JPH02151856A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide color photographic sensitive material having superior color reproducibility and improved characteristic for inhibiting color stain by incorporating a specified cyan coupler and a specified compd. into the silver halide photographic sensitive material. CONSTITUTION:The silver halide photographic sensitive material contains at least one kind of compd. selected from compds. expressed by the formula II, etc. Inm the formula I, each R and Y is an H atom or a substituent; X is H atom or a group eliminable 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 with a pyrazole ring together with a residue expressed by the formula III; RA1 is a univalent group; 1 i is an integer I-4, wherein plural RA1 may be same or different to each other. Thus, a silver halide color photographic sensitive material having high color reproducibility without deteriorating photographic sensitivity, and generating extremely scarce color stain even in a thin film state, is obtd.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic material, and more particularly to a silver halide color photographic material with excellent color reproducibility and improved color staining. .

[Background of the Invention] After a silver halide photographic material is exposed to light and subjected to color development processing, an oxidized aromatic primary amine color developing agent and a dye-forming coupler react to form a dye. A color image is formed.

Generally, this photographic method uses a subtractive color reproduction method to form yellow, macenta and cyan color images.

Until now, phenols or naphthols have been widely used as cyan image forming couplers.

However, cyan images obtained from conventionally used phenols and naphthols have serious problems in color reproduction. The problem is that the absorption is not sharp on the short wavelength side, and there is unnecessary absorption, that is, asymmetric absorption, in the edge region. As a result, in the case of negatives, it is necessary to correct the asymmetric absorption by masking or the like, and in the case of paper, there is no means for correction, and the current situation is that the color reproducibility is considerably deteriorated.

Furthermore, dye images obtained from conventionally used phenols and naphthols have some problems in their storage stability. For example, U.S. patent cylinders 2 and 3
The dye images obtained with the 2-acylaminophenolic cyan couplers described in U.S. Pat. No. 67,531 and U.S. Pat. Dye images obtained from the 2,5-diacylaminophenolic cyan coupler described in . Insufficient in terms of heat fastness.

Also, U.S. Patent No. 4,122,369 and Japanese Unexamined Patent Application No. 5
Hydroxy groups are added to the 2,5-diacylaminophenol cyan couplers described in specifications such as No. 7155538 and JP-A-57-157246, and the ballast moiety described in U.S. Patent No. 3,880,661. The 2,5-diacylaminophenol cyan coupler has not yet achieved a sufficiently satisfactory level in terms of fastness to light and heat and generation of yellow stain in order to preserve the dye image for a long period of time.

In order to solve this problem, Japanese Patent Application No. 61-203450, No. 62-203451, No. 63-7204, No. 63-
No. 36086, No. 63-32094, No. 63-379
No. 98, No. 63-237681, etc., various pyrazolopyrimidone and pyrazoloquinazolone type cyan couplers,
Proposed.

It is true that the cyan images obtained from these cyan couplers have extremely excellent color reproducibility, and the thermal stability of the cyan images is also extremely excellent, but color contamination is caused by other problems such as those mentioned above. Larger drawbacks than cyan couplers are also observed.

When a multilayer color photographic material containing a color-forming coupler in a silver halide photographic emulsion is developed using a color developing agent such as paraphenylene diamine, the color developing agent oxide produced during development causes the adjacent images to It is well known that the phenomenon of so-called "color turbidity" (color mixing) occurs, in which undesirable pigments are formed by migration into the forming layer. Furthermore, it is known that an inconvenient "color fog" phenomenon occurs due to oxidation of the developing agent, fog of the emulsion, etc. during color development. In the following,
This "color turbidity" and "color capri" are collectively referred to as "color pollution J."

In recent years, in the field of manufacturing technology for color photographic materials, in order to obtain even higher quality color photographs, it has become possible to more efficiently prevent color contamination and improve sharpness without reducing photographic sensitivity. Significant efforts have been made to develop thin layered color photographic materials.

However, in the case of pyrazoloazole cyan couplers, especially in thin layered color photographic materials, color developing agent oxides generated in other layers during development migrate to the pyrazoloazole cyan coupler-containing layer. However, the drawback is that undesirable color staining is greater than that of conventional phenolic or naphthol cyan couplers.

[Objective of the Invention] The object of the present invention is to provide a silver halide color photograph that uses a specific cyan coupler, has excellent color reproducibility without reducing photographic sensitivity, and has extremely low color staining even in a thin film state. Our purpose is to provide photosensitive materials.

Structure of the Invention] An object of the present invention is to combine at least one cyan coupler represented by the following general formula [I] with the following general formula [mA], [
This is achieved by a silver halide photographic material containing at least one compound selected from I[B] and [IIIC].

