JPH02149842A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material causing scarcely contamination generated by a dyestuff after development, and having improved sharpness and color reproducibility by incorporating a specified compd. into a photograph constituting layer and a specified cyan coupler into a red-sensitive silver halide emulsion layer. CONSTITUTION:Compd. expressed by the formula (I) is contained in a concentration range of 1-100mg/m<2> in a photograph constituting layer; silver halide particles consisting substantially of AgCl are contained in a photosensitive silver halide emulsion layer, and a cyan coupler expressed by the formula (II) is contained in a red-sensitive silver halide emulsion layer. In the formula, each R<1> and R<2> is an alkyl group, aryl group, or heterocyclic group; each R<3> and R<4> is a cyano group, carboxyl group, etc.; each R and Y is an H atom or a substituent; X is an H atom or a substituent eliminated by a reaction with an oxidized body of a color developing agent; Z is a group of nonmetal atoms necessary for forming an N-contg. 6-membered heterocyclic ring by condensing together with -N(Y)- to form a pyrazole ring. Thus, a silver halide color photographic sensitive material having high sharpness, and superior color reproducibility and causing scarce contamination generated by a dyestuff after development, is obtd.

Description

[Detailed Description of the Invention] [Technical Field] The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, the present invention relates to a silver halide color photographic light-sensitive material, which can be rapidly processed, has little dye staining, has high sharpness, and has brown color reproducibility. This invention relates to a silver halide color photographic material with good quality.

[Background of the Invention] Usually, in a color image forming method using a silver halide color photographic light-sensitive material, after imagewise exposure, unoxidized P is removed.
- 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, magenta, and yellow dye images corresponding to red, green, and blue are formed on respective photosensitive layers.

In recent years, when forming such color images, in order to shorten the development processing time, 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 one-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,
In particular, the shape of the grains of the photosensitive silver halide emulsion used,
The size and halogen composition greatly affect the development speed,
Furthermore, the latter is easily influenced by the conditions of the color developer, especially the type of development inhibitor, and it has been found that silver chloride particles in particular exhibit a significantly high development rate under certain conditions.

Silver halide color photographic materials whose silver halide is essentially silver chloride enable rapid processing, and development can be completed in less than 90 seconds, but a new drawback is that dye staining tends to occur after processing. 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. Therefore, it may be possible to reduce the amount of anti-irradiation dye used to prevent dye staining, but in this case, the original purpose of anti-irradiation dye is The quality deteriorates.

In light of the above, silver halide color photographic materials containing silver halide grains consisting essentially of silver chloride can be processed quickly, have little dye staining, and have good color reproducibility. In order to form a dye image with high sharpness, there are various problems to be solved, and there is a very high demand for a silver halide color photographic light-sensitive material that satisfies all of these problems.

[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 forming 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 reflective support. In the silver halide color photographic light-sensitive material, a compound represented by the following general formula [I] is contained in at least one of the photographic constituent layers at 1 mg/m2 to 10
0mg/m2, and at least one layer of the light-sensitive silver halide emulsion layer contains silver halide grains consisting essentially of silver chloride, and the red-sensitive silver halide emulsion layer contains the following general General formula [I] of a silver halide color photographic light-sensitive material characterized by containing at least one cyan coupler represented by the formula [nl] [In the formula, R1 and R2 may be the same or different, and an alkyl group, aryl group, heterocyclic group, and these groups may be substituted.R3R' may be the same or different, and represents a cyan group, carboxyl group, -COR
5 groups (R5 represents an alkyl group, an aryl group, a heterocyclic group, and these groups may be substituted), -CR'
represents a group (Ra represents an alkyl group, an aryl group, or a heterocyclic group, and these groups may be substituted).

1 to L5 represent an optionally substituted 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. ] General numerical counter ■ [In the formula, R and Y represent a hydrogen atom or a substituent,
X represents a hydrogen atom or a substituent that leaves by reaction with an oxidized product of a color developing agent; Z represents a nonmetallic atom necessary to form a nitrogen-containing six-membered heterocyclic ring by condensation with the pyrazole ring together with N-; represents a group, the 6-membered ring may have a substituent, and may be fused with a benzene ring in addition to the pyrazole ring.

