JPS6076745A - Method for processing color photographic sensitive material - Google Patents

Abstract

PURPOSE:To form a color photographic image of high quality by adding a bleaching accelerator and a specified thiourea compound to a bleaching bath, a bleach-fix bath or the preceding bath to carry out bleaching in a short time without causing delay in fixing action. CONSTITUTION:A bleaching accelerator (A) selected among compounds each having a mercapto group or a disulfide bond such as a compound represented by formula I , thiazolidine derivs. such as a compound represented by formula IIand isothiourea derivs. such as a compound represented by formula III and a compound (B) represented by formula IV (where each of R1-R3 is H, lower alkyl, amino, allyl or the like) are added to a bleaching bath, a bleach-fix bath or the preceding bath. When a color photographic sensitive silver halide material is desilvered after exposure and color development, a color photographic image of high quality is formed. Preferred examples of the compound (B) are compounds represented by formulae V, VI.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide color photographic material for developing, bleaching, and fixing an exposed silver halide color photographic material (hereinafter referred to as blade 2-photosensitive material). This method relates to a material processing method C (hereinafter referred to as a color photographic processing method), and in particular accelerates the bleaching action, shortens the processing time, and provides sufficient
The present invention relates to an improved bleaching process that can perform whitening and form color photographic images of good quality without interfering with the fixing action.

Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. That is, the exposed silver halide color photographic material is subjected to a color development process. Here, silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former to provide a dye image. Afterwards, the color photographic material is subjected to a desilvering process. Here, the silver produced in the previous step is oxidized by the action of an oxidizing agent (commonly called a whitening agent), and then dissolved and removed by lead removal of silver ions, commonly called a fixing agent. Therefore, only a dye image is produced in the photocopy that has gone through these steps. In addition to the two basic steps of color development and desilvering mentioned above, the actual development process includes auxiliary steps such as preserving the artist's photographic and physical product IR or improving image retention. Contains processes. For example, a hardening bath is used to prevent excessive softening of the photosensitive layer during processing, a stop bath is used to effectively stop the development reaction, an image stabilization bath is used to stabilize the image, and a backing solution for the support is excluded. Examples include membrane removal baths for

In addition, the desilvering process mentioned above is carried out in two steps, with the bleaching bath and fixing bath being separate baths, and in other cases, the processing process is simplified for the purpose of speeding up processing and saving labor, and the bleaching agent and fixing agent are used together. In some cases, it is carried out in one step using a bleach-fixing bath.

(Prior art) Generally, bleaching agents include red blood salt, dichromate, and dichloride.
Iron, ferric ion complex salts, persulfates, etc. are known.

However, among these bleaching agents, red blood salt, dichromate, and ferric chloride have strong oxidizing power and are good bleaching agents, but red blood salt releases cyanide by photolysis, and dichromate Since the salt is a divalent chromium compound, it also poses a pollution problem, and special treatment must be taken to render the treated waste liquid harmless.

In addition, bleaching solutions using ferric chloride as a bleaching agent have a very low pH and a very high oxidizing power, so they have the disadvantage that the components of the processing solution filled with them are easily corroded. It has the disadvantage that iron hydroxide is precipitated in the emulsion layer in the subsequent water washing process, resulting in staining.

Ferric ion complex salts (e.g. aminopolycarboxylic acid ferric ion/complex salts, etc., especially iron ethylenediaminetetraacetate (l
[l) Complex salts] are used as bleaching agents in bleach-fix solutions for color photographic paper, etc. (German Patent No. r6A&Os, German Patent No. 27J≠IO, British Patent No. 7≠tjt
Specification No. 7, Specification No. y33orr, No. 10/1
(No. 1396 Akira Jl fJ) The ferric ion/complex salt can also be used as a bleaching bath by containing bromide.

However, since ferric ion complex salts have a relatively small oxidizing power and do not have an adequate bleaching edge, products using this as a bleaching agent are, for example, low-sensitivity silver halide color photographs based on silver chlorobromide emulsions. The desired purpose can be achieved when the material is subjected to sh treatment or bleach-fixing treatment, but silver chlorobromoiodide or silver iodobromide emulsion is used as the main emulsion,
And when processing high-sensitivity silver halide color photographic photosensitive materials, especially color reversal photosensitive materials for photography using high silver content emulsions, and color negative photosensitive materials for photography, bleaching action is required. This has the disadvantage that insufficient desilvering may occur or that bleaching takes a long time.

