JPH02176750A - Processing method for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the white ground property of an unexposed part at the time of a rapid processing by incorporating at least one kind of water soluble non-bleach type dyes into a stabilizer substitutive for washing and specifying the processing time for the stabilization substitutive for washing. CONSTITUTION:The stabilizer substitutive for washing contains at least one kind of the water soluble non-bleach type dyes which are 510 to 560nm in absorption wavelength of an aq. soln. and the processing time for the stabilization substitutive for washing is specified to <=120 seconds. The water soluble magenta dyes of the non-bleaching type are hardly affected by the compd. coexisting in the processing solution, are small in the change of the optical density of the soln. and are stable. The stable white ground performance is, therefore, obtd. The white ground property of the unexposed part of color paper is good in the rapid processing as well in this way and the fungusproofing effect in a stabilizing tank is improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for processing silver halide color photographic light-sensitive materials (hereinafter also referred to as light-sensitive materials). The present invention relates to a method for processing a photosensitive material that improves the whiteness of exposed areas, enhances the anti-high effect, and enables rapid processing.

[Background of the Invention] In general, in order to obtain a color image by processing an imagewise exposed light-sensitive material, the generated metallic silver is desilvered after the color development process, and then washed with water, stabilized or stabilized as an alternative to water washing, etc. A processing step is provided.

However, although photosensitive materials are processed on a running basis in automatic processing machines installed at each photo lab, as part of our efforts to improve our services to users, we have developed and returned them to users on the same day they are received. In recent years, it has become even necessary to return items within a few hours of receiving them, and there is an urgent need to develop rapid processing technology.

As a result, the processing time, process, and temperature of the current major color paper photosensitive materials have reached the following levels. That is, for example, the development time for color photographic paper is 8.5 minutes,
The processing temperature is 33°C and the breakdown of processing time is color development 3.5
It consists of three steps: 1.5 minutes of bleach-fixing, and 3.5 minutes of washing.The system technology involved is U.S. Patent 3,582,
No. 322 and OLS 2,160,87
It is disclosed in No. 2, etc.

More recently, rapid processing of color paper called Process RA-4 (development time is 3 minutes, processing temperature is 35°
The breakdown of processing time is 45 seconds for color development, 45 seconds for bleach fixing.
A method (consisting of three steps of 90 seconds and 90 seconds of stability) has also been proposed by Eastman Kodak Company.

However, if the processing time is shortened in this way, the whiteness of the unexposed areas of the color paper deteriorates, making it substantially difficult to perform rapid processing. Therefore, in order to improve these problems, a method has been proposed in which a photosensitive material using a specific dye is treated with a stabilizing solution containing a hardening agent, as shown in JP-A-61-151538. After various studies, we found that the faster the stabilizing tank is used for processing, the less effective it becomes, due to problems with the structure of the processing machine, the stability of the stabilizing solution itself, and the stability of the dye itself. Furthermore, it was found that the anti-piping effect deteriorated due to components eluted from the photosensitive material in the stabilizing bath.

[Object of the Invention] Therefore, an object of the present invention is to provide a method for processing a photosensitive material in which the whiteness of unexposed areas of a color paper is good even in rapid processing, and the anti-piping effect in a stabilizing bath is improved.

[Structure of the Invention] The processing method of the present invention that achieves the above-mentioned object is to perform a color development treatment on a photosensitive material after imagewise exposure, and then to process it with a processing solution having a fixing ability, and then to stabilize the material as an alternative to water washing without substantially washing with water. When processing with a washing substitute stabilizing solution, the washing substitute stabilizing solution contains at least one water-soluble non-bleaching dye whose aqueous solution has an absorption wavelength of 510 to 560 nm, and the washing substitute stabilizing treatment time is 12
It is characterized by being 0 seconds or less.

The embodiment of the present invention described above is characterized in that the water-soluble non-bleaching dye is a compound represented by the general formulas [I] to [m] below.The present invention will be described in further detail below.

The non-bleached water-soluble magenta dye used in the present invention is hardly affected by compounds coexisting in the processing solution, and the change in optical density of the solution is extremely small and stable. Therefore, unlike conventional dyes, it can provide stable white background performance.

Non-bleaching water-soluble dyes preferably have general formulas [I] to [m
] These are acidic azo dyes and azomethine dyes.

The compound represented by the general formula [11% Formula % In] Z'=Z' The compound represented by the general formula [II] is further represented by the general formula [IV]
The compounds shown below are preferably used.

General formula [TV] In the formula, R', I+2. R3, R', 115. R6 and R
7 represents a hydrogen atom or a substituent, and may be the same or different from each other.

M represents a hydrogen atom or a cation.

nl and R2 each represent an integer from 0 to 2, but n'+n''
≧2.

The compounds represented by the above general formulas [II, [II], [■] and [■] will be explained in detail below.

In the general formula [II, the aryl group represented by Ar' includes a phenyl group and a naphthyl group. These groups can be substituted with any group, specifically unsubstituted alkyl groups (for example, chained/branched groups such as methyl, ethyl, isopropyl, etc.), substituted alkyl groups (for example, pencil, phenethyl, sulfomethyl, hydroxyethyl, etc.). ), alkoxy groups (e.g., methoxy, methoxyethyl, methosulfonyl, pencyloxy, etc.), aryloxy groups (e.g., phenoxy, P-methylphenoxy, 4-naphthoxy, etc.), hydroxy groups, amino groups (e.g. amino,
Substituted or unsubstituted groups such as methylamino, sulfomethylamino, and phenylamino), carboxy groups, cyano groups, and halogen atoms (e.g., atoms such as fluorine, chlorine, bromine, and iodine)
, carbamoyl group (e.g. carbamoyl, substituted/unsubstituted groups such as N-methylcarbamoyl), sulfamoyl group (e.g. sulfamoyl, N-methylsulfamoyl,
Substituted/unsubstituted groups such as N-phenylsulfamoyl, N,N-pentamethylene-sulfamoyl, etc.), acylamino groups (e.g., acetylamino, methanesulfonylamino, benzoylamino, etc. groups), heterocyclic groups (e.g., 2
-thienyl, 2-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl, etc.), 21-ro groups, alkenyl groups (e.g. allyl groups), sulfonyl groups (e.g. methanesulfonyl, benzenesulfonyl, toluenesulfonyl, etc.) ), azo groups (e.g., phenylazo, P-methoxyethylaso, P-dimethylaminophenylazo, etc.), acyl groups (e.g., acetyl, benzoyl, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl, etc.) ), unsubstituted aryl groups (e.g. phenyl,
naphthyl, substituted aryl groups (eg, sulfophenyl, 3-hydroxyphenyl, etc.).

The naphthyl group represented by Ar2 can be substituted with any group as mentioned for Ar'.

In the above general formula [II], the alkyl group represented by [10] is an unsubstituted alkyl group (for example, methyl,
(linear or branched groups such as ethyl, isopropyl, t-methyl), substituted alkyl groups (such as benzyl 1, sulfopencyl, disulfopencyl, sulfopropyl, hydroxyethyl, cyanoethyl, carboxymethyl, ethoxycarbonylmethyl, etc.) Aryl groups include unsubstituted aryl groups (for example, phenyl, naphthyl, etc.), substituted aryl groups (for example, p-sulfophenyl, 2.
5-disulfophenyl, p-sulfamoyl, p-sulfomethylphenyl, 2.5-bis-sulfomethylphenyl, etc.), and examples of heterocyclic groups include sulfolanyl group, 2-pyridyl group, piperazinyl group, Examples include groups such as 6-sulfo-2-benzothiazolyl group.

The substituent represented by R11 includes any arbitrary group, and specifically, unsubstituted alkyl groups (for example, methyl,
Chain/branched groups such as ethyl and isopropyl), substituted alkyl 2! (e.g., groups such as pensylphenethyl), alkoxy groups (e.g., groups such as methoxy, benzyloxy, etc.), aryloxy groups (e.g., groups such as phenoxy, P-methylphenoxy, 4-naphthoxy, etc.), hydroxy groups, amino groups (e.g., amino , methylamino, sulfomethylamino, phenylamino, etc.), carboxy groups, cyano groups, carbamoyl groups (e.g. carbamoyl,
Substituted/unsubstituted groups such as N-methylcarbamoyl), acylamino groups (e.g. acetylamino, methanesulfonylamino, benzoylamino, etc.), heterocyclic groups (e.g. 2-thienyl, 2-pyridyl, 2-pyrimidinyl,
2-pentthiazolyl, etc.), acyl groups (e.g., acetylbenzoyl, etc.), alkoxycarbonyl groups (e.g., ethoxycarbonyl, etc.), unsubstituted aryl groups (e.g., phenyl, naphthyl, etc.), substituted Examples include aryl groups (eg, sulfophenyl, 3-hydroxyphenyl, etc.).

