JPH0235449A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the graininess and the brightness of reflectivity of the title material at the same time by incorporating a compd. capable of forming a development restrainer and a specified cyan coupler in the sensitive material. CONSTITUTION:The compd. (A) in which the reaction product with the oxidant of a development main agent is further allowed to react with the oxidant, thereby being formed a development restrainer, and the phenol type cyan coupler (B) which has a group shown by formula I at 2-position of a phenol nucleus and a group shown by formula II or III, etc., at 5-position of said nucleus, are incorporated in the photosensitive material. In the formula, R1 is (cyclo)alkyl group, etc., R2 is hydrogen atom or alkyl group, etc., R3 is (cyclo)alkyl group, etc., R11 is (cyclo)alkyl group, R12 is alkyl group, L is oxygen or sulfur atom, X1 is halogen atom or cyano group, etc., X2 is aryl sulfonamide or aryl sulfamoyl group, X3 is a substituting group, (l1) and (l3) are each 0 or 1, (l2) is 0-3. The component (B) is composed of a compd. shown by formula IV wherein R1 is C2H5 group, R2 and Z1; are each hydrogen atom, R3 is C16H33 group, etc. The component (A) is composed of a compd. shown by formula V, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a silver halide color photographic light-sensitive material, and more particularly to a color light-sensitive material for photographing in which graininess and sharpness are simultaneously improved.

[Background of the invention]

In recent years, silver halide color photographic materials have made remarkable progress, and sensitive materials with higher sensitivity and higher image quality have been released one after another.
Small format film (
Although it has become possible to obtain reasonably good photographs even with high-magnification prints from (for example, 110 film, disc film), it has still not reached a level that satisfies general users, and color There is a strong desire to further improve the image quality of photographic materials, particularly to simultaneously improve sharpness and graininess.

As a technique for improving graininess, it has been proposed to use a monodisperse silver halide emulsion, but it has drawbacks such as narrow exposure latitude and poor graininess in high exposure areas. Furthermore, it has been proposed to use a monodisperse emulsion in which the interior of the silver halide grains has a high silver iodobromide content with a DIR compound that releases a development inhibitor with a certain degree of development inhibition, and this has improved graininess and sharpness. ing.

It is also known to use DIR compounds with timing groups to improve sharpness, color reproduction, and graininess.

Furthermore, in order to improve the sharpness, techniques are known in which the film is made thinner by using a highly colored coupler or a polymer coupler, or by the use of a dye to reduce light scattering.

However, the improvement effects achieved by these techniques alone were still insufficient.

[Purpose of the invention]

An object of the present invention is to provide a color photographic material having excellent graininess and sharpness.

[Structure of the invention]

The above object of the present invention is characterized in that the reaction product with the oxidized form of the developing agent further contains a compound that produces a development inhibitor as a result of the reaction with the oxidized form of the developing agent, and the following phenolic cyan coupler. (d) This was achieved using silver rhodanide color photographic light-sensitive materials.

Phenolic cyan coupler: Cyan coupler In the above groups, R1 and R2 are an alkyl group, a cycloalkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group, R3 is an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, k represents O or l, and R2 is the first
When it is a class alkyl group, R1 is a group having at least 2 carbon atoms, R1+ is an alkyl group or a cycloalkyl group, R1□ is an alkyl group, L is an oxygen atom or a sulfur atom, Xl is a halogen atom, Cyano group, nitro group, alkyl group, aryl group, cycloalkyl group, heterocyclic group, C0(0)(23R13, C0NR13R14, O
R+3, SR+3, OSO□R1, -SO□(0)LR
z, -NR,,So,R,,,SO□R13R14 or -NR14COR13, R13 is an alkyl group or an aryl group, R1 is a hydrogen atom, an alkyl group or an aryl group, Ql and Q are 0 or 1 When Ql-0, R1+ is an arylalkyl group or a branched alkyl group, R1□ is an alkyl group having at least 2 carbon atoms, and X2 is an arylsulfonamide group or an arylsulfamoyl group. , X represents a substituent, Q2 represents 0 to 3, each X may be the same or different when Q-2 to 3, R2+ represents a hydrogen atom or an alkyl group, x4
is a cycloalkyl group, aryl group, heterocyclic group or Xl
R25, R23 is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or X7R2
6, R24 is a hydrogen atom, a halogen atom, an alkyl group,
Cycloalkyl group, aryl group, heterocyclic group or -Xl
R2B is an alkyl group, a cycloalkyl group, an aryl group, or a heterocyclic group, and Xl is -Co(0)m
2, -802(NR2a)m2- or -CONR2゜-, m2 is 0 or l, R26 is a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group,
X represents a nonmetallic atom group necessary to form a ring with X, X represents a substituent, m represents 0-10, and when m+ is 2 or more, each X6 may be the same or different. . Also, R1~
Rs, R, +, R+z, Rz+, X + -X s.