Persulfates are known as bleaching agents other than ferric ion complex salts, and persulfates are usually used as bleaching solutions in the form of chlorides. However, a disadvantage of bleaching solutions using persulfates is that they have a weaker bleaching edge than ferric ion complexes and take a significantly longer time to bleach.

In this way, bleaching agents that are not polluting or corrosive to equipment are associated with weak bleaching blades, and therefore bleaching agents with weak bleaching blades, especially bleaching solutions or bleaching using ferric ions/complex salts or persulfates, are recommended. It is desired to increase the bleaching capacity of fixers.

In order to perform sufficient bleaching using bleach solutions containing ferric ion complex salts or persulfates, or ti bleach-fixing agents, which have insufficient bleaching blades, it is necessary to add various bleaching accelerators to the processing bath. is proposed.

For example, as a bleaching accelerator for a bleaching solution of a sulfur complex salt or a bleach-fixing solution in combination with thiosulfate ions, US Pat. /≠/Various mercapto compounds as described in Publication A23, compounds having a disulfide bond as described in JP-A-53-25630, 'l'J Kosho J3-TSP Publication Thiazolidine derivatives as described in JP-A-53-712.2
The isothiourea derivatives described in Japanese Patent Publication No. 7, Japanese Patent Publication Sho ≠ 5-trot Publication, Japanese Patent Publication No. 4c Ta-2 Atrt
Thiourea derivatives as described in Japanese Patent Application Publication No. 3! ;-2tjOA, such as dithiocarbamates as described in Publication No. 2tjOA.

In addition, as a bleaching accelerator for persulfate bleaching solution, Re5ea
rcJ Disclosure &/5704'(Ma
y/ri77) and U.S. Pat. No. 377,202-+18
Examples include mercapto compounds, compounds having a disulfide bond, and isothiourea derivatives as described in .

However, among the above bleaching accelerators, thiourea derivatives, thioamide compounds, and dithiocarbamates do not have sufficient bleaching accelerating effects and cannot achieve the purpose of speeding up the bleaching process.

In addition, some compounds that have mercapto groups or disulfide bonds in their molecules, thiazolidine derivatives, and isothiourea derivatives have a substantially sufficient bleaching promoting effect, but they all delay the fixing action. It has a big drawback.

In particular, if color photographic materials containing silver iodobromide are continuously processed, such as by replenishing the processing solution, the fixing action will be significantly delayed and desilvering may occur, resulting in poor image quality. It becomes impossible to obtain color photographic images.

(Objective of the Invention) The first object of the present invention is to provide a processing method that is excellent in bleaching speed and capable of forming color photographic images of good quality without causing a delay in the fixing action. .

A second object of the present invention is to provide a color photographic processing method that has low toxicity and meets the requirements for pollution prevention.

In addition, the purpose of 8g3 of the present invention is to increase the bleaching edge without delaying the fixing action in bleaching or bleach-fixing processing using a bleaching agent with a weak bleaching edge, especially a ferric ion complex salt or a common value 11 parent salt. The purpose is to provide a method.

(Structure of the Invention) As a result of various studies, the present inventors have developed the following color photographic processing method capable of achieving the above object.

That is, the present inventors used at least one compound selected from compounds having a mercapto group or a disulfide linkage, thiazolidine derivatives, and isothiourea derivatives as a bleaching accelerator.
When using these bleaching accelerators, a thiourea compound represented by the general formula (1) in F is included in the whitening bath, bleach-fixing bath, or their pre-bath. It has been found that color photographic images of good quality can be obtained, with the bleaching accelerator's effect significantly reduced and the effect of the bleach accelerator not lost in the slightest.

The prebath herein means a bath used after color development and before processing with a bleach bath or bleach-fix bath.

In the present invention, the bleach accelerator and the compound of general formula (1) may be added to the same bath or may be contained in separate baths, but preferably in the same bath.

General formula (i) In the formula, R1, R2, and R3 may be the same or different, and each is a hydrogen atom or a lower alkyl group that may have a substituent (preferably one having 1 to 3 carbon atoms. For example, methyl group, ethyl group, hydroxylmethyl group, hydroxyethyl group, carboxyethyl group, carboxyethyl group, etc.), optionally substituted amino groups (for example, those substituted with lower alkyl groups, i.e., methylamino group, ethyl It represents an alkylamino group such as an amino group, a dialkylamino group such as a dimethylamino group or a diethylamino group), or an allyl group. However, at least one of R, ′fL2, 几
One is a hydrogen atom, and R□, lmo2, and ■ are connected to each other to form a structure (for example, a saturated or unsaturated j-A membered ring).
may be formed.