As the alkyl group represented by H+2, llJ+3,
Unsubstituted alkyl groups (e.g. straight chain, branched groups such as methyl, ethyl, isopropyl, t-methyl), substituted alkyl groups (e.g. pencil 1, sulfopencyl, disulfopencyl, sulfopropyl, hydroxyethyl, cyanoethyl, aryl groups include unsubstituted aryl groups (e.g. phenyl, naphthyl, etc.) and substituted aryl groups (e.g. p-sulfophenyl, 2,5-disulfophenyl). , p-sulfamoyl, p-sulfomethylphenyl,
25-bis-sulfomethylphenyl, etc.).

Examples of the halogen atom represented by R14 include a fluorine atom, a chlorine atom, and a bromine atom; examples of the alkyl group include lower alkyl groups having 1 to 4 carbon atoms (e.g., methyl, ethyl, etc.); has 1 or more carbon atoms
4 lower alkoxy groups (eg, methoxy, propyloxy, etc.).

In the above general formula [H], the substituents represented by R20 and R21 have the same meaning as R11 described above.

111fi, R111 has the same meaning as 112, R1:l described above, and R24 has the same meaning as R14, described above.

In the above general formula [IV], l+', R'', R3
, Ij'R5R6[7 can be selected from any substituent, and specifically, unsubstituted alkyl groups (for example, chained/branched 2 groups such as methyl, ethyl, isopropyl, etc., substituted alkyl groups ( For example, groups such as pencil, phenethyl, sulfomethyl, hydroxyethyl, etc.), alkoxy groups (such as methoxy, methoxyethyl, methosulfonyl, benzyloxy, etc.), aryloxy groups (such as phenoxy, P-methylphenoxy, 4-naphthoxy, etc.), groups), hydroxy groups, amine groups (e.g. substituted or unsubstituted groups such as amino, methylamino, sulfomethylamino, phenylamino, etc.), carboxy groups, cyano groups, halogen atoms (e.g. fluorine, chlorine, bromine, iodine, etc.) atom),
Carbamoyl group (e.g. substituted/unsubstituted groups such as carbamoyl, N-methylcarbamoyl, etc.), sulfamoyl group (
For example, sulfamoyl, N-methylsulfamoyl, N
-Phenylsulfamoyl, N,N-pentamethylene-
(substituted/unsubstituted groups such as sulfamoyl), acylamino groups (such as acetylamino, methanesulfonylamino,
various prefectures such as pensoylamino), heterocyclic groups (e.g. 2-
thienyl, 2-pyridyl, 2-pyrimidinyl, 2-pentthiazolyl, etc.), nitro group, alkenyl group (e.g. allyl group), sulfo [compound examples] Nyl group (e.g. methanesulfonyl, pencenesulfonyl, toluene) sulfonyl, etc.), aso groups (e.g., phenylazo, P-methoxyphenylazo, P-dimethylaminophenylazo, etc.), acyl groups (e.g., acetyl, benzoyl, etc.), alkoxycarbonyl groups (
Examples include groups such as ethoxycarbonyl), unsubstituted aryl groups (such as phenyl and naphthyl), and substituted aryl groups (such as sulfophenyl and 3-hydroxyphenyl).

The naphthyl group represented by "Ar" can be substituted with any group as mentioned for Ar'.

Next, specific examples of compounds represented by general formulas [I] to [III] of the present invention will be illustrated.

However, the present invention is not limited to these.

03Na N=N The compound represented by the general formula [I] can be easily synthesized by diazo coupling with a sulfo-substituted naphthol derivative such as H acid or G acid. Most of them are available as acid dyes from dye manufacturers. Also, general formula [11]
or [ml] is obtained by coupling an aromatic-class amine with the corresponding coupler under oxidizing conditions, and is disclosed in JP-A-80-32851 and Go-1.
The method described in No. 8.8587 can be used.

As a method of processing with a stabilizing solution in the presence of a compound represented by the general formula [I] to [ml, it may be added directly to the stabilizing solution, or it may be added to a prebath and attached to the photosensitive material. You can also try to bring it in.

Among the compounds represented by the above general formulas [I] to [I[I], the compound represented by the general formula [I] is more preferable, and two or more of these compounds may be used in combination. do not have.

In addition, the amount of replenishment of the processing solution during continuous processing is preferably one replenishment amount for each set of the color development step and bleach-fixing step before the stabilization treatment, or 1 sentence per 1 m' of the photosensitive material.
More preferably, it is 600 mJ1 or less. The amount of stabilizing solution to be refilled is 21 per m' of photosensitive material.
The length is preferably 1 sentence or less, more preferably 1 sentence or less, and most preferably 50011 JL or less.

In the present invention, the stabilizing solution preferably contains a sulfite, and the sulfite may be any organic or inorganic substance as long as it releases sulfite ions, or preferably an inorganic salt. Specific compounds include sodium sulfite, potassium sulfite, ammonium sulfite, ammonium orthosulfite, potassium bisulfite, sodium bisulfite, sodium metabisulfite, potassium metabisulfite, ammonium metabisulfite, and hydrosulfide.

The sulfite is present in the stabilizing solution in an amount of at least 1 x 10-'
It is preferable that the amount is added to be mol/i,
More preferably, it is added in an amount of 5 x 10-' moles/or ~10-1 moles/state.

Although it may be added directly to the stabilizing solution, it is preferable to add it to the stable replenisher.

In the present invention, the number of stabilizing tanks may be 1 to 4, but the effect of the water-sprinkling invention is more pronounced when the number of stabilizing tanks is small.

Particularly desirable compounds to add to the stabilizer used in the present invention include ammonium compounds.

These are supplied by ammonium salts of various inorganic compounds, including ammonium hydroxide, ammonium bromide, ammonium carbonate, ammonium chloride, ammonium hypophosphite, ammonium phosphate, ammonium phosphite, and fluoride. Ammonium, acidic ammonium fluoride, ammonium fluoroborate, ammonium arsenate, ammonium bicarbonate, ammonium hydrogen fluoride, ammonium hydrogen sulfate, ammonium sulfate, ammonium iodide, ammonium nitrate, ammonium pentaborate, ammonium acetate, ammonium adipate, tricarboxylic laurate Ammonium acid, ammonium benzoate, ammonium carbamate, ammonium citrate, ammonium diethyldithiocarbamate, ammonium formate, ammonium hydrogen malate, ammonium hydrogen oxalate, ammonium phthalate, ammonium hydrogen tartrate, ammonium thiosulfate, ammonium sulfite, ethylenediaminetetraacetic acid Ammonium, ferric ammonium ethylenecyaminetetraacetate, ammonium lactate, ammonium malate, ammonium maleate, ammonium oxalate, ammonium phthalate, ammonium picrate, ammonium pyrrolidine dithiocarbamate, ammonium salicylate, ammonium succinate, ammonium sulfanilate , ammonium tartrate, ammonium thioglycolate, 2,4,1t-)linitrophenol ammonium, and the like. These C may be used alone or in combination of two or more.

The amount of ammonium compound added is 0.00 per inch of stabilizing liquid.
It ranges from 1 mol to 1.0 mol, preferably 0.00 mol.
It is in the range of 2 to 2.0 moles.

In the present invention, the pH of the stabilizer is preferably in the range of 3.0 to 8.5, and further preferably adjusted to pH 3.5 to 8.0 in order to obtain the desired effects of the present invention.

Further, in the present invention, it is particularly preferable for the stabilizer to contain a chelating agent having a chelate stability constant of 8 or more for iron ions.

Here, the chelate stability constants are: L, G, 5ille
N.A.E. Martell, “5tabilit
y Con5tants of ) Ital-ion
Complexes, The Chemica
l 5ociety.

London (1984), Chabere, S.
? A. Ejlarte11, “Organic S
Equestering Agents, Wile
y (1959) etc. means a constant generally known.

Examples of chelating agents having a chelate stability constant of 8 or more for iron ions that are preferably used in the stabilizing liquid include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds.

Note that the above-mentioned iron ion means ferric ion (Fe3.).