[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 consisting essentially of silver chloride used in the present invention (hereinafter referred to as "silver halide grains of the present invention") are those having a silver chloride content of 90 mol% or more. In the silver halide grains, the silver bromide content is 10 mol% or less, and the silver iodide content is 0.5 mol%.
It is preferable that the silver bromide content is below, more preferably 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 silver halide grains having different compositions, or 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 between the inside and outside of the grain may be different, or the composition between the inside and outside of the grain may be different. , the composition may change continuously or discontinuously.

The grain size of the silver halide grains of the present invention is not particularly limited, but in consideration of rapid processing properties, sensitivity, and photographic performance, it is preferably 0.62 to 1.6 μm, and more preferably 0.6 μm to 1.6 μm.
It is in the range of 25 to 1.2 μm. In addition, the above particle diameter is
It can be measured by various methods commonly used in the art.

A typical method is Loveland's "Particle Size Analysis Method J.
(A, S, T, M, Symposium on Light
Microscopy, 1955, pp. 94-122) or ``The Theory of the Photographic Process'' (by Mies and James, 3rd edition, published by Macmillan, 1966).
Chapter).

This 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 fairly accurately measure this as a diameter or projected area. can be expressed.

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

Preferably, the silver halide grains are monodisperse silver halide grains having a coefficient of variation of 0.22 or less, more preferably 0.15 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 forming seed particles.The method for forming and growing seed particles may be the same or different.

In addition, the soluble root 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 it is preferable to use a method obtained by a simultaneous mixing method. As one type of method, the pAg-chondrold-double jet method described in JP-A-54-48521 etc. can also be used.

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

Any shape of the silver halide grains of the present invention can be used. One preferred example is a cube having the +1oot plane as the crystal surface.

Further, particles having shapes such as octahedron, tetradecahedron, dodecahedron, etc. can 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 can be produced by using cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or complex salt, rhodium salt or lead salt, iron salt or lead salt in the grain formation process and/or growth process. Add metal ions to the inside of the particles and/or
The particles can be included in the surface of the particles, and reduction sensitizing nuclei can be provided inside the particles and/or on the surfaces of the particles by placing the particles in an appropriate reducing atmosphere.

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. When the salts are removed, the method described in Research Disclosure No. 17643 can be used.

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

In the present invention, chalcogen aggravating agents can be used. Chalcogen sensitizer is a general term for sulfur sensitizers, selenium sensitizers, and tellurium sensitizers, and sulfur sensitizers and selenium sensitizers are preferred.As the sensitizers, for example, thiosulfate , allylthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Other U.S. patents 1,57
No. 4,944, No. 2,410,689, No. 2,278
, No. 947, No. 2.728.668, No. 3.501.
No. 313, No. 3,656,955, West German Application Publication (O
L S ) No. 1,422,869, JP-A-56-2
Sulfur sensitizers described in JP-A No. 4937 and JP-A No. 55-45016 can also be used. T? The amount of sensitizer added varies over a considerable range depending on various conditions such as pH, temperature, and size of silver halide grains, but as a guide, it is 10-7 mol to 10-1 mol per 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.

The amount of the compound represented by the general formula [I] used in the present invention is in the range of 1 mg/m2 to 100 mg/m2, more preferably 2 tax/rr? ~50
mg/m2. If the amount used is less than 1 mg/m2, irradiation cannot be prevented and sharpness deteriorates. On the other hand, if it exceeds 100 mg/m2, the decolorizing property will be insufficient, especially in rapid processing, resulting in color staining.

