JPH03216650A - Composition having bleaching ability for silver halide color photographic sensitive material and processing method using same - Google Patents

Abstract

PURPOSE:To obtain bleaching ability without environmental pollution by incorporating a ferric complex salt of a specified compd. as a bleaching agent. CONSTITUTION:A ferric complex salt of a compd. represented by formula I and/or that of a compd. represented by formula II is incorporated as a bleaching agent. In the formula I, W<1> is <=3C alkylene, each of L<1>-L<4> is alkylene or arylene and each of M1-M6 is H or a cation. In the formula II, W<2> is a divalent combining group, each of L<5>-L<8> is alkylene or arylene and each of M7-M11 is H or a cation. The deterioration of working environment, the corrosion of the metal of peripheral equipment and appliances and the deterioration there of can be prevented.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a composition having bleaching ability for halogen/silver oxide color light-sensitive materials and a processing method using the same. In addition to silver processing, there is no bleaching fog, and there is no stay / when saving images after processing.
The present invention relates to a composition having a bleaching ability that can perform processing with less generation of gold, and a processing method using the composition.

(Prior Art) Generally, the basic steps of processing a halo/silver oxide photosensitive material (hereinafter referred to as a color photosensitive material) consist of a color development step and a desilvering step. In the color development process, exposed halide/silver oxide is reduced by an aromatic primary amine color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to form a dye image. give. In the next desilvering step, the silver produced in the color development step is oxidized and then dissolved by a silver ion/complexing agent commonly called a fixing agent. Through this desilvering process, only the dye image remains on the color photosensitive material.

The above desilvering process can be carried out using two baths, a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, a method using a starch fixing bath containing a bleaching agent and a fixing agent, or a method using a method using a starch fixing bath containing a bleaching agent and a fixing agent. There are only combinations. ′! Each bath may consist of vI number of treatment vessels.

In addition to the basic steps mentioned above, the actual development processing includes other auxiliary processing steps for the purpose of preserving the photographic and physical quality of the image or improving the storage stability of the image. There is. Examples include dura mater bath, stop bath, image stabilization bath, and water wash bath.

In recent years, with the spread of small-sized in-store processing service systems commonly known as minilabs, there has been a strong demand to respond quickly to customer processing requests and to shorten the time required for the processing. In particular, the highest demand is to shorten the desilvering process, which conventionally occupied most of the processing time, and within this, there is a need to speed up bleaching.

The next step to shortening the bleaching time is to use a strong oxidizing agent (S
It is well known that it is better to use whitening agent). Such bleaching agents include inorganic compounds such as red blood salts, ferric chlorides, persulfates, and dichromates, or metal chelating agents substituted with aminobolic poly(RtcC) complex salts. Particularly in recent years, from the viewpoint of environmental conservation and safety in handling k4yl, the development of aminobolite/iron acid chelates with high oxidizing power has been promoted, and /,3-propanediami/iron(III) tetraacetate complex salt (/, j- PD'L'
A-k'eC111)). Glycol ether diamide/
Iron tetraacetate < ltl ) ha salt ( (jEDjL'A
− k'e (river), etc. have been considered.

However, using aromatic primary amine color determinants'
If the fc color development process is followed by a bleach bath containing these strong oxidizing agents or a bleach bath containing these strong oxidizing agents, the developing chemicals brought in with the film will be oxidized and react with the color forming agent, resulting in a phenomenon called bleach fog. It is known to cause major problems with severe color staining (as described by James, The Theory of
Photographic Process, Z (The the
ory of Photographic Process
ss) 1st edition [177th year]≠j page 2, etc.) This hindered the speeding up of bleaching.

In order to avoid this, it is necessary to provide a stop bath or washing bath after the development process to remove the developing agent in the film, and then perform a bleaching or bleach-fixing process.

However, this involves an increase in the number of processing baths, and the original objective of shortening the processing time cannot be achieved.

Furthermore, apart from this problem of white capri, a new problem arises in that short-term processing in such bleaching or bleach-fixing baths results in a significant increase in nutein during storage of the processed color light-sensitive materials. It became clear that this was going to happen.

One way to solve this problem of increasing bleaching power is to increase the PLL value of the bleaching solution by 2. j−≠． Is there a way to lower it to λ? JP-A-Hei/1. 2/J 6 j 7, and an embodiment similar to VC (containing acetic acid, pH H.
3 bleaching solution) is officially used for C-≠/kLA processing, but this method does not sufficiently solve the above problems, and the work is difficult due to evaporation of the acetic acid used to lower pli. Environmental deterioration, metallurgy in equipment and utensils
4) It has been found that there are problems such as corrosion and deterioration, (Problems to be solved by the present invention) Therefore, the first purpose of this paper is to develop a process that has hot bleaching ability without energy or environmental pollution. The aim is to provide the following. A second object of the present invention is to provide a processing solution and a processing method that can perform iron removal processing without causing white mark fog and with less occurrence of staining after processing. A third and eleventh object of the present invention is to provide a processing agent and a processing method that achieve the above-mentioned objects and have a bleaching ability that enables rapid desilvering with excellent desilvering properties.

(The above objectives were achieved by the method listed below.)

(1) A composition having bleaching ability containing a compound represented by formula (1) and/or a ferric complex salt of a compound represented by formula (n) as a bleaching agent.

(2) After color development of the imagewise exposed silver halide color photographic light-sensitive material, a compound represented by the general formula (1) and/or a ferric compound represented by the general formula (II) is added. 1. A method for processing a silver halide color photographic light-sensitive material, which comprises processing with a composition having bleaching ability containing a complex salt as a color whitening agent.

General formula (1) (In the formula, Ji stands for an alkylene group having a total carbon number of 3 or less, 1, 1 1, 2 1.3 and L4 each independently represent 7 alkylene groups and 1 arylene group, M1 to
M6Fi each represents a hydrogen atom or a cation/t. ) General formula (n)? In the formula, W2 represents a divalent linking group. L5LL and L each represent an independent alkylene/arylene group or an arylene group. M7, M8, ~l9, M and 1ν1■
■ is the bottom of Mizuki Atom or Kachi 1G On, respectively. ) The compounds represented by the general formulas (1) and (n) will be described in detail below.

The substituent may be an alkali/ih having a total of 3 or less carbon atoms, and a substituent may be M. The total number of carbon atoms of 3 or less means that the number of carbon atoms including the substituents in the alkylene/group with M substituents and the substituents is 3 or less. Substituents include alkyl groups, aralkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, amino groups, acylamino groups, sulfonylamino groups, 9-reido groups, talethane groups, sulfamoyl groups, carbamoyl groups, alkylthio groups, sulfonyl groups, and sulfinyl groups. , hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, phosphono group, acyl group, alkoxycarbonyl group, acyloxycarbonyl group, acyloxy group, carbonamide group, sulfo/amide group, nitro group, and the like.

Substituents include t, alkyl group (more preferably methyl group), alkoxy group (more preferably methoxy group), amino group (more preferably tt, < is amino group, methylamine &)
, a sulfonylamino group (more preferably a meta/sulfonylamino group), a sulfamoyl group (more preferably a sulfamoyl group, a methylnullamoyl group), a carbamoyl group (more preferably a carpamoyl group, an alkylthio group) (more preferably a methylthio group), a hydroxyl group, a halogen/atom, a cyano group, a sulfo group, a carboxyl group, a honuhono group, a nitro group, and the like.

w2 represents a divalent linking group. As a divalent linking group,
Preferably, an alkylene group having from 1 to t carbon atoms, an alkylene group having from 1 to IO carbon atoms, a 21-lohexane group, 21-lohexane group, 21-lohexane group, 21-lohexane group, 21-lohexane group, 21-lohexane group, m represents a lekylene group, m represents 7 to 3), -W
-N-W22- (A is hydrogen, hydrocarbon water wood, A -L -C (J (JM, -L -P (73M2, A
A-L
A-(Jl-1-LA-SO3M (LA is the number of carbon atoms/
An alkylene/group of t to t or an aryle/group of carbon number t to /O, M represents a hydrogen atom or a cation (alkali metal, ammonium, etc.). )), and combinations thereof may also be used. These divalent linking groups may have a substituent +li-, and examples of the substituent include an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryl group, a substituted amine group,
Acylamino group, nulfonylamino group, ureido group, urethane/group, ryoryloxy group, sulfamoyl group, carpamoyl group, alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen/atom, nano group, nurpho group, carboxyl group, phosphono group,
Examples include aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxycarbonyl group, carbo/amide group, nurphonamide group, and nitro group.

L - L are each independently an alkylene group or an arylene group, preferably a methylene group or an ethylene group. Furthermore, it is particularly preferable that at least one of L to L in the general formula (I) is an ethylene group.

M, to M11 are each a hydrogen atom or a cation. Cations include alkali metals (lithium, sodium, potassium, etc.), ammonium, viridinium, and the like.

Among compounds represented by general formula (1) and fc#'icU), compounds represented by general formula (II) are more preferred.

Specific examples of compounds represented by the general formula (1)-ffi or (II) are listed below, but the present invention is not limited thereto.

l0, 22 23. Kobutsu λ Mako l 3/. L;fl, -IN\CH2CUE)NaFor the compound represented by the general formula (1), Zhurnal Lj
It can be constructed by referring to the method described in Bshchei Khirnii, Vol. 4L6, No. JOl Negative (1976), Vol. 7, Page 23, No. 6 (1977). Next, specific synthesis examples of representative compounds are shown below.

Synthesis example t Synthesis of component 1 C: k-13CNkiCH2CH2NH2+αCH2C
O2C2H511 0 /-A /-H /-C / / -(υ Synthesis of compound / -H 8-acetyl ethylene/diami7C/-A)/0λ'/(
/． 0 mol) was dissolved in 100 ul of acetonitrile, and 30 μt (2.λ mol) of potassium carbonate was added. Stir at room temperature and add ethyl chloroacetate. 270y (co.2 mol) was added dropwise, and after fC, the mixture was heated under reflux for 2 hours. After cooling in Murogata 1, the product was separated from each other, the P solution was concentrated under reduced pressure, and then subjected to silica gel column chromatography (developing solvent: dichloromethane/ethylacetate A/=#// (VO 1 /vo
By refining with l), an oily substance /-13/Jco?
(0.≠j mol) was obtained. Collection '4■] / 1 (2J Synthesis of compound /-C l-(l)T: Obtained compound /-H/JcofCO.p
r mol) in 4,100 ml of water, 77. After adding Of (/, 23 mol), the mixture was heated under reflux for 1 hour. After cooling to room temperature, concentrated hydrochloric acid JOO1d (J.
J mol) was added, and the generated sodium chloride was distributed from door to door.

After concentrating solution F under reduced pressure to about 3005 liters, 3 liters of ethanol was added.
00 ml was added, the resulting crystal tF was collected, and the /-C was crystallized under water and ethanol. 7? (0.JI
mole) obtained.