Specific examples of compounds of chelating agents having a chelate stability constant of 8 or more with ferric ions include, but are not limited to, the following compounds. Namely, ethylenediaminediorthohydroxyphenylacetic acid, diaminopropanetetraacetic acid, nitrilotriacetic acid, hydroxyethylenediaminetriacetic acid, dihydroxyethylglycine, ethylenediaminediacetic acid, ethylenediaminenipropionic acid, iminodiacetic acid, diethylenetriaminepentaacetic acid, hydroxyethyliminodiacetic acid, diamino Propanoltetraacetic acid, transcyclohexanediaminetetraacetic acid, glycol ether diaminetetraacetic acid, ethylenediaminetetrakismethylenephosphonic acid, nitrilotrimethylenephosphonic acid, l-hydroxyethylidene-1,1-diphosphonic acid, 1,1-diphosphonethane-2-carboxylic acid acid, 2-phosphonobutane 1.2.4-)licarponic acid, l-hydroxy-1-phosphonopropane-1,2,3-)licarponic acid, catechol-3,5-diphosphonic acid, sodium pyrophosphate, tetrapolyline and sodium hexametaphosphate, particularly preferably diethylenetriaminepentaacetic acid, nitrilotriacetic acid, nitrilotrimethylenephosphonic acid, and 1-hydroxyethylidene-1,1.
-diphosphonic acid, among which l-hydroxyethylidene-1,1-diphosphonic acid is most preferably used.

The usage amount of the above Kiri-1 agent is 0.01 to 0.01 per liter of stabilizer.
Good results are obtained with an amount of 50 g, preferably between 0.05 and 20 g.

Other commonly known compounds that can be added to the stabilizer include polyvinylpyrrolidone (PVPK-15, ni-30, ni-110), organic acid salts (citric acid, acetic acid,
succinic acid, oxalic acid, benzoic acid, etc.), pH adjusters (
phosphates, borates, hydrochloric acid, sulfuric acid, etc.), fungicides (phenol rust conductors, catechol derivatives, imidazole derivatives, triazole derivatives, thiabendazole derivatives, organic halogen compounds, etc.), and other slime control agents in the paper and pulp industry. (known antifungal agents, etc.) or optical brighteners, surfactants, preservatives, Bi, Mg, Z
There are metal salts such as n, Ni, AJl, Sn, T1, Zr, etc., but these compounds are necessary to maintain the pH of the stabilizing bath according to the present invention, and also to improve the stability of color photographic images during storage and the prevention of precipitation. Any compound may be used in any combination as long as it does not adversely affect the development.

The processing temperature during stabilization treatment is 15°C to 70°C.
1 Preferably, the temperature is in the range of 20°C to 55°C. Further, in the present invention, it is essential that the processing time is 120 seconds or less, preferably 100 seconds or less, more preferably 3 seconds to 90 seconds, and most preferably 6 seconds to 50 seconds. When the stabilization treatment time exceeds 120 seconds, the effect of the dye of the present invention is small. After the stabilization treatment according to the present invention, no water rinsing treatment is required at all, but rinsing with a small amount of water in a very short time, surface cleaning, etc. can be optionally performed as necessary.

In a preferred embodiment of the present invention, the presence of a soluble iron salt in the stabilizing solution is preferable in order to achieve the effects of the present invention, and examples of the soluble iron salt include ferric chloride, ferrous chloride, ferric phosphate, Ferric bromide, 2% nitric acid, inorganic iron salts such as ferrous nitrate and ferric ethylenediaminetetraacetic acid, ferric 1-hydroxyethylidene-1,1-diphosphonate, 1-hydroxyethylidene-1, Ferrous 1-diphosphonate, ferrous ethylenediaminetetraacetate, ferric diethylenetriaminepentaacetate, ferrous diethylenetriaminepentaacetate, ferric citrate, ferrous citrate, ferric ethylenediaminetetramethylenephosphonate , organic acid iron salts such as ferrous ethylenediaminetetramethylenephosphonate, ferric nitrilotrimethylenephosphonate, ferric nitrilotriacetate, and ferrous nitrilotriacetate. These organic acid iron salts may be of free acid type, sodium salt, potassium salt, ammonium salt, lithium salt, or alkylammonium salt (triethanolammonium salt, trimethylammonium salt, tetramethylammonium salt, etc.).

In the present invention, organic acid iron salts are more preferred as soluble iron salts.

These soluble iron salts should be present in the stabilizing solution at least 5 x 10-3
used at a concentration of mol/state, preferably 8 x 1
It ranges from 0-3 to 150X 10-3 mol/state.

More preferably it is in the range of +2X 10-3 to 100X40-3 mol/state.

In addition, these soluble iron salts may be added to the stabilizing solution (tank solution) by adding them to the stabilizing solution replenisher, or they can be added to the stabilizing solution (tank solution) by being eluted from the photosensitive material in the stabilizing solution.
It may be added to the stabilizing solution (tank solution) by attaching it to the photosensitive material to be processed from the pre-bath and bringing it there.

In the color developing solution used in the present invention, hydroxylamine and a hydroxylamine derivative represented by the general formula [H-III, which is a derivative thereof, are used as a preservative. Preference is given to using the hydroxylamine conductor shown below.

General Formula [H-n] In the formula, R4 and R5 each represent an alkyl group or a hydrogen atom. However, both R4 and R5 are not hydrogen atoms at the same time. Further, R4 and R5 may form a ring.

In the general formula [H-III, R4 and R5 are not hydrogen atoms at the same time, but each represents an alkyl group or a hydrogen atom, but the alkyl groups represented by R4 and R5 may be the same or different, and each has a carbon number 1 to 3 alkyl groups are preferred. The alkyl groups of R4 and R5 include those having substituents, and R4 and R5 may be combined to form a ring, for example, a heterocyclic ring such as piperidine or morpholine.

Specific examples of the hydroxylamine compound represented by the general formula [H-rl] include U.S. Pat. No. 3,287,125, U.S. Pat.
It is stated in the number etc.

The concentration of the compound represented by H-III of the present invention in the color developing solution is usually 0.2 g #1 to 50 g/i, preferably 0.5 g #L to 30 g/l, more preferably Ig / polished ~ 15g/mata.

The color developing solution used in the present invention has the general formula [H-II
'] and at least one compound selected from the compound represented by the general formula [H-■'1 (hereinafter,
It is preferable to contain a chelating agent of the present invention).

General formula [H-II'l n1 General formula [H-m'1 General formula [H-II'], [H-m'l R1, R
2, R3 and R4 are each a hydrogen atom, a halogen atom,
Sulfonic acid group, alkyl group having 1 to 7 carbon atoms, -〇R5,
-GOOR6, represents an integer. Further, R5, R6, R7 and R8 each represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

However, when R2 represents -OH or a hydrogen atom, R1 is a halogen atom, a sulfonic acid group, an alkyl group having 1 to 7 carbon atoms, -○R5, and the alkyl group represented by R1, R2, R3, and R4 is, for example, Methyl group, ethyl group, 1so-propyl group,
Examples include n-propyl group, t-butyl group, n-butyl group, hydroxymethyl group, hydroxyethyl group, methylcarboxylic acid group, benzyl group, etc., and examples of the alkyl group represented by Rs, Rh, R1 and R8 include the above. It has the same meaning, and further examples include octyl group.

Examples of the phenyl group represented by R1, R2, R3 and R4 include a phenyl group, a 2-hydroxyphenyl group, and a 4-7 minophenyl group.

Typical specific examples of the chelating agent of the present invention are listed below, but the invention is not limited thereto.

(H-n'-1) (H-11'-2) (H-11'-3) (H-II'-4) (H-11'-5) (H-11'-El) (H -n' -7) (H-II' -8) (H-m' -1) 4-isopropyl-1,2-dihydroxybenzene 1.2-dihydroxybenzene-3,5-disulfonic acid 1.2.3 -) dihydroxybenzene-5-carboxylic acid 1.2.3-) dihydroxybenzene 5-carboxymethyl ester 1.2.3-trihydroxybenzene 5-carboxy-n-butyl ester 5-tert-butyl-1,2, 3-) Dihydroxybenzene 1.2-dihydroxybenzene-3,5,8 trisulfonic acid 1.2-dihydroxybenzene-3,4,5 trisulfonic acid 2.3-dihydroxynaphthalene-6-sulfonic acid (H-III'- 2) 2,3.8-)lihydroxynaphthalene-6-sulfonic acid (H-m'-3) 2.3-dihydroxynaphthalene-6-carboxylic acid (H-m'-4) 2.3-dihydroxy-8- Impropyl-naphthalene (H-m'-5) 2,3-dihydroxy-8-chloro-naphthalene-6-sulfonic acid Among the above compounds, a compound particularly preferably used in the present invention is 1,2-dihydroxybenzene- 3,
Examples include 5-disulfonic acid, which can also be used as alkali metal salts such as sodium salts and potassium salts.

In the present invention, the chelating agent of the present invention can be used in an amount of 5+ag to 20g per developer solution,
Preferably 10 mg to 10 g, more preferably 20+
Good results are obtained by adding between wg and 3g.