Includes those that form a dimer or more multimer with any of X6.

The present invention will be explained in detail below.

In the above phenolic cyan coupler used in the present invention, the alkyl groups represented by R1 and R2 preferably have 1 to 20 carbon atoms, particularly preferably 2 to 14 carbon atoms.

The alkyl group represented by R2 preferably has 1 to 4 carbon atoms.

The cycloalkyl group represented by Rl+R2, Rs preferably has 3 to 8 carbon atoms in the ring.

The alkylcarbonyl group and alkoxycarbonyl group represented by R and R2 preferably have an alkyl moiety having 1 to 20 carbon atoms.

The alkyl group represented by R1 preferably has 1 to 24 carbon atoms, and the aryl group preferably has 6 to 24 carbon atoms.
The heterocyclic group is preferably a 3- to 8-membered ring in which the hetero atom contains an atom selected from nitrogen, oxygen, and sulfur.

A preferred combination of R1 and (R2)k is that R1 is an alkyl group having 1 to 20 carbon atoms, and k is 0 or k is l.
This is the case where R2 is an alkyl group having 1 to 4 carbon atoms, particularly when R3 is an alkyl group having 2 to I4 carbon atoms, and k is 0.

Bancha represented by R1 and R2 includes those having a substituent, and examples of the substituent include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 8 carbon atoms.

Bancha represented by R3 includes those having a substituent, and examples of the substituent include a halogen atom, alkyl,
Aryl, alkoxy, aryloxy, alkylthio, arylthio, hydroxyl, alkoxycarbonyl, aryloxycarbonyl, acyl, carboxyl,
Examples include acyloxy, amido, carbamoyl, sulfonamide, sulfamoyl, alkylsulfonyl, and arylsulfonyl bancha, including those having further substituents.

The alkyl group represented by R1+ has 1 to 24 carbon atoms.
The cycloalkyl group is preferably a 3- to 8-membered one, and when R11 is an arylalkyl group, the alkyl moiety preferably has 1 to 2 carbon atoms. Particularly preferred as R11 are alkyl groups having 1 to 10 carbon atoms and cycloalkyl groups having 4 to 7 carbon atoms.

The alkyl group represented by R1□ has 1 to 16 carbon atoms.
(In particular, l-10) is preferable, the alkyl group represented by xl has 1 to 24 carbon atoms, the aryl group has 6 to 24 carbon atoms, and the cycloalkyl group has 3 to 8 members. The heterocyclic groups include nitrogen, oxygen,
A 4- to 7-membered group containing an atom selected from sulfur is preferable, and the alkyl group represented by R+s and Rz has 1 to 12 carbon atoms, and the aryl group has 6 to 24 carbon atoms. is preferably an oxygen atom.

The polygroups represented by R11 and R1□ include those having substituents, such as halogen atoms, hydroxyl groups, cyano groups, nitro groups, trifluoromethyl groups, amino groups (substituted amino groups, (containing a cyclic amine group).

The polygroup represented by Examples include 1 to 6 alkoxy groups and amino groups (including substituted amino groups and cyclic amino groups). Particularly preferable xl is a chlorine atom, a cyano group, or a carbon number of 1 to 4.
These are an alkyl group, an alkoxycarbonyl group, and an alkylsulfonamide group.

As X2, an arylsulfonamide group is preferable, and the aryl moiety includes those having a substituent (eg, hydroxyl or carboxyl group).