Yield: 7.1 - (3) Formation of chemical compound / - Chemical compound obtained in (2) / - CP4I. 7y(0
．． Dissolve 3fmol) in 100ml of water and add salt to θ0m
/ ( / . J% le), sub1) 冫鑑4! ,Af/(0.
1 mol) was added thereto, and the mixture was heated to reflux. 37% while refluxing
77 f/(0.2 j mol) of formalin was slowly added dropwise to the axillary portion of the water bath, and after the addition was completed, the mixture was further heated under reflux for 3 hours. After cooling to room temperature 1, 100 ml of ethanol was added to precipitate a white paste-like substance.

By recrystallizing this paste with water and methanol, a white solid is obtained! 6.7 f/(0./6 mol) was obtained. Yield ≠. 2 regrets H. NJL Compound/J no Taisei 0/Ko A/J-8 ・. 2kiCl/2-C/. 2-D Co(1) Compound/Synthesis of 2-B Heacetyl l,3-propanediamine l2-A//
l, if (/.0 mol), potassium carbonate 30μ? (λ.
λ mol), ethyl chloroacetate. From 270f, /-(1
) Same operation as VC to oily substance /J-B /Jrl?
(0.1 j mol) was obtained. Yield: 36% (2) Synthesis of compound lλ-C Synthesis of compound lλ-ByjltCO. j
j mol) and sodium hydroxide T) mlrl. Off (2.2
θ mole) to /− (2) similar method K to f and compound l
λ1C/λtf (0.gt mol) was obtained. Yield 4t7% Co(3) conversion table/. Compound obtained by 2-D Taisei Co. (2) /JC, /24? (
0. mol) in 4 AOO, l of water and hydroxylate it. Tricum toy (0.0 mol) was added, and a solution of 4!ir.6y (0.jJ mol) of glyoxylic acid monohydrate in water/Ottzl was added to the mixture while stirring under water cooling.

This reaction fe! Forgive me/0%Pd-(,'Ko f wo loe,
After removing the catalyst, water was distilled off under reduced pressure, 200 ml of concentrated salt was added, and ethanol was further added to precipitate a white solid.

This white solid was crystallized from water-ethanol to obtain /2-D (0.Jλ mol).

Yield: 67 liters/. Synthesis of 2/-1 code D, ioλ obtained in (3)? (0.3 mol) and subhydrochloric acid IcO. tarmol), phosphorous acid!
7, It (0.7/mol), 37 Man formali/water soluble gt
4t. rt<o. By the same operation as in (3), a white solid/. 6 l, It (0./I mole) of 2 was obtained. Collection S$ 6 attack combination example 3. The composition of the compound CoO (.'}130NHC}l2C:H2Nl{211 0 + H2C=CHCUOH / -A Co0-B ・CoHα J θ-C ?1-1■Uli2e(J(JH / ・211Cl 2o -J) J-(1) Synthesis of 20-H Heaceteletere/diami/(/-A)/0 coy (i.o mol) was dissolved in 200 ml of water, and acrylic acid was dissolved under room reflux. /j/f(
2. /mol) was slowly added dropwise, and the mixture was heated under reflux for one hour. After concentrating the reaction solution, gold ether was added to precipitate a white solid.

By collecting the crystals and precious crystals from methanol/ether, we obtained Kadaimono-0-B/jilt (0.tJ
mole) 倚Friend. Yield 63% J-(2) Synthesis of compound λυ-C 3-(1) Compound co0-B/. t≠f(0.
63 mol) and sodium hydroxide jOfc/. Kotamor)
From the same method as in (2), the compound CO/C is obtained.
≠iy (o.ji mole) was obtained. Yield rl - (3) Synthesis of compound 20-D Synthesis of compound 20-D (2) Obtained compound 2o-C,i/f<o .rtscru) and X sodium oxide r7Afj? (0.7 mol), glyoxylic acid~bonate!/, j? (0,!t mol) to compound 20-J) fYY. O
ff(0.JO%k) obtained fF-.

yield! Ta attack 3 - (4) Synthesis of conversion object 20 J - (3) TLQ et al. 7c combination 'llll J2 0 -
D, TaYW (o, 30 mol) and concentrated hydrochloric acid 1
0ml<0・Tajゝ′)・Ali/gl(jHiro.Jr((
7. AJ mol), J 7% formalin aqueous solution tO. Ifl
CO'. 7! Mol) and /- Compound 20 in the same manner as (3)! 2.39 (0./j mol) was obtained. Yield jO
s In the present invention, a composition having bleaching ability is a processing liquid having the ability f to bleach (oxidize) silver generated in the development process, and commonly referred to as Kanpaku liquid (#! White bath), bleaching fixed! a(
It is called a white fixing bath).

According to the present invention, an intermediate bath such as a water washing bath may be provided between color development and bleaching treatment, but since the effects of the present invention are significantly exhibited, bleaching is performed immediately after color development. Preferably, it is treated with the ability to

In the present invention, bleaching ability '5I: A mark with the general formula (■) 1 or (fl) contained in the t1 yield (hereinafter also referred to as a treatment solution having bleaching ability tl-) White powder powder, le portrait. Ojmol~ko. J mole. When the processing solution having bleaching ability is a bleaching solution, it is preferably 0.7 mol to 0.0 mol/l, particularly O. λ mol A
-7.2 mol is preferred. In addition, when the processing solution with bleaching ability M is a diagonal white fixing solution, /l/t)o. osmol~i,
s mol is preferred, particularly 0.7 mol to O.s mol. 1 t mol is preferred.

The ferric complex salt of the M organic acid expressed by the general formula (1) If (It) used in the present invention may be added as an isolated complex compound, or it may be added as an isolated complex compound, or it may be added as an isolated complex compound with the B organic acid. It may also be formed by mixing iron salts (eg, ferric sulfate, ferric nitrate, ferric chloride, etc.) in solution. When using complex salts with cedar, Fi,/type complex salts may be used, and complex salts of one or more types may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and n M isoic acid represented by the general formula (1) or (II), t'! ．． You may use more than 1 types of iron salts or λ yuzu types. Furthermore, general formula (1) or (
If), one or more types of organic acids may be used. Further, in any of the Js units, the M acid represented by the general formula (1) or (it) may be used in excess of the amount required to form a complex salt with the ferric ion.

The diiron complex salt of M-acid of the present invention may be used in combination with the known diiron complex salt of aminobocarboxylic acid.

The aminobolicarbo/acid or its salt of the aminobolicarbo/ferric complex salt that can be mixed with the ferric acid complex salt of the present invention includes: H-/ethylenediaminetetraacetic acid B-1 ethylenediamine/tetraacetic acid Dinatrichum salt B -J Etele/diami/tetraacetic acid diammonium salt H -1 B-1 H-1 B-7 B -4 B1taB -/0 H -// H -/CoB -/J Ethylenediaminetetra Tetra(trimethylammonicum) acetate salt ethyle/diami/tetrapotassium tetraacetate ethyle/diami/tetranatricum tetraacetate salt ethyle/diaminetetraacetate trisodium salt diethyle/triaminebentaacetate cyethylenetriami/petaacetate/thanatriwam Salt ethylene/diamiy-N-(β-oxyethyl)-1,N
', N'-} trisodium acetate ethylenediamine/-N-(β-oxyethyl), to', N'-} trisodium acetate ethylenediamine/-N-CI-oxyethyl) -N
, N', fV'-} triammonium acetate salt l, λ-diaminopropa/tetraacetic acid B-ipi, λ-diaminopropane tetraacetic acid disodium salt B -/! Nitrilotriacetic acid H-# 2} Lilotriacetic acid trinatricum salt H-/7
/,2-diaminocyclohexanetetraacetic acid H-/I/,2-diaminocyclohexanetetraacetic acid dinatricum salt H-/Timinodiacetic acid B-20 Dihydroxyethylglyci/B-co/
Examples include ethyl ether diamine tetraacetic acid B-2λ glycol ether diamine tetraacetic acid B-co3 ethylene/diami/tetraprobionic acid H-2Hiroshi/J diaminopropane tetraacetic acid. The ferric complex salt of sulfuric acid and the ferric complex salt of aminobolycarbonate of the present invention may be used in combination with each of the seven or more glazes, or each of the two or more may be used in combination. You may.

Furthermore, the diiron complex salt of the organic acid of the present invention and the above-mentioned aminobolicarbo/oxidation compound may be used in combination.

The ratio when the ferric complex salt of the M organic acid of the present invention and the above-mentioned ferric aminobolycarboxylic acid complex salt are used together is a molar ratio ///
It is preferable that 0−/θ//, especially l/! ~j/
/ is preferably 1.

The pH of the treatment solution having whitening ability of the present invention is adjusted to
Good! shi(i, [3~l1Family #''[.g~j
Out. r) H buffering agents include, for example, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, Additives known to be used in processing liquids having normal whitening ability, such as citric acid, citric acid, sodium chloride, inorganic acids with a lactic acid content or higher than that of lactic acid, and their salts. It is possible to use

In the case where the agent having bleaching ability of the present invention is a bleaching solution,
It is preferred to include halogenating agents such as bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, sodium chloride, ammonium chloride. In particular, it is preferable to contain bromide. The most preferred bromide is ammonium bromide. The concentration of the rehalog/curing agent is usually between o, i and j molar in the bleaching solution, preferably /. l≠〜! molar, particularly preferably i.
r Hiro P-3 moles.

Further, it is preferable to use ammonium nitrate as a metal corrosion inhibitor.

When having bleaching ability according to the present invention, a bleaching accelerator may be included.

For alternative bleach accelerators, see, for example, US %FF No. 3,193, III, German Patent No. 1,2YO
, Ill, UK 'PM'F No. i, i3r, reco,
Akira Machikai 3-tazt3og. v Tech Disclosure Younger Brother/. Mercapto group 1 or disnole 7 ide-lI! ．． The imidazole compound described in JP-A No. 3, the thiazolidi/vj conductor described in JP-A No. 3, U.S. Patent No. J,704,! 4/
Thiourine X derivative described in No. 7% Kaishoyu J'-/t2J
Iodide described in No. J, German Patent No. 2,7 $J', 1
Polyethylene oxides described in No. 130, Tokkosho +
The polyamine compounds described in No. t-rIrJt can be used.

Particularly preferred are mercapto compounds as described in British Patent No. i, i3r, r4Aλ.

These bleaching accelerators can also be used by being added to the pre-bath of the processing liquid having bleaching ability of the present invention.

In the process of the present invention, the amount of replenishment of the solution having bleaching ability is if-t- per 1m2 of the photosensitive material, and the preferable tL< is 200
~IOtxt, even better IL, < is 300~lOyal.

In the same process, the white liquor containing iron(III) complex salt is subjected to air foaming (aeration) to produce iron(III).
(2) It is preferable to reoxidize the complex salt.

It is already known to aerate bleaching, and is known in the USIN published by Eastma/Kodakka/Pani
g Process C-Hiroshi/( /ta t2, Z-
/ 2 / Third Edition) Page AHL-2 or Monitoring the per
formation of the process
C-1/ bteach (/Tarco, Z-ico/L)
It is stated in detail that keeping the #4 white liquor in a completely oxidized state through sufficient aeration is extremely important for preventing conjugation and the formation of leucocyan dyes.