The chelating agent of the present invention may be used alone or in combination with two
The above may be used in combination. Furthermore, aminopolyphosphonic acids such as aminotri(methylenesulfonic acid) or ethylenediaminetetraphosphoric acid, oxycarboxylic acids such as citric acid or gluconic acid, phosphonocarboxylic acids such as 2-phosphonobutane-1,2,4 tricarboxylic acid, tripolyline Other chelating agents such as acids or polyphosphoric acids such as hexametaphosphoric acid may be used in combination.

The color developing agent used in the color developer of the present invention is preferably a p-phenylenediamine compound having a water-soluble group.

p-phenylenediamine compound having a water-soluble group;
Compared to p-phenylenediamine compounds that do not have water-soluble groups such as N,N-diethyl-p-phenylenediamine,
Not only does it have the advantage of not causing contamination of photosensitive materials and does not cause skin irritation, but it also has the advantage that the object of the present invention can be effectively achieved by combining it with the compound represented by the general formula [I]. can be achieved.

Examples of the water-soluble group include p-phenylenediamine compounds [exemplified color developing agents having at least one amine group or benzene nucleus on the benzene nucleus, and a specific example of the water-soluble group is (CI2). -CH20H1 (CI2)m-NH3O2-(CI2)n-C:)I3
, ((I2)'5-O-(CI2)n-CH3, -(C
) I2CH20) ncsH2's, + (m and n each represent an integer of 0 or more, ), -COOH group, -
3(13)1 group etc. are mentioned as preferable ones.

Specific examples of color developing agents preferably used in the present invention are shown below.

N11゜Among the color developing agents exemplified above, examples No. 1, (A-1), (A-2), and (A-3) are preferred for use in the present invention.
), (A-4), (A-6), (A-7) and (A-1
This is the compound shown in 5).

The above-mentioned color developing agents are usually used in the form of salts such as hydrochloride, sulfate, and P-toluenesulfonate.

The concentration of the color developing agent having a water-soluble group used in the present invention is preferably within the range described below.

The color developer of the present invention may contain the following developer components in addition to the above components.

As an alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, tripotassium phosphate, borax, etc. may be used alone or in combination to achieve the above effects, that is, precipitation. They can be used in combination as long as they do not cause the occurrence of oxidation and maintain the pH stabilizing effect. Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borates are used for purposes such as dispensing needs or to increase ionic strength. can do.

Additionally, inorganic and organic antifoggants can be added as necessary.

Furthermore, a development accelerator can also be used if necessary. Examples of development accelerators include benzyl alcohol, various pyridinium compounds typified by U.S. Pat. No. 2,848,804, U.S. Pat. cationic dyes such as, neutral salts such as thallium nitrate, U.S. Pat.
No. 31,832, No. 2,950,970, No. 2.57
Nonionic compounds such as polyethylene glycol, derivatives thereof, and polythioethers described in 7.127 and Japanese Patent Publication No. 44-9504, organic solvents and organic amines described in Japanese Patent Publication No. 44-9509, ethanolamine, ethylenediamine, diethanolamine, Contains triethanolamine, etc. Also, phenethyl alcohol and others described in U.S. Patent No. 2,304,925,
Examples include acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, and amines.

Furthermore, the color developing solution of the present invention may optionally contain ethylene glycol, methyl selonlube, methanol, acetone, dimethylformamide, β-cyclodextrin, and other substances described in Japanese Patent Publication Nos. 4733378 and 44-9509. The compound can be used as an organic solvent to increase the solubility of the developing agent.

Furthermore, auxiliary developers can also be used with the developing agents. These auxiliary developers include, for example, N-methyl-p-7 minophenol hexulfate (methol), phenidone.

N,N-diethyl-p-aminephenol hydrochloride, N,
N,N,N-tetramethyl-p-phenylenediamine hydrochloride and the like are known, and the amount added is usually 0.
01 g/l to 1.0 g/l is preferred. In addition, competitive couplers, fogging agents, colored couplers,
A development inhibitor-releasing coupler (so-called I) IR coupler), a development inhibitor-releasing compound, etc. can be added.

Furthermore, other anti-stain agents, anti-sludge agents,
Various additives such as a multilayer effect accelerator can be used.

Each component of the above color developing solution can be adjusted by sequentially adding and stirring to a certain amount of water. In this case, components with low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. More generally, a plurality of components, each of which can stably coexist, is prepared in advance in a small container as an aqueous solution or in a solid state, and then added to water and stirred to prepare the color developing solution of the present invention. can be obtained as

In the present invention, the above color developing solution can be used in any pH range, but from the viewpoint of rapid processing, p)l is 11.5 to 1.
The pH is preferably 3.0, more preferably pH 8,
8 to 12.0.

The processing temperature for color development using the color developer of the present invention is arbitrarily selected within a range that achieves the effects of the present invention, but is preferably 30°C or higher, more preferably 33°C or higher.

Conventionally, the color development time was generally about 3 minutes and 30 seconds at 33°C to 38°C, but in the present invention, the shorter the processing time, the more noticeable the effect of the short embedded wood invention is, especially the 2 minute development time. The effect is large within the range.

In the present invention, a compound represented by the following general formula [I a] is preferably used in the color developer.

General formula [Ia] (In the formula, RI8 is a hydroxyalkyl group having 2 to 4 carbon atoms or an alkoxyalkyl group, and R19 and R2O are each a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group having 2 to 4 carbon atoms. (Indicates an alkyl group.) Preferred specific examples of the compound represented by the general formula [1al] are as follows.

Ethanolamine, jetanolamine, 1-reethanolamine, sea-inflopanolamine, 2-methylaminoethanol, 2-ethylaminoethanol, 2-
Dimethylaminoethanol, 2-diethylaminoethanol, 1-diethylamino-2propanol, 3-diethylamino-1-propanol, 3-dimethylamino-
1-Propertool, Isopro and Ruaminoethanol, 3
-Amino-1-propatol, 2-amino-2-methyl-1,3-propanediol, ethylenecyaminetetrainpropanol, pencil ethanolamine, 2-
Amino-2-(hydroxymethyl)-1,3-propanediol, methoxyethylhydroxylamine, ethoxymethylhydroxylamine, methoxypropylhydroxylamine, ethoxypropylhydroxylamine,
Methoxymethylhydroxylamine, ethoxymethylhydroxylamine.

The compound represented by the general formula [Ia] is 1, for example, US Pat.
, No. 823,017 and Japanese Patent Application No. 51-292960 describe its use in color developing solutions.

The amount of the compound of general formula [Ia] used is 0.1 to 50 g1
The amount is preferably 0.5 to 20 g/m, more preferably 0.5 to 20 g/m.

The concentration of the color developing agent in the present invention is 1. Ox is preferably 10-' mol or more, more preferably 1.2x 10-' mol or more, particularly preferably 1.3x 10-' mol or more and 2x 10-' mol or less.

Specific examples of application of the present invention include -bath treatment,
Various other processing methods may also be used, such as a spray method in which the processing liquid is atomized, a web method in which contact is made with a carrier impregnated with the processing liquid, or a developing method using a viscous processing liquid. Alternatively, it is preferable that the processing steps essentially consist of steps such as color development, bleach-fixing, washing with water (including stabilization treatment in place of washing with water), and the like.

In the present invention, it is preferable to provide a bleach-fixing step immediately after the color development treatment step in view of speed and achieving the effects of the present invention.

Although the bleaching agent that can be used in the bleach-fix solution used in the present invention is not limited, it is preferably a metal complex salt of an organic acid. The complex salt contains iron, cobalt,
It is coordinated with metal ions such as copper. The most preferred organic acids used to form such metal complexes of organic acids include polycarboxylic acids or aminopolycarboxylic acids. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

Specific representative examples of these include the following.

