JPH043154A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve color reproducibility and sharpness even if rapid processing is possible by incorporating specific cyan couplers into at least one layer of red photosensitive silver halide emulsion layers and incorporating specific compds. at 1 to 100mg/m<2> into at least one layer of photograph constituting layers. CONSTITUTION:This photosensitive material contains at least one of the cyan couplers expressed by formulas I, II, etc., in at least one layer of the red photosensitive silver halide emulsion layers and contains 1 to 100mg/m<2> compds. expressed by formula III into at least one layer of the photograph constituting layers. In addition, at least one layer of the photosensitive silver halide emulsion layers contain silver halide particles substantially consisting of silver chloride. In the formulas I, II, R1 and R3 denote a hydrogen atom or substituent; R2 denotes a substituent; X denotes a hydrogen atom or the substituent to be eliminated by reaction with the oxidant of a color developing agent; (n) denotes 0 to 4 integer. In the formula III, R1, R2 denote an alkyl group, aryl group, etc.; R3, R4 denote a cyano group, carboxyl group, etc. The rapid processing is possible in this way and the high sharpness and the good color reproducibility are obtd. in this way.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it is capable of rapid processing, has little dye staining, has high sharpness, and has high sharpness. This invention relates to a silver halide color photographic material with good color reproducibility.

[Background of the Invention] Usually, in a color image forming method using a silver halide color photographic light-sensitive material, oxidized P is removed after imagewise exposure.
- A color image is formed by reacting a fluorinated diamine color developing agent with a dye image-forming coupler. In this method, a subtractive color reproduction method is usually applied, and cyan, opaque, and yellow dye images corresponding to red, green, and blue are formed on each photosensitive layer. In recent years, in order to shorten the development processing time when forming such color images, high-temperature development processing and labor-saving processing steps have generally been carried out. In particular, in order to shorten the development processing time by high-temperature development processing, it is extremely important to increase the development speed in color development. The development speed in color development is influenced by three aspects. One is a silver halide color photographic light-sensitive material, and the other is a color developer. In the former case, the shape and size of the grains of the light-sensitive silver halide emulsion used, as well as the halogen composition, greatly influence the development speed, and in the latter case, the conditions of the color developing solution, especially the use of development inhibitors, greatly influence the development speed. It has been found that silver chloride grains in particular exhibit significantly higher development rates under certain conditions.

Silver halide color photographic light-sensitive materials consisting essentially of silver halide or silver chloride have the disadvantage that rapid processing is possible, and that development can be completed even if the development time is less than 90 seconds, and dye staining is likely to occur after processing. or was newly discovered.

As a result of various studies on this dye contamination, we found that the anti-irradiation dye added to the photosensitive material leaks into the processing solution during short-term processing, resulting in insufficient decolorization of the photosensitive material after processing. It was found that there were some remaining.

Therefore, it may be possible to reduce the amount of the irradiation prevention dye used to prevent dye staining, but in this case, the sharpness, which is the original purpose of the irradiation prevention dye, would deteriorate.

As described above, silver halide color photographic materials containing silver chloride/10 silver grains can be processed quickly, have little dye staining, and have good color reproducibility. In order to form dye images with high sharpness, there are various problems that need to be solved, and the demand for a silver halide color photographic material that satisfies all of these problems is as follows:
Some are very expensive.

[Problems to be Solved by the Invention] The present invention has been made in view of the above, and is capable of rapid processing, has good color reproducibility and sharpness, and has little dye staining after development processing. The technical problem is to provide a silver halide color photographic material.

[Means for Solving the Problem] The above technical problem is achieved by having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer on a support. In the silver halide photographic material, at least one of the red-sensitive silver halide emulsion layers contains at least one cyan coupler represented by the following general formula [Al-[1], and
At least one of the photographic constituent layers contains the following general formula [II
] 1 a+g/rrf~10
According to a silver halide photographic light-sensitive material containing 0°3/g, and at least one of the light-sensitive silver halide emulsion layers containing silver halide grains consisting essentially of silver chloride. resolved.