Furthermore, the position of X2 is preferably the p-position of Xl.

Examples of the substituent represented by X include those exemplified as the substituent of the polygroup represented by R1 described above.

The alkyl group represented by R21 has 1 to 20 carbon atoms, the alkyl group represented by R2□, R23+R24, R25 and R26 has 1 to 24 carbon atoms, and the cycloalkyl group has 3 to 8 members. aryl group has 6 to 24 carbon atoms, heterocyclic group has nitrogen,
A 3- to 8-membered one containing an atom selected from oxygen and sulfur is preferred.

The ring formed by X is preferably a 4- to 7-membered alicyclic ring or a heterocyclic ring, and may be a monocyclic ring or a fused ring.

Examples of the substituent represented by X6 include a halogen atom,
Hydroxyl group, amino group (including substituted amino group, cyclic amino group) cyano group, nitro group, carboxyl group, sulfo group, alkyl group, aryl group, cycloalkyl group, heterocycle 1&, Xy Rzs (X7 and R2S are as described above) (synonymous with).

The polygroups represented by R2□ to R2B include those having substituents, and examples of the substituents include those exemplified as the substituents possessed by the group represented by R1 described above.

As stated above, among the phenolic cyan couplers, preferred are those represented by any of the following formulas.

In the formula, 2, . 22 and Z represent a hydrogen atom or a coupling-off group, and the others are as defined above.

Examples of coupling-off groups include halogen atoms (e.g., fluorine, chlorine, bromine atoms, etc.), amino groups (e.g., amino, acylamino, diacylamino, alkylamino,
arylamino group, etc.), azo group, aryloxy group (e.g., p-methoxyphenoquine, p-butanesulfonamidophenoxy, p-carboxyphenoxy group, etc.), alkoxy group (e.g., methoxy, 2-methoxyethoxy group, etc.)
, arylthio groups (e.g. phenylthio, p-carboxyphenylthio groups, etc.), alkylthio groups (e.g. methylthio, 2-hydroxyethylthio groups, etc.), heterocyclic thio groups (e.g. l-ethyltetrazole-5-thioyl, 2-
pyridylthio group, etc.), heterocyclic group (e.g. 1-pyrazolyl,
l-imidazolyl, 2,5-pyrazolinedione-1-yl group, etc.), carboxyl group, sulfo group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloquinecarbonyl group, and the like.

Among these, as Zl to Z, p-alkoxyphenoxy group and p-alkylphenoxy group are preferable.

Next, specific examples of the cyan coupler described above are shown below, but the present invention is not limited thereto.

-C2H.

-csH7(t) -CIiH21 -C,H.

-C,H.

-CI6H33 C1J3s CH3 -c, 8H37 -C16H33 -CH.

-CI.

+NH302C+aHs -C,H.

(ToSO□c, 6H33 No.

R.

R1 Z.

No.

R1+ ZA: Z8: No.

R No.

l8H37 zA: zB: The above-mentioned phenolic cyan coupler is produced by reacting p-cyanophenyl isocyanate with an aminonitrophenol compound with a protected If hydroquine group to form a ureido group, and then reducing the nitro group. to form an amino group, and further reacted with an acid chloride.

The cyan coupler of the present invention is preferably used in a light-sensitive silver halide emulsion layer or a layer adjacent thereto in a light-sensitive material, and is particularly preferably used in a red-sensitive silver halide emulsion layer. The red-sensitive silver halide emulsion layer preferably consists of two layers of high sensitivity and low sensitivity, or three layers of high, medium and low sensitivity, and is preferably used for any layer.

The amount used varies depending on the coupler, but is preferably IX per mole of silver halide present in the additive layer or adjacent layer.
10-' to 1 mol, more preferably 5 x 10-3 to 5
X is in the range of 10-' moles.

The cyan couplers of the present invention may be used alone or in combination of two or more. Furthermore, cyan couplers other than the cyan coupler of the present invention may be used in combination.

