JPS6346454A - Method for processing silver halide photographic sensitive material with suppressed fogging - Google Patents

Abstract

PURPOSE:To form rapidly a color image by developing a photosensitive material which is sensitized a silver halide emulsion layer with a specific sensitizing dye in the presence of a hydroxyl amine type compd. and a nitrogen contg. heterocyclic mercapto compd. CONSTITUTION:At least one layer of the silver halide emulsion layers is sensitized with the sensitizing dye shown by formula I wherein Z1 and Z2 are each an atom group capable of forming a thiazole ring or a selenazole ring, etc., R1 and R2 are each alkyl or aryl group, R3 is hydrogen or methyl group, etc., X1<-> is an anion, (l) is 0 or 1. The photographic sensitive material is developed with a color developing agent of an aromatic primary amine, after image-wisely- exposing it. Said material is processed with the developing solution contg. the hydrozyl amine type compd. shown by formula II such as N,N-dienthyl amine and the nitrogen contg. heterocyclic mercapto compd. In the formula II, R4 and R5 are each hydrogen atom or alkyl group. Thus, as the photosensitive material is developed in the presence of the hydroxyl amine type compd., etc., generation of fog and change of gradient is lowered and good sensitivity is obtd.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for processing silver halide photographic materials, and in particular, a method that enables rapid processing, has good processing stability, and can prevent an increase in fog. The present invention relates to a method for processing silver halide photographic materials.

[Background of the Invention] In general, silver halide color photographic light-sensitive materials include three types of silver halide colors that are selectively spectral sensitized to have sensitivity to blue light, green light, and red light on a support. A photographic emulsion layer is coated.

For example, in a color negative light-sensitive material, a blue-sensitive emulsion layer, a green-sensitive emulsion layer, and a red-sensitive emulsion layer are generally coated in this order from the exposed side, and there is a layer between the blue-sensitive emulsion layer and the green-sensitive emulsion layer. A bleachable yellow filter layer is provided to absorb the blue light transmitted through the blue-sensitive emulsion layer. Furthermore, each emulsion layer is provided with other intermediate layers for various special purposes, and a protective layer III is provided as the outermost layer. Furthermore, for example, in light-sensitive materials for color photographic paper, a red-sensitive emulsion layer, a green-sensitive emulsion layer, and a blue-sensitive emulsion layer are generally coated in this order from the exposed side, and each layer has a special layer, similar to the light-sensitive material for color negatives. For this purpose, intermediate layers including an ultraviolet absorbing layer, protective layers, etc. are provided. It is also known that each of these emulsion layers can be provided in a different arrangement from the above, and each emulsion layer can be formed into a photosensitive layer consisting of two layers sensitive to substantially the same wavelength range for each color light. It is also known to use transparent emulsion layers. In these silver halide color photographic materials, exposed silver halide grains are developed using, for example, an aromatic primary amine color developing agent as a color developing agent, and the resulting color developing agent is oxidized. A dye image is formed by reaction of the product with a dye-forming coupler.

In this method, cyan couplers, magenta couplers, and yellow couplers are typically used to form cyan, magenta, and yellow dye images, respectively.

In recent years, in the industry, silver halide color photographic materials (hereinafter referred to as color photosensitive materials) that can be processed quickly, have high image quality, have excellent processing stability, and are low cost have been developed. In particular, silver halide color photographic materials that can be rapidly processed are desired.

In other words, silver halide photographic materials are subjected to running processing in automatic processing machines installed at each processing laboratory, but as part of an effort to improve service to users, processing is carried out on the same day that the development is received. In recent years, it has even become necessary to return the product within a few hours of receiving it, and the development of silver halide color photographic materials that can be processed more quickly is becoming more and more important. It's urgent.

Generally, such dye image formation involves subjecting an exposed color light-sensitive material to color development, bleaching, and fixing (or bleach-fixing), and then washing with water. In the required color photographic paper, shortening the color development process is of considerable technical and practical importance.

In order to speed up the color development process, the most common method is
Measures may be taken, such as raising the development temperature, lowering the concentration of bromide ions, which are the main component of the development inhibitor, increasing the concentration of the color developing agent, or increasing I)H.

Furthermore, rapid color development processing can also be achieved by processing a silver halide photographic material containing silver halide grains consisting essentially of silver chloride in the absence of bromide ions in a color developer. Ru.

However, there are problems with speeding up the various color development processes mentioned above, such as slight fluctuations in conditions (temperature, pH for 1 hour, etc.), changes in composition (bromide ion concentration, color developing agent concentration), and changes in the bleach-fix solution. There is a drawback that fogging is particularly likely to occur when there is a minute amount of contamination.

On the other hand, in recent years, there has been an extremely strong demand for the removal of benzyl alcohol as a color development improver from color developing solutions as a pollution control measure.

If benzyl alcohol is removed from the color developer, the color development rate will decrease. That is, when a color developing agent develops exposed silver halide grains, the reactivity of the resulting oxidized color developing agent with the coupler suddenly decreases, making it difficult to obtain high color density. .

It has been found that the problem of removing benzyl alcohol (decreased color density) becomes a significant drawback, especially with hydroxylamine salts commonly used as preservatives in color developing solutions.

The above-mentioned hydroxylamine salts are known to be preservatives against air oxidation of color developing agents in conventional color developing solutions, especially when used with sulfites; When processed with a color developing solution containing benzyl alcohol at around -10, the effect on color development was extremely small.

However, when developing with a color developing solution that does not contain benzyl alcohol as mentioned above, hydroxylamine specifically reduces the degree of color development, so a preservative in place of hydroxylamine is used to increase the maximum concentration and There is a need for a method that reduces adverse effects on gradation and quickly performs color development processing.