In other words, the white solution of ferric complex salt oxidizes the developed silver in the first step and changes to the ferric complex salt by receiving the color developing solution in the previous step, so sufficient aeration is required. It has been thought that it is appropriate to completely oxidize the ferrous/iron complex salt to the ferrous iron complex salt for complete bleaching.

The oxidation state of the raw white liquor of such iron complex salts is
and ferrous io/y expressed in terms of redox potential based on the t ratio of
It is conceivable from the general knowledge of electrochemistry that, in fact, in the white fixing solution of ethylenediamine/iron tetraacetate complex,
It has been disclosed that increasing the oxidation potential of gold prevents the formation of leucosia/color buildup.

When the treatment solution having bleaching ability of the present invention is used for bleaching, a known stabilizer can be added as a stabilizing agent. For example, sodium thiosulfate, thio'tiltM a/
moniwum, ThioWt#Rammoni9munatrichum, thiosulfates such as potassium thio{lift acid, sodium thiocyanate, ammonium thiocyanate/ammonium thiocyanate, thiocyanate/acid salts such as thio7a/potassium acid, thiourea, thioether, etc. can be used. Among them, a/moni thiosulfate 9
It is preferable to have a river. Elephant M of these fixing agents is preferably 93 mol or less per liter, particularly O. j−λ moles are preferred.

The sensitive material treated with the processing liquid having bleaching ability of the present invention is then treated with a liquid having fixing ability (fixing agent, bleach-fixing liquid). The process can be used as an example of failure.

■ Whitening bath, fixed layer bath ■ Bleach bath, one prefecture white fixing bath ■ One bleach bath, one washing bath, one layer bath ■ One bleach bath, one white fixing bath, one pair of bathing ■ One bath, one pair of bathing ■ Here, each bath is one tank. But more than two tanks (for example, λ
~Hirotan) may be used. When the treatment bath is composed of two or more tanks, it is preferable to use a countercurrent supplementation system.

The fixing agent used in the fixing solution has a fixing ability that can be added to the bleach-fixing solution.

In addition, from the viewpoint of promoting fixation, the above-mentioned ammonium thiocyanate (Rhoda/ammonium), thiourea, thioether (
For example, dJ, J-dithia/, l-octanediol)
It is also preferable to use these compounds in combination, and fE1' of these compounds to be used in combination is a transfer liquid or a Qinbai fixer ll! Current F) 0.0
1 mole to 0. Generally, the amount is about / mole, but in some cases, using ~3 moles can greatly increase the foot layer promotion effect.
You can also

The fixing solution or bleach-fixing solution used next to the processing solution having bleaching ability of the present invention contains sulfites as preservatives, such as sodium sulfite, potassium sulfite, ammonium sulfite, and hydroxyl. It can contain minerals such as acetaldehyde, sodium sulfite, bisulfite adducts of aldehyde compounds, and acetaldehyde.

In addition, various fluorescent whitening agents, antifoaming agents, and surfactants,
Organic solvents such as polyvinylpyrrolidone and methanol can be contained, but in particular, as a preservative, JP-A-62
It is also preferable to use the Nurufi 7rR-forming device described in Specification No. 1 of Reference No. 7≠30.

In addition to the ferric complex salt of the organic acid of the present invention, the bleaching agent used next to the treatment liquid having bleaching ability of the present invention may contain the above-mentioned known whitening agent.

Aminobolicarbo 7rII/ferric complex salt is preferred.

In the original white solution which is used next to the processing solution having bleaching ability of the present invention, the bleaching constant solution/l of the bleaching agent of this invention ranges from 0.0/mol to O. j mole, and the favorable IL< is 0.0.
2 mol to 0.3 mol, particularly preferably 0.3 mol. QJ~
O. It is 2 moles.

In the present invention, the bleach-fix solution (mother liquor) at the start of processing is
Dissolve the compound used in the bleach-fix solution mentioned above in water and v! 4, but it may also be prepared by appropriately mixing a bleaching solution and a fixing solution that have been separately prepared. The pH of the fixer is preferably from j to ta, more preferably from 6.7 to f. 1
fc, @p}i of the white fixer is 6 to I. j is good 1
In addition, 4. j~r. o is preferred.

In the present invention, a fixing solution; a white fixing solution has a pKa of t. o~ta. It is preferable to contain at least one pole of an O compound from the viewpoint of preventing white fog.

Examples of these compounds include imidazoles such as aziridine, ibadazole, /1-ethyl-imidazole, l-methyl-imidazole, and λ-methyl-imidazole, and hearylmorpholyl, /-benzene. Irubipasijin etc. can be opened.

The addition t of these compounds is 0.7 P-/θ mol/l, preferably 0.2 to 3 mol/l.

The amount of replenishment of the fixing solution and bleaching fixing solution used next to the processing solution having bleaching ability of the present invention is as follows:
fC vJ 0 011J to 3000tpil or 1
but more preferably from JOOyxl/300II
It is Ll.

Furthermore, it is preferable to add various aminobodies and organic phosphor/acids to the fixing solution and printing fixing solution used next to the processing solution having bleaching ability of the present invention for the purpose of stabilizing the solution. Yes.

The shorter the total processing time of the iron removal process of the present invention, the more effective the present invention will be for the customer. The preferred time is / minute ~ Hirobu,
More preferably, it is 30 seconds to 3 minutes/minute. Further, the processing temperature is λj'-10°C, preferably Jj'C-4cj'C
It is. In a preferred temperature range, the desilvering rate is improved and post-processing stay/starting is effectively prevented.

In the desilvering step of the present invention, it is preferable that the stirring be as strong as possible in order to more effectively exhibit the effects of the present invention.

A specific method for strengthening stirring is JP-A-62-/IJ4A.
A method of impinging a processing jet on the emulsion surface of a photosensitive material described in tO No. 1-cho 6-ko IRS-Hiro 6/No.
J-/♂3≠TL's rotation means Kanagawa is a method to improve the stirring effect, and furthermore, the wiper blade is placed in the liquid and the photosensitive material is moved while the wiper blade and the emulsion surface are in contact, creating turbulence on the six sides of the emulsion. By doing so, a method of improving the stirring effect and a method of increasing the circulation flow Ik of the entire processing liquid are unsuccessful. Such means for improving agitation is effective in any of bleaching solutions, bleach-fixing solutions, and fixing solutions. Improving stirring speeds up the supply of bleaching agent and shielding agent into the emulsion film, and increases the desilvering speed as vermilion.
It is considered that the

1. The above-mentioned stirring improvement method is effective depending on the situation where a bleaching accelerator is used, and can significantly increase the whitening accelerator effect and eliminate the problem of fixed layer inhibition caused by the bleaching accelerator. I'm leaving the country.

The automatic developing machine used in the present invention is JP-A-60-/Y/
2j No. 7, Ir=] 60-/P / 2j F No., 60-/Ta/Ko! Photosensitive material conveying means described in No. 7'
Preferably kNL. Said Japanese Unexamined Patent Publication No. 60-1/
As described in No. 2!7, such transportation means are MiJ
The carry-over of the processing liquid from the bath to the post-bath can be significantly reduced, which is highly effective in preventing deterioration in the performance of the processing liquid. Such effects are particularly effective in shortening the processing time in each step and reducing the amount of replenishment required for processing.

The color developing solution used in the present invention contains a known aromatic primary amino/color developing agent.

Preferred examples include p-7 enylenediamine derivatives,
Representative examples are shown below, but the invention is not limited thereto.

D-/N,N-jether-p-phenyle/diamine D-2 2-amino-! -diethylaminetoluene D-J λ-amino-! -(N-ethyl-N-laurylamino)toluene D Kazuhiro-[N-ethyl-(β-hydroxyethyl)amine]anili/ D-j Komethyl-Hiroshi-[N-ethyl-[β-hydroxyethyl] Amine] Aniline D-6 tt-amino-3-methyl-to-ethyl-? -[β-(methanesulfonamido)ethyl]-anili/ D-7. N-(2-amino-diethylaminophenylethyl)meta/sulfo/amide D-ffN,N-dimethyl-p-7enylenediamine D-1 ≠-amino-3-methyl-N-ethyl-hemethoxyethylanili/ 11 -io Hiro-amino-3-methyl-■ monoethyl-he β-ethoxyethylanili/ IJ-// ≠-amino-3-methyl-heethyl-
N-J-Butquinetheranili/Among the above p-phenylene/diami/derivatives, particularly preferred are exemplified compounds D-j and D-A.

In addition, these ρ-phenylenediamide/derivatives may be salts such as sulfate, hydrochloride, sulfite, p-}rue/nurho7rR salt, and the like. The amount of the aromatic primary amine color developing agent used is preferably about o, i
t to about 0.00 m, more preferably about o. zy ~ approx./02 ll! It is once.

In addition, sodium sulfite, preservatives are added to the color developer.
Calicum sulfite, sodium bisulfite, bisulfite {liilC
Sulfites such as #R potassium, sodium metasulfite, potassium metasulfite, and carbonyl sulfite adducts can be added as necessary.

Preferably, the preservative is added to a color developing solution;
zy~iot, more preferably /f-41.

Further, the aromatic primary amine color developing crude drug is contacted with EG,
Preservative compounds include various hydroxylamines, tv hydroxamic acids listed in JP-A No. 63-+3/Jt+3H1, hydrazines and hydrazides described in JP-A No. 63-1 No. 63-17060, and hydrazides described in JP-A No. 63-17060. -μ reference A
j7 and lmJ 6 j - j J'san 4'j d
7 enols listed in C;
It is preferable to remove hydroxyketo/s, α-aminoketo/s, and/or various saccharides described in No. 1 J6J-J, 4λp4A. My father, along with the above-mentioned Kadaimono, published JP-A No. 63-1-da-23j, t3-λ4I-ko-j, and JP-A No. 63-
Ko76≠No. 7, 6J-/≠60 No. 0, 63-27
Monoamines described in No. 114Il and No. lkTl4j-2jtju, etc., No. 43-3014Ij, tJ
Diamines described in -/460170, t3 Kazuhiro J/J Ta, etc., 4Aj-J/617, and 43-21
．． 6! Polyamides/classes described in No. 63-1 p6zz, nitroki Z radicals described in No. 43-jtJjjI, No. 43-443/No. θ, and g
Alcohol distributed in 3-s3z4A issue, 46j-jt
Oximes described in Aj4A, and Aj4A 63-2324t
It is preferable to use the tertiary amines described in μ7.

Other examples of maintenance cutting include the Tanigoku Kinsharui described in JP-A-17-U4I/4111 and J7-jtJ7≠TA, and JP-A-Sho! Salicylic enemies described in the Tartrozrr issue, Tokukai Shoj
Alkanolamide 7fAs described in US Pat. It is permissible to include the aromatic polyhydroxy compounds listed in Reference No. Re as necessary. Particularly preferred is the addition of aromatic polyhydroxylated compounds.

The color developer gI solution used in the present invention preferably has p}l
ta~/ko, more favorable-zt, <hata~//. 0 and its color vision? #! The solution may also contain other known derivatives of developer components.

In order to maintain the above pH, it is preferable to use a buffering agent for each food.