[1] Ethylenediaminetetraacetic acid [2] Diethylenetriaminepentaacetic acid [3] Ethylenecyamine-N-(β-oxyethyl)N,N',N'-triacetic acid [4] Propylenecyaminetetraacetic acid [51 Nitrilotriacetic acid [6] ] Cyclohexanediaminetetraacetic acid [7]
Iminodiacetic acid [8] Dihydroxyethylglycine citric acid (or tartaric acid) ]91 Ethyl ethercyamine tetraacetic acid [10]
Glycol etheramine tetraacetic acid [111 Ethylenediaminetetrapropionic acid [12] Phenylenediaminetetraacetic acid [13] Ethylenecyaminetetraacetic acid disodium salt [141 Ethylenediaminetetraacetic acid tetra(trimethylammonium) salt [15J Ethylenethiaminetetraacetic acid Sodium salt [16] Diethylenetriaminepentaacetic acid pentasodium salt [17] [181 [191 Ethylenediamine-N-(β-oxyethyl)-N,N
',N'-Triacetic acid sodium salt Propylenecyamine tetraacetic acid sodium salt Nitriloacetic acid sodium salt [20j Cyclohexanecyamine tetraacetic acid sodium salt These bleaches are used at a rate of 5 to 450 g/Jj, more preferably 20 to 250 g/u. do. The bleach-fixing solution contains a silver halide fixing agent in addition to the above bleaching agent, and if necessary, a sulfite salt as a preservative. Also, a bleach-fixing solution consisting of an ethylenediaminetetraacetate iron (m) acetic acid bleach and a large amount of a halide such as ammonium bromide other than the silver halide fixing agent, and furthermore an ethylenediaminetetraacetate iron (m) acetic acid bleach A special bleach-fix solution or the like having a composition consisting of a combination of a bleaching agent and a large amount of a halide such as ammonium bromide may be used. 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. may also be used. I'll come.

The silver halide fixing agent contained in the bleach-fixing solution is a compound that reacts with silver halide to form a water-soluble complex salt, such as potassium thiosulfate, mono- to lithium thiosulfate, which is used in ordinary fixing processing. , thiosulfate such as ammonium thiosulfate, thiocyanate such as potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate, thiourea, thioether and the like. These fixing agents are used in an amount of 5 g/u or more within the range of dissolution, or generally 70 g/u to 250 g/u.

The bleach-fix solution contains boric acid, borax, sodium hydroxide,
Various pH buffering agents such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate, and ammonium hydroxide may be contained alone or in combination of two or more. Furthermore, various optical brighteners, antifoaming agents, or surfactants may be contained. Also hydroxylamine,
Preservatives such as hydrazine and bisulfite adducts of aldehyde compounds, organic chelating agents such as aminopolycarboxylic acids, stabilizers such as nitroalcohols and nitrates, organic solvents such as methanol, dimethylsulfamide, dimethylsulfoxide, etc. can be included as appropriate.

The bleach-fix solution used in the present invention includes Japanese Patent Application Laid-Open No. 46280,
Japanese Patent Publication No. 45-8506, Japanese Patent Publication No. 46-556, Herky Patent No. 770,910, Japanese Patent Publication No. 45-8836, Japanese Patent No. 5
3-9854, JP-A No. 5471634 and JP-A No. 49-
Various bleaching accelerators such as those described in No. 42349 can be added.

The PLL of the bleach-fix solution is generally PLL 4.0 or higher,
pH! Used at 1°5 or less, preferably pll4.5
As mentioned above, p) is used at a pH of 18.5 or less, and more specifically, the most preferable pH is 5.0 or more and 8.5 or less. The treatment temperature is 80°C or lower, preferably 55°C or lower to prevent evaporation. Bleach-fixing processing time is 3
The time is preferably from seconds to 60 seconds, more preferably from 5 seconds to 50 seconds.

The silver halide grains used in the silver halide color photographic light-sensitive material applied to the present invention may be any of silver chloride, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, and preferably silver chloride or silver chlorobromide. It is chemical silver. Particularly preferably silver chloride is at least 8
Silver halide grains containing 0 mol % or more, particularly preferably 90 mol % or more.

The silver halide emulsion containing the silver halide grains of the present invention contains silver bromide and/or silver halide as a silver halide composition in addition to silver chloride.
or silver iodide, in which case silver bromide is 20
mol % or less, preferably 10 mol % or less, more preferably 3 mol %, and 1 mol % when silver iodide is present.
The content is preferably 0.5 mol% or less. Such silver halide grains containing 80 mol % or more of silver chloride may be applied to at least one silver halide emulsion layer, but preferably they are applied to all silver halide emulsion layers. .

The crystals of the silver halide grains used in the present invention may be regular crystals, twin crystals, or other crystals, and have [1,O,O] planes and []
, 1.1] Any ratio of the planes can be used. Furthermore, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or it may be a layered structure in which the inside and outside are heterogeneous (a core-shell 2! layered structure). Further, these silver halides may be of a type in which a latent image is mainly formed on the surface or a type in which a latent image is formed inside the grain.
113934, Japanese Patent Application No. 170070/1983) may also be used.

The silver halide grains used in the present invention may be obtained by any preparation method such as an acid method, a neutral method, or an ammonia method.

Alternatively, for example, seed particles may be prepared using an acid method, and then grown using an ammonia method, which has a high growth rate, to grow to a predetermined size. When growing silver halide grains, the pH, pAg, etc. in the reaction vessel are controlled, and the amount of silver ions commensurate with the growth rate of silver halide grains is controlled, for example, as described in JP-A-54-48521. and halide ions are preferably implanted and mixed at the same time).

Preferably, the silver halide grains according to the present invention are prepared as described above. A composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions contain active gelatin; sulfur sensitizers such as allylthiocarbamide, thiourea, cystine, selenium sensitizers; reduction sensitizers such as stannous salts, thiourea dioxide, Polyamines, etc.; noble metal sensitizers, such as gold sensitizers, specifically potassium aurithiocyanate, potassium chloroaurate, 2-aurothiol-3-
Sensitizers such as methylbenzthiazolium chlorite or water-soluble salts such as ruthenium, palladium, platinum, rhodium, iridium, etc., specifically ammonium chlorovaladate, potassium chloroaurate and sodium chloroparadate (these They act as sensitizers or fog suppressants depending on the amount. It may also be chemically sensitized (for example, in combination with a sensitizer).

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during, or after this chemical ripening, a nitrogen-containing emulsion having at least one hydroxytetrazaindene and mercapto group is produced. It may also contain at least one type of terocyclic compound.

The silver halide used in the present invention has a sensitizing dye of, for example, 5 X 10-' to 3 X 1 per mole of silver halide, in order to impart photosensitivity to a desired wavelength range.
Optical sensitization may be achieved by adding 0-'mol.

Various sensitizing dyes can be used, and each sensitizing dye can be used alone or in combination of two or more.

In addition, in the light-sensitive material to which the present invention can be applied, a dye is formed by reacting with a coupler, that is, a fused form of a color developing agent, in a red-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer, and a green-sensitive silver halide emulsion layer, respectively. It is preferable to use a compound containing a compound capable of forming .

Yellow couplers that can be used include closed ketomethylene compounds, active point -〇-aryl substituted couplers called so-called 2-equivalent couplers, active point -〇-acyl substituted couplers, active point hydantoin compound substituted couplers, and active point urazole compounds. Substituted couplers and active point succinimide compound substituted couplers, active point fluorine substituted couplers, active point chlorine or bromine substituted couplers, active point -0-sulfonyl substituted couplers, etc. can be used as effective yellow couplers. Specific examples of yellow couplers that can be used include U.S. Pat.
, No. 551.155, No. 3,582,322, No. 3,582,322, No.
No. 3,725,072, No. 3,891,445, West German Patent No. 1,547,868, West German Application Publication No. 2.21! I
, No. 917, No. 2, 26], No. 16, No. 2,414
, No. 006, British Patent No. 1,425,020, Special Publication No. 5
No. 1-10783, JP-A-47-26133, JP-A No. 48
No. 73147, No. 51-102636, No. 50-63
No. 41, No. 50-123342, No. 50-13044
2, No. 51-21827, No. 50-876509, No. 52-82424, No. 52-115219, No. 5B-95346, and the like.

Examples of magenta couplers that can be used include pyrazolone-based, pyrazolotriazole-based, virazolinobenzimitazole-based, and indasilone-based compounds. These magenta couplers may be not only 4-equivalent couplers like the yellow couplers but also 2-equivalent couplers. Specific examples of magenta couplers that can be used include U.S. Pat. Nos. 2,600,788 and 2,983,608
No. 3,052,653, No. 3,127,269
No., No. 311,478, No. 3,419.391
No. 1, No. 519,429, No. 3,558,3
No. 19, 3.582. : No. 122, 3,615,
No. 506, No. 3,834,908, No. 3,891,
445, West German Patent No. 1,810,4611, West German Patent Application (OLS) No. 2,408,655, West German Patent Application No. 2,1117
．． No. 945, No. 2,424,467, Special Publication No. 1977-6
No. 031, JP-A No. 51-20826, JP-A No. 52-589
No. 22, No. 4″9-129538, No. 49-7402
No. 7, rP1150-159336, rP1150-159336, 52-421
No. 21, No. 49-74028, No. 50-60233, No. 51-26541, No. 53-55122, Japanese Patent Application No. 110943/1980, and the like. A particularly preferred magenta coupler is described in JP-A-63-106655 (pages 510 to 518), which is effective in quickness and prevention of yellow stain after processing.
It is a magenta coupler represented by the general formula [Ml].