On the other hand, several preservatives for color developing solutions have been proposed in place of hydroxylamine, but among them, hydroxylamine-based compounds have a sufficiently high concentration in the color developing solution and do not contain benzyl alcohol. Even so, it is useful as a compound that has a sufficient preservative effect without significantly reducing color development.

On the other hand, when a hydroxylamine-based compound is used as a preservative instead of hydroxylamine, dye images of silver halide photographic materials can be rapidly formed when processed with a color developing solution that does not contain benzyl alcohol. However, when the maximum density is reached, it tends to cause fogging.

It has been known that mercapto compounds are preferably used as fog suppressants. Mercapto compounds are effective antifogging agents, or, as mentioned above, are difficult to obtain sufficient antifogging effects by themselves to suppress the fog that tends to occur when color development processing is accelerated.

[Object of the present invention] The present invention has been made in view of the above-mentioned circumstances, and an object of the present invention is to reduce the pollution load by removing benzyl alcohol from a color developing solution, and to reduce the pollution load of hydroxylamine compounds. To provide a method for processing a silver halide photographic light-sensitive material, which hardly causes fog when rapidly forming a dye image by performing a color development process in the presence of a dye, and has small changes in sensitivity and gradation due to pH fluctuations. It is in.

[Structure of the Invention] The object of the present invention is to provide a silver halide photographic material having a silver halide emulsion layer containing at least one diffusion-resistant hydrophobic coupler on a support, after imagewise exposure. In the method of processing with a color developing solution containing an aromatic primary amine color developing agent, at least one of the silver halide emulsion layers is sensitized with a sensitizing dye represented by the following general formula [I]. A silver halide photographic sensitizer comprising silver halide grains having the following properties and processed in the presence of a hydroxylamine compound and a nitrogen-containing heterocyclic mercapto compound represented by the following general formula [II]. This is achieved through material processing methods.

General formula [I] [wherein zl and Z2 each form a thiazole nucleus, benzothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzimidazole nucleus, naphthoimidazole nucleus, pyridine nucleus or quinoline nucleus represents the atomic group necessary for

R1 and R2 each represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group. R3 represents a hydrogen atom, a methyl group or an ethyl group.

X+" represents an anion, and 2 is O or 1. 1 General formula []I] R5 R+ -N-○H [wherein, R4 and R5 may each have a hydrogen atom or a substituent Represents an alkyl group having 1 to 4 carbon atoms.

However, R4 and R5 are never both hydrogen atoms. Furthermore, R4 and R5 may be combined to form a ring. ] Regarding the above-mentioned drawbacks, as a result of extensive research by the present inventors, it was found that an emulsion sensitized with a certain sensitizing dye surprisingly has the effect of specifically reducing fog. The inventors have discovered that the objects can be achieved, and have come up with the present invention.

Next, the present invention will be explained in detail.

In the general formula [I], the heterocyclic nucleus represented by Z+ and Z2 includes a thiazole nucleus, a benzothiazole nucleus,
A selenazole nucleus, a benzoselenazole nucleus, and a naphthoselenazole nucleus are preferable, a thiazole nucleus, a benzothiazole nucleus, a selenazole nucleus, and a benzoselenazole nucleus are more preferable, and a benzothiazole nucleus is most preferable.

These nuclei may be substituted with various substituents,
Preferred substituents are a halogen atom, a human Oxyl group, a cyano group, an aryl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group. More preferred substituents are a halogen atom, a cyano group, an aryl group, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group, and particularly preferred are a halogen atom, a cyan group, a methyl group, an ethyl group, a methoxy group, and an ethoxy group. It is the basis.

R+ and R2 represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group, and the alkyl group represented by R1 and R2 is an alkyl group having 1 to 6 carbon atoms. A group is preferable, and an ethyl group, a propyl group, and a butyl group are particularly preferable.

This alkyl group may be substituted with various substituents, and preferred substituents include carboxyl and sulfo groups. In this case, a salt may be formed with an alkali metal ion or an ammonium ion.

At least one of R+ and R2 is preferably an alkyl group substituted with a sulfo group. Examples of the alkenyl group include an allyl group, and examples of the aryl group include a phenyl group.

R3 represents a hydrogen atom, a methyl group or an ethyl group, preferably a hydrogen atom.

)<e represents an anion. Preferred are chloride ion, bromide ion, iodide ion, and p-toluenesulfonic acid ion.

2 is an integer of 0 or 1. In addition, when at least one of R1 and R2 is a group that itself has a minus character, such as a carboxyl group or a sulfo group, 1 is O.

Typical specific examples of the sensitizing dye represented by the general formula [I] are shown below, but the present invention is not limited thereto.

<1-6) (I-9n(+-12) (+-13) (+-15) (+-16) (+-17) (+-22) (+-24) The above general of the present invention The sensitizing dye represented by formula [I] can be easily synthesized, for example, according to the methods described in British Patent No. 660.408 and US Pat. No. 3.149.105.

In order to add the sensitizing dye represented by the general formula [I] of the present invention to a silver halide emulsion, it is preferable to dissolve it in an f1 solvent such as methanol or ethanol which is miscible with water. .

Although it may be added at any stage during the emulsion manufacturing process, it is generally preferable to add it during chemical ripening.

The amount added varies depending on the type of sensitizing dye and the type of silver halide emulsion, but it is usually preferable to add 0.01 to 0.5 g per mole of silver halide.

The hydroxylamine compound represented by the general formula [1[] used in the processing method of the present invention is preferably added to the color developing solution, but it may be included in the light-sensitive material in advance and used for color development. A system is also possible in which the hydroxylamine compound is replenished into the color developer while the photosensitive material is continuously processed while replenishing the replenisher.