General formula [A] General formula [B] General formula [C] General formula [D] General formula [G] General formula [E] General formula [H] General formula [F general formula [I] '-Z [Formula In the formula, R1 and R1 represent a hydrogen atom or a substituent, and R7 represents a substituent. X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent, n represents an integer of 0 to 4, and Z represents a group of nonmetallic atoms necessary to form a heterocycle. ] General formula [0] [In the formula, RI R2 may be the same or different, and represent an alkyl group, an aryl group, or a heterocyclic group, and these groups may be substituted. RjR4 may be the same or different, and may be a cyano group, a carboxyl group, -CO
R5 group (R5 represents an alkyl group, aryl group, heterocyclic group, these (R6 R7 may be the same or different, and represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, these groups may be substituted), -CR' group (R8 represents an alkyl group, aryl group, or heterocyclic group, and these groups may be substituted).L1 to L5 may be substituted. Represents a good methine group.

Further, at least one of R1 to R4 has a sulfo group, a carboxyl group, a phosphono group, a phosphoryl group, a hydroxyl group, or a sulfate group. ] [Specific Structure of the Invention] In the present invention, it is necessary that at least one of the photosensitive silver halide emulsion layers contains silver halide grains consisting essentially of silver chloride.

The silver halide grains contained in the silver halide emulsion layer other than those mentioned above may be any silver halide grains such as silver chlorobromide grains and silver chloroiodobromide grains, and are not particularly limited.

The silver halide grains substantially consisting of silver chloride used in the present invention (hereinafter referred to as silver halide grains J of the present invention) are those having a silver chloride content of 90 mol 96 or more. say. In the silver halide grains, the silver bromide content is preferably 10 mol 9b or less, and the silver iodide content is 0.5 mol % or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

The silver halide grains of the present invention may be used alone, or
It may be used in combination with other silver halide grains having different compositions. Further, it may be used in combination with silver halide grains having a silver chloride content of 10 mol % or less.

Further, in the silver halide emulsion layer containing the silver halide grains of the present invention, the proportion of the silver halide grains of the present invention in the total silver halide grains contained in the emulsion layer is 60% by weight or more, Preferably it is 80% by weight or more.

The composition of the silver halide grains of the present invention may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. Furthermore, when the composition inside and outside the particle is different, the composition may change continuously or discontinuously.

There is no particular restriction on the particle size of the silver halide grains of the present invention, but considering other photographic performance such as rapid processing properties and sensitivity, it is preferably 0.2 to 16 μm, more preferably 0.2 μm.
It is in the range of 5 to 1.2 μm. Note that the particle size can be measured by various methods commonly used in the technical field.

A typical method is Loveland's "Particle Size Analysis Method J.
(A, S, T, M, Symposium on Light Microscopy 1955, 94-1.22J
N) or "Theory of the Photographic Process" (co-authored by Mies and James, 3rd edition, published by Macmillan Publishing Co., Ltd. (1966))
Chapter 2).

The particle size can be measured using the particle's projected area or diameter approximation. If the particles are of substantially uniform shape, the particle size distribution can be described fairly accurately as diameter or projected area.

The grain size distribution of the silver halide grains of the present invention may be polydisperse or monodisperse.

Preferably, the silver halide grains are monodispersed silver halide grains having a coefficient of variation of 0.22 or less, more preferably o, [5 or less, in the grain size distribution.

The silver halide grains of the present invention may be obtained by any of the acid method, neutral method, and ammonia method.

The particles may be grown all at once, or may be grown after seed particles are produced. The method of creating and growing the seed particles may be the same or different.

Further, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a forward mixing method, a back mixing method, a simultaneous mixing method, or a combination thereof, but those obtained by a simultaneous mixing method are preferable. Further, as a type of simultaneous mixing method, it is also possible to use the pAg-chondrold double jet method described in Japanese Patent Application Laid-Open No. 54-48521.

Furthermore, if necessary, a silver halide solvent such as 1,000 onythyl may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound, or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide grains of the present invention may have any shape. One preferred example is a cube having a flooi plane as a crystal surface.

Further, particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can also be used. Furthermore, particles having twin planes may be used.

The silver halide grains of the present invention may be of a single shape or may be a mixture of grains of various shapes.

The silver halide grains of the present invention contain metal ions using cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts, iron salts or complex salts during the grain formation process and/or growth process. inside the particles and/or
Alternatively, it can be included in the particle surface, and by placing it in a suitable reducing atmosphere, reduction sensitizing nuclei can be provided inside the particle and/or on the particle surface.