As 几, 〜I(3), a hydrogen atom or a lower alkyl group which may have a substituent is particularly preferable.

Thiourea compounds other than those represented by the general formula (1) have little effect on reducing the delay in fixing, and on the contrary, they sometimes significantly increase the delay in fixing.

Preferred specific examples of the compound of general formula (1) are shown below.

([) -11) (1) -L2J CI)-(3) (1)-(4) (1) -(b) (1)-(6) 1 (1) -(7) 1 (1) -(8) (1)-(9) (1)-(11 ([)-αη CI)-(2) All of the compounds represented by the general formula (1) of the present invention are known compounds, and , can be synthesized by a known method.

The compound of general formula (i) may be contained only in the bleach bath or bleach-fix bath or a pre-bath thereof, or may be contained in both the bleach bath or bleach-fix bath and the pre-bath. The amount of the compound of the present invention to be added to these solutions varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc. , 10 to 7θ mol, preferably /X10 , /XlO mol.

The bleaching accelerator to be used in combination with these thiourea compounds is selected from compounds with mercapto groups or disulfide bonds, thiazolidine derivatives, and isothiourea derivatives, and has the effect of accelerating bleaching. It is good if there is, but preferably N4)
It is expressed as

General formula (11) In the formula, 1L4 and R5 may be the same or different, and are a hydrogen atom, a lower alkyl group (preferably carbon number/~51, particularly a methyl group, an ethyl group, and a propyl group) or an acyl group ( Preferably, the number of carbon atoms is 1 to 3, such as an acetyl group or a propionyl group, and □ is an integer of 1 to 3.

R4 and R5 may be linked to each other to form a ring.

As 几4 and 几, a lower alkyl group is particularly preferable.

General formula (1) In the formula, 几6 and 几7 are R4 and 几 of general formula (II).

is synonymous with n is an integer from 1 to 3.

(2) and R7 may be linked to each other to form a ring.

As 几6 and 几7, lower alkyl groups are particularly preferred.

General formula (■) In the formula, ■ represents a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a lower alkyl group (preferably carbon number/-j, especially a methyl group, an ethyl group, a propyl group) group), alkyl group-containing amino/group (methylamino group, ethylamino group, dimethylamino group, diethylamino group, etc.) or -8(CI(2)nNl(I
9R1o group, n represents an integer of 1 to 3,
, le □. may be the same or different and represent a hydrogen atom or an alkyl group having carbon number/~).

In the general formula (V), 几, 几 and 2 may be the same or different, and each represents a hydrogen atom, an alkyl group which may have a substituent (preferably a lower alkyl group, such as a methyl group, an ethyl group). , propyl group, etc.), a phenyl group that may have a substituent, or a heterocyclic group that may have a substituent (more specifically, a heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.) Heterocyclic groups containing one or more such as pyridine ring, thiophene ring, thiazolidine ring, benzoxazole ring,
(benzotriazole ring, thiazole ring, imidazole ring, etc.), and □3 is a hydrogen atom or a lower alkyl group which may have a substituent (for example, a methyl group, an ethyl group, etc.).

Preferably, the number of carbon atoms is 7 to 3 degrees.

Here, examples of the substituents R□1 to R□3 include a hydroxyl group, a carboxyl group, a sulfo group, an amide group, and a lower alkyl group.

几□4 represents a hydrogen atom or a xyl group.

General formula (1) In the formula, 几, 几, and L17 may be the same or different, and each represents a hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group, etc., preferably having a carbon number of 1 to 3 degrees). .

■ and 几 or fL17 are connected to each other to form ring 15 and 16 It may be completely formed.

X represents an amide group which may have a substitution or & (for example, a lower alkyl group such as a methyl group, an alkoxyalkyl group such as an acetoky7 methyl group), a sulfonic acid group, or a carboxyl group.

As 几 to 几, 7 is particularly preferably a hydrogen atom, a methyl group or an ethyl group, and as X, amine 7
or dialkylamino groups are preferred.

In the present invention, as the bleach accelerator, in particular, the general formula (
II), compounds represented by general formula (1) and general formula (Vl) are preferred. Further, when a persulfate is used as a bleaching agent, a compound represented by the general formula (Vl) is preferable.

Preferred specific examples of the compounds of general formulas (It) to l) are shown below.