Specific examples of buffering agents include sodium carbonate, potash carbonate, sodium bicarbonate, potassium carbonate, ri7eR tripotassium, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, and boric acid. potassium,
Sodium tetrafoate (borax), potassium tetrafolate, 0
- Sodium hydroxyl zozoate (sodium salicylate 9)
), 0-hydroxybenzoic acid potassium,! - Sodium sulfo-hydroxybenzoate (!-sodium nurphosalicylate), potassium j-sulfo-hydroxybenzoate (j-sulfosalicylate potassium), and the like. However, the present invention is not limited to these embodiments.

The amount of the buffer added to the color imaging solution is preferably 0.1 mol/l or more, particularly 0.1 mol/l or more. 4
Particularly preferred is I mol/l.

In addition, various chelating agents may be used in the color developing solution as an anti-settling agent for calcium or machinic acid, or for improving the stability of the color developing solution.

As the chelating agent, specific acid compounds are preferred, such as aminobolicarpo/@, M-honuho/#R, and phosphonolycarbohydrates.

Specifics below? 1Jk is shown, but is not limited to these.

Nitrilotriacetic acid, diethyl/triaminopentaacetic acid, ethylene/diami/tetraacetic acid, N,N,N-}limethylenephosphonic acid, ethylene/diamine-N, N, N/, N'-
Tetramethylene/phospho/#% }Lance cyclohexane/diami/tetraacetic acid [%/, cordiaminopo, ? Tetraacetic acid, hydroxyethyliminodiacetic acid, IJ col ether diamide/tetraacetic acid, ethylenecyamine orthohydroxy 7-enyl acetic acid, 11 phosphonobuta/1 l, λl Koichi tricarbo 7fR%/1 hydroxyethylide/-/, /-diphospho/acid, ˜,N'-bin(cohydrochloride/diyl)ethylenediami/-N,N'-diacetic acid.

Two or more of these chelating agents may be used in combination if necessary.

These chelating agents may be added in an amount sufficient to sequester metal ions in the color developer.

For example, 0.00 per liter. /t~iot authority.

Any development accelerator can be added to the color developer VC if necessary. However, the color developing solution of the present invention is polluting and F! In terms of 14a properties and color stain prevention,
Dyl alcohol 1fr: Preferably, it does not substantially contain it. Here, "substantially" means development ffi. /l Toyu Shiko pxl Below, good IL< means that it does not contain M at all.

Other development accelerators include Tokuko Shoj7-/4ortr
No. 37-j t7, Jl-7Ir. 2 Otsu, Oka II II - / 2 JIO, f5J41!
-90/Y and US patent @j, J'/J, -24t7
The thioether conversion device referred to in No. 6, etc., JP-A-Shoj. 2
Ichihirota J' Kota and Hidou 10-/J'! Number 1)-722/Jiami/Keikaidaimono, JP-A-Sho. T.O.
-l37726, special public Akihiro goo! ≠ class ammonium salts represented in JP-A No. 007μ, JP-A-JA-/J61kot and 4JKohiro 3≠Kota, U.S. Pat. /No.12, 11.2J
O,726, No. 3,2j3, Ta/ta, Special Publication Shogu/1//≠3l, U.S. Patent No. J,1712, j4A4
No., same J, jFA,? No. 26 and Iil! JJ,! I-co, 3≠≦, etc., 1-piece amine thread compound, special public interest public 1977-
/tOJ'! No. 1λ-λ120/, U.S. Patent No. 3
, /2g, itJ issue, special public show 4A/-//III/ issue,
Dako λ3trJ and U.S. Patent No. J, 33-2,
! Polyalkylene/oxide, others/-7 enyl-3-virazolid, imidazoles, etc. can be added as necessary.

In the present invention, any antifoggant can be added as necessary. As antifoggants, alkali metal halides such as sodium chloride, potassium bromide, potassium iodide, and antifoggants can be used. Examples of organic antifouling agents include habe/zotriazole, 6-nitrobe/zimidazole, and! -Nitroiso/dazole, methanebentriazole,! -Nitrobe/Ntriazole! -Nitrogen-containing heterocyclic compounds such as chloropenzotriazole, cochiazolylbenzimidazole, λ-thiazolylmethylbenzimidazole, indasolyl, hydroxyazaindolidi/, adenyl/, and/-7 enyl- ! monomercaptotetrazole,
Examples include mercazoto-substituted heterocyclic compounds such as λ-mercaptobe/zimidazole and λ-mercaptobenzotheazole, as well as mercapto-substituted aromatized compounds such as theosalicylic acid.

These antifoggants include those that are eluted from the color photosensitive material into the photosensitive material during processing.

The color developing solution used in the present invention may contain a fluorescent whitening agent. As the fluorescent brightener, ≠,v'-diamino-[lambda],2'-dinurphostilbe/based compound is preferred.

The addition m is θ~rt/l, preferably o. /t-pt/l
Demeru.

Also, upon request, alkyl sulfo/I! j1', arylsulfonic acid, aliphatic acid/acid, aromatic acid 7rR
It is also possible to add active cutting of the Taniyu surface.