In the emulsion containing the silver halide grains of the present invention (hereinafter referred to as the emulsion of the present invention), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed, or the unnecessary soluble salts may be left in the emulsion. . In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 1711i43.

The silver halide grains of the present invention are preferably grains in which a latent image is formed mainly on the surface, but may also be grains in which an a-image is formed inside the grain.

In the present invention, a chalcogen sensitizer can be used. The chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Others, US Patent 1.57
No. 4,944, No. 2.410,689, No. 2,278
．． No. 947, No. 2,728.668, No. 3, 501
, No. 31.3, No. 3.658.955, West German Publication (OLS) No. 1,422,889, JP-A No. 1973
Sulfur sensitizers described in Publications No. 6-24937 and No. 55-45016 may also be used. The amount of sulfur sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and the size of silver halide grains, but as a guide, it is 10 mol to 10 mol per 1 mol of silver halide. A molar level is preferable.

The emulsion of the present invention can be produced by a reduction sensitization method using a reducing substance, a noble metal sensitization method using a noble metal compound, or the like.

Next, the cyan couplers represented by general formulas [A] to [1] contained in the red-sensitive silver halide emulsion layer according to the present invention will be explained.

The cyan coupler of the present invention is fused with a pyrazole ring,
It has a structure in which a 6-membered hetero ring is formed, and R□, R7
and the substituent represented by R5 (7 is not particularly limited,
Typically, alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio,
Each group such as alkenylroalkyl may be mentioned, and in addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloquine, aryleoquine, Heterocyclicoxy, siloxy, acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxysulfonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, funorboxyl, hydroxy , mercapto, nitro, and sulfonic acid groups, as well as spiro compound residues, bridged hydrocarbon compound residues, and the like.

The above alkyl group preferably has 1 to 32 carbon atoms, and may be linear or branched.

As the aryl group, a phenyl group is preferred.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group include the above-mentioned alkyl groups and aryl groups.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to I, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 12 carbon atoms, especially 5
-7 is preferred.

Sulfonyl groups include alkylsulfonyl groups, arylsulfonyl groups, etc.; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alcoquinephosphonyl groups, aryloquinephosphonyl groups, and arylphosphonyl groups. Examples of near-acyl groups such as nyl groups include alkylcarbonyl groups and arylcarbonyl groups.

Carbamoyl groups include arylcarbonyl groups, arylcarbamoyl groups, etc. Sulfamoyl groups include alkylsulfamoyl groups,
Arylsulfamoyl group ring; As an acyloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, etc.; As a carbamoyloxy group, an arylcarno〈moyloxy group, an arylcar 1〈moyloxy group, etc.; As a ureido group, an alkylureido group, an arylureido group. Groups, etc.; Examples of the sulfamoylamino group include an alkylsulfamoylamino group, an arylsulfamoylamino group, etc. The heterocyclic group 2 is preferably a 5- to 7-membered one, specifically a 2-furyl group, a 2- The heterocyclic oxy groups such as thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, and 1-tetrazolyl group preferably have a 5- to 7-membered heterocycle, for example, 3, 4, 5.6 -tetrahydrobilanyl-2-oxy group, 1-phenyltetrazole-5-
Oxy group, etc.: As the abdominal ring thio group, a 5- to 7-membered abdominal ring 1,000 ring group is preferable, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy1.3.5- Siloxy groups such as 1-lyazole-6-thio group include trimethylsiloquine group, triethylsiloxy group, and methylbutyrunroxy group; imide groups include succinimide group, 3-heptadecylsuccinimide group, and phthalimide group. , kultarimide group, etc.; as a spiro compound residue, spiro[3,3]hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
]Heptan-1-yl, trinculo[3°3.1.1'
-7] Decane-1-yl, 7,7-dimethyl-bicyclo[2,2,1]hebutan-1-yl, and the like.

The above group may further have a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

Groups that can be separated by reaction with the oxidized color developing agent represented by X include, for example, chlorogen atoms (chlorine atoms, bromine atoms, fluorine atoms, etc.), alkoxy, aryloxy,
Heterocyclicoxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkyloxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylamino, aryloxycarboniamino, Carboquine represents a group. ) and the like, preferably a haloken atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

Next, representative examples of cyan couplers represented by general formulas [A] to [N used in the present invention will be shown, but the present invention is not limited thereto.