(n) - (1) CI ) - (2) (II) - (3) (It ) - (4) (■Two (5) (nl ) - (1) (111) - (2) (nl ) -(3) (III)-(4) (III)-(5) (II/)-(1) (fV)-(2) (V)-(1) (IV)-(3) (V) -(2)(IV)-
(4) (■) - (3) (IV) - (5) (V) - (4) (V) - (6) ( (V) - (7) ( (V) - (8) ( Vl) -(1) 1-3+ Vl)-(2) W)-(3) (Vl)-(4) (Vl)-(5) (Vl)-(61 (Vl)-(7) (■ N-1 (8-(Vl)-(9) (Vl)-μQ (Vi)-CII) All of the above compounds can be synthesized by known methods, but in particular, the compound of general formula (Ill) is synthesized in JP-A No. 53 - Tag Publication No. 727, regarding the compound of general formula (IV),
Japanese Patent Publication No. J-≠-j Koj3f, the compound of general formula (V) is disclosed in Japanese Patent Publication No. Shoj3-7rs4A, Japanese Patent Application Shoj
r-text No. u) Hg3, and for the compound of general formula (Vl), refer to JP-A-53-TAG No. 727.

The compound having a mercapto group or a disulfide bond in the molecule used in the present invention, a thiazoline derivative or an isothiouretic derivative may be contained only in a bleach bath or a European silver fixing bath or a pre-bath thereof, or may be contained in a bleach bath or a bleach bath or a bleach bath. Alternatively, it may be contained in both the bathing area and the front surface. The amount of the compound of the present invention to be added to these solutions varies depending on the type of processing solution, the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc. ．． 10 mol is suitable, preferably lX10 -jXlo'' mol.

In order to add the bleaching accelerator and thiourea compound used in the present invention to the processing solution, it is common to add them as they are or to dissolve them in water, alkali, organic acid, etc. in advance, but it is not necessary to add them.・! Even if it is added after being dissolved in an organic solvent depending on the situation, the effect will not be affected in any way.

When the bleach accelerator and thiourea compound used in the present invention are contained in a pre-bath of a bleach solution or a bleach-fix solution, a variety of compositions can be used as the pre-bath. The prebath with the simplest composition is an aqueous solution in which the bleach accelerator and thiourea compound of the present invention are simply dissolved, but acids such as acetic acid and boric acid, alkalis such as sodium hydroxide, or sodium sulfate and sodium acetate are An aqueous solution containing appropriate salts such as sodium thiosulfate, ditrium borate, sodium carbonate, sodium bicarbonate, etc. can also be advantageously used as the pre-bath. Any pH value can be used for the pre-bath, and any pH value can effectively reduce the effect of the present invention, but if the pH value is too high, stain may occur, so in general, Preferably used below.

In the pre-bath, if necessary, a suspending agent made of various compounds, a hardening agent made of various compounds including alum-based and aldehyde-based, and pH! It may contain additives, fixing agents for halogen salts, antioxidants such as sulfites, hydroxylamine, and hydrazine, anti-swelling agents such as sodium sulfate and magnesium sulfate, surfactants, and the like.

For example, washing treatment, stopping treatment, stopping fixing treatment, etc. can be interposed between the pre-bath and the bleaching bath or bleach-fixing bath, but even in such cases, the bleaching accelerator of the present invention may be used in the pre-bath. When an agent and a thiourea compound are added, the same egg white promoting effect without delay in fixing action can be obtained.

However, when the bleach accelerator and thiourea compound of the present invention are contained only in the prebath, it is preferable that the prebath be used in the step immediately before the bleach bath or bleach-fix bath. .

A bleaching agent with a weak bleaching blade is used in the whitening solution or bleach-fixing solution that constitutes the entire invention. One example is a ferric ion complex, which is a complex of ferric ion and a chelating agent such as an aminopolycarboxylic acid, an ami/polyphosphonic acid, or a salt thereof. Aminopolycarboxylate or Ami/I'I soliphosphonic acid weir is Ami/Polycar, 1
Alkali metal monophosphonic acid or aminopolyphosphonic acid,
It is a salt with ammonium and water-soluble amines. Examples of alkali metals include sodium, potassium, and lithium, and examples of water-soluble amines include methylamine, diethylamine, triethylamine, alkylamines such as butylamine, ring amines such as chlorohexylamine, aniline, and m-toluidine. Arylamines, and V! such as pyridine, morpholine, and piperidine. It is a basic amine.