General Formula [I] [In the formula, RA□ represents a monovalent group, i is an integer of 1 to 4, and when i is 2 to 4, the plurality of RAls may be the same or different. general formula [I[[B] [wherein R and Y represent a hydrogen atom or a substituent,
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 nonmetallic atom group necessary to form a nitrogen-containing 6-membered hetero ring by condensing with the pyrazole ring together with N-, and the 6-membered ring may have a substituent, and the pyrazole ring In addition, it may be condensed with a benzene ring. ] General formula [I[A] H [wherein, Rtz represents a monovalent group, j represents an integer of 1 to 6, and when J is 2 to 6, the plurality of RBl may be the same or different .

k is 2 or 3, and when k is 2, the two -OH are at the ortho or meta positions, and when k is 3, the three 10H are bonded to each other at adjacent positions 6Q, --- -- represents that a naphthalene ring may be formed together with a benzene ring. 1 or less margin General formula CI [C] [wherein A represents -CO- or -8O2-, Rc and Rc2 each represent an alkyl group, an aryl group, a heterocyclic group, or an amino group, and Rc3 is 1 Represents a valence group.

j represents an integer from 0 to 2, and when J is 2, each -NH-A-
Rc2 may be the same or different, and m represents an integer of 0 to 2. However, the sum of (and m is l or 2.

Furthermore, at least one of NHA Rc2 and -○H must be bonded to -NHS O2Rc+ at the ortho or para position.

n is an integer from O to 6, and when D is 2 to 6, Rc3 may be the same or different <, ---QC may be combined with a benzene ring to form a naphthalene ring represents something.

[Specific composition of the invention] Next, the present invention will be specifically 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 the substituent represented by R is not particularly limited, but typically includes alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cyclo. Examples include multiple groups such as alkyl, halogen atoms, cycloalkenyl, alkynyl, heterocyclic, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyan, alkoxy, sulfonyloxy, aryloxy, heterocyclic oxy, Siloxy,
Acyloxy, carbamoyloxy, amine, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxy, mercapto, nitro, sulfone Also included are polygroups 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 cycloalkenyl group represented by R has 3 to 3 carbon atoms.
12, especially those of 5 to 7 are preferred.

Sulfonyl groups represented by R include alkylsulfonyl groups, arylsulfonyl groups, etc.; 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 arylcarbonyl group, an arylcarbonyl group, etc.; As a carbamoyl group, an alkylcarbamoyl group, an arylcarbamoyl group, etc.; As a sulfamoyl group, an alkylsulfamoyl group,
Niacyloxy groups such as arylsulfamoyl groups include alkylcarbonyloxy groups, arylcarbonyloxy groups, etc.; carbamoyloxy groups include alkylcarbamoyloxy groups, arylcarbamoyloxy groups, etc.; ureido groups include alkylureido groups, arylureido groups, etc. etc.; Examples of the sulfamoylamino group include an alkylsulfamoylamino group, an arylsulfamoylamino group, etc.; Preferably the heterocyclic group is a 5- to 7-membered one, specifically 2-furyl group, 2-thienyl group, etc. group, 2pyrimidinyl group,
2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc. The heterocyclic oxy group preferably has a 5- to 7-membered heterocycle, for example, 3,4.5.6-tetrahydropyranyl-2-oxy. group, 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-diphenoxy13.5-)lyazole-6- 1,000 groups; siloxy groups include trimethylsiloxy group, triethylsiloxy group, dimethylbutyl group:!
xy group, etc. Imide groups include succinimide group, 3-heptatecylsuccinimide group, phthalimide group, glutarimide group, etc. Nispiro compound residues include spiro[3,3]hebutane-
1-il et al.

As a bridged hydrocarbon compound residue, bicyclo[22,1''
heptan-1-yl, tricifo[3°31.137 cotecan-1-yl, 7,7-dimethyl-picyclo[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, Alkoxycarbonyloxy, aryloxycarbonyl, alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkyloxydithiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocycle bonded with N atom, alkyloxycarbonylamino , aryloxycarboniamino, carboxyl, general formula [I[] Y″χ″ (R′ is the same as the above R, Z′ is the same as the above Z, Ra and Rb are hydrogen atoms, aryl groups, (representing an alkyl group or a heterocyclic group).
Preferably it is a halogen atom. Among these, particularly preferred ones represented by X are hydrogen atoms and chlorine atoms.

A preferred specific example of the compound represented by the general formula [I] is represented by the following general formula [n].

The following blank space [wherein Z'' is condensed with the pyrazole ring to form a nitrogen-containing hetero 6R ring containing at least one -N- and at least one carbonyl group or at least one sulfonyl group. The six-membered ring may have a substituent and may be condensed with a benzene ring in addition to the pyrazole ring. R' and Y'' represent a hydrogen atom or a substituent, and x'' represents a hydrogen atom or a substituent that is eliminated by reaction with an oxidized product of a color developing agent. ] The compound represented by the general formula [I] will be explained in more detail.

In the general formula [I], the nitrogen-containing 6-membered heterocyclic ring formed by Z is preferably a 6π electron system or an 8π1 electron system, and contains at least one -N- and contains 1 to 4
The at least one carbonyl group contained in the six-membered ring represents a group such as >C-O or >C=S. Further, as a specific example containing the 6-membered ring, the following -
Formula II]I-a], [■b], [II-c] and [
Examples include compounds represented by I[-d].

Margin below represents.

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

- Among the compounds represented by the formula [II, one is preferably the general formula [■ General formula [n-b general formula [ff-c] general formula [■ d] [wherein R,, R2 and R9 are General formula [synonymous with R in general formula II, X is synonymous with X in general formula II, Y is general formula [synonymous with Y in general formula II] - In formula [II-b], n represents an integer of 0 to 4, and when n is an integer of 2 to 4, a plurality of R2s may be the same or different. ] R2 and R3 in general formula I [-a], [II-C] and [II-d] are represented by general formula [I
It has the same meaning as R in I, except that R2 is not a hydroxy group.