The processing temperature of the color developing solution of the present invention is 20 to 50°C, preferably 30 to 45°C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 15 seconds. It is preferable that the amount of replenishment is small, but it is 100 to 1500 mj per 1 piece of light-emitting material.
! Preferably it is 100 to 1000 ml. More preferably 200mj! ~900mj! It is. Further, the color developing bath may be divided into two or more baths as necessary, and the color developing replenisher may be replenished from the first bath or the last bath, thereby shortening the developing time and reducing the amount of replenishment. The processing method of the present invention can also be used for color reversal processing. The black-and-white developer used at this time is a so-called black-and-white first developer, which is commonly used in the reversal process of color luminescent materials. Various well-known additives that are added to the black and white developer used in the processing solution for black and white halogenated iN photosensitive materials can be added to the black and white developer for color reversal photosensitive materials.
It can be included in the developer. Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, 2-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, and development inhibitors consisting of trace amounts of iodides and mercapto compounds. can be given. The processing method of the present invention comprises processing steps such as color development, bleaching, bleach-fixing, and fixing as described above. Here, after the bleach-fixing or fixing process, processing steps such as water washing and stabilization are generally performed, but after a bath with fixing ability, stabilization processing is performed without substantial water washing. You can also use a simple processing method. The rinsing water used in the rinsing process may contain known additives as necessary. For example, hard water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, etc.
A disinfectant that prevents the growth of various bacteria and algae. Antifungal agents (for example, intiazolone, organic chlorine disinfectants, penzotriazole, etc.), surfactants to prevent drying load and unevenness, etc. can be used. Or L. E
．． West, “Water Quality Cr.
iteria” % Photo.Sci.and En
g. , vol. 9. Fh6, page 3
4 4 to 3 5 9 (1965) and the like can also be used. The stabilizing liquid used in the stabilization process is a processing liquid that stabilizes the dye image. For example, a solution having a buffering capacity of pH 3 to 6, a solution containing an aldehyde (for example, formalin), etc. can be used. The stabilizing solution contains ammonium compounds, Bi, Aj!, if necessary. Metal compounds such as, optical brighteners, chelating agents (e.g. ■-hydroxyethylidene-l.l-diphosphonic acid), bactericides, fungicides, hardeners, surfactants, alkanolamines, etc. can be used. In addition, the water washing step and the stabilization step are preferably performed using a multistage countercurrent method, and the number of stages is preferably 2 to 4.The replenishment amount is 1 to 50 times the amount brought in from the previous bath per unit area, preferably 2. ~30 times, more preferably 2 to 15 times.Water used in these washing steps or stabilization steps includes tap water as well as Ca
, Mg1 degree is 5+ag/j! It is preferable to use deionized water, water sterilized with halogen, ultraviolet germicidal lamps, etc. In each of the above processing steps for color photosensitive materials, when continuous processing is performed using an automatic processor,
Concentration of the processing solution due to evaporation may occur, especially when the processing amount is small or the opening area of the processing solution is large. In order to correct such shrinkage of the processing liquid, it is preferable to replenish an excess amount of water or correction liquid. Further, the amount of waste liquid can be reduced by using a method in which the overflow liquid in the water washing step or the stabilization step is allowed to flow into a bath having a fixing ability, which is a pre-bath. The bright light material of the present invention only needs to have at least one layer of a blue S color layer, a green S color layer, and a halogenated emulsion layer, which is often a red light color layer, on a support. There are no particular restrictions on the number or order of the anti-emulsion layer and the non-optical layer. A typical example is a silver halide photographic material having on a support a light scattering layer consisting of a plurality of silver halide emulsion layers having substantially the same color properties but different brightness. The photosensitive layer is a unit photosensitive layer that is sensitive to blue light, green light, or red light, and in multilayer silver halide color photographic light-sensitive materials, generally the unit is photosensitive. The layers are arranged in the following order from the support side: a red-chromic layer, a green-metachromic layer, and a blue-chromic layer. However, depending on the purpose, the above installation order may be reversed, or the installation order may be such that different color-sensitive layers are sandwiched within the same color-sensitive layer. Above, halogenated il! Non-optional layers, such as various intermediate layers, may be provided between the photochromic layers and between the top and bottom layers. The intermediate layer includes JP-A Nos. 61-43748 and 59-1.
No. 13438, No. 59-113440, No. 61-20
Coupler, DIR compound, etc. as described in No. 037 and No. 61-20038 may be included,
It may also contain commonly used color mixing inhibitors, ultraviolet absorbers, stain inhibitors, etc. The plurality of halogen silver emulsion layers constituting each vehicle position light suspension layer are
West German Patent No. 1,121,470 or British Patent No. 9
As described in No. 23,045, a two-layer structure consisting of a high-sensitivity emulsion layer and a low-turbidity emulsion layer can be preferably used. Usually, it is preferable to arrange the halogen emulsion layers so that the optical flux decreases in order toward the support, and a non-photosensitive layer may be provided between each halogen emulsion layer. Also, JP-A-57-
No. 112751, No. 62-200350, No. 62-2
As described in No. 06541, No. 62-206543, etc., a low-sensitivity emulsion layer may be provided on the side far from the support, and a high-sensitivity emulsion layer may be provided on the side close to the support. As a specific example, from the side farthest from the support, low-anger blue light-sensitive layer (BL) / high-sensitivity blue light-sensitive layer (BH) 7' high-sensitivity green light-sensitive layer (CGH) / low anger light-sensitive layer (A) The order of photosensitive layer (GL) / high sensitivity red light sensitive layer (RH) / low sensitivity red light sensitive layer (RL),
Or B H/B L/G L/G H/R H/R
In order of L or B H/B L/GH/GL/RL/R
They can be installed in the order of H, etc. Further, as described in Japanese Patent Publication No. 55-34932, the blue-sensitive layer/G H/
They can also be arranged in the order of R H/G L/R L.
Furthermore, as described in JP-A-56-25738 and JP-A-62-63936, the blue-sensitive layer/GL/R L/C and H/R H are arranged in this order from the farthest side from the support. You can also. Also, special public service 15493/1973
As described in the publication, the upper layer is a silver halide emulsion layer with the highest luminous intensity, the middle layer is a silver halide emulsion layer with lower luminous intensity, and the lower layer is a silver halide emulsion layer with even lower luminous intensity than the middle layer. An example is an arrangement consisting of three layers with different sensitivities, in which the emulsion layer is arranged and the sensitivities gradually decrease toward the support. Even when it is composed of three layers with different photosensitivity, as described in JP-A No. 59-202464, in the same color-sensitive layer, from the side remote from the support, the medium-sensitivity Emulsion Ji5/High sensitivity emulsion layer/
They may be arranged in the order of low-melt emulsion layers. As mentioned above, various layer configurations and arrangements can be selected depending on the purpose of each photosensitive material. Any of these layer arrangements can be used in the color photosensitive material of the present invention, but in the present invention, the dry film thickness of all the constituent layers of the color photosensitive material excluding the support and the undercoat layer and back layer of the support is 20. In order to achieve the object of the present invention, it is preferable that it is 0μ or less. More preferably, it is 18.0μ or less. These film thickness regulations are determined by the color developing agent that is incorporated into these layers of the color photosensitive material during and after processing, and depending on the amount of remaining color developing agent, there may be bleaching problems or stains that occur during image storage after processing. By having a large impact on In particular, the increase in color of magenta, which is thought to be caused by the chlorotic color layer, is greater than the increase in color of other cyan and yellow colors.
Note that it is desirable that the lower limit value in the film thickness regulation be reduced within a range that does not significantly impair the performance of the photosensitive material based on the above regulation. The lower limit of the total dry film thickness of the constituent layers excluding the support of the reflective material and the undercoat layer of the support is 12.0μ, and the lower limit of the total dry film thickness of the constituent layers excluding the support of the reflective material and the undercoat layer of the support is 12.0 μm. The lower limit of the total dry film thickness of the constituent layers is 1.0μ. Furthermore, the film thickness may be reduced in either the photosensitive layer or the non-photosensitive layer. The film thickness of the multilayer color photosensitive material in the present invention is measured by the following method. The sensitive material to be measured is stored at 25°C and 150% RH for 7 days after making the suspension material. First, measure the total thickness of the sensitive material, then remove the coated layer on the support, measure the thickness again, and use the difference to calculate the total thickness of the coated layer of the sensitive material excluding the support. Let the film thickness be . This thickness can be measured using, for example, a film thickness measuring device (^nritu) using a contact-type piezoelectric transducer.
s Electric Co. Ltd. , K −
4 0 2 B Stand. ) can be used for measurement. The coating layer on the support can be removed using an aqueous sodium hypochlorite solution. Next, using a scanning electron microscope, take a cross-sectional photograph of the above-mentioned photosensitive material (magnification is preferably 3,000 times or more), measure the total thickness on the support and the thickness of each layer, and measure the thickness of the previous film. The thickness of each layer can be calculated by comparing it with the total thickness measured by a thickness measuring device (absolute value of the actual thickness). Swelling rate of the photosensitive material of the present invention [(Equilibrium swelling film thickness at 25°C, H*0 - Dry total film thickness at 25°C.55% RH/Dry total film thickness at 25°C. Film thickness) X100) is preferably 50 to 200%, more preferably 70 to 150%. If the swelling ratio deviates from the above value, the amount of color developing agent remaining will increase, and this will have a negative impact on photographic performance, image quality such as derooting ability, and film properties such as film strength. Furthermore, the swelling rate of the photosensitive material of the present invention is 9% of the maximum swelling film thickness in a color developing solution (30°C, 3 minutes 15 seconds).
When 0% is the saturated swelling film thickness and the time taken to reach this l/2 is defined as the swelling rate T'A, T+A is 1.
Preferably, the time is 5 seconds or less. More preferably T! 4 is 9 seconds or less. The photographic emulsion of the color light-sensitive material used in the present invention is silver bromide, silver iodochloride, or silver iodochlorobromide. Preferred silver halides are silver iodobromide, silver iodochloride, or silver iodochlorobromide, containing up to about 30 mole percent silver iodide. Particularly preferred is silver iodobromide containing from about 2 mole percent to about 25 mole percent silver iodide. Silver halide grains in photographic emulsions include those with regular crystals such as cubes, octahedrons, and tetradecahedrons, those with irregular crystal shapes such as spherical and plate shapes, and those with twin planes. It may also be a type with crystal defects, or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.2 microns or less or large grains with a projected area diameter of about 10 microns, and may be a polydisperse emulsion or a monodisperse emulsion. Silver halide photographic emulsions that can be used in the present invention include, for example, Research Disclosure (RD), Na17643
(December 1978), pp. 22-23. “I. Emulsion preparation and
Nal 8716 (1979)” and Nal 8716 (1979
(November 2013), 648 pages, "Physics and Chemistry of Photography" by P. Glafkide, published by Beaumontel (P. Glafkide)
s, Chemic et Physique Photo
ographique Paul Montel+19
67), “Photographic Emulsion Chemistry” by G. F. Duffin, Focal Press (G. F. Duffin, Photog)
rapicEmulsion Chemistry
(Focal Press + 1 9
6 6)), “Production and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V.L., Zel
iksan et at. Making and Co
ating Photographic Emulsi
on, Focal Press. 1 9 6
It can be prepared using the method described in 4). U.S. Patent No. 3,574.628, U.S. Patent No. 3,655,39
Monodisperse emulsions such as those described in British Patent No. 4 and British Patent No. 1.413.748 are also preferred. Tabular grains having an aspect ratio of about 5 or more can also be used in the present invention.
Tabular grains are described in Gutoff, Photographic Science and Engineering.
Photographic Science and
Engineering), Volume 14, 2
4 8-257 (1970); U.S. Patent No. 4,
No. 434,226, No. 4,414,310, No. 4,4
33,048, British Patent No. 4,439,520, and British Patent No. 2,112.157. The crystal structure may be uniform, the inside and outside may have different halide compositions, it may have a phase structure, and silver halides with different compositions may be joined by epitaxial joining. It may also be bonded with a compound other than silver halide, such as silver rhodan or lead oxide. Silver halide emulsions in which a mixture of crystalline grains of seed h may be used are usually those that have been subjected to physical ripening, chemical ripening, and spectroscopic amplification. Additives used in such processes are listed in Research Disclosure Toru 17.
643 and N [118716], and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the relevant descriptions are shown in the table below. 1 Chemical sensitizers 2 Sensitivity enhancers 3 Spectral sensitizers, supersensitizers 4 Brighteners 5 Antifog agents and stabilizers 6 Light absorbers, filter dyes UV absorbers 7 Stain inhibitors 8 Dye image stabilization Agent 9 Hardener IO Binder 1l Plasticizer, lubricant 12 Coating aid, surfactant 13 Static inhibitor RD 7643 23 pages 23-24 pages 24 pages 24-25 pages 25-26 pages 25 right column page 25 26 pages 26 pages 27 pages 26-27 pages 27 pages RD8716 648 pages right same page 648 right column ~ 649 right column 649 pages right column ~ 649 right column ~ 650 left column 650 pages left to right column 651 pages left Column Same as above, page 650 Right column Same as above Same as above Various color couplers can be used in the present invention, and specific examples thereof are described in the patent described in RDkl 7 6 4 3, There is. As a yellow coupler, for example, U.S. Patent No. 3,933.501
No. 4,022,620, No. 4,326,024, No. 4,401,752, No. 4,248,961, Japanese Patent Publication No. 58-10739, British Patent No. 1,425,
No. 020, No. 1,476,760, U.S. Patent No. 3,9
No. 73,968, No. 4,314,023, No. 4,51
1;649, European Patent No. 249,473A, etc. are preferred. As magenta couplers, 5-pyrazolone and virazoloazole compounds are preferred, and European Patent No. 73,6
No. 36, U.S. Patent No. 4,310,619, U.S. Patent No. 4,35
No. 1,897, No. 3,061,432, No. 3,725
, No. 064, No. 4,500.630, No. 4,540,
No. 654, No. 4,556,630, RD Nll2
4220 (June 1984), RD Chu24230
(June 1984), JP 60-33552, JP 601-43659, JP 61-72238, JP 60-
No. 35730, No. 55-118034, No. 60-18
No. 5951, WO (PCT) 8 8/0 4 79
Particularly preferred are those described in No. 5. The effects of the present invention on bleaching fog and staining are particularly noticeable for virazoloazole couplers. As a cyan coupler,
Phenolic and naphthol couplers include U.S. Pat. Nos. 4.052.212 and 4,146.396.
No. 4', 228.233, No. 4,296,20
No. 0, No. 2,369.929, No. 2,801,171
No. 2,772,162, No. 2,895,826, No. 3.772,002, No. 3,758,308,
4,334.011, 4,327,173, West German Patent Publication No. 3,329,729, European Patent No. 121
．． No. 365A, No. 249.453A, U.S. Patent No. 3,
No. 446.622, No. 4,333.999, No. 4,7
No. 53.871, No. 4,451,559, No. 4,42
No. 7.767, No. 4.690,889, No. 4,254
, No. 212, No. 4,296,199, JP-A-61-4
Those described in No. 2658 and the like are preferred. Colored couplers to correct unnecessary absorption of coloring dyes are RD
Paragraph ■-G of No. 17643, U.S. Patent No. 4,163,67
No. 0, Japanese Patent Publication No. 57-39413, U.S. Patent No. 4.00
No. 4,929, No. 4,138.258, British Patent No. 1
, 146,368 is preferred. In addition, couplers that correct unnecessary absorption of coloring dyes using fluorescent dyes released during coupling as described in U.S. Pat. No. 4,774.181, and couplers that react with developing agents as described in U.S. Pat. It is also preferable to use a coupler having as a leaving group a dye precursor which can be used to form a dye. As a coupler in which a coloring dye has a good diffusivity, U.S. Pat. No. 4,366,237 and British Patent No. 2,125 are known.
．． Preferred are those described in No. 570, European Patent No. 96.570, and German Patent Publication No. 3.234,533. Typical examples of polymerized dye-forming couplers are U.S. Pat.
It is described in British Patent No. 4,367,282, British Patent No. 4,409.320, British Patent No. 4,576,910, British Patent No. 2,102.173, etc. Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. DIR couplers that release development inhibitors are disclosed in the patents described in RDl7643, Sections ① to F above, JP-A-57-151944, JP-A-57-15423-4,
Preferably, those described in US Pat. No. 6G-184248, US Pat. No. 63-37346, US Pat. As a coupler that releases a nucleating agent or a development accelerator imagewise during development, British Patent No. 2.097,140, British Patent No. 2,131.188,
Those described in JP-A-59-157638 and JP-A-59-170840 are preferred. Other couplers that can be used in the photosensitive material of the present invention include the axial couplers described in U.S. Pat. No. 4,130,427, etc., and U.S. Pat. , 4,310,618, etc. DIR redox compound releasing couplers, DIR coupler releasing force pullers, DIR described in JP-A-60-185950, JP-A-62-24252, etc.
Coupler-releasing redox compound or DIR redox-releasing redox compound, European Patent No. 173,302A
A coupler that releases a dye that restores color after WI removal, as described in the issue of
RD Koji 11449, 2424l゛, JP-A-61-20
Bleach accelerator-releasing power blurr described in US Pat. No. 4,774.181, which emits a fluorescent color, and the like. The couplers used in the present invention can be introduced into the photoreceptor material by various known dispersion methods. Examples of high-boiling point solvents used in the oil-in-water dispersion method are described in U.S. Patent No. 2,322.027, etc.; Specific examples of boiling point organic solvents include phthalate esters (dibutyl phthalate, dicyclohexyl fucrate,
Di-2-ethylhexyl phthalate, decyl phthalate, bis(2,4-di-L-7milphenyl) phthalate, bis(2,4-di[-amyl phenyl) inphthalate, bis(1,1-diethylpucupil) phthalate ), esters of phosphoric or phosphonic acids (triphenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, trisichexyl phosphate, tri-2-ethylhexyl phosphate, tridodecyl phosphate, tributoxyethyl phosphate, trichloropropyl phosphate, di-2-ethylhexyl phenyl phosphonate, etc.), benzoic acid esters (2-ethylhexylbenzoate, dodecylbenzoate, 2-ethylhexyl p-hydroxybenzoate, etc.) ), amide i (N,N-diethyldodecanamide, N,N-diethyllaurylamide,
N-tetradecylpyrrolidone, etc.), alcohols or phenols (isostearyl alcohol, 2.4-
di-term-amylphenol, etc.), aliphatic carboxylic acid esters (bis(2-ethylhexyl) sebacate, dioctyl azelate, glycerol tributyrate, isostearyl lactate, trioctyl citrate, etc.), aniline derivatives (N,N- (dibutyl-2-butoxy-5-tert-octylaniline, etc.), hydrocarbons (paraffin, dodecylbenzene, diisopyrnaphthalene, etc.), etc.As the auxiliary solvent, the boiling point is about 30°C or higher, preferably Organic solvents having a temperature of 50°C or more and about 160°C or less can be used, and typical examples include ethyl acetate, butyl acetate, ethyl propionate,
Examples include methyl ethyl ketone, cyclohexanone, 2-ethoxyethyl acetate, and dimethylformamide. Specific examples of latex dispersion process steps, effects, and latex for impregnation are described in U.S. Pat.
41.230 etc. These couplers can also be impregnated into loadable latex polymers (e.g., U.S. Pat. No. 4,203,716) in the presence or absence of the high-boiling organic solvents described above.
Alternatively, it can be dissolved in a water-insoluble but organic solvent-soluble polymer and emulsified and dispersed in an aqueous hydrophilic colloid solution. Preferably, the homopolymers or copolymers described on pages 12 to 30 of International Publication No. W088/00723 are used. In particular, the use of acrylamide-based polymers is preferable for stabilizing color images. Suitable supports that can be used in the present invention include, for example, the above-mentioned R
D. K17643, page 28, and Ll8716, page 647, right column to page 648, left column. The present invention can be applied to various color photosensitive materials. Color negative film for general use or motion pictures. , color reversal film for slides or televisions, color paper, color positive film, and color reversal paper.