Examples of cyan couplers that can be used include phenolic and naphthol couplers. And these cyan couplers are 4 like the yellow couplers.
It does not have to be an equivalent type coupler, but may be a 2-equivalent coupler. Specific examples of cyan couplers that can be used include U.S. Pat. Nos. 2,369.92'1 and 2,434,272
No. 2,474,293, No. 2.52] 19G8, No. 2,895. f11Zfi issue, same 3. ,034,8
No. 92, No. 3.311,476, No. 3/158.3
] No. 5, same No. 3,1176.563.

No. 3,583,971, No. 3,591,383, No. 767.411, No. 3,772,002, No. 3,933,494, No. 4,004.929, West Germany Patent Application (OLS) No. 2,414,830, No. 2,45
4.329, JP-A No. 48-5983, JP-A No. 51-26
No. 034, No. 4B-5055, No. 51-146827
Examples include those described in Japanese Patent Publication No. 52-69624, No. 52-90932, No. 58-95346, and Japanese Patent Publication No. 11572-1972. Particularly preferable cyan couplers are represented by general formulas (C-1) and (C-2) described in JP-A-63-106655 (pages 518 to 526), which are effective for staining and rapidity after processing. It is a cyan coupler.

Couplers such as colored magenta or colored cyan couplers and polymer couplers may be used in combination in the silver halide emulsion layer and other photographic constituent layers. Regarding colored magenta or colored cyan couplers, patent application No. 193611/1982 (Japanese Patent Application Laid-open No. 72235/1989) filed by the present applicant
For polymer couplers, please refer to Japanese Patent Application No. 172151/1983 (Japanese Patent Application Laid-Open No.
-50143) can be referred to.

In the present invention, in particular, JP-A-63-106655
General formula [M-■] as described on page 26 of the specification of the No.
Magenta couplers shown in (Specific examples of these magenta couplers include No. 1-No. 77 described on pages 29 to 34 of JP-A-6310E1855), also described on page 34. The general formula [C
-I] or [C-II] (specific examples of cyan couplers include the same specification, No. 37 to
(C′-1) to (C″-82), (C″) described on page 42
-1) to (C″-38)), also No. 20
(Y'-1) to (Y'-38) described on pages 21 to 26 of the same specification are listed as specific examples of cyan couplers). It is preferable to use them in combination with other materials in view of the desired effects of the present invention.

Further, in the present invention, the film swelling degree of the emulsion layer is 2.0 to 4,
5, the effect of the present invention is more pronounced. Membrane swelling can be measured by a known method, and a degree of swelling of 2.0 to 4.0 is preferably used as an embodiment of the present invention.

The I11 moisture level can be adjusted as appropriate by adjusting the amount of hardener and degree of hardening.

In the present invention, when a nitrogen-containing heterocyclic mercapto compound is used in combination with a high silver chloride light-sensitive material, not only the desired effects of the present invention are well achieved, but also the bleach-fixing solution is not mixed into the color developing solution. In the present invention, it can be cited as a more preferred embodiment because it has the advantage of minimizing the influence on photographic performance that occurs during the process.

Specific examples of these nitrogen-containing heterocyclic mercapto compounds are disclosed in JP-A-1999-106655, Nos. 42-45.
Examples include (I'-1) to (I'-87) described on page.

The silver halide color photographic light-sensitive material used in the present invention may contain various other photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, optical brighteners, color image fading inhibitors, antistatic agents, hardeners, and surfactants described in Research Disclosure No. 17643. , plasticizers, wetting agents, etc. may be used.

In the silver halide color photographic light-sensitive material used in the present invention, the wood-philic colloid used to prepare the emulsion is preferably gelatin, and other examples include derivative gelatin,
Synthesis of single or copolymers of graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose derivatives and carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinylimidazole, polyacrylamide, etc. Any of hydrophilic polymers and the like may be included.

Supports for the photosensitive material used in the present invention include baryta paper, polyethylene-coated paper, polypropylene synthetic paper, transparent supports with a reflective layer, such as glass plates, polyester films such as cellulose acetate, cellulose nitrate, and polyethylene terephthalate. , polyamide film, polycarbonate film, polystyrene film, etc., and other ordinary transparent supports may be used. These supports are appropriately selected depending on the intended use of the photosensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hot bar coating can be used to coat the silver halide emulsion layer and other photographic constituent layers used in the present invention. Also, US Patent 2,7
It is also possible to use a simultaneous coating method of two or more layers by the method described in No. 61,791 and No. 2.941,898.

In the present invention, the coating position of each emulsion layer can be determined arbitrarily. For example, in the case of a full-color photosensitive material for photographic paper, a blue-sensitive silver halide emulsion layer, a blue-sensitive silver halide emulsion layer,
It is preferable to arrange an A11l light-sensitive silver halide emulsion layer and a red-sensitive silver halide emulsion layer. Each of these photosensitive silver halide emulsion layers may consist of two or more layers.

In the photosensitive material of the present invention, it is optional to provide an intermediate layer with an appropriate thickness depending on the purpose, and a filter layer,
Various layers such as an anti-curl layer, a protective layer, and an antihalation layer can be used in appropriate combinations as constituent layers.

In these constituent layers, wood-philic colloids that can be used in the emulsion layer as described above can be used as a binder, and they can also be contained in the emulsion layer as described above. Various photographic additives can be included.

In the method for processing a light-sensitive material of the present invention, silver halide color photographic light-sensitive materials can be used as color papers, color negative films, color positive films, etc., as long as they contain a coupler in the light-sensitive material and are processed by the so-called internal development method. It can be applied to any silver halide color photographic material such as film, color reversal film for slides, color reversal film for movies, Ocolor reversal film for TV, reversal color paper, etc.

[Effects of the Invention] According to the present invention, it is possible to provide a method for processing a photosensitive material in which the whiteness of unexposed areas of a color paper is good even in rapid processing, and the anti-piping effect in a stabilizing bath is improved.

[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but the embodiments of the present invention are not limited to these.

Example 1 A photosensitive material was prepared by sequentially coating the following layers on a polyethylene coated paper support from the support side.

Note that polyethylene coated paper has an average molecular weight of 10
6.5% by weight of anatase-type titanium oxide was added to a mixture of 200 parts by weight of polyethylene with an average molecular weight of 0,000 and a density of 0.95 and 20 parts by weight of polyethylene with an average molecular weight of 2,000 and a density of 0.80, and extrusion coach ink was prepared. The thickness is 0.035mm on the surface of high-quality paper with a weight of 165g/m' by the method.
A coating layer of 0.0411 um in thickness was formed on the back surface of only polyethylene. The polyethylene-coated surface of this support was pretreated by corona discharge, and then the following layers were sequentially applied.

The first layer is a blue-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.2 mol % of silver bromide. The emulsion contains 340 g of gelatin per mol of silver halide, and The sensitizing dye [m] was sensitized using 2.4X 10-' mol (using isopropyl alcohol as solvent) of 2,5-, dissolved and dispersed in dibutyl phthalate.
2. 200 mg/nf of di-t-butylhydroquinone and [Y-1] of the following structure as a yellow coupler per mole of silver halide. ]X Contains 10-' mole, silver amount 2
It is coated at a concentration of 70 mg/m'.

2nd layer: 290 mg/m' of di-t-octylhydroquinone dissolved and dispersed in cysotyl phthalate 2-(2'-hydroxy-3',5'-t-butylphenyl)benzotriazole as UV absorber 2-(2'-hydroxy-5'-t-butylphenyl)penztriazole, 2-(2'-hydroxy-3'-t-phthyl-5'-
200 mg of a mixture of (methylphenyl)-5-chloro-hensitriazole and 2-(2''-hydroxy-3',5''-di-t-butylphenyl)-5-chloro-benzotriazole (1:1:1:l) /m'
2000mg/m' of gelatin in the gelatin layer containing
It is coated to make it look like this.

Third layer: A green-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.3 mol% of silver bromide.The emulsion contains 460 g of gelatin per mol of silver halide, and has the following structure per mol of silver halide: sensitizing dye [I] 2,5-di-t dissolved in a solvent consisting of dibutyl phthalate and tricresyl phosphate 21.
-Butylhydroquinone and magenta coupler [M-1] having the following structure per mole of silver halide 1.5
It contains 10"' mole of silver, and is coated so that the amount of silver is 220 B/rn'. In addition, 2,2
．． 0.30 mol of 4-trimethyl-6-lauryloxy-L-octylchroman was added per mol of coupler.