In the present invention, in order to incorporate the cyan coupler of the present invention into a light-sensitive material, conventionally known methods can be used, such as known dibutyl heptatarate, tricresyl phosphate,
After dissolving the cyan coupler of the present invention alone or in combination in a mixture of a high boiling point solvent such as dinonylphenol and a low boiling point solvent such as butyl acetate or propionic acid, gelatin containing a surfactant is prepared. Mixed with an aqueous solution, then emulsified and dispersed using a high-speed rotation mixer, colloid mill, or ultrasonic dispersion machine, and then added directly to the emulsion, or after setting the emulsified dispersion, shredded and washed with water. This may then be added to the emulsion.

Next, a compound (
Hereinafter, it will be referred to as a WI compound. ) will be explained in detail.

In the Wl compound, the "reaction product" may be a compound that is directly produced by the reaction between the W compound and the oxidized form of a developing agent, or it may be a compound that is directly produced by further causing a cleavage reaction, etc. , it may be a compound that is produced for the first time. Further, the development inhibitor may be directly produced by the reaction between the reaction product and the oxidized form of the developing agent, or may be produced only after the directly produced compound undergoes further cleavage reaction or the like.

The Wl compound is represented by the following general formula (W-1), for example.

General formula (W-1) FR-(-T1-)Q-5R+T2 clear INH formula, FR
is (TI-)FS due to the reaction with the oxidized form of the developing agent.
R-C-T 2 Is the component that produces INH Tl(T,)? 7-3 After R-(-T2%INH is generated, SR is a component that cleaves R-(-Tz)ylNH, and after 5RiT2%INH is generated, SR is an oxidized product of the developing agent. By the reaction of (T2--INH), T2 is (T2 crucible, after INH is produced, IN
H is a component that cleaves, INH is a development inhibitor, Q and m are
represent 0 or l, respectively.

The components represented by FR and SR may be those that produce the above-mentioned components by reaction with the oxidized product of the developing agent.
Examples include a coupler component that undergoes a coupling reaction with an oxidized form of a developing agent, and a redox component that undergoes a redox reaction with an oxidized form of a developing agent.

Coupler components include acylacetanilides, 5-
Pyrazolones, pyrazoloazoles, phenols, naphthols, acetophenones, indanones, carbamoylacetanilides, 2(5H)-imidacylones, 5-ynoxacilones, uracils, homophthalimides, oxacilones, 2 .5-Thiadiazoline-1
, 1-dioxides, triazolothiadiazines, indoles, etc., yellow couplers, magenta couplers, cyan couplers, and other compounds that produce various dyes or those that do not produce dyes may be used.

If PR is a coupler component, (TI) SR(Tz)m
Preferably, INH is bound to the active site of the coupler component.

Also, if SR is a coupler component, SR is FR−fT+
)- to function as a coupler for the first time after cleavage from FR-(-T, U- and ÷-T, U-INHQ
It is combined with m.

For example, when the coupler component is a phenol or nalatol, the oxygen atom of the hydroxyl group is the oxygen atom of the hydroxyl group at the 5-position of the tautomer, or the nitrogen atom at the 2-position is the tautomer. In addition, in acetophenones and indanones, the oxygen atom of the hydroxyl group of the tautomer is bonded to FR(-TI-), and -(-T2 piece IN
Preferably, H is bound to the active site of the coupler.

Preferred coupler components as FR include phenols, naphthols, 5-pyrazolones, pyrazoloazoles,
These are acylacetanilides, carbamoylacetanilides, and indanones.

When FR and SR are redox components, examples include hydroquinones, catechols, pyrogallols, aminephenols (eg If (p-aminophenols, 0-amitubuenol)), naphthalene diols (eg 1. 2-naphthalene diols, 1.
4-naphthalene diols, 2,6-naphthalene diols), or aminonaphthols (e.g. 1,2-aminonaphthols, 1,4-aminonaphthols, 2.6
-aminonaphthols), etc.

If FR is a redox component, +”r 4S R+T
z-5■NH is bonded to a position where it does not interfere with the reaction between the FR and the oxidized product of the developing agent.

For example, it may be bonded to the 2-position in hydroquinones, or to the nitrogen atom of the amino group in aminophenols and aminonaphthols.

Also, if SR is a redox component, SR is F R(-T
F
Combines with NH.

