-// of the 9th layer of sample 10/, yellow couplers of the present invention Y-<t♂, Y-4tq, Y-
An equimolar substitution was made for to, and accordingly, the amount of the high-boiling organic solvent was reduced in order to keep the ratio between the amount of the high-boiling organic solvent and the amount of the coupler constant. In addition, in order to match the physical properties of gelatin membrane (mainly membrane strength),
The amount of gelatin was reduced so that the ratio between the sum of the amount of coupler and the amount of high-boiling organic solvent (amount of oil-soluble component) and the amount of gelatin binder was constant. Sample 706 was prepared from sample 1o4t in the same manner as sample /θ/ except for the above. (Creation of sample/θ7.101) Compound Z that releases the development inhibitor of the present invention in place of the coupler Cp-<t (development inhibitor-releasing coupler, hereinafter referred to as DIR coupler) in the 9th layer of sample/θ/ Sample 107 was prepared in the same manner as Sample 10/, except that -2,2- was replaced with equimolar
．． 101 was created. (Preparation of Samples 10 and 10) Same procedure as Sample 10♂ except that the coupler Cp-// in the second layer of sample /θ♂ was replaced with comparative couplers Cp-72 and Cp-73 in equimolar amounts. Samples /θ and //θ were created. (Preparation of Samples ///, //2) Samples/// //, //2 was created. (Creation of samples //J', //l) Sample 10! Except that the DIR coupler in the second layer was replaced with equimolar compounds 2-co and 2-♂ of the present invention.
Samples //3 and //ri were prepared in the same manner as sample /θ. (Preparation of samples //!, //B) Samples// /! , //Created B. When the samples /θ/ to /101 prepared as described above were exposed to white imagewise light and subjected to color development as described below, almost the same sensitivity and gradation were obtained. The MTF values and conventional RMS (Root M
The graininess was measured by the ean 5 square method. The method for measuring MTF is T.A.T. James (
T. H. James), 'The Theory on the Photographic Process' (ed.
of the Photographic Pro
Mac Mi 11
an) Sha Publishing, 7972), No. tot, pages t-607. Regarding the RMS method, please refer to “Photographic Science
and engineering (Photographic 5science and
Engineering)” vol./9:
A4t (/971), pages 23j to 3♂ - RMS
Granularity; Determination of Just Known Differences (RMSGr)
annularity; Determination
of Just Noticeable Different
The aperture used was 4trμ. The measurement results are summarized in Table 1. (Development process) The exposed sample was developed at 3~0C according to the following processing steps. Color development 3 minutes/! seconds Bleaching 6 minutes 30 seconds water washing - minutes 10 seconds Fixing 9 minutes 20 seconds water washing 3 minutes/! seconds Stable / minute θ! seconds Processing solution composition used in each step The color developer was as follows: Diethylenetriaminepentaacetic acid 7.0g/-Hydroxyethylidene-/,/-diphosphonic acid λ, og Sodium sulfite 4t, 0g Potassium carbonate
3θ, 0g potassium bromide
/, 41g potassium iodide
/, 3 mg hydroxylamine sulfate
J, 4tg (N-ethyl-N-β- and droxyethylamino)-2-methylaniline sulfate 11.1g was added to pH 7.01, pH 10. Bleach solution Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide /! θ, og ammonium nitrate Add 70.0g water
/, 01 pH 4,0 Fixer ethylenediaminetetraacetic acid disodium salt i, og sodium sulfite g, og ammonium thiosulfate aqueous solution (70%) /7j, 0ml Sodium bisulfite 11.4g Add water
/, 0ljpHt, stabilized liquid formalin (4to%) J, Oml
Add 0.3 g of polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) /, O1 (Effects of the invention) As is clear from Table 1, the present invention deteriorates graininess. To provide a multilayer silver halide color photographic material with improved sharpness without adding color. This effect is produced by the combination of the low molecular weight type yellow coupler of the present invention and the development inhibitor-releasing compound of the present invention, and is less effective for couplers having molecular weights outside the range of the present invention.

Claims (1)

[Claims] Represented by the following general formula [A], the equivalent molecular weight is from 250 to
680, or at least one lipophilic two-equivalent yellow coupler having an equivalent molecular weight of 250 to 700 represented by the following general formula [B], and at least one compound represented by the following general formula [I]. A silver halide color photographic light-sensitive material. General formula [A] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the general formula [A], R_1 is an aliphatic group, R_2 is a hydrogen atom, a halogen atom, or an aliphatic oxy group, and R_
3 represents a group (including atoms) that can be substituted on the benzene ring, l represents an integer of 0 to 4, and X_1 represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, when l is plural, (R_3)_l may be the same or different. Further, R_1, R_2, R_3 or X_1 may serve as a divalent to tetravalent linking group to form a dimer to tetramer of the yellow coupler represented by the general formula [A]. General formula [B] ▲ Numerical formulas, chemical formulas, tables, etc. are included. m represents an integer of 0 to 5, n represents an integer of 0 to 4, and X_2 represents a group that can be separated by a coupling reaction with an oxidized aromatic primary amine developer. However, when m is plural, (R_4)_m may be the same or different, and similarly when n is plural, (R_4)_m may be the same or different.
R_6)_n may be the same or different. Also R_
4, R_5, R_6, or X_2 may serve as a divalent to tetravalent linking group to form a dimer to tetramer of the yellow coupler represented by the general formula [B]. General formula [I] A-PDI In the general formula [I], A represents a group that cleaves PDI by reacting with an oxidized developing agent, and PDI is A-PDI.
Represents a group that reacts with an oxidized developing agent to produce a development inhibitor after being cleaved.