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

Margin below Engineering~3 03Na ChK to SO* 303T.

l-10 to SO3 ■-11 ■-12 ■ ■ O3K ■-14 ■-15 ■ One ■-20 ■-21 OzK U3Na O3K 03Nx ■-22 ■-23 ■-24 ■ ■-31 CH2CH2SO3K CH2CH2S03■ ■-27 ■-32 ■-33 ■-34 CH2 H C)13 H l-35 I-38 ■ ■-39 ■-37 The following margin is CH25O K CH2SO3 The compound of general formula [I] of the present invention is Tokuko Sho 54, respectively.
-38129 publication, 52-38056 publication, 52-38056 publication
5-10059, JP 59-168438, JP 51-77327, JP 58-143342
No. 59-111641, No. 59-111
No. 640, No. 60-218641, No. 62-
Contains compounds described in Japanese Patent Application No. 273527, No. 63-139949, No. 63-262649, Japanese Patent Application No. 83-2591, and Japanese Patent Application No. 63-2592. It can be synthesized by the method described in the book.

Next, general formula [II] will be explained in detail.

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 the substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cyclo. Each group such as alkyl is mentioned, and this group includes a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyan, alkoxy, sulfonyloxy, aryloxy, heterocycleoxy, Siloxy,
Acyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro, sulfone Examples include various groups such as acids, spiro compound residues, bridged hydrocarbon compound residues, and the like.

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

The aryl group represented by R is preferably a phenyl group.

Examples of the acylamino group represented by R include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group represented by R include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and aryl component in the alkylthio group and arylthio group represented by R include the alkyl group and aryl group represented by R above.

The alkenyl group represented by R preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkyl group represented by R has 3 to 1 carbon atoms.
2, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl group rings; sulfinyl groups include alkylsulfinyl groups, arylsulfinyl groups, etc.; phosphonyl groups include alkylphosphonyl groups, alkoxyphosphonyl groups, and aryloxyphosphonyl groups. , arylphosphonyl group, etc.; As an acyl group, an alkylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Arylsulfamoyl groups, etc.; Acyloxy groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. ; As the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; as a heterocyclic group, a 5- to 7-membered one is preferable, and specifically, a 2-furyl group, a 2-thienyl group , 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc.; As the heterocyclic oxy group, one having a 5- to 7-membered heterocycle is preferable, for example, 3,4.5.6- Tetrahydropyranyl-2-oxygen, 1-phenyltetrazole-5-
Oxy group etc.: The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, such as 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole- 6-1000 groups, etc.; siloxy groups include trimethylsiloxy, triethylsiloxy, dimethylbutylsiloxy, etc.; imide groups include succinimide, 3-heptadecylsuccinimide, phthalimide, glutarimide, etc. ; As a spiro compound residue, spiro[3,31 hebutane-
1-yl, etc.; As a bridged hydrocarbon compound residue, bicyclo[2°2.1
] heptan-1-yl, tricyclo[3゜3゜1.13
-7]Decan-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 product of the color developing agent represented by X include, for example, halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.), alkoxy, aryloxy, heterocyclic oxy, acyloxy, sulfonyloxy, alkoxy Carbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded via N atom, alkyloxycarbonylamino , aryloxycarboniamino, carboxyl, (R' is the same as the above R, 2' is the same as the above Z, Ra and Rb represent a hydrogen atom, an aryl group, an alkyl group, or a heterocyclic group) Examples include various groups such as,
Preferably it is a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

Preferred specific examples of the compound represented by the general formula [■] are represented by the following general formula [I[[].

General formula [I[[] [wherein Z'' is fused with the pyrazole ring to form a nitrogen-containing compound containing at least one -N- and at least one carbonyl group or at least one sulfonyl group. Represents a group of nonmetallic atoms necessary to form a 6-membered hetero ring, and the 6-ring may have a substituent (in addition to the pyrazole ring, it may be fused with a benzene ring, R '' and Y'' represent a hydrogen atom or a substituent, and X'' represents a hydrogen atom or a substituent that leaves upon reaction with an oxidized product of a color developing agent.] More details about the compound represented by the general formula [I[] explain.

In the general formula [Ill, the nitrogen-containing 6-membered heterocyclic ring formed by Z is preferably a 6π electron system or an 8π electron system, and contains 1 to 4 nitrogen atoms including at least one -N-. At least one carbonyl group included in the 6-membered ring represents a group such as >C=O or >C=S, and at least one sulfonyl group included in the 6-membered ring is -
Represents an 8- group.