(Example) The present invention will be explained in more detail with reference to Examples below.
The present invention is not limited to these. Example l On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photosensitive material consisting of each layer having the composition shown below, was prepared. (Composition of photosensitive layer) The coating amount is the amount expressed in g/rd of silver for silver halide, colloidal silver and coupler, and the amount of halogenated in the same layer for sensitizing dye! It is expressed as the number of moles per mole of I. 1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-1
0. IUV-2
0. 2Cpd-10.05 Solv-1 0. 01So
lv-2 0.01So
lv-3 0.08 second
Layer: Intermediate layer fine particle bromide 1! (Equivalent sphere diameter 0.07μ) Silver coating amount 0
．． 15 Gelatin 1, OCpd-
2 0. 2 3rd layer: 1st red-sensitive emulsion layer Silver iodobromide emulsion (Agl 1 0.0 mol%, internal high Agl type, equivalent sphere diameter 0.7μ, coefficient of variation of equivalent sphere diameter 14%, 14-hedral grains) Silver coating amount 0.26 Silver iodobromide emulsion (Agl 4.0 mol%, internal high Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, 14-hedral grains) Silver coating amount 0.2 gelatin
1. OExS-1
4. 5xlO-'mol E
xS-2 1.5X10-'tsEx
S-3 0.4X10-'tsExS
-4 ExC-1 ExC-7 ExC-2 ExC-3 ExC-6 4th layer: 2nd red light emulsion layer Silver iodobromide emulsion (Agll 6 mol%, internal high A.I type, equivalent sphere diameter 1.0μ , coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 4.0) Silver coating amount 0. 55 0.7 3 X 1 0-'IXIO-'0.3X10-'0.3X10-' 0. 05 0.10 0. 08 0. 3 X 1 0-'t4 0. l5 0. l5 0.009 0.023 0. 14 Gelatin ExS-I ExS-2 ExS-3 ExS-4 ExC-3 ExC-4 ExC-6 5th layer: 3rd red-sensitive emulsion layer Silver iodobromide emulsion (Agl 1 0.0 mol%, inner high eight 8! type, equivalent ball diameter 1.2 μ, coefficient of variation of equivalent ball diameter 2
8%, plate-shaped particles, diameter/thickness ratio 6.0) Silver coating amount 0. Gelatin 0. ExS-1
2XIExS-2
0. 6XIExS-3
0. 2XIExC-40. ExC-50・Solv-10. SOLv-20. 6th layer: middle layer gelatin 1. Cpd-4
0. 7th layer: 1st green-sensitive emulsion layer Silver iodobromide emulsion (AJI1 1 0.0 mol%, internal high Agl type, equivalent sphere diameter 0.7μ, 96 0-4 0-4 0-4 07 06 l2 l2 O 1 Coefficient of variation of equivalent sphere diameter 14%, 14-hedral grains) Silver coating amount iodobromide emulsion (8gl 14.0 mol%, internal high Agl type, equivalent sphere diameter 0.4μ, coefficient of variation of equivalent sphere diameter 22%, 14-hedral grains) Silver coating amount Gelatin ExS-5 ExS-6 ExS-1 ExM-1 ExM-6 ExM-2 ExM-5 Solv-1 Solv-5 8th layer: 2nd green emulsion layer Odor Silveride emulsion (8 g! 10 mol%, internally high iodine type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 25%, 0.1 1.2 5xlO-'2X10-'1xto-' 0. 20 0. 25 0. 10 0. 03 0. 40 0. 03 0. 2 Platy particles, diameter/thickness ratio 3.0) Silver coating amount 0.4 Gelatin 0.35ExS-
5 3. sxto-'ExS-6
1. 4xto-'ExS-7
0.7X10-'ExM-10.0
9 ExM-30.01 Solv-1 0.15Sol
v-5 0.03 9th layer: Intermediate layer gelatin 0.5 10th layer: 3rd green emulsion layer Silver iodobromide emulsion (8gllO.o mol%, internal high Agl type, equivalent sphere diameter 1.2μ , coefficient of variation of equivalent sphere diameter 28%,
Plate-shaped particles, diameter/thickness ratio 6.0) IL coating amount 1. 0 Gelatin 0.8ExS-5
2X10-'Ext-60. Ext-70. ExM-3 ExM-4 ExC-4 Solv-1 11th layer: Yellow filter layer CPd-3 Gelatin Solv-1 12th layer: Intermediate layer gelatin Cpd-2 13th layer: First blue-sensitive emulsion layer Silver iodobromide Emulsion (AglO mol%, internal high iodine type, equivalent sphere diameter 0.7 μ, coefficient of variation of equivalent sphere diameter 14%, 14-hedral grains) Silver coating amount Silver iodobromide emulsion (Agl 4.0 mol%, internal high Iodine type, ball equivalent diameter 0.4 8X10-'8X10-' 0. O l O. 04 0.005 0.2 0.05 0.5 0. ■ 0.5 0.1 0.1 μ, ball equivalent Coefficient of variation in diameter 22%, tetradecahedral particles) Silver coating amount 0. gelatin
l. ExS-8
3XIExY-10. ExY-30. ExY-20. Solv-10. 14th layer: 2nd blue emulsion layer Silver iodobromide emulsion (8gll 9.0 mol%, internal high Agl type, equivalent sphere diameter 1.0 μ, coefficient of variation of equivalent sphere diameter 16%, tetradecahedral grains) Silver Application amount 0, gelatin
0. ExS-8
2XIExY-10. Solv-10, 15th layer: Intermediate layer fine grain silver iodobromide (Agl 2 mol%, uniform type, equivalent sphere diameter 0.13μ) Silver coating amount 0. Gelatin 0. 16th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (Agl 4.0 mol%, internal high Agl type, equivalent sphere diameter 1.5 μ, coefficient of variation of equivalent sphere diameter 28%, tabular grains, Diameter/thickness ratio 5.0) i Application amount 1. Gelatin 0. ExS-8
1. 5XIExY-10. Solv-10. 17th layer: 1st protective layer gelatin l. UV-1
0. UV-2
0. Solv-10. Solv-2 0. ．． 18th layer: 2nd protective layer Fine particle bromide 11 (equivalent sphere diameter 0.07u) 2 36 Silver coating amount Gelatin polymethyl methacrylate (diameter 1.5μ) W-1 H-1 Cpd-5 Rate particle UV-1 COOCH2 UV-2 ExM-3 ExC-1 0H ExC-2 ExC-3 0H ExC-6 0H ExC-7 ExC-4 ExC-5 0H CIJ! S ExM-1 CH3 1 ExM-2 ExM-4 ExM-5 Shiki ExM-6 ExY-1 ExY-2 ExY-3 ExS-1 ExS-2 ExS-3 ExS-4 czos ExS-5 C. H, ■ ExS-8 (CL) asOs e? CI{t) 4SO3H − N(C■H,),Ex
S-7 Solv-1 Solv-2 Solv-3 8 8 8 'self゛≧ The fabricated sample was cut and processed into 35 m wide pieces, exposed to a wedge of white light (light source color temperature 4800°K), and subjected to the following process. Processing was performed using a cine-type automatic processor using the processing steps shown.
However, the samples to be evaluated for performance were subjected to imagewise exposure until the cumulative amount of color developer replenishment reached three times the volume of the mother solution tank, and then the samples were processed. The composition and pH of the bleaching solution at this time were changed as shown in Table 1, and the conditions for aeration of the bleaching solution were adjusted every time from a piping section with many 0.21IIIlφ pores provided at the bottom of the bleaching solution tank. The treatment was carried out while foaming for 200 Id. Treatment process Treatment time Treatment temperature Replenishment amount 1 3 minutes 15 seconds 37.8°C 23Jd50 seconds 38
．． 0 ”C 5d 1 minute 40 seconds 38.0℃ 30jd 30 seconds 38.0℃ 20 seconds 38.0℃ 30at 20 seconds 38.0℃ 2M Tank capacity lOl 5l 10l 5j! 5l 5j! Process color development bleaching fixing Washing with water (1) Washing with water (2) Stable drying 1 minute 55 ℃ 0 Replenishment amount is the amount per 1 m of 35-meter width Washing with water is a countercurrent method from (2) to (1) In addition, the bleaching process of the developer is brought in The amount of fixing solution and the amount of fixer carried into the washing process were 2.5 d and 2.0 d per 1 m length of photosensitive material of 35 m width, respectively. Also, the crossover time was 5 seconds in each case, and this time is included in the processing time of the previous step.The composition of the processing solution is shown below. (Color developer) Mother solution (6) Replenisher (self) Diethylenetriaminepentaacetic acid 1.0 1.01-Hydroxyethylidene-1.1 -diphosphonic acid 3.0 3.2
Sodium sulfite 4.0 4.9 Potassium carbonate 30.0 30.0 Potassium bromide 1.4 Potassium iodide 1.5 m Hydroxylamine sulfate + Da 3. t (pH whitening solution by adding β-hydroxyethylamino)-λ-methylaniline sulfate solution) l. j／． 01/0. 01 6 Mamoru/. Ol/0. /0 Mother liquid, replenisher, whitening agent (substitutes are listed in /) 0. j0 0. jj mole mole chelating table (same as above) o. oz o. ozz
mole mole ammonium bromide 9m/tao. oy 70 f nitric acid a/monicum ta 0. Of/koj. Add water and t. ol i. ol9H
t. ot. Here, the chelating material refers to the organic acid that constitutes the organic acid ferric ammonium salt used in the bleaching agent.