4th layer 30 mg/m' of di-t-octylhydroquinone dissolved and dispersed in dioctyl phthalate and 2-(2'-hydroxy-3'',5'-di-butylphenyl)benzotriazole as a UV absorber; 2-(2'-hydroxy-5'-t-butylphenyl)penztriazole, 2-(2'-hydroxy-3'-t-phthyl-5'-
a mixture of (2: 1.5: 1.5 + 2) 500I
It is a gelatin layer containing I1g/m', and gelatin 1
It is coated at a concentration of 900mg/m'.

Fifth layer: red-sensitive silver halide emulsion layer consisting of a silver chlorobromide emulsion containing 0.2 mol % of silver bromide, the emulsion containing 500 g of gelatin per mol of silver halide; Sensitized using sensitizing dye [H] 2.5 x 10-5 moles having the following structure, 150 mg/m of 2,5-sheet t to tutylhytroquinone dissolved and dispersed in dibutyl phthalate.
' and [C-1] having the following structure as a cyan coupler per mol of silver halide, containing 3.5 x 10-1 mol,
It is coated with a silver content of 270 B/m'.

Sixth layer: This is a gelatin layer, and gelatin is coated at 1000 mg/ln'.

The silver halide emulsions used in each light-sensitive emulsion layer (layers 1, 3, and 5) were prepared by the method described in Japanese Patent Publication No. 7772/1983, and were prepared using sodium thiosulfate pentahydrate and gold chloride, respectively. Chemically sensitized using acid, 4-hydroxy-6-methyl-1°3.3a,7-titrazaindene (2.5 g per mol of silver halide) as a stabilizer, and bis(vinylsulfonylmethyl) as a hardener. ) ether (>10 mg/g gelatin) and saponin as a coating aid.

In addition, the following [Al-1] and [Al-
2] was added at 15 mg/m'.

Sensitizing dye [■ Sensitizing dye [II Sensitizing dye [■ Ko (M-1)] [Al-1 [Al-2] After exposing the color vapor prepared by the above method, the following processing steps are carried out. The treatment was carried out using a treatment solution.

Processing steps (1 tank each) (1) Color development 38°C 20 seconds (2) Bleach fixing 35°C ZO seconds (3) Stability (1 tank) 35°C 20 seconds (4) Drying 60°C - 80°G, 30 seconds [Color developing tank liquid Codiethylene glycol 10 g Potassium bromide 0.01 g Potassium chloride 2.3 g Potassium sulfite (50% solution) 0.5 m Color developing agent (
3-Methyl-4-amino N-ethyl-N-(β-methanesulfonamidoethyl)-aniline sulfate 7.0 g diethylhydroxylamine (85%) 5.0 g triethanolamine 101 g potassium carbonate 30 g diethylenetriaminepentaacetic acid Sodium salt 2.0g Fluorescent brightener (Uvitex GK, manufactured by Ciba Geigy)
2.0 g of water was added to make one sentence, and the p++ was adjusted to 10.15 with potassium hydroxide or sulfuric acid.

[Color developer replenisher codiethylene glycol potassium chloride potassium sulfite] Og 3.0g 0.5m (50% solution) Color developer (3-methyl-4-amino N-ethyl-N
-(β-Methanesulfonamidoethyl)-Aniline sulfate Diethylhydroxylamine (85%) Triethanolamine Potassium carbonate Diethylenetriamine Sodium pentaacetate Optical brightener (manufactured by Ciba Geigy) Add water to make one sentence, sulfuric acid pt+ Adjusted to 10.40.

Uvitevx GK) 2.5g potassium hydroxide or 8.0g 7.0g 10.0g 0g 2.0g [Bleach-fix tank fluid and replenisher] Diethylenetriaminepentaacetic acid ferric ammonium salt f15. Og diethylenetriaminepentavinegar fi 3.0g ammonium thiosulfate (70% solution) 100.0ml
5-Amino-1,3,4-thiadiazole-2-thiol 0.5g ammonium sulfite (40% solution) 27°511g Adjust to 50 with aqueous ammonia or glacial acetic acid and add water to total volume is one sentence.

[Stable tank fluid and replenisher fluid] Ortho-phenylphenol Tinopal SFP (manufactured by Ciba Geigy) Uvitex CK (tt) 1.0 g g 2.0'g 1-hydroxyethylidene-1,1 diphosphonic acid (60% aqueous solution) ZnSOn・7H20 Potassium sulfite (50% solution) PVP (polyvinylpyrrolidone) 8.0g 6.0g 10.0+s Exchange 1, O8 Ammonia water (ammonium hydroxide 25% aqueous solution) 2.5g water to make one sentence, ammonia water and sulfuric acid and set pl+9.0.

Running treatment was performed using the prepared color vapor and treatment liquid.

In the running process, the automatic processor is filled with the above-mentioned color developing tank solution, as well as the bleach-fixing tank solution and the stabilizing tank solution, and the above-mentioned color developing replenisher is added every 3 minutes after processing the color vapor sample. This was done while replenishing the bleach-fix replenisher and stable replenisher through a metering pump.

The amount to replenish the color developing tank is 1r of color paper.
160m per n', the amount of replenishment to the bleach-fixing tank is 220ml of bleach-fixing replenisher per 1m', and the amount of replenishing to the stabilizing tank is 250mJ of stable replenisher per 1m'.
2 supplemented.

The running process was carried out continuously until the amount of stable replenisher liquid replenished into the stable tank liquid was 3 times the volume of the stable tank liquid9.

After the running process was completed, a dye was added as shown in Cloth 1, and the whiteness of the processed color paper, particularly cyan-magenta stain, was observed.

After that, the treated solution was stored at room temperature for one month to eliminate bacteria.
The growth of mold was observed.

The results are summarized in Table 1.

However, the above evaluation criteria were as follows.

(Occurrence of stain) Occurrence of O stain is not visually observed △ Occurrence of stain is slightly observed visually × Occurrence of stain is visually observed (occurrence of bacteria and mold) No formation of bacteria and mold is observed 7. Slight occurrence of Hectilia and mold. 0. Occurrence of bacteria and mold. → 0. A large number of occurrences of bacteria and mold. Table Comparison 1 Comparison 2 Comparison 3 As is clear from Table 1, the dye of the present invention was used. When used, the occurrence of cyan and magenta stains was improved to such an extent that it could no longer be visually observed, and the piping prevention effect was also confirmed, although the reason is unclear. On the other hand, the comparison dyes were cyan stain and magenta stain so bad that their commercial value was significantly reduced.

Example 2 The above-mentioned water-washing alternative stabilizer was stored at 40°C for one week, and then the same evaluation as in Example 1 was performed again.The water-washing alternative stabilizer containing the dye of the present invention showed almost no change in whiteness. On the other hand, the comparison dye had even worse cyan staining.

Example 3 The same evaluation as in Example 1 was performed except that the experiment number of Example 1, 1-1.1-3.1-5, was used and the washing alternative stabilization treatment time was changed as shown in Table 2.

The results are shown in Table 2.

■ No stains are visually observed and it is good as a white background O No stains are visually observed, but there is a slight tendency towards M (magenta) or C (cyan)Δ Stains are visually observed × Stains are visually observed Table 2 As is clear from Table 2, the effect of the dye of the present invention is particularly remarkable when the treatment is short-term, and as the treatment time increases, the white background tends to deteriorate, probably due to re-adhesion. Recognize.

On the other hand, when there is no dye or when a comparative dye is used, the results are significantly worse after a short treatment time, and although there is a tendency toward improvement as the treatment time becomes longer, the cyan stain is not reduced much.

Example 4 The film swelling degree of the silver halide color photographic light-sensitive material of Example 1 was adjusted by adjusting the amount of hardening agent to prepare a light-sensitive material having a film swelling degree of 1.5 to 5.0. When the same evaluation as in No. 3 was conducted, it was found that the stain occurrence status was preferably 2.0 to 4.5, and particularly good results were obtained when the stain was 2.5 to 4.0.

Example 5 The magenta coupler in the silver halide color photographic light-sensitive material of Example 1 was replaced with M as described in JP-A-83-106855.
' -1, 2, 4, 21, 37, I (1 and 83,
The cyan coupler is C'-2, 27, 32 described in the same publication.
, 33° 34.3B, 37, 38, 38, 53. C”
-2, 8, and 9, respectively, and the same evaluation as in Example 3 was performed, and the overall stain level was lower, and the effect was remarkable even in short-time treatment.

Example 6 An inner tank emulsion (Em-1) was prepared as follows.