In the general formula [Ill, Y represents a hydrogen atom or a substituent, and the preferable substituent represented by Y is, for example, one which is eliminated from the compound of the present invention after the compound reacts with the oxidized developing agent. However, for example, the single substituent represented by Y may be a group that can be separated under alkaline conditions as described in JP-A No. 61-228444, etc., or a group that can be separated under alkaline conditions as described in JP-A No. 56-133734, etc. Examples include substituents which are coupled off by reaction with the oxidized developing agent as described above, but preferably Y is a hydrogen atom.

-i Among the compounds represented by the formula [■], preferred specific examples include the following general formulas [I[[-a], [■-b], [
Examples include compounds represented by I[[-c] and [II[-d].

The following margins indicate general formula [I[[-a] general formula [11[-b] general formula [1 [[-C] R1 general formula [II[-d], where R,, R2 and R1 are general formula It has the same meaning as R in [II], X has the same meaning as X in general formula [I[], and Y has the same meaning as Y in general formula [II]. General formula [1 [[-b], n represents an integer from 0 to 4, and when n is an integer from 2 to 4, multiple R2 may be the same or different.] General number counter I [I -a], [I
R2 and R3 in [I-c] and cm-ct
is synonymous with R in general formula [1r], but,
R2 is never a hydroxy group.

Preferred examples of R2 and R3 include groups such as an alkyl group, an aryl group, a carboxyl group, an oxycarbonyl group, a cyano group, an alkoxy group, an aryloxy group, an amino group, an amide group, and a sulfonamide group, and a hydrogen atom, Such as halogen atoms.

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

The following is a margin: Below is a margin: Below is a margin: Below is a margin: Below is a margin Below is a typical synthesis example of the compound of the present invention.Synthesis Example 1 [Synthesis of compound (A-13)] [Synthesis of compound (A-13) and compound a] 15 -;'9tr (0.1 mol) of 5-amino-3-phinylvirazole and 15.9 g (0.1 mol) of 2-ethoxycarbonylacetimidic acid ethyl ester in 20
After heating and refluxing the 0 reaction solution for 2 hours in dehydrated ethanol, the P solution was cooled, and the formed precipitate was collected, washed with cold ethanol, and then dimethylformamide and water. Recrystallization was performed using a mixed solvent of 17.8 g (0,079 mol) of white needle crystals of compound a.

(Compound a) Contact point: 300″C or higher NMR spectrum and mass spectrum show that Compound a
The structure of was confirmed.

[Synthesis 1 of compound (A-13) from compound a Compound a1
7.0 g (0,075 mol) of ethyl acetate solution 600
100 ml of an ethyl acetate solution of compound b31.2E (0,075 mol) was added to m1, and 7.8 g of triethylamine was further added, and the mixture was stirred at room temperature for 2 hours, and the precipitated crystals were collected. This was washed with water and further recrystallized with acetonitrile to give a compound (A-13) of white needle-like crystals of 23.0. (0,038 mol) was obtained.

The compound (
The structure of A-13> was confirmed.

Synthesis Example 2 [Synthesis of Compound (B-1)] [Synthesis of Compound] The above compound 16.2+r (0.1 mol) and the above compound 34.8. (0.1 mol) was dissolved in 40 ml of methanol, stirred at room temperature for 2 hours, and then 9.8 g
of sodium carbonate was added, and the mixture was stirred at 50°C for 2 hours. After pouring the reaction solution into 300 ml of water, it was neutralized using hydrochloric acid, and the resulting solid was recrystallized from a mixed solvent of toluene and acetonitrile to obtain 12.8 g of the above compound e in the form of white crystals ( 0.03 mol) was obtained.