The following blank space (R' has the same meaning as R1 above, Z' represents a group of nonmetallic atoms necessary for condensing with the pyrazole ring to form a nitrogen-containing six-membered heterocycle, and Ra and Rb represent hydrogen atoms. , an aryl group, an alkyl group or a heterocycle R.

R2 ClsL- H Cl1H23SO□N)! ClJ2sO- -OCH, (2) C.I. (C)+3)2CH- -QC, □H2, (3) -Cノ C) I, 5 -NH5OzC+Jbs(4) ■ One theta CLSH31- H C.J. C12H2SO- H C.I. HI- -NH5O7fCaH17 C4H90 (2! H 12H25 Margin below Margin below D-7 IJ13 R1 N) ICOC+ 1H23 l2H25 l5H31 -N)lCOCtJ27 -OC1]3 NHCOC8+lht Margin below *-3O2NHu C6)+13 C+ 2H2SO- H C.I. l5HII H C.I. C+J2500SOJH<Σ -NHCOCtb H ((L)zCH- -NHCOC+ +27 C.I. Ct &, 0+ -NHCOC, J2゜ H Margin below R5 C,H.

OC,l(9 (CL)3C- -NHCOCsH,712) ■ H ■ Margin below ■ ■ ! -4 The above coupler according to the present invention is disclosed in Japanese Patent Application No. 63-3214.
No. 88, No. 64-36996, No. 64-41183, No. 6452293, No. 64-97598, No. 64
-9884 and 64-1.25052, and can be synthesized according to the synthetic methods described therein and the synthetic methods described in the cited literature.

The cyan coupler of the present invention usually has a content of lX to -3 mol to 1 mol per mol of silver halide, preferably lXl
It can be used in the range of 0-2 mol-8X10-' mol.

The amount of the compound represented by the general formula [IN] used in the present invention is 1 mg/rd to 100 mg/+t
f range, more preferably 2 mg/rr
r~50mg/rrf. Usage amount is 1mg/
Below rrr, irradiation cannot be prevented and sharpness deteriorates. On the other hand, if it exceeds 100 mg/m2, the decolorizing property is insufficient, especially in rapid processing.
Causes color contamination.

Specific examples of the anti-irradiation dye represented by the general formula [II] used in the present invention are listed below, but the dye is not limited thereto.

■-3 O.C.H.

Margin below U-5 ■-10 ■-11 ■-12 OyK ■ ■-13 ■-14 ■-15 O.J. 03K S+Lh8 ) to lJ3 ■ ■-17 ■-18 ■ ■ ■-24 ■-19 ■-20 low 21 SOJ! ■-26 ■ C) 13 )su3N2 L ■ CH2CH2SO,K CH2CH2SO3 ■-29 2H5 C.J.

Low 31 CHCH2SOJ CH2C) 11sO3 ■ CHsC) 120sOJ C1 (pcHsO5OJ ■ CH-CH=CH2 CH-C) l=c[(2 ■-37 ■ ■-33 ■-34 ■ ■-39 H Below the margin of the present invention The compounds of the general formula [mouth] are each
-38129 publication, 52-38056 publication, 52-38056 publication
Publication No. 5-10059, JP-A-5! Publication J-168438, Publication No. 51-77327, Publication No. 5B-14334
Publication No. 2, Publication No. 59-184i, Publication No. 59-111
No. 840, No. 80-218641, No. 62-
Contains compounds described in Japanese Patent Application No. 273527, No. 63-139949, No. 63-282649, Japanese Patent Application No. 63-2591, and Japanese Patent Application No. 63-2592. It can be synthesized by the method described in the book.

The cyan coupler of the present invention can also be used in combination with other types of cyan couplers.

In order to incorporate the cyan coupler according to the present invention into the color photosensitive material of the present invention, known techniques used for ordinary cyan couplers can be applied.

It is preferable to dissolve the coupler in a high-boiling point solvent and, if necessary, in combination with a low-boiling point solvent, disperse the coupler in the form of fine particles, and add it to the silver halide emulsion according to the present invention.

At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

The red-sensitive silver halide emulsion layer afqing the cyan coupler according to the present invention can be obtained by optically sensitizing the red region using a dye known as a sensitizing dye in the photographic industry. can.

When the silver halide color photographic light-sensitive material of the present invention is used as a full-color light-sensitive material, a macenta cobra yellow coupler is used in addition to the cyan coupler of the present invention. As the magenta coupler and yellow coupler, any known one can be used without any particular restriction.