For example, in hydroquinones, F R + T r
q- is the oxygen atom of the hydroxyl group, and + T x+
-I N H is bonded to the 2-position.

Examples of the groups represented by T and T2 include (1) a group that causes a cleavage reaction using an electron transfer reaction along a conjugated system, and (2) a group that causes a cleavage reaction using an intramolecular nucleophilic substitution reaction. (3) a group that utilizes the cleavage reaction of hemiacetal, (4) a group that utilizes the cleavage reaction of iminoketal,
(5) A group using an ester hydrolytic cleavage reaction can be mentioned.

Regarding the group (1), for example, JP-A-56-11
No. 4946, No. 57-154234, No. 57-188
No. 035, No. 58-98728, No. 58-16095
No. 4, No. 58-209736, No. 58-209737
No. 58-209738, No. 58-209739, No. 58-209740, No. 62-86361, and No. 62-87958, and for the group (2), for example, JP-A No. 57-56837, U.S. Patent 4,248.
No. 962, regarding the group (3), for example, JP-A No. 6
No. 0-249148, No. 60-249149, and U.S. Pat. No. 4,146.396, for the group (4), see, for example, U.S. Pat. No. 4,546.073, and for the group (5), , for example, West German published patent 2,
No. 626,315 describes this in detail.

As the development inhibitor represented by INH, for example, U.S. Pat. No. 3,227.554, U.S. Pat.
, 615゜506, 3,617.291, 3
, 733.201 and U.S. Pat. No. 1,450.479.
Mercaptotetrazole, selenotetrazole, mercaptobenzothiazole, selenobenzothiazole, mercaptobenzoxazole, selenobenzoxazole, mercaptobenzimidazole,
These include selenobenzothiazole, benzotriazole, benzodiazole, and iodide, and those that change into something that does not substantially affect photographic performance after flowing out into the developer are also preferably used. For example, JP-A-60-
No. 211750, No. 60-218644, No. 60-2
No. 33650, No. 61-11743, U.S. Patent No. 4,4
77.563 etc.

The Wl compound may be a dimer or even a polymer.

W! The compound is preferably added to a light-sensitive silver halide emulsion layer in a light-sensitive material or a layer adjacent to the light-sensitive silver halide emulsion layer. When the layer consists of two layers (high and low sensitivity layers), it is preferably added to the low sensitivity layer, and when it consists of three layers (high, medium, and low sensitivity layers), it is preferably added to the medium and/or low sensitivity layer.

The amount added is 1 x to-' per mole of silver halide.
l x 10-' mol is preferred, more preferably 5
X to-' to 5 X 10-'' moles.

It may also be used in combination with couplers that form other image dyes, and the ratio is 0.0 to 1 mole of other couplers.
0.01 to 10 mol is preferable, especially 0.01 to 10 mol. Preferably it is 0.5 mol.

As a method for adding the Wt compound, a method similar to that for the above-mentioned phenolic cyan coupler is used.

Further, the Wl compound may be used in the same layer as the above-mentioned phenolic cyan coupler, or may be used in a separate layer.

For more details about WI compounds, see, for example, JP-A-63-
No. 23152, No. 63-24237, etc., No. 60-72378, No. 60-78013, No. 60-75040, No. 60-121285, No. 60
It can be synthesized based on the descriptions in No. 185950, No. 60-203943, and the like.

Next, typical examples of Wl compounds are shown, but the present invention is not limited thereto.

l-1 I-2 W ■ ■ ■ H l-7 ■ ■ W ■ ■ ■ ■ Js H H H ■ ■ ■ H H I M Wl-20 W+-21 T-26 W　　　　　-27 *C02CH.

The silver halide emulsion used in the light-sensitive material of the present invention includes:
Any of the conventional silver halide emulsions can be used.

The emulsion can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Further, it is particularly preferable that the amount of silver in the photosensitive material is 5.0 g/m'' or less.

Antifoggants, stabilizers, etc. can be added to the silver halide emulsion. Gelatin is advantageously used as binder for the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

Couplers are used in the emulsion layer of color photographic materials.