These aminopolycarboxylic acids and amino, I? Typical examples of chelating agents such as polyphosphonic acid or their mfz are: A-/ Ethylenediaminetetraacetic acid A-2 Ethylenediaminetetracn dirff disodium salt A-j Ethylenediaminetetraacetic acid shea/monisim salt A-l Ethylenediaminetetraacetic acid tetra (Tri7methylammonium) salt A-1 Ethylenediaminetetraacetic acid tetrapotassium salt A-4 Ethylenediaminetetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid trisodium 1 A-ff Diethylenetriaminepentaacetic acid 79 Diethylenetriaminepentaacetic acid pentasodium salt A -/θ Ethylenediamine-N-(β-oxyethyl)-N, N', N'-1acetic acid A-// Ethylenediamine-N-(β-oxyethyl)-N, N',
N'-) trisodium acetate salt A-72 ethylenediamine-N-(β-oxyethyl)
-N, N', N'-) Triammonium acetate A-/3 Propylenediaminetetraacetic acid A-/<4
Zoropylene diamine tetraacetic acid disodium salt A-is Nitrilotriacetic acid A-/A Nitrilotriacetic acid trisodium salt A-/
7 Cyclohexanediaminetetraacetic acid A-/I Cyclohexanediaminetetraacetic acid disodium salt A-/Timinodiacetic acid A-20 Dihydroxyethylglycine A-2/Ethyl etherdiaminetetraacetic acid A-,2
2 Glycol ether diamine tetraacetic acid A-23 Ethylenediamine tetrapropionic acid A-211 Phenylenediamine ketora/, J-diami/propa/-ru N
,N.

N/,N/-tetramethylenephosphonic acid A-2j Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid A-Jl,/,3-propylenediamine-N,N.

Examples include N', N'-tetramethylenephosphonic acid, but are not limited to these exemplified compounds.

Among these compounds, A-/-A-≠, A-/7
~A-/ri and A-J group A-J A are preferred.

Ferric ion complex salts may be used in the form of complex salts, or may be used in combination with ferric salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate, etc. A ferric ion complex salt may be formed in solution using a chelating agent such as aminopolycarboxylic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid. When used in the form of a complex salt, one type of complex salt or more than one type of complex salt may be used. On the other hand, when forming a liquid-liquid complex salt using a ferric salt and a chelating agent, one type or two or more types of ferric salts may be used. Furthermore, chelating agent i/type or -
241 may be used in a similar manner or more. In any case, the chelating agent may be used in excess of the amount needed to form the ferric ion complex.

Further, the bleach solution or bleach-fix solution containing the ferric ion complex may contain a metal ion complex salt other than iron, such as cobalt or copper, or hydrogen peroxide.

The persulfate used in the bleach solution or bleach-fix solution constituting the present invention is an alkali metal persulfate such as potassium persulfate or sodium persulfate, or ammonium persulfate.

In addition to bleaching agents such as ferric ion complex salts and the above-mentioned compounds, the bleaching solution constituting the present invention includes bromides such as potassium bromide, sodium bromide, ammonium bromide or chloride,
For example, re-logenating agents such as potassium chloride, sodium chloride, ammonium chloride, and the like can be included. other,
Inorganic acids with pH buffering capacity of 144 or higher, such as borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, organic acids Additives commonly known for use in bleaching solutions, such as acids and their salts, can be added.

In this case, the amount of bleach per liter of bleaching solution is between 007 and 2 mol, and the pH of the bleaching solution when used is 3.0-4.0°, especially ≠, θ, in the case of ferric ion complex salts. It is desirable that it be ~7.0. In addition, in the case of persulfate, the pH is 1 to
j is preferably 1 to 3.

The bleach-fixing solution constituting the present invention includes thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate as a fixing agent.
Sodium thiocyanate, ammonium thiocyanate,
The thiocyanate salt of potassium thiocyanate can be used.

Moreover, the addition amount is preferably o, i to 10 mole/l.

The first aromatic amino color developer used in the color developer of the present invention includes known ones that are widely used in various color photographic processes. These developers include aminophenol and p-phenylenediamine derivatives. These compounds are generally used in the form of salts, such as hydrochlorides or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present at a concentration of about o, ig - about 3 Of per liter of color developer, more preferably about /f - about iz of per liter of color developer.
Use at a concentration of y.

Examples of aminophenol-based developers include 0-aminophenol% I'-aminophenol, j-amino-2
-oxy-toluene, 2-amino-3-oxy-toluene, cooxy-3-amino-/, 4'-dimethyl-
Contains benzene, etc.