Preferred examples of R2 and R3 include polygroups such as alkyl groups, aryl groups, carboxyl groups, oxycarbonyl groups, cyano groups, alkoxy groups, aryloxy groups, amino groups, amide groups, and sulfonamide groups, and hydrogen atoms; These include halogen atoms.

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

X ■ Next, a typical synthesis example of the compound of the present invention is shown below. Synthesis Example 1 [Synthesis of Compound (A-13>)] Compound (A
-13) [Synthesis of compound a] 15.9 g (0.1 mol) of 5S amino 3-phenylpyrazole and 15.9 g (0.1 mol) of 2-ethoxycarbonylacetimidic acid ethyl ester were combined with 20
The mixture was heated and refluxed for 2 hours in 0oo1 dehydrated ethanol.

After filtering the reaction solution while hot, the P solution was cooled, and the formed precipitate was collected, washed with cold ethanol, and recrystallized with a mixed solvent of dimethylformamide and water to obtain white needles, which is compound a. 17.8 g <0.079 mol) of crystals were obtained.

(Compound a) Melting point: 300°C or higher NMR spectrum and mass spectrum show that Compound a
Check the structure of.

Synthesis of compound (A-13) from compound a Co-compound a1
7.0 g (0,075 mol) of ethyl acetate solution 600
100 ml of an ethyl acetate solution containing 31.2 g (0,075 mol) of Compound b was added to m1, and 7.8 g of triethylamine was further added, followed by stirring at room temperature for 2 hours, and the precipitated crystals were collected. This was washed with water and further recrystallized with acetonitrile to give white needle-like crystals of compound (A13) 23. Og<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 e] 16.2 g (0.1 mol) of the above compound c and 34.8 g (0.1 mol) of the above compound d were added to 40 ml of methanol. After cooling, stir at room temperature for 2 hours, then 9.8
g of sodium carbonate and then 2 g of sodium carbonate at 50°C.
Do not stir for a while. After pouring the reaction solution into 300 onl of water, it was neutralized using hydrochloric acid, and the solid precipitated thereby 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
mole) obtained.

For [synthesis of compound (B-1) from compound e], 10.0 g (0,023 mol) of this compound e was added to 100
ml of acetic acid, and 35 ml of 35% hydrogen peroxide solution was slowly added dropwise to the resulting solution.
Stir for hours. Add 300ml of water to this solution and
After neutralizing with an aqueous sodium hydroxide solution at a temperature below C and extracting the resulting solution with ethyl acetate, ethyl acetate is distilled off from the extract, and the resulting precipitate is recrystallized using acetonitrile. The compound 'l! crystallized in the form of a white powder. 1 (B-1) is 8.5g (0,0
18 mol) was obtained.

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

Synthesis Example 3 [Synthesis of Compound (C-5>) [Synthesis with Compound] Ethyl-3,5-diaminopyrazole-4-carboxylic acid 17.0 g (0.1 mol), p-dodecaoxyphenylsulfonyl chloride 36 .br (0.1 mol) and 15.2 g (0.15 mol) of triethylamine
The mixture was added to 00 ml of ethyl acetate and heated under reflux for 1 hour.

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

[Synthesis of compound products from compound engineering] 29.1 g (0,059 mol) of compounds f and 14
．． 6 g (0,089 mol) of α-chloroacetoacetic acid ethyl ester was heated in 600 ml of toluene for 6 hours.
The mixture was refluxed to perform a dehydration reaction.

The reaction solution was concentrated under reduced pressure to obtain crude crystals, which were recrystallized with ethanol to obtain 16.1 g of white needle-shaped crystals produced by the compound.
(0,027 mol) was obtained.

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

[Synthesis of compound (C-5) from compound product 15]
．． 4g (0,026 mol) of acetic acid, sulfuric acid, compound ((
,-5) Dissolve in 130 ml of water mixed solvent (100:25:5) and heat under reflux for 1 hour. After adjusting the pH to 5 with an aqueous solution of 1-lium hydroxide, the mixture was extracted with ethyl acetate, the solvent was dried over magnesium sulfate, and then evaporated. Recrystallize the residue with acetonitrile to obtain 7-3 g of white needle-like crystals of compound (C-5).
(0,014 mol) was obtained.

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

Synthesis Example 4 [Synthesis of Compound (D-5)] C00C2H6 Compound (D-5> [Synthesis of Compound] 45 g (0.1 mol) of Compound L (used in Synthesis Example 3)
and 22 g (0.1 mol) of ω-acetophenonesulfonyl chloride were added to 1" of chloroform, and
Add 2 g ((1,12 mol) of triethylamine,
After heating and refluxing for an hour, it was cooled, and the reaction solution was washed twice with diluted hydrochloric acid, and then chloroform was distilled off under reduced pressure.
The mixture was recrystallized twice to obtain 30 g of white powder crystals (1,045 mol) of compound h3.

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

[Synthesis of compound i from compound RI] 20g (0, (13 mol) of compound RI) 140-1
After heating at 60° C. for 1 hour and cooling, the precipitated crystals were recrystallized with ethanol to obtain gray-white powder crystals, compound %i.9.
8 g (0,015 mol) were obtained.