Furthermore, by coupling with a colored coupler having a color correction effect, a competitive coupler, and an oxidized form of a developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent,
Photographically useful seven-ragment releasing compounds such as toning agents, hardeners, capri agents, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, and an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A formalin scavenger, a fluorescent whitening agent, a matting agent, a lubricant, an image stabilizer, a surfactant, a color antifoggant, a development accelerator, a development retarder, and a bleach accelerator can be added to the photosensitive material.

As a support, paper laminated with polyethylene, etc.
Polyethylene terephthalate film, baryta paper, cellulose triacetate, etc. can be used.

To obtain a dye image using the photosensitive material of the present invention, after exposure,
Commonly known color photographic processing can be performed.

〔Example〕

The present invention will be specifically explained below using Examples.

Example 1 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material consisting of each layer having the composition shown below was prepared.

(Composition of photosensitive layer) The coating amount is g of silver for silver halide and colloidal silver.
/ff12, and for couplers, additives and gelatin in g/m', and for sensitizing dyes in the number of moles per mole of silver rhodanide in the same layer. Indicated.

1st layer (antihalation layer) Black colloidal silver...0.2 gelatin °゛1・3Cp-8・
...0.06 UV-1...0. l UV-2...0.2 071-1...0.
020i1-2...0
．． 02 Second layer (intermediate layer) Fine grain silver bromide (average grain size 0.07μ+s)...0
．． 15 Gelatin...1.
0Cp-2...0.02 0i1-1...0.
1 Third layer (first red-sensitive emulsion layer) Silver iodobromide emulsion (Agr 6 mol%, internal high Agl type equivalent sphere diameter 0.3 μm 1 sphere equivalent diameter variation coefficient 29% Coated silver amount
...0.4 Gelatin ...0.6SD
-1... 1. OX 10-' 5D-2...3. OX 10-' 5D-3...1. OX 10-'. p-2...0.03 Cp-3...0.06 Cp-4...0.06 Cp-7...0.03 0i+-1...0.03 0i1-3...・0.0
12 Fourth layer (second red-sensitive emulsion layer) Silver iodobromide emulsion (Ag 17 mol%, internal high Agl type equivalent sphere diameter 0.6 μm, coefficient of variation of equivalent sphere diameter 25% Coating amount of silver
...0.7 Gelatin ...0.63D
-1... 1. OX 10-' 5D-2...3. OX 10-' 5D-3...1. OX 10-' Cp-2...0.04 °, -3...0.24 Cp-4...0.24 Cp-7...0.04 0i1-1...0.1
50i1-3...0.
02 Fifth layer (third red-sensitive emulsion layer) Silver iodobromide emulsion (Agl 8 mol%, internal high Agl type equivalent sphere diameter 0.8 μm Coefficient of variation of one sphere equivalent diameter 16% Coated silver amount
...1.0 Gelatin ...1.05D
-1... 1. OX 10-' 5D-2...3. OX 10-' 5D-3... 1. OX 10 Bow Cp-5...0.05 Cp-6...0.1 0 il -1-0,01 0il 2
...0.05 6th layer (middle layer) Gelatin ...1.0AS
-1...0.03 0il l...0
．． 05 7th layer (first green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 16 mol%, internal high Agl type sphere equivalent diameter 0.3 μm 1 sphere equivalent diameter variation coefficient 28% Coated silver amount
...0.30 gelatin
...1.05D-4...5. OX to-
'5D-5...2. OX 10-' 5D-6... 0.3X 10 Ichiban Cp-8...
0.03 Cp-9...0.2 C+>-14...0.02 0i1-1
...0.5 8th layer (second green-sensitive emulsion layer) Silver iodobromide emulsion (Agl 7 mol%, internal high Agl type sphere equivalent diameter 0.6 μm 1 sphere equivalent diameter variation coefficient 25% Coated silver amount
...0.4 Gelatin ...0.53D
-4...5. OX 10-' S D -5-2, OX 10-' 5D-6...0.3X 10-' Cp-8...0.03 Cp-9...0.25 Cp-10...・0.015 Cp-14...0,01 Oi1-1...0.
2 9th layer (3rd green-sensitive emulsion layer) Silver iodobromide emulsion (Ag 18 mol%, internal high Agl type sphere equivalent diameter 1.0 μm 1 sphere equivalent diameter variation coefficient 16% Coated silver amount
...0.85 gelatin
...1.05D-7...3.5X 10-
' 5D-8... 1.4X 10-'Cp-8...
0.02 Cp-11...0.0I Cp-12...0.03 Cp-13...0.20 Cp-15...0.015 0i1-1
...0.200i1-1
...0.05 1st
θ layer (yellow filter layer) Gelatin yellow color S-2 11th layer (first blue-sensitive emulsion layer) Silver iodobromide emulsion (8gl 7 mol%, internal high Agl type sphere equivalent diameter 0.5μm 1 sphere equivalent diameter Variation coefficient 15% coated silver amount
...0.4 Gelatin ...1.05D
-9...2. OX 10-' Cp-14...0.07...1.2...0.08...0.1...0.3 Ido Silver Cp-16...0.9 0il l
...0.2 12th layer (second blue-sensitive emulsion layer) Silver iodobromide emulsion (Agl 10 mol%, internal high Agl type equivalent sphere diameter 1.3 μm, coefficient of variation of equivalent sphere diameter 22% Coated silver amount ...0.5 ...0.6 ...1.OX 10-' ...0.25 ...0.07 Gelatin D-9 Cp-16 13th layer (first protective layer) Gelatin V-1 V-2 14th layer (second protective layer) Fine grain silver bromide (average particle size 0.07 μm) Silver coating amount Gelatin...0.8...0.1...0.2 ・...0.02 ...0.02 ...0.5 ...0.45 Polymethyl methacrylate particles (diameter 1.5 μm) ...0
．． 2H-1...0.4 Cpci-A...0
゜5Cpd-B...
0.5 In addition to the above components, a surfactant was added to each layer as a coating aid.