In the general formula [1r], the alkyl group having 1 to 4 carbon atoms represented by R4 and R5 may have a substituent, and examples of such substituents include 1 to 3 carbon atoms. Examples include an alkoxy group, a carboxy group, a sulfo group, an amino group, and a hydroxy group, but an alkoxy group is preferable. Furthermore, when R+ and R5 combine to form a ring,
Examples of such a ring include a piperidine ring, a piperazine ring, a morpholine ring, and a pyrrolidine ring, with the morpholine ring being preferred. The ring may have a substituent.

In general formula [I], particularly preferably R4 and R5
are both alkyl groups, and in particular, an ethyl group is most preferred as the alkyl group.

Specific examples of the hydroxylamine compound represented by the above general formula [I[] include the following compounds.

Exemplary compound n-lll-2 It-311-4 11-5n-6 1[-71-8 II-9n-10 II -11I[-12 ■-13■-14 n''-15ll-46 11-17u- t8 17-19 [-2
0n −zt n
-zzn -23n -24 11-27ll-28 HO-CH2-NH-OHCH, -0-C2H, -NH
-OHn-Z9 If
-30HO-C,H4-NH-OHHOOC-C,H,
-NH-OHII -31It -32 HOsS-CtH4-NH-OHNxH-C*H*-N
HOHn-33 CH, -0-C,H, -NH-OH These compounds are usually in the form of salts such as hydrochloride, sulfate, p-toluene, oxalate, phosphate, and acetate. may be used in

The hydroxylamine compound represented by the general formula [I[] is used in an amount of 0.2 to 159, preferably 0.50 to 10CI, per 12 of the color developing solution. Furthermore, the above-mentioned hydroxylamine compound may be used in combination with hydroxylamine as long as it does not impair the effects of the present invention, but preferably the amount of hydroxylamine is about 1 g or less per color developing solution. is 0.5g
The amount added is as follows. (NH20H, 1/2 H2So
In addition, when a hydroxylamine compound represented by the general formula [II] is contained in a photosensitive material and the color developing solution is replenished during continuous processing, the hydroxylamine compound is added to the photosensitive material. Approximately 0.0 per 1f of material
It is in the range of 5 to 5 g, preferably o, ig to 2 g.

Next, the nitrogen-containing heterocyclic mercapto compound used in the present invention will be explained.

The nitrogen-containing heterocyclic mercapto compound used in the present invention includes an imidaline ring, an imidazole ring, an imidasilone ring, a pyrazoline ring, a pyrazole ring, a pyrazolone ring, an oxazoline ring, an oxazole ring, an oxacilone ring, a thianrin ring, a thiazole ring, and a thiazolone ring. ring, selenazoline ring,
selenazole ring, selenazolone ring, oxadiazole ring, thiadiazole ring, triazole ring, tetrazole ring, benzimidazole ring, benztriazole ring, indazole ring, benzoxazole ring, benzthiazole ring, benzselenazole ring, pyrazine ring, pyrimidine ring, selected from a lidazine ring, a triazine ring, an oxazine ring, a thiazine ring, a tetrazine ring, a quinazoline ring, a phthalazine ring, a polyazaindene ring (for example, a triazaindene ring, a tetrazaindene ring, a pentazaindene ring, etc.) This is desirable.

Among these, preferable nitrogen-containing heterocyclic mercapto compounds include mercaptooxadiazole, mercaptothiadiazole, mercaptotriazole, and mercaptotetrazole represented by the following general formula [I[[].

General formula [I[1] In the formula, X is a hydrogen atom, an amino group which may have a substituent,
Hydroxyl group, hydrazino group, alkyl group that may have a substituent 4tJ4 Alkenyl group that may have a substituent, cycloalkyl group that may have a substituent, 71,1-
/lz group, -NHCORs group, -NH3O2Rs group or -3R7 group.

Y is a water atom, an amino group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group which may have a substituent. basis,
Aryl group, -CON HR.

group, -CORs group, -Nl-I CORto group, or -NH8O2RIO group.

2 represents a nitrogen atom, a sulfur atom, or an oxygen atom. n represents 1 when Z is a nitrogen atom, and represents O when Z is an oxygen atom or a sulfur atom.

R6, R7, R8, R9 and Rho each represent an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a cycloalkyl group or an aryl group which may have a substituent.

To further explain the general formula [I[1] in detail, the alkyl group represented by X and Y has 1 to 18 carbon atoms.
Preferred examples include methyl group, ethyl group, propyl group, butyl group, octyl group, benzyl group, etc., and examples of cycloalkyl groups include cyclohexyl group,
The cyclopentyl group, etc., and the alkenyl group preferably have 2 to 18 carbon atoms, such as allyl group,
Examples of the aryl group include a phenyl group and a naphthyl group.

Furthermore, the alkyl group represented by R6, R7, R8, R9 and Rho is a straight chain or branched one having 1 to 18 carbon atoms, such as a methyl group, ethyl group, propyl group, butyl group, hexyl group, etc. Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group, and examples of the alkenyl group include a group having 2 to 1 carbon atoms.
8 is preferred, and examples thereof include allyl group, octenyl group, octadecenyl group, etc., and examples of the aryl group include phenyl group, naphthyl group, etc.

Moreover, the above X, Y, Rs, R7, Ra, Rs and R
The alkyl group, cycloalkyl group, alkenyl group, and aryl group represented by +o may each have a substituent, and examples of such substituents include alkyl group, cycloalkyl group, aryl group, and alkenyl group. , a halogen atom, a nitro group, a cyam L mercapto group, an amino group, a carboxyl group, a hydroxyl group, and the like.