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

[Synthesis of compound (D-5) from compound i] Compound (D-5) was obtained from 6.3 g (0.01 mol) of compound i in exactly the same manner as in Synthesis Example 3 to obtain compound (C-5) from compound foot. -5) white powder crystal 2.9f (0,00
5 mol) was obtained.

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

The cyan coupler of the present invention is usually txlo-' mol-1 mol, preferably 1 x 10-' mol, per mol silver halide.
It can be used in the range of 2 mol-8X 10-' mol.

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 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, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

One of the color stain inhibitors that can be used in combination with the cyan coupler of the present invention is a compound selected from hydroquinone compounds represented by the formula [I[[A].

In the general formula [I[A] H , the monovalent group represented by RA l includes, for example, a halogen atom, an aliphatic group, an aromatic group, an alkylthio group,
Arylthio group, carbamoyl group, cyano group, formyl group, aryloxy group, alkoxy group, acyloxy group, carboxyl group or its salt, sulfo group and its salt, alkoxycarbonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, - CORA2
, -So2RAs, -CoNHRA, and -NHC
ORA, RA2, RAI, RA4 and RA
S each represents an aliphatic group, an aromatic group or a heterocyclic group.

i represents an integer of 1 to 4, and when i represents an integer of 2 to 4, the plurality of RAIs may be the same or different.

Next, as representative examples of specific compounds represented by the general formula [I[[A], the following are listed as a table.

Heretofore, in order to prevent color staining, various methods using hydroquinone have been proposed. For example, regarding the use of monolinear alkylhydroquinone, U.S. Pat.
No. 728,657 and JP-A-47-106329, etc.
Further, regarding the use of monobranched alkylhydroquinone, US Pat.
It is described in No. 49-106329.

Furthermore, regarding dilinear alkylhydroquinone, U.S. Patent No. 2.728.657, U.S. Pat.
British Patent No. 752.146, British Patent No. 1,086,208,
"Chemical, Abstract" magazine, vol. 58, 6367h
etc., and for di-branched alkylhydroquinones,
U.S. Patent No. 3,700,453, U.S. Patent No. 2,732,300
No., British Patent No. 1.086,208, above-mentioned “Chemical
Abstracts'' magazine, JP-A-50-156438, JP-A-50-21249, JP-A-5640818, etc.

In addition, the use of alkylhydroquinone as a color stain prevention agent is disclosed in British Patent Nos. 558.258 and 557750.
(Corresponding U.S. Patent No. 2,360,290), No. 557,8
No. 02, No. 731,301 (corresponding U.S. Patent No. 2.701)
．． 197), U.S. Patent No. 2,336,327, U.S. Patent No. 2,
No. 403,721, No. 3,582.333, West German Patent Publication No. 2,505,016 (corresponding to Japanese Patent Publication No. 1103-1983)
37) and Japanese Patent Publication No. 56-40,816.

Also, Research Disclosure Magazine No. 176 (19
(1978), page 17643, ■■■.

However, there is no description in these techniques that color staining is significantly improved by using the above-mentioned hydroquinone color stain inhibitor in combination with the cyan coupler of the present invention.

Another type of color stain inhibitor that can be used in combination with the cyan coupler of the present invention is a compound selected from pyrogallol compounds, resorcinol compounds, and catechol compounds represented by the formula [I[B]. be.

In the general formula [[[B], examples of the monovalent group represented by RB+ include a halogen atom, an aliphatic group, a cycloalkyl group, an aromatic group,
Alkylthio group, carbamoyl group, cyano group, formyl group, aryloxy group, acyloxy group, carboxyl group or its salt, sulfo group or its salt, alkoxysulfonyl group, cycloalkoxycarbonyl group, aryloxycarbonyl group, CORB2, SO2R
! 13, -CON HRB< and -N HCORA5
, and RB□, RB3, RE4 and RB each represent an aliphatic group, an aromatic group or a heterocyclic group.

j represents an integer of 1 to 6, and when j represents an integer of 2 to 6, a plurality of R111 may be the same or different. k is 2 or 3; when k is 2, the two -OHs are at ortho or meta positions; when k is 3, the three -OHs are bonded to adjacent positions. -----Q,------
represents that it may be combined with a benzene ring to form a naphthalene ring.

Next, the following are listed as representative examples of specific compounds represented by the general formula [IB].

Regarding the above-mentioned pyrogallol compounds, catechol compounds, and resorcinol compounds, Berggi et al. Patent No. 868,44
No. 1, JP-A-58-156993, etc.

However, the above-mentioned cited documents and patents do not mention that color staining is significantly improved by using the above-mentioned pyrogallol-based compounds, catechol-based compounds, and resorcinol-based compounds in combination with the cyan coupler of the present invention. .

Yet another type of color stain inhibitor that can be used in combination with the cyan coupler of the present invention is of the general formula [1
It is a sulfonylamino compound represented by 11C1.

In the general formula [T[C], A represents 100- or -8O2-, and Ra+ and RC□ each represent an alkyl group, an aryl group, a heterocyclic group, or an amine group.