The sample prepared as described above is designated as sample 101.
.

Next, Samples 102 to Ill were prepared by replacing the cyan coupler in the 3rd, 4th and 5th layers and the DIR compounds in the 3.4th and 7.8th layers of Sample 1 inch with the compounds shown in Table 1.

Next, the chemical structural formulas or chemical names of the compounds used in the present invention are shown below.

N x/y=7/3 (weight ratio) V Bis(2-ethylhexynyl) 7-talate p-2 aO3S S○, Na p-3 p-4 p-5 CH2 C(CH3)3 Cp-6 Cp-7 Cp-8 Cp-12 Cp-13 Cp-14 Shiri ShiU Cp-9 Cp-10 Cp-11 Cp-15 Cp Cp-17 a CH.

Cp-18 Cp-19 Cp-20 Cp-21 D D D-5 D-6 CH2COOCH3 しυ011 C2) 1° S R il S H H D ■ D D D D ■１ ■ CH□=CH 302-CH2-CONH-CH.

Ct12=CHSO2CH2C0NHC+(2cpa
-J Cpd-B This photographic element was given an exposure of 25 CMS using a tungsten light source with a color temperature adjusted to 4800°K using a filter, and then processed at 38°C using an automatic processor according to the processing steps below. Development processing was performed.

Color development 3 minutes 15 seconds bleaching 6 minutes 30 seconds fixation 4 minutes 20 seconds water
Washing Stable for 3 minutes and 15 seconds
1 minute 05 seconds The composition of the treatment liquid used in each step was as follows.

<Developer> ■-Hydroquinethylidene-1,1-diphosphonic acid Sodium sulfite Potassium carbonate Potassium bromide Potassium iodide Hydroxylamine sulfate 4-(N-Ethyl-N-β-Hydroquinethylamino)
-2-Methylanili 3.3g 4.0g 30.0g 1.4g 1.3mg 2.4g sulfate 4.5g i, oQ lOoo Add water <bleaching solution> Ethylenediaminetetraacetic acid ferric ammonium salt 120.
0g Ethylenediaminetetraacetic acid disodium salt 10.0g Ammonium bromide 150.0g Ammonium nitrate IO, 0g Add water
1.012pl+
6.0 <Fixer> Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 200.011+2 Sodium bisulfite 4.6 g Add water 1. OQp H6, 6 <Stabilizer> Holimarin (40%) 2.0m12 Polyoxyethylene-P-7nononylphenyl ether (average degree of polymerization #10) Add 0.3g water
1.012 The MTF value (relative value with comparative sample 101 as 100) at a frequency of 40 lines per mm of magenta and cyan images of these samples and a value 1000 times the conventional RMS representing graininess were determined.