Furthermore, the compound represented by the general formula [13] of the present invention exhibits the following tautomerism, and the present invention also includes these tautomers.

~□NN-N1-1 Examples of specific compounds represented by the general formula [11[] are listed below, but the present invention is not limited thereto.

fil-1m-2 11-311t-4 [[1-7l11-8 m-9lll-10 II-110l-12 In-13l11-14 m-1511-16 III-17[1-18 IN IN m-191T+- ri11 ■-24 -N 1f-25 ■-26 ■-27 ■-28 ll-29 ■-30 ■-31 ■-32 ff-33 ■-34 ■-35 ■-36 ■-37 ■-39 ■ -41 ■-43 ■-44 ■-45 ■-49 ■-50 ■-51 ■-52 ■-53 ■-54 -s s ■-56 ■-58 ■-60 The above compounds are generally known. , for example, JP-A-51-107129, JP-A-4G-102621, JP-A-55-59463, JP-A-59-124333.
No. 1, and British Patent No. 1.204.623.

Furthermore, the general formula [11[
Examples of mercapto compounds other than those represented by
For example, the following compounds can be mentioned.

■-1■-2 ■-3N-4 111-5ri'-6 N-8■-9 7-40■-11 ■-12 ff-13W
-14■-15 17-16 ■-17I
Y-18ff-19 ff-201Y-21 The above compound was published in the Journal of Chemical Society (J, Chew, Soc, ) 49.1
748.1927, Journal of Organic
Chemistry LJ, Org, Chew, )
39.2469.1965, JP 50-89034, JP 55-79436, JP 51-102639, JP 55-594634, Ann.
, Chem, ), 44-3.1954, Special Publication No. 40-28496, Chemical Berichte (Chem,
Ber, ) 20.231.1887, U.S. Patent No. 3
, No. 259,976, Chemical and Pharma-
Tikal Piuretan ((:hemica! and
Pharn+aceutica13ulleHn)
(Tokyo) Volume 26, 314 (1978),
Berichte der Deutschen Hemisien Goesersdraft
tscenChemischen Ge5ellsdr
at) 82, (1948), U.S. Pat. No. 2,843.
, No. 491, No. 3.017.270, British Patent No. 9
40.169, Journal of American Chemical Society, 44.1502-1510, etc., for synthesis.

In particular, the above compound is used in combination with the sensitizing dye represented by the general formula [I] when the photosensitive silver halide emulsion is pre-contained in a light-sensitive material consisting essentially of silver chloride. As a result, when a bleach-fixing process is performed following a color development phenomenon, the ratio of color developing solution mixed into the bleach-fixing solution increases during the running process, and the pH of the bleach-fixing solution increases. It also has the advantage of being less prone to fogging. Among them (IV-14) to (IV-
The mercaptotetrazole compounds represented by 21) are most preferred.

These nitrogen-containing heterocyclic mercapto compounds may be added to the color developing solution or to the light-sensitive material, but it is preferable to include them in the light-sensitive material. When added to the color developing solution, 10-6 to 10% of the color developing solution is added.
1o → mole.

The nitrogen-containing heterocyclic mercapto compound of the present invention can be added to a light-sensitive silver halide emulsion layer and/or a non-light-sensitive photographic constituent layer, but it is preferably added to a light-sensitive silver halide emulsion layer. .

The nitrogen-containing heterocyclic mercapto compound of the present invention may be contained in two or more types, and may be contained in two or more different layers. These nitrogen-containing heterocyclic mercapto compounds of the present invention are generally used in an amount of 10-8 mol to 10-4 mol, preferably 10-7 mol to 10-5 mol, per 112.

Further, the nitrogen-containing heterocyclic mercapto compound of the present invention may be added as an alkali metal salt, such as a sodium salt, potassium salt, lithium salt, or the like.

In the processing method of the present invention, the antifogging effect due to the combination of the sensitizing dye represented by the general formula [I] and the nitrogen-containing heterocyclic mercapto compound is achieved simply by the spectral sensitization by the sensitizing dye. It is possible not only to reduce fog in a silver halide emulsion layer containing silver halide grains, but also to reduce fog in a different silver halide emulsion layer, which can be easily achieved using conventional techniques. This was something that could not have been predicted.

The silver halide composition of the silver halide grains used in the present invention may be any composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, silver iodide, etc., but preferably Silver chlorobromide is particularly preferred, and silver chloride bromide containing 10 mol% or more of silver chloride is particularly preferred.

There is no particular restriction on the average particle size of the monodisperse silver halide grains, but it is preferably 1.0μI or less, and 0.8μI or less.
More preferably, it is less than μm.

Further, the shape of the silver halide grains used in the present invention may be regular shapes such as cubes, octahedrons, or tetradecahedrons, or irregular shapes such as spherical shapes.

The silver halide emulsion of the photosensitive silver halide emulsion layer is
During or after particle formation, the particles may be doped with platinum, palladium, iridium, rhodium, ruthenium, bismuth, cadmium, copper, or the like.

Furthermore, this silver halide emulsion can be sensitized by chemical sensitization. Specifically, allylthiocarbamide, N,
N-diphenylthiourea, sodium thiosulfate, sulfur sensitizers such as cystine, gold compounds, palladium compounds, platinum compounds, ruthenium compounds, rhodium compounds,
Sensitization can be achieved using noble metal sensitizers, such as iridium compounds, or combinations of such sensitizers. Alternatively, reduction sensitization can be performed using a reducing agent such as hydrogen gas or stannous chloride.