In the general formula [IC], the alkyl groups represented by RC1 and Rcm may be linear or branched, and preferably have 1 to 30 carbon atoms.

The aryl group represented by RC1 and RC2 preferably has 6 to 30 carbon atoms.

The heterocyclic group represented by RCI and RC2 preferably has 5 to 30 carbon atoms and has at least one of 0 and N as a heteroatom.

The amino groups represented by RCI and Rc2 include those substituted with an alkyl group or an aryl group.

The groups represented by Rc + and RC2 include those having substituents.

RC3 may be the same group as R Bl shown in the general formula [I[[Bl.

The layer represents an integer from O to 2, and when the layer is 2, each -NH-A-
Rc2 may be the same or different.

River represents an integer from 0 to 2. However, the total number of layers and marks is 1 or 2.

Furthermore, at least one of -NH-A-Rc2 and -OH must be bonded to -NH3O□RCI at the ortho or para position.

n is an integer of 0 to 6, and when n is 2 to 6, Rc3 may be the same or different.

---Q and ------ represent that a naphthalene ring may be formed together with a benzene ring.

The compound represented by the general formula [I[[C] can be synthesized by a known method.
No. 247, No. 59-192247, No. 59-1952
No. 39, No. 59-204040, No. 60-10884
No. 3, No. 60-118836, etc. can be referred to.

However, these publications do not mention at all that color staining is significantly improved by using a sulfonylamino color staining inhibitor in combination with the cyan coupler of the present invention.

Next, specific compound examples of the sulfonylamino color stain inhibitor will be shown.

Below margin ■c-i I[C-2 ■(, -3 H c-4 IC H IC-6 H I[[C-7 H IC H 111C-13 H IC H 11[C H NH3O2C1] H1゜IC IC IC H3 IC H I[IC H NHCOCF3 11C 11[C-19 0H Below margin The color stain preventive agent according to the present invention may be contained in the same layer as the cyan coupler according to the present invention, and It may be contained in a non-photosensitive layer, so-called an intermediate layer or a protective layer, which is adjacent to a layer containing such a cyan coupler and does not contain a photosensitive silver halide emulsion.

In the present invention, the color stain prevention according to the present invention is added to the intermediate layer adjacent to the layer containing the cyan coupler according to the present invention and between the layer containing the magenta coupler or the layer containing the yellow coupler. It is most preferred to include an agent. In the present invention, the amount of the color stain inhibitor to be used for the cyan coupler of the present invention is 1 x 10''3 mol to 1 mol, preferably 1 x 10''3 to 1 mol, per 1 mol of the coupler.
The range is -5 x 10-' moles.

The color stain preventive agent is contained in an emulsion layer containing the cyan coupler of the present invention or in a non-photosensitive layer adjacent to the emulsion layer, and prevents undesirable migration from other emulsion layers other than the emulsion layer. It reacts with the oxidized color developing agent to remove it, and plays an important role in preventing the formation of an undesired cyan image in the emulsion layer, resulting in color contamination.

When the above-mentioned color stain inhibitor is used in combination with the cyan coupler of the present invention, the oxidized product of the color developing agent becomes more efficient than when used in combination with the conventional phenol-type and naphthol-type cyan couplers, which was not initially predicted by the inventors. It was discovered that the reaction can be removed by the good properties of the compound.

In particular, by using the cyan coupler of the present invention in combination with the color stain inhibitor of the present invention, it has become possible to provide a thin multilayer color photographic material with significantly less color stain.

The coupler and color stain inhibitor of the present invention can be added using various methods such as solid dispersion method, latex dispersion method, oil-in-water emulsion dispersion method, etc., as well as the method of adding numerically hydrophobic compounds. This can be appropriately selected depending on the chemical structure of the hydrophobic compound such as the coupler.

The oil-in-water emulsion dispersion method can be applied to a method of dispersing a hydrophobic compound such as a coupler. Usually, a high-boiling point organic solvent with a boiling point of about 150°C or higher is used, and if necessary, a low-boiling point and/or water-soluble organic solvent is added. Dissolve using a solvent and a stirrer using a surfactant in a hydrophilic binder such as an aqueous gelatin solution.
It may be emulsified and dispersed using a dispersing means such as a homogenizer, colloid mill, flow jet mixer, or ultrasonic device, and then added to the desired hydrophilic colloid layer. A step of removing the low boiling point organic solvent may be included after or simultaneously with the dispersion.

Examples of high-boiling organic solvents include phenol derivatives, phthalate esters, phosphate esters, citrate esters, benzoate esters, alkylamides, fatty acid esters, trimesate esters, etc. that do not react with the oxidized form of the developing agent. Organic solvents are used.

High boiling point organic solvents that can be preferably used in the present invention include compounds with a dielectric constant of 6.0 or less, such as esters such as phthalates and phosphates with a dielectric constant of 6.0 or less, organic acids These include amides, ketones, and hydrocarbon compounds.

Preferably dielectric constant is 6.0 or less and 1.9 or more and 100'C
It is a high boiling point organic solvent with a vapor pressure of 0.5 mmHg or less. Also more preferred are phosphoric acid esters. Furthermore, the high boiling point organic solvent may be a mixture of two or more kinds.6 One of the preferable high boiling point organic solvents used in the present invention is a phosphoric acid ester compound as shown by the formula []V]. It will be done.