As the magenta coupler, 5-pyrazolone type, virazolobensimidazole type, pyrazoloazole type, open chain acylacetonitrile type coupler etc. are used.
-Pyrazolone and pyrazolotriazole magenta couplers are preferred.

Typical specific examples of magenta couplers are shown below.

Below is the margin Q ShiQ Q \ (Q (Q Q M-9 CI 2H25 C1oH2, C3Hu(t) OC41 (9 \ 0C4) 19 \ + (+7 (1) M-1, for example, -11.1C31, 56
-133734, fiO-143337, fiO[i
No. l-90155, No. 61-158329, No. 61-
No. 189540, same 6! No. 38483, 62-59
953, U.S. Pat. No. 3, 51.9, 429, U.S. Patent No. 3
, No. 684.514.

Among the upper X self magenta couplers, M-7 Ka and M-16
It is preferable to use a pyrazoloazole type magenta coupler as shown in 1 because it not only makes it possible to save silver, but also suppresses the occurrence of fog, and also improves raw storage and image storage properties.

As the yellow coupler, for example, annulacetanilide couplers can be used, including benzoylacetanilide and pivaloylacetanilide compounds.

In the present invention, known techniques can be applied to incorporate the coupler into the color light-sensitive material.

The coupler is dissolved in a hydrophilic binder such as an aqueous solution of seratin by simultaneously dissolving the coupler together with other compounds in a high boiling point organic solvent and, if necessary, in combination with a low boiling point and/or water-soluble organic solvent. After emulsifying and dispersing using a surfactant, aim! It is preferable to add it to the silver halide emulsion layer.

The above-mentioned high boiling point organic solvents include phenol derivatives that do not react with the developing agent, phthalate esters, citric acid esters, benzoic acid esters, trimesic acid esters, etc. with a boiling point of 1.
Examples include organic solvents having a temperature of 50°C or higher. In addition, examples of low boiling point and/or water-soluble organic solvents include ethyl acetate, cyclohexanol, methyl ethyl ketone, and the like.

In the present invention, the above-mentioned known techniques can be applied to incorporate the cyan coupler according to the present invention into the silver halide emulsion layer, but in this case, the following general formula [
It is preferable to use a compound represented by IV because it improves the maximum density, lengthens the maximum absorption wavelength, reduces absorption in the green area, and increases the light resistance of the cyan dye image.

General formula [m] [wherein R3, R32 and R31 represent an alkyl group, a cycloalkyl group or an aryl group. ] The above general formula [
m], the alkyl group, cycloalkyl group, or aryl group represented by R33, R32, and R33 will be explained.

Such alkyl groups are preferably linear or branched having 1 to 32 carbon atoms, and these alkyl groups also include those having substituents. Examples of such alkyl groups include linear or branched butyl groups, hexyl groups, octyl groups, dodecyl groups, octadecyl groups, and the like. Among these alkyl groups, those having 4 to 18 carbon atoms are particularly preferred, and more preferably 6 to 18 carbon atoms.
~12.

Examples of the cycloalkyl group include a cyclopentyl group,
Examples include cyclohexyl group and cyclohebutyl group.

These cycloalkyl groups also include those having substituents. Particularly preferred among such cycloalkyl groups is a cyclohexyl group.

Examples of the aryl group include a phenyl group and a naphthyl group, including those having substituents. Specific examples of such aryl groups include phenyl, p-cresyl, m-cresyl, 0-cresyl, p-chlorophenyl, p-orbutyl-phenyl, and the like.

Specific examples of the above-mentioned high boiling point organic solvents are shown below.

The following margins The high boiling point IK Fa solvent mentioned above is, for example,
No. 727, JP-A No. 33-13923, JP-A No. 54-119
No. 235, No. 54-119921, No. 59-1199
22, No. 55-25057, No. 55-36869, No. 56-81836, etc., and can be synthesized by the methods described in these publications. can.

The amount of the above-mentioned high boiling point organic solvent used is not particularly limited;
It is preferable to use it in the range of 0g to 500g.

When dissolving or dispersing the cyan coupler according to the present invention in the above-mentioned high-boiling point organic solvent, the above-mentioned high-boiling point organic solvent may be used alone, or the above-mentioned other high-boiling point organic solvent may be used in combination, and If necessary, a low boiling point organic solvent, a water-soluble organic solvent, etc. may be used in combination.