A particularly useful primary aromatic amino color developer is N.

It is an N-dialkyl-p-phenylenediamine compound, and the alkyl group and phenyl group may be substituted or unsubstituted.

Among them, examples of particularly useful compounds include N,N-dix
p-p-phenylenediamine jJ [[, N-1f p-phenylenediamine hydrochloride, N.

N-dimethyl-p-phenylenediamine hydrochloride, koaminoj-(N-ethyl-N-dodecylamino)-)toluene, N-ethyl-N-β-methanesulfonamidoethyl-3-methyl-+-7minoaniline sulfur e salt, N-ethyl-N-β-hydroxyethylaminoaniline, l-amino-3-methyl-N,N-diethylaniline, quaamino-N-(2-methoxyethyl)-N-ethyl-3-
Mention may be made of methylaniline-p-)luenesulfonate.

The alkaline color developer used in the present invention includes, in addition to the first lf group amino color developer,
Various components normally added to color developing solutions, such as alkaline agents such as sodium hydroxide, sodium carbonate, and potassium carbonate, alkali metal instant salts, alkali metal bisulfites, alkali metal thiocyanates, and alkali metal halides. , benzyl alcohol, water softeners, thickeners, and the like may optionally be included. The pn value of this color developing solution is usually 7 or more, most commonly about 1/3 to about 1/3.

The method of the invention can also be used for color reversal processing.

In the present invention, the black-and-white developer used at this time can be a so-called black-and-white first developer used in the reversal processing of color photographic light-sensitive materials, which is commonly known, or a developer used in the processing of black-and-white light-sensitive materials. In addition, various well-known additives that are generally added to black and white developers can be included.

Typical additives include l-phenyl-3-biglide 7, developing agents such as metol, 1DroV-non, preservatives such as sulfites, sodium hydroxide, thorium carbonate, Accelerators consisting of alkalis such as potassium carbonate, potassium bromide, λ-methylbenzimidazole,
Development inhibitors may include inorganic or organic inhibitors such as methylbenzthiazole, water softeners such as polyphosphates, amounts of iodide, and mercapto compounds.

According to the present invention, the color light-sensitive material processed in the presence of the compound of the present invention is a known color light-sensitive material, preferably a coupler-containing multilayer negative plastic color light-sensitive material or a color print light-sensitive material. It can be used particularly advantageously in processing color photosensitive materials made for reversal color processing, as well as color X-ray photosensitive 4A materials, single-layer specialty color photosensitive materials, and also U.S. Pat. 273/2ri No. 7 specification, 3ri02ri or
Specification, JP-A Sho KA-A≠332, JP-A Sho, t
, 4-137≠r, and 3-pyrazolidones described in JP-A-56-g57119;
I, No. 33≠2327, No. 33 μ25 Tata No. J7/Tag Octopus No. J, /1IO
It is also possible to process color light-sensitive materials in which the 611 precursor of the color developing agent described in II7 and JP-A-53-13Kg2g is incorporated into the light-sensitive material. Alternatively, there is no problem even if the coupler is present in the developed surface and subjected to -C processing.

Example 1 A multilayer color photosensitive material sample was prepared on a polyethylene terephthalate film support, each layer having the composition shown in Section F.