The binder used in the constituent layers of the silver halide photographic light-sensitive material according to the present invention is most commonly gelatin such as alkali-treated gelatin or acid-treated gelatin. Derivative gelatin such as carbamoyl gelatin, albumin,
Agar, gum arabic, alginic acid, partially hydrolyzed cellulose derivatives, partially hydrolyzed polyvinyl acetate, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers of these vinyl compounds can also be used in combination.

After imagewise exposure, the silver halide photographic material of the present invention is subjected to color development treatment to form a dye image. A particularly useful color developing agent used in the color developing solution is N,N-diethyl-p-phenylenediamine ffiMj! ! , N-methyl-p-phenylenediamine hydrochloride, N,N-dimethyldimethyl-p-phenylenediamine hydrochloride, 2-amino-5-(N-ethyl-
N-dodecylamino)-toluene, N-ethyl-N-β
-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-βhydroxylethylaminoaniline [[,4-amino-3-methyl-N
, N-diethylaniline hydrochloride, N-ethyl-N-β-
Examples include hydroxylethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-methoxyethyl-3-methyl-4-aniline-pt-luenesulfonate, and the like.

These coloring agents can be used alone or in combination of two or more. Further, the concentration of the color developing agent can be appropriately selected within the range of 0.01 to 0.05 mol per 12 parts of the color developing solution.

The color developing solution of the present invention may contain various photographic developing additives in addition to the color developing agent and the hydroxylamine compound as a preservative. Such examples include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metaborate,
Alkaline agents such as tribasic potassium phosphate, pH buffers such as sodium hydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, potassium bicarbonate, organic solvents such as methanol, ethylene glycol triethanolamine, etc., as appropriate. It can be selected and used. In the color developer of the present invention, benzyl alcohol as a color development improver is
Although it is preferable not to contain it, it is also possible to contain a small amount.

The amount of benzyl alcohol contained in the color developer is O to 5 vR, preferably O to 3 vR per 12 of the color developer.

In addition to the hydroxylamine compound, a small amount of sulfite M salt such as sodium sulfite or potassium sulfite is used in combination with the color developer of the present invention in order to enhance the storage stability of the color developer over time. preferable. Sulfite is color developer 1! per o, osg~2g1 preferably 0
．． It is used in a range of 1 g to 0.3 g.

The color developer of the present invention may contain a known phenomenon inhibitor as a development inhibitor. Examples include bromides such as sodium bromide and potassium bromide, chlorides such as potassium chloride and sodium chloride, and organic development inhibitors such as penztriazole and benzimidazole.

The effect of the present invention is remarkable when the concentration of the color developing solution of the present invention is about 0.00 mol or more, and especially when the concentration is 0.01 mol or more, the effect of the present invention is achieved when the hydroxylamine compound is used. The effect of suppressing the occurrence of fog caused by rapid processing is extremely large. The term "quick processing" as used herein means that the color development processing time is within 90 seconds.

The temperature of the color developing solution is 20°C to 50°C, preferably 30°C.
~40°C.

In the rapid processing method of the present invention, after forming a dye image by color development, it is necessary to remove undeveloped silver halide and developed image silver by bleach-fixing time.

The bleach-fixing time is within 90 seconds, preferably within 60 seconds.

As the bleaching agent used in the bleaching and fixing solutions, metal complex salts of organic acids are used, such as polycarboxylic acids, aminopolycarboxylic acids, oxalic acid, citric acid, etc., and iron, cobalt,
Coordinated metal ions such as copper are used. Among the above organic acids, the most preferred organic acids include polycarboxylic acids and aminopolycarboxylic acids. These polycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts. Specific examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenediamine-N-(β-oxyethyl)-N, N', N
' -Triacetic acid [4] Propylenediaminetetraacetic acid [5] Nitrilotriacetic acid [6] Cyclohexanediaminetetraacetic acid [7] Iminodiacetic acid [8] Dihyroxyethylglycinene pa < or tartaric acid) [91 Ethyl ether diamine tetraacetic acid [10] ] Glycol ether diamine tetraacetic acid [11] Ethylenediamine tetrabrobionic acid [12]
Phenylenediaminetetraacetic acid [13] Ethylenediaminetetraacetic acid disodium salt [14] Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15] Ethylenediaminetetraacetic acid tetrasodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [171 Ethylenediamine-N- (β-oxyethyl'
) -N,N',N'-Triacetic acid sodium salt [18] Propylene diamine tetraacetic acid sodium salt [19] Nitri-O acetic acid sodium salt [20] Cyclohexanediamine tetraacetic acid sodium salt These bleaches have a rating of 5 to 450! ll#! , more preferably 20 to 2500/l.

In addition to the above-mentioned bleaching agent, the bleach-fixing solution may contain a sulfite salt as a preservative, if necessary. It also includes ethylenediaminetetraacetate iron(III) complex salt bleaching agents, and halides such as ammonium bromide may be added.

As the halides, in addition to ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide, etc. can also be used. can.

Silver halide fixing agents used in bleach-fix solutions include compounds that react with silver halide to form water-soluble complex salts, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate, which are used in ordinary fixing processes. Typical examples include thiosulfates such as, thiocyanates such as potassium thiocyanate, sodium thiocyanate, and ammonium thiocyanate, thioureas, thioethers, and the like. These fixing agents are used in a range where they can be dissolved at 5 g/2 or more, but are generally used at 25 to 250 g/2.

In addition, various pl-1m such as boric acid, borax, monolithium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide are used in the bleach-fix solution. Shocking agents may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants can be contained. In addition, preservatives such as hydroxylamine, i-drazine, bioxylic acid adducts of aldehyde compounds, N,N-dialkylhydroxylamines, organic chelating agents such as aminopolycarboxylic acids, and stabilizers such as nido-O alcohols and nitrates. , methanol, dimethylsulfamide, dimethylsulfoxide, and other organic solvents may be appropriately contained.