[Synthesis of Compound (B-1) from Compound Reference] Next, 10.0 g (0,023 mol) of this compound reference was added to 100 ml
of acetic acid, and add 35% hydrogen peroxide solution to the resulting solution.
After slowly dropping 5ml, the mixture was stirred at 50°C for 3 hours. 300 ml of water was added to this solution, and the solution was neutralized with an aqueous sodium hydroxide solution at a temperature below 5°C. The resulting solution was extracted with ethyl acetate, and the ethyl acetate was distilled off from the extract. When the precipitate was recrystallized using acetonitrile, 8.5 g (0,018 mol) of Compound (B-1) crystallized as a white powder was obtained.

The compound (
The structure of B-1) was confirmed.

Synthesis Example 3 [Synthesis of compound (C-5)] Compound (C-S) [Synthesis using compound] Ethyl-3,5-diaminopyrazole-4-carvone 1
17.0 g (0.1 mol), 36.1 g (0.1 mol) of ρ-dodecaoxyphenylsulfonyl chloride and 15.2 g (0.15 mol) of triethylamine (50
The mixture was added to 0 ml of ethyl acetate and heated under reflux for 1 hour.

After cooling, the precipitated crystals were collected with P and washed with water to give 29.6 g (o
, oe mol) of compound f was obtained.

[Synthesis of compound product from compound product] 29.1 g (0,059 mol) of compound product and 14
．． 6 g (1,089 mol) of α-chloroacetoacetic acid ethyl ester was heated and refluxed in 600 nnl of toluene for 8 hours to perform a dehydration reaction.

The reaction solution was concentrated under reduced pressure to obtain crude crystals, which were recrystallized from ethanol to obtain white needle-shaped crystals ie, i,
, (0,027 mol) was obtained.

The structure of the compound was confirmed by NMR spectrum and mass spectrum.

Synthesis of compound (C-5') from the product of the compound Co-compound 41
5.4 g (0,026 mol) was dissolved in a mixed bath of acetic acid, sulfuric acid, and water (1130 ml (100:25:5)), and 1
The mixture was heated to reflux for an hour. After adjusting the pH to 5 with an aqueous sodium hydroxide solution, extraction was performed with ethyl acetate, the solvent was dried over magnesium sulfate, and then evaporated. The residue was recrystallized from acetonitrile to give 7.3t (0,0
14 mol) was obtained.

The compound (
The structure of C-S) was confirmed.

Synthesis Example 4 [Synthesis of Compound (D-5)] Compound (D-5) [Synthesis of Compound 45 g (0.1 mol) of Compound L (used in Synthesis Example 3)
and 22K (0.1 mol) of ω-acetophenonesulfonyl chloride at 1.1! of chloroform, and further added 12 g (0.12 mol) of triethylamine, heated and refluxed for 5 hours, cooled, and diluted the reaction solution with dilute hydrochloric acid.
After washing twice, chloroform was distilled off under reduced pressure, and recrystallized twice from methanol to obtain 30 g of white powder crystals, which is the compound
(0,045 mol) was obtained.

The composition of the compound was confirmed by NMR spectrum and mass spectrum.

[Synthesis of compound i from compound RI] 20g (0.03 mol) of compound RI 140-16
After heating at 0'C for 1 hour and cooling, the precipitated crystals were recrystallized with ethanol to obtain gray-white powder crystals on the compound 9.
．． 8K (0,015 mol) was obtained.

Compound i by NMR spectrum and mass spectrum
The structure of was confirmed.

[Synthesis of compound (D-5) from compound i] In exactly the same manner as the method for obtaining compound (C-5) from the compound product in Synthesis Example 3, compound -5) white powder crystals 2.9g (0,00
5 mol) was obtained.

The compound (
The structure of D-5) was confirmed.

The cyan coupler of the present invention usually contains lXl0-' mol-1 mol, preferably IX1 per mol of silver halide.
It can be used in a range of 0-2 moles to 8 x 10-' moles.

The 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 brightening material of the present invention, known techniques used in 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 the dispersion to the silver halide milk 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 containing 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 magenta coupler and a yellow coupler are used in addition to the cyan coupler of the present invention. There are no particular restrictions on the magenta coupler and yellow coupler, and known ones can be used.

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

Typical specific examples of magenta couplers are shown below.