First layer; antihalation layer; black gelatin layer containing colloidal silver; λth layer; intermediate layer λ,! - Gelatin layer containing an emulsified dispersion of D-t-octylhydroquinone Third layer: Low-sensitivity red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide = j morti...silver coating amount/, A
9/m” Sensitizing dye 1・・・・・・・・・・・・Ixlo-5 mol sensitizing dye for 1 mol of silver For /, !rx10 molar coupler EX-/...0.0 g mole for 1 mole of silver coupler EX-j...0.003 mole for 1 mole of silver coupler gx-+... for 1 mole of silver Teo, ooo6
Mol first layer: Highly sensitive red-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; lO morch)...Silver coating amount
1. g/m2 Sensitizing color J & I・・・・・・・・・3×10-5 mol sensitizing dye per 1 mol of silver ■・・・・・・・・・・・・ Silver 1.2 x lO moles per mole coupler EX-,2...0.02 moles per mole of silver coupler EX-j...o, ooit per mole of silver
Mole number j1-; layer with the same number as the second intermediate layer; low-sensitivity green-sensitive emulsion layer monodispersed silver iodobromide emulsion (silver iodide; mol %)... coated silver amount 1.2 g/m2 j 11 & Dye ■・・・・・・・・・3X1O mol per mole of silver Sensitizing dye ■・・・・・・・・・1’1. / 0 molar coupler EX-≠...o, oj for 1 mole of silver molar coupler EX-7...o, oor for 1 mole of silver molar coupler HX-A...O+0O7j for 1 mole of silver
Mole 7th layer: Gray-sensitive green-sensitive emulsion layer Silver iodobromide emulsion (silver iodide; lO7ruti)...Amount of coated silver
l, 3g/m2 Sensitizing dye■・・・・・・・・・2+j×lO mol sensitizing dye■・・・・・・・・・・・・1 silver per 1 mol of silver 00g per mole A layer of 0.003 mol yellow filter; yellow colloidal silver and 2,1-di-t-
Gelatin layer '7i containing an emulsified dispersion of octylhydroquinone ↓ layer: low-sensitivity green-sensitive emulsion layer method 4-limit emulsion (iodide; t mol)...coated silver amount 0
．． 79/ln2 Coupler EX-1'...O++zz per 1 mole of silver
Molar coupler EX-A... o, ois molar for silver l mo ρ 10th layer; highly sensitive emulsion layer Silver iodobromide (silver iodide; t mole)... coated silver amount 3 g 7 m
2 Coupler EX-♂...0.0 per mole of silver (, mole 11% // layer; first retention layer silver iodobromide (1 mole of silver iodide, average grain size 0.07μ)・
-Amount of coated silver 0.'y 72nd gelatin layer containing an emulsified dispersion of ultraviolet absorber tJV-/; 2nd protective layer trimethyl meth/acrylate particles (diameter approx./.

Coat with a gelatin layer containing jμ).

In addition to the above composition, gelatin hardener I (-/) and a surfactant were added to each layer.

Compounds used to prepare the sample Dye 1: Anhydro j,j'-dichloro=3.
3/-di(γ-sulfopropyl)-2-ethyl-thiacarbocyanine hydroxide pyridinium salt sensitizing dye ■Nia/hydrodeethyl-3,3'-di(r-sulfopropyl)-Hiro, j, Gl-j'-dibenzothiaca A/rH cyanine hydroxide ° triethylamine salt sensitizing dye ■: Anhydroterethyl-! , j/-dichloro3.3/-di(r-sulfopropyl)oxacarbocyanine sodium salt sensitizing dye ■: Anhydro'+ '<lj/lAl-tetrachloro-7ll'-
Diethyl-3,3'-di(β-[β-(r-sulfopropyl)ethoxy]ethylimidazolocarbocyanine hydroxide sodium salt coupler EX-/C3H1□(1) EX-, z 〆 \ 1 After the color negative film thus obtained was wedge exposed, it was developed according to the following developing process. The thiourea compound of the present invention or a thiourea compound other than the present invention (comparative compound), and various nickel silver promoters were added to the whiteboard.

Processing process Heat storage Time color development 3103 minutes Bleach 3r 0C/min 3θ seconds Fixation 31 0C7 minutes Water washing JI"CJ minutes Stabilization 3t C'C7 minutes Note that the development process using the above process is performed using each processing solution with the following composition. Each time a color negative film J j Ocyx was processed, 1 m 2 of the processing solution was continuously replenished with each processing solution having the following composition.

<Color development lα> Mother solution Replenisher Sodium nitrilotriacetate /, Of /, tf Mother solution Replenisher Sodium sulfite Hiroshi, Of '1. llf sodium carbonate 30.0y j, of potassium bromide /, gf θ
, 7f Hydroxylamine sulfate Ko, Hirog no, AI Hiro-(N-ethyl-N-β-hydroxyethylamino)-2-methylaniline sulfate ≠+sgs, oIl Add water /l /1 Bleach Solution> Mother solution Replenisher ammonium bromide It, 0. Of /74 f/77
Moni 7 water (21%), ts, 01t/j me ethylenediamine-tetraacetic acid sodium iron salt /30,09 /113 f/glacial acetic acid /≠, Omi /μ, Oml Thiourea compound (Table - Mother solution Replenisher lK (Listed) Amounts listed in Table 1 Amounts listed in Tables 1 and 4 white accelerators listed (11 and 4% in Table 7) Sodium polyphosphate 2. Of 2. ,lf Sodium sulfite ≠,Of 4! , uf ammonium thiosulfate (70%) 17! , 0 @ l / l 3, 0.1 Tono Sodium Sulfate Hiroshi, tf j, tf Add water i l
ig <Stabilizing solution> Mother solution Replenisher formali 7 1. Ogl ta, θwl All water added /l 111 The processed film sample (i.e., the so-called Free
The amount of silver remaining in the highest concentration part of the sample was measured by fluorescent X-ray analysis for the film samples treated with sh solution and the film samples treated with Lanndinda solution. Furthermore, the same film samples were subjected to a writing fixing process for 30 minutes using an unused fixing solution (mother liquor) having the above composition, and then the amount of residual silver was measured in the same manner. The results are shown in Table 1.