While controlling the gelatin-containing aqueous solution at 50°C, a silver nitrate aqueous solution and an aqueous solution containing potassium bromide and sodium chloride (KBr:Na (lA, -55:45 in molar ratio) were added simultaneously by a controlled double jet method. By doing this, a cubic emulsion with an average grain size of 0.35 gm was obtained.Sodium thiosulfate and potassium chloroaurate were added to the core emulsion thus obtained, and chemical ripening was performed at 55°C for 120 minutes. This emulsion was designated as emulsion A.

An aqueous solution containing Emulsion A as a core and an aqueous solution of silver nitrate, potassium bromide and sodium chloride (KBr in molar ratio)
:Na (,1-20:80) was added at the same time to obtain tetradecahedral particles with average particle diameters of 0.46p and 0.46m. This emulsion is referred to as Emulsion F.

Sodium thiosulfate was added to this emulsion F to perform chemical sensitization, and after completion of the chemical sensitization, 9 mg of 1-phenyl-5-mercaptotetrazole was added per mole of silver halide.

The photographic material shown below was prepared using the inner bath type emulsion (Em-1).

[Preparation of inner layer type silver halide photosensitive material] The following layers were sequentially coated from the support side onto a paper support laminated with polyethylene to prepare an internal latent image type photosensitive material sample.

First layer: dian-forming red-sensitive silver halide emulsion layer: cyan coupler, 2,4-dichloro-3-methyl-8-[α-(
2,4-di-tert-amylphenoxy)butyramide]phenol 85 g, 2,5-di-tert-octylhydroquinone 2 g, tricresyl phosphate 50
g, paraffin 180 g and ethyl acetate 50 g are mixed and dissolved, gelatin solution containing sodium dodecylbenzenesulfonate is added, and sensitizing dye (m
) was added to an internal latent image type silver halide emulsion (Em-1) sensitized with 3.3X 10-5 moles of silver [H400m
g/m', AI dye [I] 19 mg/m', coupler ii 380 mg/m'.

2nd layer: Intermediate layer ff color 100 ml of a 2.5% gelatin solution containing 5 g of colloidal silver and 10 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate with an amount of colloidal silver of 3? It was applied so that it was Omg/m'.

Third layer: Magenta forming green-sensitive silver halide emulsion layer Magenta coupler, I-(2,4,e-trichlorophenyl)-3-(2-chloro-5-octadecylsuccinimidoanilino)-5-pyrazolone 100 g, 2 ,5-
Mix and dissolve 5 g of G-tert octyl hydroquinone, 100 g of Sumilizer [IP (manufactured by Sumitomo Chemical Co., Ltd.), 200 g of paraffin, 50 g of dibutyl phthalate] and 50 g of ethyl acetate, add gelatin solution containing sodium dodecylbenzenesulfonate, and dissolve silver halide. 3. of sensitizing dye (II) per mole. An internal latent image type silver halide emulsion (Em-1) sensitized with OX 10-' mole was added, the silver amount was 320 mg/m', and AI dye [TI]
It was applied so that the amount of coupler was 20 mg/m' and the amount of coupler was 380 mg/ln'.

4th layer: Yellow filter layer A 2.5% gelatin solution containing 5 g of yellow colloidal silver and 5 g of 2,5-di-tert-octylhydroquinone dispersed in dibutyl phthalate was mixed with 180 g of colloidal silver.
It was applied so that it became mg/m'.

5th layer: Yellow-forming blue-sensitive silver halide emulsion layer Yellow coupler, α-[4-(1-benzyl-2phenyl-3,5-dioxo-1,2,4-1-riazolidinyl)]-]α Vivariru 2-chloro5-γ-(2,
Mix and dissolve 120 g of 4-di-tert-amylphenoxy)butyramide] acetanilide, 3.5 g of 2,5-di-tart-octylhydroquinone, 200 g of paraffin, 110 g of Tinuvin (manufactured by Ciba Geigy), 90 g of dibutyl phthalate, and 70111 grams of ethyl acetate. Then, gelatin solution containing sodium dodecylbenzenesulfonate was added, and sensitizing dye [II] was added per mole of silver halide.
3. Add internal latent image type silver halide emulsion (Em-1) sensitized with OX lo = molar, and add silver amount 400 mg/m'
, the amount of coupler was 400 mg/m'.

6th N = protective layer It was applied so that the amount of gelatin was 200 mg/m'.

Incidentally, all of the above layers contained saponin as a coating aid. Further, as a hardening agent, sodium 2,4-dichloro-6-hydroxy=s-triazine was added to layers 2.4 and 6 in an amount of 20 mg per Ig of gelatin, respectively.

Sensitizing Dye I Sensitizing Dye ■ AI Dye [1] AI Dye [IT] Sensitizing Dye II AT Dye 4 [mco] After exposing the above light-sensitive material sample through an optical wedge, it was processed in the following steps.

paratoluenesulfonic acid sodium di(methoxyethyl) hydroxylamine g 2.5g potassium carbonate 5 g 7 g Ubitex CK (manufactured by Ciba Geigy) potassium sulfite diethylenetriaminepentaacetic acid Color developing agent (CD-1 below) Color developing agent (CD-2 below) g g g g 2.4g g 4.2g g 4.5g 3.0g The composition of each treatment liquid is as follows.

[Color developer] Tank liquid diethylene glycol 10 g Benzyl alcohol
10 g polyvinylpyrrolidone 1.
0g diethylhydroxylamine 4.0g cerous sulfate 10mg potassium bromide
1.1g replenisher 2 g 1 g 1.2g 5.0g 3 mg g Add pure water to make one sentence each, and adjust the pH to 10.1 (tank liquid)
, 10.5 (replenisher).

However, p)I was adjusted using 50% potassium hydroxide and 50% sulfuric acid.

D-1 D-2 0・”\10.1.01 N.H.

J.I.B.

[Bleach-fix solution] (Common to tank solution and replenisher solution) Iron diethylenetriaminepentaacetate (m) Aqueous ammonia 85g Ammonium thiosulfate 85g Sodium hydrogen sulfite 15g Sodium metabisulfite
Add 2g ethylenediaminetetraacetic acid-disodium 2g pure water to make one sentence, and adjust to p)I = 8.0 with aqueous ammonia or acetic acid.

[Water washing alternative stabilizer solution] (Common to tank solution and replenisher solution) Ortho-phenylphenol 0.2g Ethylenediaminetetraacetic acid 2g 1-Hydroxyethylideneso 1.1 Diphosphonic acid (EO% aqueous solution) 5.0g Bismuth chloride 3g Ammonia water
Add 3.0g polyvinylpyrrolidone and 0.5g water to make 11, and make p)I=7.0 with aqueous ammonia and sulfuric acid.

The above processing solution was placed in an automatic developing machine and a running test was conducted under the above conditions.

The running processing amount is 3 of the tank liquid capacity of the washing alternative stabilizing liquid.
The treatment was continued until the replenisher was refilled to double the volume. After treatment, the same evaluation as in Example 1 was performed. The results are shown in Table 3.

table I was able to obtain the following results.

Claims (1)

[Scope of Claims] 1. A silver halide color photographic light-sensitive material is subjected to color development treatment after imagewise exposure, and then treated with a processing solution having fixing ability, and then processed with a water-washing substitute stabilizing solution without substantially washing with water. In this case, the water washing alternative stabilizer has an absorption wavelength of 510 to 5.
1. A method for processing a silver halide color photographic light-sensitive material, comprising at least one water-soluble non-bleaching dye having a wavelength of 60 nm and a stabilizing treatment time as an alternative to water washing of 120 seconds or less. 2. The water-soluble non-bleaching dye has the following general formulas [I] to [
2. The method for processing a silver halide color photographic material according to claim 1, wherein the compound is a compound represented by [III]. General formula [I] Ar^1N=N-Ar^2 In the formula, Ar^1 represents an aryl group, and Ar^2 represents a naphthyl group. However, at least two sulfo groups are substituted in the entire molecule. General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R^1^0 represents an alkyl group, aryl group, or heterocyclic group, R^1^1 represents a substituent, and R^1 ^
2 and R^1^3 each represent a hydrogen atom, an alkyl group, or an aryl group, and may be the same or different from each other. R^1^4 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. n^1^0 indicates an integer of 1 or 2. However, the molecule as a whole must contain at least one sulfo group.
Replace. General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, Z^1 and Z^2 are each a nitrogen atom or =C-R^2
Represents ^0 group, and may be the same or different from each other. R^2^0 and R^2^1 each represent a hydrogen atom or a substituent, R^2^2 and R^2^3 each represent a hydrogen atom, an alkyl group, or an aryl group, and these may be the same as each other. May be different. R^2^4 represents a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. n^2^0 indicates an integer of 1 or 2. However, at least one sulfo group is substituted for the entire molecule.