Also, reducing the processing time of photographic materials is an important issue for the photographic industry. In other words, photographic elements are processed by running processing using automatic processing machines installed in each laboratory, but as part of our efforts to improve our services to users, we are developing them on the same day that they are received and providing them to users. In recent years, it has become necessary to return items within several hours or even tens of minutes from the time of receipt, and there is a strong demand for short processing times in order to shorten delivery times.

Conventionally, Hensyl alcohol has been used in color developing solutions to achieve rapid processing. If the color developing solution does not substantially contain Hensyl alcohol, the maximum density of the characteristic curve will be lowered, the development time will have to be extended, and the speed will be impaired.

Therefore, in order to save money and improve environmental pollution, the color developing solution contains substantially benzyl alcohol, and even with low replenishment, rapid processing is possible, photographic performance is maintained constant, and brown color reproduction is possible. At present, the emergence of a method for processing photographic elements with superior properties is strongly desired.

The silver halide photographic light-sensitive material of the present invention can meet the above requirements even when developed using a color developing solution that does not substantially contain benzyl alcohol.

The term "substantially free of Hensyl alcohol" refers to 211 II or less Hensyl alcohol per 11 parts of the color developing solution. If the amount is 2 ml or less, there is almost no problem in terms of environmental pollution.

The color developing agent used in the color developing solution in the present invention includes known color developing agents that are widely used in various color photographic processes.

These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Further, these compounds are generally used in a concentration of about 0.1 g to about 30 g per color developer solution 11, preferably about 1 g to about 15 g per 1 g of color developer solution.
Use at a concentration of

Examples of aminophenol-based developers include 〇-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxy/toluene, and 2-aminophenol.
Includes oxy-3-amino-14-dimethylbenzene and the like.

Particularly useful primary aromatic amine color developers include N, N
It is a '-dialkyl-p-phenylene amine compound, and the alkyl group and phenyl group may be substituted with any substituent. Among them, particularly useful compound examples include N,N'-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-methyl-p-phenylenediamine hydrochloride, 2-amino/-5-(N-ethyl-N-Fdecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N- β-Hydroquine ethylaminoaniline, 4-amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methquinethyl)-N-ethyl-3-methylaniline-p-
Examples include toluene sulfonate.

In addition to the above-mentioned primary aromatic amine color developer, known developer component compounds can be added to the color developer applied to the processing of the silver halide photographic material of the present invention.

For example, alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal thionanates, alkali metal halides, water softeners, and thickening agents may optionally be contained.

Sulfites and hydroxylamine compounds are used as preservatives in the color developing solution.

As the hydroxylamine compound, general formula [IV]
A sulfate salt of the compound represented by is preferred.

General Formula [IV] [In the formula, R41 and R4□ represent hydrogen or an alkyl group having 1 to 5 carbon atoms which may have a substituent. Tatami R41 and R
42 will never take hydrogen at the same time. ] Examples of the substituent include a sulfonic acid group, a hydroxy group, an alkoxy group (such as a methquine group, an ethoxy group, and a probyluoquine group), a carboxyl group, and an amino group. No. 293.034,
Examples include the human roquinylamines described in No. 3.287.1.24 of the same.

Preferred specific compounds represented by the general formula [IV] are shown below.

(IV-1) CH, -NH-OH (TV-2) C2H, -NH-OH (rV-3)
iso-C3H, -NH-OH (TV-4)
C, H, -NH-OH (TV-5) HO-CH2-
NH-OH(rV-6) CH1-0-C2H4-N
H-OH(IV 7) HOC2H4NH0H(r
V-8) HOOC-C2H4-NH-OH(IV-
9) HO35-C2H4-NH-OH (IV-10
) HN2-C3H6-NH-OH (TV 11)
CH30C2H4NH0H (IV-12) HO
-C2H4-0-C2H4-NH-OH (IV-13) (■ 0H par-, \ /N -OH ノ/ CH,' CH,,, \, /N -OH C2H6/ (IV -15) CH2X. , , /N -OH (rV-18) 0H・\ / 1socxH7/ (■ °8゛0°'1"\, (TV -21) CH30C2H4\ (IV -23) 1°3SC2H,\HO,SC, H,/”' (rV -26) HOOCC2H4 \ (IV-28) HO3SC5H,Q\ The pH value of the color developer is usually above 7, most commonly about 10 to 1.
It is 3.