Bleach-fix solutions include JP-A No. 46-280 and JP-A No. 45-Sho.
No. 8506, No. 46-556, Belgian Patent No. 770
．． No. 910, Special Publication No. 45-8836, No. 53-985
No. 4, JP-A No. 54-71634 and JP-A No. 49-4234
Various bleaching accelerators such as those described in No. 9 can be added.

The pH of the bleach-fix solution is 5.0 to 9.0, preferably 5.
．． It is in the range of 5 to 8.5.

The processing temperatures for each actual processing step of the silver halide color photographic light-sensitive material according to the present invention, such as color development, bleach-fixing (or bleaching, fixing), and further water washing, stabilization, and drying as necessary, are as follows: 25℃ or higher, preferably 3℃ from the viewpoint of
Preferably, the temperature is 0°C or higher.

The silver halide photographic light-sensitive material of the present invention is disclosed in Japanese Unexamined Patent Publication No. 58-14
No. 834, No. 58-105145, No. 58-1346
No. 34 and No. 58-18631 and patent application No. 58-2
A stabilization treatment as an alternative to water washing as shown in Japanese Patent Application No. 709 and No. 59-89288 may also be performed.

[Examples] Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

Example-1 On a 170Q/f paper support laminated with polyethylene on one side and polyethylene containing 11% by weight of anatase titanium dioxide on the other side, the following layers were sequentially applied on the titanium dioxide-containing polyethylene side. Painted,
Halogen and other prefecture color photographic materials No. 1 to 25 were prepared. Note that the amount added is expressed per 1 volt unless otherwise specified.

Layer 1...1.9 g of gelatin, (1,39 (1 (silver equivalent)) blue-sensitive silver chlorobromide emulsion (Note-1) and 1.2 x 1
0-3 moles of the yellow coupler shown in Y-1, 0.3 g
of the following light stabilizer 5TB-1, 0.050 of the following color stain inhibitor (1-IQ-1), o, sog of di(2-ethylhexyl) phthalate (hereinafter referred to as DOP) and mercapto as shown in Table 1. A layer containing a system compound (0.08m (1/f')).

Layer 2...0.79 gelatin, 15+no irradiation dye (A I-1), 1C) no (
AI-2) and 0.05 g of the above color stain inhibitor)-I
Intermediate layer containing DOP of 0, (150) in which Q-1 was dissolved.

Layer 3...1.25 (+gelatin, 0.22j) green-sensitive silver chlorobromide emulsion (silver chloride composition 70 mol%), 0.3
A layer containing 45 g of magenta coupler (M-1) below and 0.02 g of)-IQ-1 dissolved in 1 DOP.

U4...1,29 gelatin, o, oag HQ-
1 and 05g of ultraviolet absorber (UV-1> dissolved in 0,
Intermediate layer containing 35g DOP.

Layer 5...1.4 g gelatin, 0.200 red-sensitive silver chloride emulsion, 0.45 (0.45 g) dissolved in 0.20 g DOP
] A layer containing the following cyan coupler (C-1) and 0.02Q of HQ-1.

Layer 6...i, ot) gelatin and o, 2og DO
A layer containing UV-1 of 0,301j dissolved in P.

Layer 7: Layer containing 0.5 g of gelatin.

In addition, as a hardening agent, 2,4-dichloro o-6-hydroxy-s-t-lyazine sodium was used in the above layer 4 and layer 7.
0.4Q of each was added immediately before coating.

(Note-1) Blue-sensitive silver chlorobromide emulsion After performing optimal sensitivity fishway chemical ripening on sodium thioriate with a silver chloride composition of 90 mol%, the sensitizing dyes shown in Table-1 (
Spectral sensitization was performed with 5×10 −3 moles per mole of silver halide).

Mountain = Free -← I-1 I-2 V-1 C5H++ (t) Each of the photosensitive materials No. 001 to No. 25 above was internally exposed through an optical wedge and then processed in the following steps.

[Processing steps] [A] [8], [C] Color development 38°C 3 minutes Bleach fixing at 35°C 1 minute
Wash at 34℃ for 1 minute and at 35℃ for 1 minute.
The compositions of the color developer and bleach-fix solution used were as follows: 30-35°C for 2 minutes and 30-35°C for 1 minute.

Color development liquid composition [A] [8], [C] Pure water
8001zo 800iN Ethylene Glycol 151β -Benzyl Alcohol 15 Dai - Preservative *1) 2
g2! J Potassium Bromide 1.2 Q
-Sodium chloride 0.39 2.00 11iI! acid potassium 2,og o,i
g Color developing agent 4.5 a 5 Q Potassium carbonate 25 G 25 g Nitrilotrimethylenephosphonic acid 2o Add 2 g of pure water to make one solution and adjust the pH 10.1 10.2*
1) Preservative ASB Hydroxylamine sulfate/1/2 sulfur? [(H
AS) CN, N-diethylhydroxylamine [I[-3] [Bleach-fix solution] Pure water 60 (hN ethylenediaminetetraacetic acid iron(III)) Ammonium 65 j7 Ethylenediaminetetraacetic acid 2-sodium m 5g Ammonium thiosulfate 859 Sodium bisulfite 10 g Sodium metabisulfite 2 g Ethylenediaminetetraacetic acid 11 -sodium 20 Q Sodium chloride +o g Color development liquid
Add 200 IN pure water to 12
Adjust the pH to 7.0 using dilute sulfuric acid.