(Common to foot dressing mother solution and replenisher solution (y) Ethylene/diaminetetraacetic acid di/.7 ammonia 9
ammonium sulfite ia. o Ammonium theosulfate 9m aqueous solution J reference 0. Od liquid (70097l) Add water /,01p}i
7・θ (washing water)
Mother liquor and replenisher common tap water'frH type strong acidic cation/conversion resin (A/NO《-Light IR-/COOB) manufactured by Rohm and Haas Co., Ltd.
Water is passed through a mixed bed column packed with JHfJ strongly basic anion exchange resin (Amberlite IRA-≠00) to treat calcium and magnesium ion #good to 3 tug/l or less, and then indium dichloride 7 Sodium Anurate-20119/l and Sodium Sulfate/jOyng/lf
t was added.

The pH of this solution is 6. It was in the range of j-7.1.

(Stable liquid) Common to mother liquid and supplementary liquid (Unit V) Formalin (37 whispers) l. 11 surfactant #7
0. 4AL C1,H,
, -(Je-C}12C:H2(Jna10H noethylene glycol /.0 Add water
/． OlρH
j, 0-7. 0 For each of the photographic materials subjected to the above-mentioned treatment, residual silver in the dark key areas with the highest color development was measured by fire source X-ray analysis. The results are shown in the meeting.

First, the NFC obtained by processing these samples is measured once, and the green element (G element) is measured from the characteristic curve.fcDmin
Read each value.

Next, as a standard whitening solution with no bleaching power, change to the following treatment solution formulation, set the bleaching time to 320 seconds, and the treatment temperature g
3y 0C, supplementary at is 21ml/3jmm sample length/
A friend that performs processing without changing anything else.

(Standard bleaching solution) Mother a(r) Replenishment <W) Etele/Jami/4/θθ. 0/co0.0 Sodium ferric acetate trihydrate ethylene/diami/4 10.0 //. 0 disodium acetate salt ambromide/moniwaum/≠o. o ito, o ammonium nitrate 30.0 31.0 ammonia water (27%) 6. 6ag Hiromu.
Add Oal water /・04 /-
04p l{t. O
j． 7. The treated sample obtained using the above standard bleaching solution was similarly measured, and from the characteristic curve, Dm
The in value was read.

These obtained Dmin@i are the iJm of the reference whitening solution.
The difference between each sample, ΔDmin1r, was determined based on the in value. In addition, the standard bleaching g. Obtained by using all f
cLlmin value is o. A friend who meets to.

Bleached turnip! j (ΔDmin) = (Dmin of each trial Q)
-(L of standard bleaching solution)mtn) The results are shown in Section 1.

Next, the above sample was used, and the increase in stay/during the sample storage after treatment was stored under the following conditions and determined from the change in concentration of L) min of the uncolored portion before and after storage.

Dark and moist heat conditions: 6θ0C, 70 kLH, ≠Weekly nut/increase (ΔD) = (lJmin after storage) - (jJmin before storage) The results are also shown in Table 1.

Comparative Compound A Comparative Compound B Comparative Compound C Comparative Compound D Comparative Compound E From the results of 6/, the compound of the present invention can reduce residual silver t compared to the comparative compound, and at the same time reduce bleaching fog and color image storage after processing. It can be seen that excellent effects are also exhibited for STAY/.

Experimental Experiment 2 On a cellulose triacetate film support with an undercoat,
Sample 20/, which is a multilayer color photosensitive material, was prepared by applying layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/rrf units, and for silver halide, the coating amount is expressed in terms of silver. However, for the sensitizing dye, the amount applied per 1 mole of the halogenated 11 of -1 is shown in moles. (Sample 401) 1st layer (antihalation layer) Black colloid 11 0.18 Gelatin 1.00 2nd layer (intermediate layer) 2.5-di-L-pentadecylhydroquinone 0. l8EX-1
0.07EX-3
0.02EX-12
0.002U-1
0.06U-2
0.08U-3
0.10HBS-1
0.10HBS-2 Gelatin 3rd layer (first red-sensitive emulsion layer) Emulsion A Emulsion B Enhanced dye I Enhanced dye ■ Sensitizing dye ■ EX-2 EX-14 EX- 1 0 HBS-1 Gelatin 4th layer (first red-sensitive emulsion layer) 2 red emulsion layer) Emulsion G Aggravating dye! Sensitizing dye ■ Exacerbating dye ■ EX-2 EX-14 0. 02 0. 90 0. 25 0. 25 9X10-'8X10-'IXIO-' 0.160 0. 185 0.020 0.060 0. 80 1. O IXIO-'4xlo-'3xlO-' 0.200 0.210 EX-3 EX-10 HBS-1 Gelatin 5th layer (third red-sensitive emulsion layer) Emulsion D Sensitizing dye I Enhanced dye ■ Enhanced dye ■ EX -3 EX-4 EX-2 HBS-1 HBS-2 Gelatin 6th layer (intermediate layer) EX-5 HBS-1 Gelatin 7th layer (first green-sensitive emulsion layer) 0.050 0.015 0.060 l ．． 20 1. 60 4X10-'4XIO-'4XlO-' 0.010 0.080 0.097 0, 22 0,10 1. 53 0.040 0. 020 0. 60 Emulsion A Emulsion B Enhanced dye ■ Sensitizing dye ■ Enhanced dye ■ EX-6 EX-15 EX-1 EX-7 EX-8 HBS-1 HBS-3 Gelatin 8th layer (second glaucoma emulsion layer) Emulsion C Sensitizing dye ■ Aggravating dye ■ Sensitizing dye ■ EX-6 EX- 1 5 0. 15 0. 15 0XIO-'oxto-'8X10-' 0.120 0.145 0. 021 0,030 0.025 0.100 o. oto O. 63 0. 45 lxlo-'Oxlo-'5xto-' 0.047 0.047 EX-8 EX-7 HBS-1 HBS-3 Gelatin 9th layer (third green-sensitive emulsion layer) Emulsion E Silver mulching dye V 3. Sensitizing dye Vl 8. Multiplying dye■
3. EX-13 EX-11 EX-1 HBS-1 HBS-2 Gelatin 10th layer (yellow filter layer) Yellow colloidal silver Silver EX-5 HBS-1 0.01B 0.026 0.160 o. ooa O. 50 1.2 5XlO-'OXIO-'OXIO-' 0.015 0. 100 0.025 0. 25 0. 10 1. 40 0. 05 0. 08 0. 03 Gelatin 11th layer (first blue-sensitive emulsion layer) Emulsion A Emulsion B Emulsion F Sensitizing dye ■ EX-9 EX- 1 6 EX-8 HBS-1 Gelatin 12th layer (second blue-sensitive emulsion layer) G Enhancement dye ■ EX-9 EX-16 EX-10 HBS-1 Gelatin 13th layer (third blue-sensitive emulsion layer) 0.95 0.08 0.07 0.07 5X10-' 0.350 0.400 0 .042 0.28 1.10 0.45 2. IXIO-' 0.070 0.093 0.00? 0.05 0.70 Silver emulsion H Silver 0.77 Sensitizing dye■ 2.2X10-'EX- 9
0. ,20HBS-1
0.07 gelatin
0.69 14th layer (first protective layer) Emulsion r tNo. 5U-4
0.11 (J-50.1
7 HBS-1 0.05 Gelatin 0.80 15th layer (2nd
Protective layer) Polymethyl acrylate particles (diameter approx. 1.5 μm) 0.54S-1
0.20 gelatin
1.10 In addition to the above ingredients, gelatin hardener H-1 and a surfactant were added to each layer. EX- 1 EX-2 (4 0■ EX-3 0H EX-4 υH 0H c.o+ff(n) 1 CJ+3(nJ EX-6 EX-7 EX-8 EX-9 EX-10 EX-11 0H EX- 12 EX- 1 3 EX-14 EX-15 EX-16 U-1 U-2 U-3 0H 011 (j) C a H ? U-4 UV-5 HBS-1 Tricresyl phosphate HBS-2 Gene - Butyl phthalate enhancing dye I Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye V Sensitizing dye ■ Sensitizing dye ■ Sensitizing dye ■ S-t CIlff ■ H-1 CHt-CI-SOt-CHx-CONI{-CHzC
Hi-CM-Sow-CHg-CONH-CHi The above photosensitive material was processed as follows. Processing method step Processing time Processing temperature Replenishment amount 0 Tank capacity Color development 3 minutes 5 seconds 38℃ 25+d 10
j! Bleach 40 seconds 38°C5jd4f
fi bleach fixing 40 seconds 38°C
4j! Fixation 40 seconds 38℃ 1
6jd 4j! Washing with water (1) 30 seconds
38°C 2j! Washing with water (2)
20 seconds 38℃ 30ad 2j! Cheap
Constant 20 seconds 38°C 20d
2Il drying 1 minute 55℃ 0 Replenishment amount is the amount per 1m length in 35cm The water washing process is (2
) to (1), and all the overflow of the bleach solution was introduced into the bleach-fixer. Further, all the overflow liquid from water washing (1) was allowed to overflow to the fixing bath, and all the overflow liquid from the fixing bath was allowed to overflow to the bleach-fixing bath. Incidentally, the amount of fixing solution brought into the water washing step in the above treatment was 35 cm/m per 1 m length of the light-sensitive material f)2d'''C.

(Color developer) Same as color developer in Example 1 (#4 day solution) Mother solution replenisher description) Add ammonium bromide/monium nitrate water to pH (Fixer) (Aqueous solution of ammonium theosulfate/monium nitrate wL) 7001//l) Add Etile/Diami/Tetraacetic acid/Sulfite/Moniwam water to pH whitening fixer) ltaOf/7. jt/. 04 6.0 Mother liquor λIOal lco. 6f ko7. jf /1 7. f 2709 coz. o't/. Ol6. O Owl Jlff tco. jt /1 j. O Bleach solution: Fixer g: Washing solution = j:/4:jO (volume ratio).