The color development treatment in the present invention is carried out at 30°C or higher and 90 seconds or less, preferably at 33°C or higher and 80 seconds or less.
Most preferably, the treatment is carried out at a temperature of 35° C. or higher and 70 seconds or less. If the treatment is carried out at a temperature of 30° C. or higher and for more than 90 seconds, the fog density is not satisfactory and the processing stability is also poor. The processing temperature is raised to complete the development in a short time, and if it is 30°C or higher and 50°C or lower, the higher the temperature, the shorter the processing time, but it is particularly preferably 33°C or higher and 48°C or lower. The most preferred temperature is 35°C or higher and 43°C or lower.

[Examples] Specific examples of the present invention will be described below, but the present invention is not limited thereto.

Example 1 On a paper support laminated with polyethylene (titanium oxide content: 2.7 g/d), the following layers were sequentially coated from the support side to obtain a silver halide color photographic light-sensitive material sample Nα1.
~NG, 39 was created.

Layer 1 =-=-1,2 g/m" gelatin, 0.3
2 g/rrl'' (in terms of silver, hereinafter) blue-sensitive silver chlorobromide emulsion (silver chloride content 99.3 mol 96), 0.50 g
/rrl' of dioctyl phthalate. , go
A layer containing Yellow Cabra (Y-1) of g/rri'.

Layer 2...0.7g/rrl' of Seratin, Table-
An intermediate layer consisting of the anti-irradiation dye shown in 1.

Layer 3 - = 1.25 g/nl' gelatin, 0
．． 22 g/rrl"+7) green-sensitive silver chlorobromide emulsion (silver chloride content 995 mol%), containing 0.82 g/d of magenta coupler (M-17) dissolved in 0.30 g/d of dioctyl phthalate layer.

Layer 4... 1.2g/rT? Intermediate layer 5 consisting of gelatin 1.40 g/rrl'' gelatin, 0.20 g/rf red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol%) 0.20 g A layer containing a cyan coupler shown in Table 1 in an amount of 0.9 mmol/I dissolved in dioctyl phthalate.

Layer 6: Intermediate layer containing 1.0 g/n-r gelatin Layer 7: Layer containing 0.50 g/rrF gelatin.

As a hardening agent, sodium 2,4-dichloro-6hydroxy-S-triazine was added to layers 2.4 and 7 in an amount of 0.017 g per 1 g of seratin.

The following margin (Y) Each of the above photosensitive material samples Nos. 1 to 39 was exposed through an optical wedge and then processed in the following steps.

Processing steps (35°C) Color development 45 seconds bleach-fixing 45 seconds stabilization 1 minute 30 seconds drying 60-80°C 2 minutes The composition of each processing solution is as follows.

Color developer (per 147) Pure water
800ml ethylene glycol
lOmjN, N-diethylhydroxylamine
2wJ potassium chloride
2g potassium sulfite 0.2gN
-ethyl-N-β-methanesulfonamidoethyl-3-
Methyl-4-aminoaniline sulfate
5g sodium tetrapolyphosphate
2g potassium carbonate
Add 30g of pure water and adjust the pH to -10.08.

Bleach-fix solution Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (75%
solution) 100 ml ammonium sulfite (40% solution) 27.5 ml potassium carbonate or glacial acetic acid
Adjust to H5.7 and add water to make a total amount of 1 g.

Stabilizing liquid 5-chloro-2-methyl-4-isothiazolin-3-one 1g 1-hydroxyethylidene-1,1-diphosphonic acid 2g Add water to make 1g, adjust to pH-7 with sulfuric acid or potassium hydroxide,
Adjust to 0.

Sensitometry was used to determine the sensitivity of the red-sensitive emulsion layer for each sample after the above treatment.

In addition, for each of the above-mentioned processed samples, the unexposed area (white area)
By measuring the optical reflection density at 650 ni, the degree of dye staining due to the residual irradiation-preventing dye was determined.

Also, for each sample, kl TF? The film was exposed to light through a #j standard Uninon and processed in the same manner as above.

For each sample after the above treatment, the MTF (~1 odulation transf
erFunction) was determined using a microdensitometer, and the N1TF values at 5 spatial frequencies were compared.