- Formula [IV] RD30 P 0Rot ORD 2 (In the formula, Rol, RD2 and R83 each represent an alkyl group, an alkenyl group, a cycloalkyl group, or an aryl group.) In the present invention, the - formula [JV] In the phosphoric acid ester compound represented by
The total number of carbon atoms in the groups represented by DI, RD2 and RD3 is preferably 24 to 48.

This is because if it is less than 24, the improvement effect aimed at by the present invention will be small, and if it exceeds 48, the function as a coupler solvent tends to be somewhat weakened.

Examples of the alkyl group represented by RDl, RD2 or Ro3 include ethyl group, propyl group, t-butyl group, hexyl group, heptyl group, 1so-octyl group, 5ec-nonyl group, dodecyl group, 15O-bentatecyl group , hexadecyl group, heptadecyl group, ophtadecyl group, etc., the aryl group is a phenyl group, a naphthyl group, etc., and the alkenyl group is a butenyl group, a pentenyl group, an ophtathecenyl group, etc. These alkyl groups, alkenyl groups, and aryl groups may have single or multiple substituents, and examples of substituents for alkyl groups and alkenyl groups include halogen atoms, alkoxy groups, aryl groups, aryloxy groups, Examples of substituents for aryl groups include alkenyl groups, alkoxycarbonyl groups, etc., and examples of substituents for aryl groups include halogen atoms, alkyl groups, alkoxy groups, aryl groups,
Examples include an aryloxy group, an alkenyl group, and an alkoxycarbonyl group. Two or more of these substituents may be introduced into the alkyl group, alkenyl group or aryl group. Preferably RDI, RD2 and RD3
or an alkyl group, for example, 2-ethylhexyl group,
n-octyl group, 3,5.5-trimethylhexyl group,
n-nonyl group, n-decyl group, 5ec-decyl group, 5e
Examples include c-dotecyl and t-octyl groups.

In the present invention, the high boiling point organic solvent represented by formula [IV] preferably has a boiling point of 175° C. or higher at 1 atm.

Typical specific examples of the high boiling point organic solvent represented by the general formula [IV] are shown below, but the invention is not limited thereto.

The following margin ■-5 Examples of the silver halide used in the silver halide emulsion layer of the sensitive material of the present invention include silver chloride, silver bromide, silver iodide,
Any of those used in conventional silver halide photographic emulsions, such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide, are included.

These silver halide grains may be coarse or fine, and the grain size distribution may be narrow or wide.

Further, the crystals of these silver halide grains may be normal crystals or twin crystals, and any ratio of [100) planes to [111] planes can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may have a layered structure with different inside and outside. Further, these silver halides may be of a type that forms a latent image mainly on the surface or of a type that forms a latent image inside the grain.

These silver halide grains can be prepared by known methods commonly used in the art.

It is preferable that soluble salts be removed from the silver halide emulsions used in the photosensitive materials of the present invention, but those in which soluble salts are not removed can also be used. In addition, two or more types of silver halide emulsions prepared separately can also be used as a mixture.6 The silver halide emulsions used in the present invention include:
Any silver halide emulsion may be used, such as silver chloride emulsion, silver chlorobromide emulsion, silver chloroiodromide emulsion, etc., but there are no particular limitations.
Silver halide emulsions having high chloride silver halide grains are preferred.

The above-mentioned high chloride silver halide grains are those having a silver chloride content of 90 mol % or more. In high chloride silver halide grains, the silver bromide content is 10 mol% or less,
The silver iodide content is preferably 0.5 mol% or less. More preferred is silver chlorobromide having a silver bromide content of 0.1 to 2 mol%.

High chloride silver halide grains do not have to be used alone, but can also be used in combination with other silver halide grains having different compositions.

For example, it may be mixed with silver halide grains having a silver chloride content of 10 mol % or less.

In addition, in a silver halide emulsion layer containing high chloride silver halide grains, the proportion of high chloride silver halide grains in the total silver halide grains contained in the emulsion layer is 60% by weight or more. The amount is preferably 80% by weight or more, and more preferably 80% by weight or more.

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

The grain size of the high chloride silver halide grains is not particularly limited, but in consideration of other photographic performance such as rapid processing and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.2 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. 194-122) or Theory of the Photographic Process (by Mies and James, 3rd edition, published by Macmillan, 1966), 2nd edition.
chapter).

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 high chloride silver halide grains 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 used in the emulsion of the present invention can be prepared by acidic method.
It may be obtained by either the neutral method or the 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. Furthermore, as a type of simultaneous mixing method, the I) Ag-controlled daughter pull jet method described in Japanese Patent Application Laid-Open No. 54-48521, etc. can also be used.

Furthermore, if necessary, a silver halide solvent such as thioether 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 used in the present invention may have any shape. One preferable example is (100)
It is a cube with planes as crystal surfaces.

Furthermore, particles having shapes such as octahedrons, tetradecahedrons, and dodecahedrons may be used.6 Furthermore, particles having twin planes may also be used.

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

The silver halide grains used in the present invention may contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts or complex salts, rhodium salts or complex salts,
Metal ions can be added to the inside of the particles and/or on the surface of the particles by using iron salts or complex salts, and reduction-sensitized nuclei can be formed inside the particles and/or on the surface of the particles by placing them in an appropriate reducing atmosphere. can be granted.