Each of the obtained samples was subjected to anti-reflection rjJ using blue monochromatic light.
Density was measured, and sensitivity, gradation, and fog were determined from the characteristic curve [8] corresponding to the yellow dye image. Fog was also measured using green monochromatic light.

The results obtained are not shown in Table 1. In the table, the sensitivity is expressed as relative sensitivity, with the sensitivity when photosensitive material 1 was processed according to processing step [A] being 100.

Moreover, the gradation represents the slope of the characteristic curve of reflection density 0.5 to 1.5.

From the results shown in Table 1, in the color developer [8] using hydroxylamine as a preservative, the color density decreases regardless of the sensitizing dye and the presence or absence of the heterocyclic mercapto compound. However, a decrease in sensitivity and a softening of the gradation are observed.On the other hand, in the color developer [C] using N,N-diethylhydroxylamine as a preservative, a decrease in sensitivity and a softening of the gradation are observed. No softening of contrast is observed, but an increase in fog is observed.

Here, as blue-sensitive silver chlorobromide emulsions, samples containing no sensitizing dye (No. 1 to 5) and samples containing an emulsion sensitized with comparative sensitizing dye-1 (No. 0.6 to 10 ), the effect of fog suppression by the heterocyclic mercapto compound is minute, but samples containing emulsions sensitized with the sensitizing dyes ■-3, I-7, and l-21 (No. 11 to 25
), particularly in the samples containing the exemplified heterocyclic mercap 1-based compounds m-24, ■-40, and ■-46, a remarkable fog-inhibiting effect was observed, and somewhat surprisingly, It can be seen that not only the yellow fog that occurs in the blue-sensitive layer but also the magenta fog that occurs in the green-sensitive layer is effectively suppressed.

Example-2 Example-1 was repeated. However, here, the spectral sensitizing dye used in the blue-sensitive silver chlorobromide emulsion used in layer 1 was changed as shown in Table 2 (5 x 1 per mole of silver halide).
0-3 mol), and further exemplified mercapto compounds are shown in Table 2.
Added to layer 1 and layer 3 as follows.

The obtained samples 26 to 38 were treated in the same manner as in Example-1, and the results shown in Table-2 were obtained.

Table 2 shows comparative sensitizing dye 1 and exemplary sensitizing dye I-3,
A sample in which exemplified mercapto compound m-24, which had the most fog suppressing effect in Example-1, was added to a layer containing a blue-sensitive silver chlorobromide emulsion sensitized with I-7 and ■-21. , [A] and [B
], [C] The results of processing with each color developer are shown. The blue-sensitive layer (
When added to layer 1), the sensitizing dye of [I] and the heterocyclic mercapto compound of [I[] were used together when treated with the color developer of [C], as in Example-1. Although the fog suppressing effect is large, when a heterocyclic mercapto compound is further added to Layer 3, which is a green-sensitive emulsion layer (Sample No.
, 31, 34, and 37), it can be seen that the yellow fog suppressing effect is remarkable.

Further, in sample F1, a heterocyclic mercapto compound was separately added to layer 1 and layer 3 (blue-sensitive layer and green-sensitive layer).
It can be seen that in No. 38, both yellow fog and magenta fog were largely suppressed when treated with color developer [C].

Example-3 Sample No. 26, No. 627, No. used in Example-2
, 35, No., 36 after imagewise exposure, processing step [8]
, [C] was processed in the same manner.

However, here, the DH of each color developer [8] and [0] used in processing steps [8] and [C] is 9.
．． 7.10.1.10.5. The gradation (slope of reflection density from 0.5 to 1.5) was determined from the characteristic curve obtained from the reflection density determination of the obtained sample using blue monochromatic light and is shown in Table 3.

From the results shown in Table 3, the sample using Comparative Sensitizing Dye 1 showed that when N,N-diethylhydroxylamine was used as a preservative in the color developer, due to the addition of a heterocyclic mercapto compound, [C] , the change in gradation increases when l)H of the color developer changes.

On the other hand, sample No. 36 of the present invention shows little variation in gradation with respect to the change (+1).

Example 4 The following layers were sequentially coated on the reflective support used in Example 1 to obtain silver halide color photographic materials No. 39 to 6.
2 was created.

Layer 1...1.4 g of gelatin, 0.3 g of blue-sensitive silver chlorobromide emulsion (Note-2) and 1. IX 10-3 moles of yellow coupler (Y-2>, 0.3 g of (STB-
1) Dissolve 0.19 g of N,N-diethyl-(2,5-diC-amylphenoxy)acetamide in IJ (HQ-1), and 0.5 g of dinonyl phthalate (DNP). Containing layer.

Layer 2: Same as layer 2 of Example-1.

Layer 3...1.25 (M-1) of gelatin, 0.26 g of green-sensitive silver chlorobromide emulsion (Note-3), 0.450 (M-1) dissolved in 0.3 g of DOP, 0 .20(+(S
TB-2>, o, iog (STB-3) and 0.0
Layer containing 2g of (+-(Q-1).

Layer 4: Same as H4 of Example-1.

Layer 5...1.4 g of gelatin, 0.20 g of red-sensitive silver chlorobromide emulsion (Note-4), 45 g of (C-1) dissolved in 0.209 DOP, 0.10 g of ( STB-
1) and a layer containing 0.021;l of (HQ-1).

Layer 6: Same as layer 6 of Example-1.

Layer 7: Same as layer 7 of Example-1.