Below margin C# M-9 C1゜H21 CaHs CI 2H2S CHl CaH+7 (tl
-133734, 60-143337, 61-
No. 90155, No. 61-158329, No. 61-18
No. 9540, No. 62-38463, No. 62-5995
No. 3, U.S. Pat. No. 3,519,429, U.S. Pat. No. 3,684.
It is described in No. 514.

Among the above magenta couplers, when pyrazoloazole type magenta couplers such as those shown in M-7 to M-16 are used, it is possible not only to save silver, but also to suppress the occurrence of fog, and to obtain a long-lasting image. This is preferable because it has good storage stability.

As the yellow coupler, for example, acylacetanilide couplers can be used, including benzacetanilide 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 co-dissolved in a hydrophilic binder, such as an aqueous gelatin solution, by simultaneously dissolving the coupler in a high-boiling organic solvent, optionally in conjunction with a low-boiling and/or water-soluble organic solvent, along with the compound in the surfactant. It is preferable to emulsify and disperse the agent using an agent and then add it to the desired 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.

(wherein R1, R2 and R3 represent an alkyl group, a cycloalkyl group or an aryl group)
], an alkyl group represented by R,, R2 and R3,
Describe a cycloalkyl group or an aryl group.

Such alkyl groups are preferably straight-chain or branched ones having 1 to 32 carbon atoms, and these alkyl groups also include those having substituents. Examples of such alkyl groups include straight-chain or branched butyl groups, Examples include hexyl group, octyl group, dodecyl group, and octadecyl group. 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 include those having substituents, and among these cycloalkyl groups, a particularly preferred one is a cyclohexyl group.

Examples of aryl groups include phenyl groups, naphthyl groups, etc., including those having substituents. Specific examples of such aryl groups include phenyl groups, P-cresyl groups, m-cresyl groups, 0-cresyl groups, etc. Examples include cresyl group, p-chlorophenyl group, and p-obutyl-phenyl group.

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

The following margins: The above-mentioned high boiling point organic solvents are, for example,
No., JP-A-33-13923, JP-A No. 54-119235
No. 54-119921, No. 59-119922, No. 55-25057, No. 55-36869, No. 5
It includes phosphoric acid ester compounds described in various publications such as No. 6-81836, and can be synthesized by the methods described in these publications.

The amount of the high-boiling organic solvent used is not particularly limited, but it is preferably used in the range of 10 g to soo g per 100 g of the cyan coupler according to the present invention.

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 solvent may be used in combination, Furthermore, a low boiling point organic solvent, a water-soluble organic solvent, etc. may be used in combination as necessary.

Also, reducing the processing time of photographic materials is an important challenge 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 a few hours or even tens of minutes from the time they are received.There is a strong demand for short-time processing in terms of shortening delivery times.

Conventionally, benzyl alcohol has been used in color developing solutions to achieve rapid processing.If benzyl alcohol is not substantially included in the color developing solution, the maximum density of the characteristic curve will decrease, making it necessary to extend the development time, resulting in rapid processing. Gender is impaired.

Therefore, in order to save money and reduce environmental pollution, the color developing solution does not substantially contain benzyl alcohol and can be processed quickly even with low replenishment, while maintaining constant photographic performance and producing brownish colors. At present, there is a strong desire for a method for processing photographic elements with excellent properties.

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 benzyl alcohol" means that the amount of benzyl alcohol is 2 ml or less per 11 color developing solutions.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 amine phenol and p-phinidine diamine 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. Additionally, these compounds are generally used in a concentration of about 0.1 g to about 3 Of for color developer solution 11, preferably about 1 g to about 1.5 g for color developer solution 1j.
Use at a concentration of g.

Examples of aminophenol-based developers include 0-aminophenol, P-aminephenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and 2-aminophenol.
Includes oxy-3-amino-1°4-dimethylbenzene.

Particularly useful primary aromatic amine color developers include N, N
It is a '-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted with any substituent.Among them, a particularly useful compound example is N,N'-diethyl-p- phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,
N'-dimethyl-p-phenylenediamine hydrochloride, 2-
Amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxy Ethylaminoaniline, 4-
Amino-3-methyl-N.