In the emulsion containing silver halide grains used in the present invention (hereinafter referred to as "emulsion of the present invention"), unnecessary soluble salts may be removed after the growth of the silver halide grains is completed;
Alternatively, it may be left as is. In the case of removing the salts, it can be carried out based on the method described in Research Disclosure No. 17643.

The silver halide grains used in the emulsion used in the present invention are:
Preferably, the particles are particles in which the latent image is primarily formed on the surface, but particles in which the latent image is formed internally may also be used.

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 sulfur sensitizers include thiosulfate and ant sensitizers. Examples include ruthiocarbazide, thiourea, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine. Others, US Patent 1574
．． No. 944, No. 2,410,689, No. 2,278,
No. 947, No. 2728668, No. 3,501,313
No. 3,656,955, West German Publication (OLS)
) No. 1,422,869, JP-A-56-2493
Sulfur sensitizers described in No. 7, No. 55-45016, etc. can also be used. The amount of sulfur 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 - 10-1 mol per mol of silver halide. degree is preferred.

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.

In the photographic constituent layer containing the cyan coupler according to the present invention,
By including the high chloride silver halide emulsion layer, faithful color reproduction can be obtained and sufficient maximum density can be obtained.

The silver halide emulsion used in the present invention can be optically sensitized to a desired wavelength range using a dye known as a sensitizing dye in the photographic industry.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugars, etc. Hydrophilic colloids such as derivatives, cellulose derivatives, synthetic hydrophilic polymeric substances such as single or copolymers can also be used.

The silver halide photographic light-sensitive material of the present invention having the above structure can be, for example, color negative and positive films, color photographic paper, etc., but in particular color photographic paper used for direct viewing can be used. In such cases, the effects of the method of the present invention are effectively exhibited.

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 the yellow coupler, and known ones can be used.

As magenta couplers, 5-pyrazolone-based, virazolobenzimitazole-based, pyrazoloazole-based, open-chain acylacetonitrile-based couplers, etc. are used.
-Pyrazolone and pyrazolotriazole magenta couplers are preferred.

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

The silver halide photographic light-sensitive material of the present invention further includes a hardening agent, an irradiation inhibitor, a color clouding prevention agent, an image stabilizer, a plasticizer, a latex, a surfactant, a hardening agent, an anti-irradiation agent, a surface active agent, a matte agent, a smoothing agent, etc. , an antistatic agent, and other additives may be used as necessary.

The silver halide photographic material of the present invention can be used to form an image by subjecting it to a color development treatment known in the art.

The pH value of the color developer is usually above 7, most commonly about 10-13.

Color development time is usually 15°C or higher, -20°C numerically.
It is in the range of °C to 50 °C. 30 for quick development
It is preferable to carry out the reaction at a temperature of 0.degree. C. or higher. Further, in conventional processing, the color development time is 3 to 4 minutes, but the color development time of the present invention for the purpose of rapid processing is generally preferably carried out in the range of 20 seconds to 60 seconds, more preferably 30 seconds. 6. The silver halide photographic light-sensitive material of the present invention has a development time of 2 m/1.12 seconds for rapid development.
Even if a color developing solution with a density of 12 or less is used, rapid development is possible without decreasing the maximum density of the characteristic curve.

After color development, bleaching and fixing are performed.

Bleaching treatment may be performed simultaneously with fixing treatment.

After the fixing process, a washing process is usually performed.

Further, as an alternative to the water washing treatment, a stabilization treatment may be performed, or both may be used in combination.

〔Example〕

Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.

Example 1 Silver halide color photographic light-sensitive material sample No. 1 was prepared by sequentially coating the following layers on a paper support laminated with polyethylene from the support side.

Layer 1---'1.2g/rr? gelatin, 0.
Blue-sensitive silver halide emulsion (silver chloride content 97 mol%) of 32 g/rn' (in terms of silver, the same applies hereinafter), 0.50 g/rn'
0.80 g dissolved in dioctyl phthalate of rrl'
/rrl' yellow coupler (YA) layer.

Layer 2...0.7g/rrr gelatin, 10■
An intermediate layer consisting of an irradiation dye of /d (AI-1) and an irradiation dye of 5 /rrf (AI-2).

7 layers 3--1.25g/ni' gelatin,
0.22g/rr? green-sensitive silver halide emulsion (silver chloride content 100 mol%), 0.30 g/rr? A layer containing 0.62 g/nr of magenta coupler (M-A) dissolved in dioctyl phthalate.

Layer 4: Intermediate layer consisting of 1.2 g/d gelatin.

Layer 5---1.40 g/rd gelatin,
0.20 g/rr' of red-sensitive silver halide hole side (silver chloride content 100 mol%), 0.45 g/rr of cyan coupler (C-A) dissolved in 0.20 g/rr of triro-octyl phosphate. A layer containing.

Layer 6: Layer containing 0.5 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 6.
Each was added in an amount of 0.017 g per 1 g of gelatin.