The results are shown in Table 2.

For RMS, measure the point of Dmin (minimum concentration) + 1.0 using a microdentometer (PDM-5 manufactured by Konica Corporation).
A), measured with an aperture area of 250μ 2
child .

As is clear from Table 2, the samples with the structure of the present invention have sharpness,
Both graininess has been improved.

Table 2 The effects of the present invention were also observed when cyan coupler 38 was used instead of cyan coupler 32 in the fourth layer of sample 108.

Example 2 Samples 201 to 204 were prepared in which the amount of silver in each photosensitive silver halide layer of the sample prepared in Example 1 was increased by 0.85 times and 0.7 times, and treated in the same manner as in Example 1. It was measured.

The results are shown in Table 3.

Table 3 In other words, when the silver amount is the same, the sample with the structure of the present invention is superior to the comparative sample in both graininess and sharpness. is getting even bigger.

Claims (1)

[Scope of Claims] A halogen characterized in that the reaction product with the oxidized form of a developing agent further contains a compound that produces a development inhibitor as a result of the reaction with the oxidized form of the developing agent, and the following phenolic cyan coupler. Silver chemical color photographic material. Phenolic cyan coupler: Has a ▲ mathematical formula, chemical formula, table, etc. in the 2nd position, and has 5
A phenolic cyan coupler that has a ▼ group, which has a mathematical formula, chemical formula, table, etc., or a ▼ group, which has a mathematical formula, chemical formula, table, etc., or a ▼ group, which has a mathematical formula, chemical formula, table, etc. (In the above groups, R_1 and R_2 are an alkyl group, a cycloalkyl group, an alkylcarbonyl group, or an alkoxycarbonyl group, and R_3 is an alkyl group, a cycloalkyl group,
an aryl group or a heterocyclic group, k represents 0 or 1, R
When _3 is a primary alkyl group, R_1 is a group having at least 2 carbon atoms, R_1_1 is an alkyl group or a cycloalkyl group, R_1_2 is an alkyl group,
L is an oxygen atom or a sulfur atom, X_1 is a halogen atom,
Cyano group, nitro group, alkyl group, aryl group, cycloalkyl group, heterocyclic group, -CO(O)l_3R_1_
3, -CONR_1_3R_1_4, -OR_1_3,
-SR_1_3, -OSO_2R_1_3, -SO_2
(O)l_3R_1_3, -NR_1_4SO_2R_
1_3, -SO_2R_1_3R_1_4 or -NR_
1_4COR_1_3, R_1_3 represents an alkyl group or an aryl group, R_1_4 represents a hydrogen atom, an alkyl group or an aryl group, l_1 and l_3 represent 0 or 1, and l
When _1=0, R_1_1 is an arylalkyl group or a branched alkyl group, and R_1_2 is at least 2
X_2 is an arylsulfonamide group or arylsulfamoyl group, X_3 is a substituent, l_2 is 0 to 3, and l=2 to
3, each X_3 may be the same or different, and R_2_
1 is a hydrogen atom or an alkyl group; -X_7-R_2_5, R_2_3 is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, or -X_7-R_2
_5, R_2_4 is a hydrogen atom, halogen atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, or -X_7-R_2_5, R_2_5 is an alkyl group, cycloalkyl group, aryl group, or heterocyclic group, X_7
is -CO(O)m_2-, -SO_2(NR_2_5)
m_3- or -CONR_2_5-, m_2 is 0 or 1, R_2_5 is a hydrogen atom, alkyl group, cycloalkyl group, aryl group or heterocyclic group, X_5 is X_4
X_6 represents a substituent, m_1 represents 0 to 10, and when m_1 is 2 or more, each X_6 may be the same or different. Also, R_1~
R_3, R_1_1, R_1_2, R_2_1, X_1
~Includes those that form a dimer or more multimer with either X_3 or X_6. )