N'-diethylaniline, 4-amino-N-(2-methoxyethyl)-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 thiocyanates, alkali metal halides, water softeners, and thickening agents may be optionally contained.

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

As the hydroxylamine compound, a sulfate of a compound represented by general formula (V) is preferable.

(In the formula, RS+ and R52 represent hydrogen or an alkyl group having 1 to 5 carbon atoms which may have a substituent, provided that R5I and R
52 does not take hydrogen at the same time.) Substituents include sulfonic acid groups, hydroxy groups, alkoxy groups (methoxy groups, ethoxy groups, propyloxy groups, etc.) carboxyl groups, amino groups, etc. For example, hydroxylamines described in US Pat. No. 3,287.125, US Pat. No. 3.293.034, US Pat.

Preferred specific compounds represented by the general formula (Vl) are shown below.

(V-1) CH, -NH-OH (V 2) C2H5NH0H (V 3) iso C3H? NH0H(V
-4) C) H7-NH-OH (V-5) HO-CH2-NH-OH (V-6)
CH3-0-CtH, -NH-OHCV-7) H
OC, H, -NH-OH (V-8) HOOC-C
, H, -NH-OH(V-9) HO3S-C2H,
-NH-OH(V-10) HN2-C, H4-NH
-OH(V-11) CH3-0-C2H, -NH-
OH (V-12) HO-C2H, -0-C, H4H
-OH (V-14) CH,\\ The pH value of the color developer solution is usually 7 or higher, most commonly about 10-13.

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 at 35°C or higher and 70 seconds or less. C or higher, when processing is performed 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 is set at 30'C or higher and 50°C or higher.
If the temperature is below 0℃, the higher the temperature, the shorter the processing time.
Particularly preferably the temperature is 33°C or higher and 48°C or lower, most preferably 35°C or higher and 43°C or lower.

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

Example 1 On a polyethylene-laminated paper support (titanium oxide content: 2.7 g lrd), the following layers were sequentially applied from the support side to prepare silver halide color photographic light-sensitive material samples No. 1 to Nα19. did.

Layer 1...1.2g/go gelatin, 0.32g
/rr? Blue-sensitive silver chlorobromide emulsion (silver chloride content 99.3 mol%), 0.50 g/
rr? of 0.80 g dissolved in dioctyl phthalate/
A layer containing a yellow coupler (Y-1) of rrr.

Layer 2...0.7g/rr? gelatin, Table 1
An intermediate layer consisting of an anti-irradiation dye shown in .

Layer 3...1.25g/rrl' gelatin, 0
．． 22g/r+f green-sensitive silver chlorobromide emulsion (silver chloride content 995 mol%), 0.30g/rr? A layer containing 0.62 g/rd of magenta coupler (M-17>) dissolved in dioctyl phthalate.

Layer 4...1.2g/rr? Intermediate layer 5 consisting of gelatin '...1.40 g/rrf gelatin, 0.20 g/rr+' red-sensitive silver chlorobromide emulsion (silver chloride content 99.7 mol%) 0□ A layer containing 0.9 mmol/M of the cyan coupler shown in Table 1 dissolved in 20 g 1rd of dioctyl phthalate.

Layer 6: Intermediate layer containing 1.0 g/rr' of gelatin Layer 7: Layer containing 0.50 g/rd of gelatin.

In addition, as a hardening agent, 2.4-dichloro-6=hydroxy-S-triazine sodium was added in layers 2.4 and 7.
Each was added in an amount of 0.017 g per 1 g of gelatin.

Margins below (Y-1) (M-17') Each of the photosensitive material samples Nos. 1 to 19 was exposed through an optical wedge and then processed in the following steps.

Processing steps (35°C) Color development 45 seconds Bleaching chamber: W 45 seconds Stabilization 1 minute 30 seconds Drying 60-80'C 2 minutes The composition of each processing solution is as follows.