In addition, gelatin in layer 4 was added at 0.9 g/ni' and 0.6 g/r.
Sample N was prepared in the same manner as Sample 1 except that ri'
02, No. 3 was created. Sample No. 1, No.
, 2, No., and 3. Samples containing the color stain inhibitor I[A-4 and I[[A-8] dissolved in dibutyl phthalate (DBP) in the amounts shown in Table 1 in the layer 4 of each of Nos. 2, No., and 3. N
o, 4 to No. 9 were created.

Furthermore, for each of samples No. 1 to No. 9, the first
As shown in the table, Sample No. 10 to No. 18 were created.

Below margin (A1 (AI below margin) The above photosensitive material samples No. 1 to No. 018 were prepared according to the usual method.
A color separation exposure was performed using a light wedge and a colored filter to expose the green sensitive emulsion layer for further processing.

Processing process> Temperature Development color development 34.7 ± 0.3°C 45 seconds bleach fixing
34,7±0.5℃ Stabilized for 50 seconds 30
Dry at ~34°C for 90 seconds 60-80°C for 60 seconds Color developer> Pure water 800mj Triethanolamine 8gN,N
-Diethylhydroxyamine 5g Potassium chloride 28N-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4 Aminoaniline sulfate 5g Sodium tetrapolyphosphate 2g Potassium carbonate
30g sub-VAa potassium
0.2g optical brightener (4,4'
- Diaminostilbendisulfonic acid derivative> Add 1 g of pure water to bring the total amount to 1.0, and adjust to p) [10,2.

Bleach-fix solution>Ethylenediaminetetra#acid ferric ammonium dihydrate 60g Ethylenediaminetetra#acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution> 27.5ml Potassium carbonate or glacial acetic acid to IIH5,7 Adjust and add water to bring the total volume to 11.

Stabilizing liquid> 5-chloro-2-methyl-4-inchazolin-3-one 1g 1-hydroxyethyrythene-1゜1-diphosphonic acid 2g Add water to make 1j, and add sulfuric acid or potassium hydroxide to p) [of
Adjust to 7.0.

Sensitometry was performed on each sample after the above treatment to determine the maximum magenta density (MDmay, ) and the maximum cyan density (CDI'lax), and the color turbidity due to cyan coloring on magenta coloring C11ax / M D
IIlax was calculated and Table 2 was obtained.

Margin below Table 2 The color becomes more cloudy due to the puller.

On the other hand, Samples Nos. 7 to 9 and Nos. 13 to 18, which were prepared by adding the color stain preventive agent of the present invention to layer 4, certainly have less color turbidity, but especially the cyan coupler of the present invention and the color stain preventive agent of the present invention. No. 1 created by combining color stain prevention agent
It can be seen that samples Nos. 3 to 18 have less color turbidity, and layer 4 is a thin film, so that even if the amount of the color stain preventive agent added is small, the effect of preventing color turbidity is large.

Example 2 Sample Nos. 19 to 30 were prepared using the combinations shown in Table 3.
was prepared and treated in exactly the same manner as in Example 1.

The following margin samples No. 1 to 3. From No. 10 to No. 12, it can be seen that the smaller the amount of gelatin in layer 4 becomes FfE, the more turbidity the color becomes. Furthermore, the cyan coupler of the present invention has a greater degree of color turbidity than the comparative cyan coupler.

In particular, as layer 4 becomes an N film, it is seen from Table 3 of Table 3 of the cyan power of the present invention that color turbidity can be greatly reduced by the cyan coupler of the present invention and the color stain preventive agent of the present invention.

[Effects of the Invention] The present invention has the effect of providing a silver halide color photographic light-sensitive material that has excellent color reproducibility and extremely little color staining even in a thin film state without reducing photographic sensitivity. .

Claims (1)

[Scope of Claims] It is characterized by containing at least one cyan coupler represented by the following general formula [I] and at least one compound selected from the following general formulas [IIIA], [IIIB] and [IIIC]. A silver halide photographic light-sensitive material. General formula [I] ▲There are 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 to form a nitrogen-containing 6-membered hetero ring by condensing with the pyrazole 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. ] General formula [IIIA] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_A_1 represents a monovalent group, i is an integer from 1 to 4, and when i is 2 to 4, multiple R_A_1 They may be the same or different. ] General formula [IIIB] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_B_1 represents a monovalent group, j represents an integer from 1 to 6, and when j is 2 to 6, multiple R_B_1 They may be the same or different. k is 2 or 3; when k is 2, two -OHs are at ortho or meta positions; when k is 3, three -OHs are bonded to adjacent positions. ----Q_B--- represents that it may be combined with a benzene ring to form a naphthalene ring. ] General formula [IIIC] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, A represents -CO- or -SO_2-, R_C
_1 and R_C_2 are each an alkyl group, an aryl group,
It represents a heterocyclic group or an amino group, and R_C_3 represents a monovalent group. l represents an integer from 0 to 2, and when l is 2, each -NH-A-
R_C_2 may be the same or different, m is 0 to 2
represents an integer. However, the sum of l and m is 1 or 2. Furthermore, at least one of -NH-A-R_C_2 and -OH must be bonded to -NHSO_2R_C_1 at the ortho or para position. n is an integer from 0 to 6, and when n is 2 to 6, R_C_
3 may be the same or different, ---Q_C--
-- represents that a naphthalene ring may be formed together with a benzene ring. ]