(Washing liquid) Same as the washing liquid in Example 1 (stable liquid) Common to mother liquor and replenisher (Unit?) Formalin (37 rice cakes) Co. OJ borioxyethylene-p-0.3 Seven nononyl 7 enyl ether (average degree of polymerization/0) Ethylenediami/tetraacetic acid di 0.02 Add sodium brine and l. Olpit
z, or. o Next, the amount of ambromide/moniwam in the prefectural white liquor was changed as shown in the first batch, and the treatment was carried out after continuous treatment without changing the other treatment methods. The obtained sample #+, which had been processed, was subjected to # side measurement, and the Dmin value measured in the green color was determined from the characteristic curve.

10,000, used in Example/fc-! Samples were treated with a semi-bleaching solution and treated in the same manner as above and -1 to determine the l) min value. Based on the Dmin value of this standard whitening solution, bleach fog and ΔDmin were determined in the same manner as in Example 1.
The value was calculated. At this time, the Dmin value using the standard bleaching solution was 0. ．． It was t7. The results are shown in Table λ.

Subsequently, using the above-treated sample, staining was carried out under the same conditions as in Example 1 for staining during image storage after processing, and the staining was evaluated in the same manner. These results are also shown in Table λ.

Furthermore, the gray density is l. Samples to which a uniform exposure was applied so as to have a uniform exposure rate were treated in the same manner as before, and the silver remaining in these samples was quantified by the hot spot xH method. These results will also be shown to the third party.

From the results, it can be seen that the compound of the present invention has further improved desilvering properties and staining when compared with Yangtai containing a large amount of ammonium bromide/monium bromide. On the other hand, when the relatively soft compound A had an increased ammonium bromide saturation, the de@erability improved, but the nutin content deteriorated slightly.

From these facts, by using the compound of the present invention and using a certain amount or more of ammonium bromide, it is possible to perform a rapid desilvering process without bleaching fog and with excellent stain and rinsing properties. I know what I can do.

Example 3 A multilayer color photographic paper having the layer structure shown below was prepared on a support that was laminated on both sides with polyethylene. The coating solution was prepared as follows. First layer coating solution preparation Yellow coupler (ExY) 19.1 g, color image stabilizer (Cpd-1) 4.4 g and color image stabilizer (Cpd-1)
-7) Add and dissolve 27.2 cc of ethyl acetate and 8.2 g of solvent (Solv-1) to 0.7 g, and dissolve this solution in 8 c of 10% sodium dodecylbenzenesulfonate.
(Emulsified dispersion A). On the other hand, silver chlorobromide emulsion A (cubic, large size emulsion A with an average grain size of 0.88-0.7
0-3:7 mixture (silver molar ratio) with small size emulsion A.
The coefficient of variation of particle size distribution is 0.08 and 0.1, respectively.
0.0, each size emulsion contains 0.2 mol % of silver bromide locally on the grain surface).
per mole for large size emulsion A, respectively 2.
For small size emulsion A, 2.5 x 10-' moles were added, and then sulfur sensitization was carried out. The above emulsified dispersion A and this silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the composition shown below. The coating solutions for the second to seventh layers were prepared in the same manner as the first layer coating solution. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloros-}riazine sodium salt was used. The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each light-sensitive emulsion layer. Sensitizing dye A for blue-sensitive emulsion layer SO3” SOsll ・N(Calls)s
Sensitizing dye B SOx” SOJH (CJs)s for blue-sensitive emulsion layer (per mole of silver halide, 2.0 each for large size emulsion A)
X 10-' mol, and 2.5X 1 G-' mol each for small-size emulsion A] Sensitizing dye C for green-sensitive emulsion layer (per 111 moles of halide, 4.OX10 for large-size emulsion B) -' mole, 5.6X10-' mole for small size emulsion B) and sensitizing dye D for green-sensitive emulsion layer (per mol of halogenated, ?.OX10-' for large size emulsion B) mol, or t.oxto-' mol for small size milk IB) Sensitizing dye for red-sensitive emulsion layer E CtHs I@CsHt + (per mole of halogenated 11, for large size emulsion C 0. For the red-sensitive emulsion layer, the following compounds are added to the halogenated 1
1. 2.6 x 10-" mol was added per 1 mol. Also, 1 mol was added per 1 mol.
-(5-methylureidophenyl)-5-mercaptotetrazole at a rate of 8.5 per mole of silver halide, respectively.
X10-'mol, ? ．． 7X10-'mol, 2.5XlO
−'mol added. Furthermore, 4-hydroxy-6-methyl-1.3.3a.
7-tetrazaindene was added in amounts of IXIG-' mol and 2XlO-' mol, respectively, per mol of silver halide.
In addition, the following dyes were added to the emulsion layer to prevent irradiation. SO3Na and (layer structure) The composition of each layer is shown below. The number is the coating amount (g/rr?)
represents. Silver halide emulsions represent coating amounts in terms of silver. Support polyethylene laminate paper [The polyethylene on the first layer side contains a white pigment (TiOz) and a bluish dye (ulmarine blue)] First layer (blue-sensitive emulsion layer) The above-mentioned silver chlorobromide emulsion A 0.30 gelatin 1 .86 Yellow coupler (ExY) 0.82 Color image stabilizer (Cpd-1) 0.19 Solvent (Solv-1) 0.35
Color image stabilizer (Cpd-7) 0.
06 Second layer (color mixing prevention layer) Gelatin 0.99 Color mixing prevention agent (Cpd-5) 0.08 Solvent (Solv-1) 0.1
6t capacity (Solv-4)
0.08 Third layer (glauclolucent emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion B with an average grain size of 0.55x and small size emulsion B with an average grain size of 0.39m):
3 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.10 and 0.08, respectively, and each size emulsion is AgB.
rO. (8 mol% was locally contained on the particle surface)
0.12 gelatin
1.24 magenta coupler (ExM)
0.2Q color image stabilizer (Cpd-2)
0.03 color image stabilizer (Cpd-3
) 0.15 color image stabilizer (Cpd
-4) 0.02 color image stabilizer (C
pd-9) 0.02 solvent (So
lv-2) 0.40 Fourth layer (ultraviolet absorption layer) Gelatin 1.58 Ultraviolet absorber (UV-1) 0.47 Color mixture prevention agent (Cpd-5) 0.0
5 Solvent (Solv-5) 0
．． 24 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion (cubic, large size emulsion C with an average grain size of 0.58μ and small size emulsion C with an average grain size of 0.45μ):
4 mixture (Ag molar ratio). The coefficient of variation of grain size distribution is 0.09 and 0.11, respectively, and each size emulsion is Ag8.
rO. (6 mol% was locally contained on a part of the particle surface)
0.23 gelatin
1.34 cyan coupler (ExC)
0.32 color image stabilizer (Cpd-6)
0. 17 color image stabilizer (Cpd
-7) 0.40 color image stabilizer (C
pd-8) 0.04t capacity (S
olv-6)
0.15 Sixth layer (ultraviolet absorbing layer) Gelatin 7 0.53 Ultraviolet absorber ([IV-1) 0. 16
Preventing color mixing (Cpd-5) 0.
02 Solvent (Solv-5)
0.08 Seventh layer (protective layer) Gelatin 1.33 Acrylic modified copolymer of polyvinyl alcohol (denaturation degree 17%)
) 0.l7 Liquid paraffin 0.03 ([! ExC) Cyan coupler CI R"CtHs, CaHq, and CI mixture in a weight ratio of 2:4 = 4 (Cpd-1) Color image stabilizer (Cpd-2) Color image stabilizer cooc yiH. (Cpd-3) Color image stabilizer (Cpd-4) Color image stabilizer CsH+ + (t) CJt+ (t) (Cpd-5) Color mixture prevention agent 0H (Cpd-6) 2:4:4 mixture of color image stabilizers (weight ratio ) (Cpd~7) Color image stabilizer-{CHt-CHh- (Cpd-8) Color image stabilizer OH (Cpd-9) Color image stabilizer (υv-1) Ultraviolet absorber CaH*(t) 4 : 2 = 4 mixture (weight ratio) (Solv-1) Solvent (Solv-2) 2:1 mixture of solvent (volume ratio) (Solv-4) Solvent (Solv-5) Solvent 000C.Hl? (CHi) a COOCJ+y (Solv-6) solvent Next, the following treatment solution was prepared.

Ridemel.

The composition is as follows: water passing through ethylenediamine/1 to I N I N',N'-tetramethylene/honuho/potassium acid bromide potassium chloride triethanolamine potassium carbonate 1 m Chemicals] Diethylhydroxylamine to ethyl (β-methaneurpho/amidoethyl) -3-methyl≠-amine 400J Co.Of O,0119 3./Tio.oy 2 7?i.oy Gu,21 Add water/ 000xl pH (coj 'c) / 0.0! Bleach-fix water A/monicum thiosulfate (70%) Sodium sulfite 4' 0 0xl /00wl 77F Add water /000txlpi
{(λz QC) A・0ri/nu quasi ion exchange water (calcicum and magnesium each
m or less] The above photosensitive material was processed as follows.

Processing process m degree time color development Jff'C reference J second bleaching
Jj”C 471 seconds re/s■ J!0C
KO seconds/su■ 3yo0C KO0sho/nu■ Jj0C 20 seconds drying to'c to seconds,
Gray density/. K uniform viscera yt. The specimens given the same amount were processed in the same way as Oka, and the remaining silver in the highest degree part of these samples was quantified by Ik1k fluorescence X-ray method. The results are shown in Table 3.

Comparative Compound C From the above results, it was found that when the present invention was used, the amount of residual silver was reduced compared to Comparative Compound C.

(Effects of the Invention) By using the M composition having bleaching ability of the present invention, rapid processing with excellent desilvering properties can be achieved with no whitening fog and less stain/occurrence after processing.

Claims (4)

[Claims] (1) A composition having bleaching ability for a silver halide color photographic light-sensitive material containing a compound represented by the following general formula (I) and/or a ferric complex salt of a compound represented by the general formula (II) as a bleaching agent. thing. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W^1 represents an alkylene group with a total number of carbon atoms of 3 or less. L^1, L^2, L^3 and L^4 are Each independently represents an alkylene group or an arylene group.M_1
, M_2, M_3, M_4, M_5 and M_6 each represent a hydrogen atom or a cation. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, W^2 represents a divalent linking group. L^5, L^
6, L^7 and L^8 each independently represent an alkylene group or an arylene group. M_7, M_8, _M9
, M_1_0 and M_1_1 each represent a hydrogen atom or a cation. ) (2) The processing solution with bleaching ability contains 1.84 mol of bromide.
/l to 5 mol/l (
1) A composition having bleaching ability as described above. (3) In the general formula (I) described in claim (1), L^
1. A composition having bleaching ability, characterized in that at least one of L^2, L^3, and L^4 is an ethylene group. (4) Processing of a silver halide color photographic light-sensitive material characterized in that the imagewise exposed silver halide color photographic light-sensitive material is processed with the composition having bleaching ability according to claim (1) after color development. Method.