Color developing solution (per 11) (CC (AI-1> NaO3SC82NH H) Bleach-fixing solution Stabilizing solution For each sample after the above treatment, the sensitivity of the red-sensitive emulsion layer was determined using sensitometry.

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.

Each sample was then exposed to light through a wedge for M TF measurement, and processed in the same steps as above.

The MTF (Modulation Transfer) of the red-sensitive silver halide emulsion layer was determined for each sample after the above treatment.
rFunction) was determined using a microdensitometer, and the MTFi at a spatial frequency of 5 lines/rQ11 was compared.

Note that the determination of image sharpness by MTF is well known among those skilled in the art, but the theory of
the photographic process
4th edition p612-p614.

In addition, the color reproducibility of each sample was confirmed by visual evaluation. That is, a color negative film [Konica Color GX-100: manufactured by Konica Corporation] and a camera [Konica FT-I HOT
OR: manufactured by Konica Corporation] was used to photograph a color checker manufactured by Macbeth. Next, color negative modern processing (
CNK-4: manufactured by Konica Corporation], and the resulting negative image was printed on a Konica color printer CL-P 2000 (
[manufactured by Konica Corporation] was used to test each sample above with 82mm
It was printed to a size of 117++n+ and processed in the same manner as above to obtain a practical print. Printer conditions during printing were set for each sample so that gray on the color checker turned gray on the print.

The color reproducibility of the obtained practical prints was visually observed and the results of 6 or higher are shown in Table 1.

Below are blank spaces 2 Cyan coupler in layer 5 *3 Sensitivity of red-sensitive emulsion layer Relative value with the sensitivity of sample 2 as 100 4 λ
= Reflection density of white background at 650 m 5 Spatial frequencies of red-sensitive emulsion layer 5/MTFfIH at 6
Color reproducibility of practical prints
5rur/rr? Sample N (11, 6, 11, 14,
No. 17 has high sensitivity and little color pollution, but
Sharpness is insufficient. Similarly 120rnt/rr? Sample 11Q3.9.13.16.1 containing AI dye of
Image No. 9 provides high sharpness, but has severe color staining and low sensitivity.

On the other hand, 20. /rr? and sample No. containing an AI dye represented by the general formula [I] of 80■/IT1',
It can be seen that 4.5.7.8.10.12.15 maintains high sensitivity and high sharpness while also having color contamination at a practically sufficient level. In addition, sample NQ18 containing an AI dye other than the present invention has significant color staining and cannot be put to practical use, and samples Nos. 1 to 3 using a cyan coupler other than the present invention
has a problem in terms of 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 color photographic photosensitive 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 reflective support. In the material, at least one of the photographic constituent layers contains a compound represented by the following general formula [I] at a concentration of 1 mg/m^2 to
100 mg/m^2, and at least one layer of the light-sensitive silver halide emulsion layer contains silver halide grains consisting essentially of silver chloride, and in the red-light-sensitive silver halide emulsion layer, A silver halide color photographic material containing at least one cyan coupler represented by the following general formula [II]. General formula [I] ▲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, may be replaced. R^3 and R^4 may be the same or different, and include cyano group, carboxyl group, ▲numerical formula, chemical formula, table, etc.▼ group (R^5 represents an alkyl group, aryl group, heterocyclic group, These groups may be substituted.), ▲Mathematical formulas, chemical formulas, tables, etc.▼Groups, (R^6 and R^7 may be the same or different, and may be a hydrogen atom, an alkyl group, an aryl group, Represents a heterocyclic group, and these groups may be substituted.), ▲ Numerical formula, chemical formula, table, etc. ▼ group (R^8 is an alkyl group,
It represents an aryl group or a heterocyclic group, and these groups may be substituted. ) represents. 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. ] General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R and Y represent hydrogen atoms or substituents,
X represents a hydrogen atom or a substituent that is eliminated by reaction with an oxidized product of a color developing agent. Z represents a group of nonmetallic atoms necessary for condensing with the pyrazole ring to form a nitrogen-containing 6-membered hetero ring, and the 6-membered ring has a substituent. The pyrazole ring may be fused with a benzene ring in addition to the pyrazole ring. ]