It should be noted that the determination of image sharpness by MTF is well known among those skilled in the art.
the photographic process
It is described in 4th edition p612 to p614.

In addition, the color reproducibility of each sample was confirmed by visual evaluation. That is, color negative film [Konica Car 7-GX-100:
Camera [Konica F T-I] manufactured by Konica Corporation
A color checker manufactured by Macbeth was machined using MOTOR manufactured by Konica Corporation. Subsequently, a color negative development process [CNK-4: manufactured by Konica Corporation] was performed, and the obtained negative image was processed using a Konica color printer CL-P 200.
0C manufactured by Konica Corporation] to each of the above samples.
It was printed to a size of +sX 117 mm and processed in the same manner as above to obtain a practical print. The printer conditions during printing were set for each sample so that the color was gray on the color checker or gray on the print.

The color reproducibility of the obtained practical prints was visually observed. The above results are shown in Table-1.

Below is the margin table-1 (1) Table-work <2) *1 Anti-irradiation dye added to layer 2 *2
Layer 5 cyan coupler 3 Red-sensitive emulsion layer sensitivity Kf4. '(o Sensitivity of 9 expressed as a relative value with south*
4 Rebellion of the white area at λ = 650rn *5
MTF value at 5 spatial layer wavenumbers/related to red-sensitive emulsion layer *6 Color reproducibility of practical print ×: Insufficient color reproducibility (tone, saturation) ○: Good As is clear from Table 1 , the content of AI dye is 0.
5mg Zrd sample N011.4.8.23.26.2
9.32 both have high sensitivity and little color staining, but the sharpness is insufficient. Similarly 120mg/rr
Sample No. containing AI dye of f, 3.7.10.2
Although 5.31.34 provides high sharpness, color contamination is severe and sensitivity is low.

On the other hand, 2011g/ni and 80a+g/rrr
Sample No. containing AI dye represented by the general formula FIN
, 5.6.9.11-22.24.27.30.33
．． It can be seen that samples Nos. 35 to 39 maintain high sensitivity and high sharpness while also having color contamination at a practically sufficient level. Further, sample Nα2 containing an AI dye other than the one according to the present invention had significant color staining and could not be put to practical use. Samples 8 to 10 using cyan couplers other than those of the present invention have problems in color reproducibility.

[Effects of the Invention] According to the present invention, rapid processing is possible, and there is little dye staining, high sharpness, and good color reproducibility.

Claims (1)

[Scope of Claims] A silver halide photographic light-sensitive material having photographic constituent layers including a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer on a support. , at least one of the red-sensitive silver halide emulsion layers contains at least one cyan coupler represented by the following general formulas [A] to [I], and at least one of the photographic constituent layers contains contains 1 mg/m^2 to 100 mg/m^2 of a compound represented by the following general formula [II], and at least one layer of the photosensitive silver halide emulsion layer consists essentially of silver chloride. A silver halide photographic material containing silver halide grains. General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [B] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [C] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [D] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [E] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [F] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [G] ▲ Mathematical formulas, chemical formulas, There are tables, etc. ▼ General formula [H] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula [I] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R_1 and R_3 represent a hydrogen atom or a substituent. , R_2 represents a substituent. X represents a hydrogen atom or a substituent which is eliminated by reaction with an oxidized product of a color developing agent, n represents an integer of 0 to 4, and Z represents a group of nonmetallic atoms necessary to form a heterocycle. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 may be the same or different, and represent an alkyl group, an aryl group, a heterocyclic group, Groups may be substituted. R^3 and R^4 may be the same or different, and include cyano group, carboxyl group, ▲mathematical formula, chemical formula, table, etc.▼ group (R^5 represents an alkyl group, aryl group, heterocyclic group, These groups may be substituted.), ▲There are mathematical formulas, chemical formulas, tables, etc.▼ groups, (R^6 and R^7 may be the same or different,
It represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group, and these groups may be substituted. ), ▲ Numerical formulas, chemical formulas, tables, etc. ▼ represents a group (R^8 represents an alkyl group, aryl group, or heterocyclic group, and these groups may be substituted). L_1 to L_5 represent an optionally substituted methine group. Further, at least one of R^1 to R^4 has a sulfo group, a carboxyl group, a phosphono group, a phosphoryl group, a hydroxyl group, or a sulfate group. ]