(STB-2) (STB-3> (Y-2) C,! (Note-2) Blue-sensitive J! Silver bromide emulsion II chloride! Cubic chlorobromide limited emulsion with a composition of 99.5T nil% ( After subjecting the sensitizing dyes shown in Table 4 (5X10-3'E-L per 111 moles of halogenide) to the optimal sensitivity fishway chemical ripening using sodium thia I sulfate and potassium chloraurate, ) and mercapto compounds (2 x 10-4 mol per mol of silver halide) (Note 3) Green-sensitive silver chlorobromide emulsion A cubic warm silver bromide emulsion with a silver chloride composition of 99.1 mol% (average grain size 0.40 μm) with sodium thiosulfate and potassium chloroaurate for optimal sensitivity, the following sensitizing dye (GSD-1) (3 µm/mol of silver halide)
X10-3 mol) and a mercapto compound shown in Table 4 (2.5X 10-4 mol per mol of silver halide) were added.

(Note-4) Red-sensitive silver chlorobromide emulsion A cubic silver chlorobromide emulsion (average grain size 0.42 μm) with a silver chloride composition of 99.6 mol% was adjusted to the optimum sensitivity point by sodium thiosulfate and potassium chloroaurate. The following red sensitizing dye (R8D-1) (silver halide 1
0.8 x 10-' mole per mole) and mercapto compounds shown in Table 4 (3 x 1 mole per mole of silver halide)
0-4 mol) was added.

N(C2HI)-5D-1 The obtained sample was subjected to tip exposure through an optical wedge and then processed according to the following processing steps.

[Processing process] [D], [E] [・F], [G]
Color development phenomenon 35℃ 45 seconds bleaching constant @
Wash with water at 35℃ for 45 seconds 3
The composition of the color developing solution used for 2 minutes at 0 to 34°C is as follows.

Treatment steps [D], ['E] Treatment steps [F], [G]
Pure water 8001Q
800112 Triethanolamine
io g 1o glt
! Acid hydroxylamine 1.8 g
-N,N-diethylhydroxylamine (II-3)
5Cl sodium chloride
2.8 (12,,8(1 1a 1 um 0.3 (
10.3g Color developing agent* 4.5 Q
4.5 Q ethylenediaminetetraacetic acid 1
．． 0 g 1.0 g Potassium carbonate 27 Q 2
7 Q Diaminostilbene optical brightener 2g
Add 2g of pure water to 1r and adjust the pH to 1.

*Color developing agent: N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfur M salt The following bleach-fix solution was used.

Processing steps [D], [F]...Processing steps [E] described in Example-1 Bleach-fix solution used in processing steps [D] and [F] and color developer used in processing step [E] Mix the solutions in a 1:1 ratio and adjust the pH to 7.0.

Processing step [G] Mix the bleach-fix solution used in processing steps [D] and [F] and the color developing solution used in processing step [G] at a ratio of 1:1, and adjust the pH to 7.0. do.

Reflection density measurements were performed on each of the obtained samples using monochromatic blue light, and sensitivity, gradation, and fog were determined from the characteristic curves.

The results are shown in Table 4t.

In the table, the sensitivity is expressed as a relative sensitivity when the sensitivity when comparative sample 39 is treated according to treatment step [F] is set as 100.

From the results shown in Table 4, it was found that the mercapto compounds ■-24, rV-14, a and IV-20 were used in the same manner as in Example-1.
The sample using the blue sensitizing dye of the present invention in combination with the processing step [D
], [Eco, [F], and [Gco. Samples (39-41) using 2,3) and the sensitizing dye of the present invention, but samples (45-47.51) using no nitrogen-containing heterocyclic mercapto compound of the present invention;
-53.57-59) have low fog values in processing steps [D] and [E], but in processing steps [F] using N,N-diethylhydroxylamine as a preservative for the color developer. ], an increase in fog is observed, especially when a color developer is added to the bleach-fix solution (processing step [G]).

It can be seen that the samples related to the present invention also have a low fog value in the treatment step CG], and the effect is particularly large when mercaptotetrazoles IV-146 and IV-20 are used.

Example-5 In samples 39 to 62 used in Example-4, half of the mercapto compound used for fat 1 was further added to layer 2.
Samples 63 to 86 were prepared and treated in the same manner as in Example-4 according to treatment steps [D], [E], [F], and [G] described in Example-4. However, here, the preservative used in the color developer used in Example-4 was replaced with ll-3.
Example 4 was repeated using ■-25 (10(1) per 12 parts of the color developing solution) in place of 1. The results obtained are shown in Table 5.

From the results shown in Table 5, the same effect as in Example 4 was obtained even when ■-25 was used as a preservative for color developer.
I know that it will happen.

Claims (1)

[Scope of Claims] After imagewise exposure, a silver halide photographic light-sensitive material having a silver halide emulsion layer containing at least one diffusion-resistant hydrophobic coupler on a support is treated with an aromatic primary amine. In the method of processing with a color developing solution containing a color developing agent, at least one of the silver halide emulsion layers comprises silver halide grains sensitized with a sensitizing dye represented by the following general formula [I]. 1. A method for processing a silver halide photographic light-sensitive material, which comprises processing in the presence of a hydroxylamine compound and a nitrogen-containing heterocyclic mercapto compound represented by the following general formula [II]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z_1 and Z_2 are respectively thiazole nucleus,
Represents the atomic group necessary to form a benzothiazole nucleus, selenazole nucleus, benzoselenazole nucleus, naphthoselenazole nucleus, benzimidazole nucleus, naphthimidazole nucleus, pyridine nucleus, or quinoline nucleus. R_1 and R_2 each represent an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group. R_3 represents a hydrogen atom, a methyl group or an ethyl group. X_1^■ represents an anion, and l is 0 or 1. ] General formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, R_4 and R_5 each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent. However, R_4 and R_5 are not both hydrogen atoms. Furthermore, R_4 and R_5 may be combined to form a ring. ]