From the results in Table 7, it is clear that bleaching accelerators selected from compounds with mercapto groups or disulfide bonds, thiazolidine derivatives, and isothiourea derivatives have excellent bleaching accelerating effects, but when the film is processed, they have a fixing effect. It can be seen that the process is delayed (Samples ko to t). On the other hand, the thiourea compound of the present invention significantly improves the delay in the fixing action caused by the whitening accelerator in a small amount. /r)l, it can be seen that this effect is not something that all thiourea compounds have, but is unique to the thiourea compound of the present invention.

Comparative Compound / Proboscis (1) Comparative Instrument (2) H3 C1 (3 Comparative Compound (3) Example 2 In place 9 of the bleaching solution and fixing solution of Example 1, bleach-fixing g, (mother liquor and The thiourea compound of the present invention and the bleaching accelerator (the amount added is determined according to the Bi
o” mol/4, replenisher concentration/, /×10-2 mol/β
The same treatment as in Example 1 was carried out (treatment temperature: 3°C), except that various thiourea compounds other than those of the present invention were used. However, the bleach-fixing time is 30 seconds, and the color NECA film 3 j Ocm 2
Bleach-fix replenishment after each process! Oysl was supplemented.

The amount of residual silver in the film was determined in the same manner as in Example 1.

Further, the re-fixing treatment of the processed film was carried out in the same manner as in Examples.

The results are shown in Table-2.

<Bleach-fix solution mother solution Replenisher ethylenediamine tetrapartite acid/ferric ammonia mother solution Replenisher lamb salt/λ hydrate ioo, optio, of ethylenediamine tetrapartite disodium/λ hydrate j, Of jjf i11j Sodium sulfate IO0θy ti,oy ammonium thiosulfate water soluble (70ti) /70+OR,l /♂7. (ht
Add 1 water -C/l/1 Comparative compound (4) Comparative compound (5) Based on the results in Table 1, a bleach accelerator selected from compounds having a mercapto group, a disulfide bond, a thiazolidine derivative, and an isothiourea derivative The agent has a good effect in the Song Dynasty, but as the film is processed, it slows down the fixing effect (Samples 2 to 6).

This ((on the other hand, the thiourea compound of the present invention has bleach-accelerating fi
Extremely effective in preventing delays in fixing action due to
]1. F”rlIIJB6-;-#Tsuru ζ(ttmo-
Thiourea compounds other than ilt% and do□anl+1 do not exhibit such effects, indicating that they may also promote delayed fixation (samples 7-j).

Example 3 A multilayer color negative light-sensitive material was prepared having each layer having the composition shown below on a cellulose triacetate film support.

7th layer Antihalation layer Black colloidal silver emulsion (emulsion/kg blackened silver 139
, containing 1 ooy of gelatin) / kg of the coating agent p-dodecylbenzenesulfonic acid sodium! A weight % aqueous solution≠Occ was added and applied so that the dry film thickness was λμ.

2nd layer Gelatin intermediate layer (Inari・■ Film thickness/, 0μ) 3rd
Layer: Red-sensitive, low-sensitivity silver halide emulsion layer: silver iodobromide emulsion (average grain size 0.3μ, emulsion/
(containing 100 y of silver halide and 709 g of gelatin per kg) was prepared by the method of n. A red-sensitive spectral sensitizer was added to this emulsion/kg. % methanol solution λ10cc was added, and then 1-methyl-7-hydroxy-2. 20 cc of a 5% by weight aqueous solution of J, 44-triazaindolizine, cyan coupler emulsion (1) and emulsion (2) according to the following formulation were added by zoog. Next, 200 cc of a 2% aqueous solution of colored cyan coupler (CC-/) was added, and then 30 cc of a 2% aqueous solution of cohydroxy≠ and sodium t-dichlorotriazine as gelatin hardeners were added to reduce red sensitivity. It was made into a halogen silver emulsion liquid. This liquid was applied to a dry film thickness of 3°jμ.

CC-1 (H Emulsion (1) ■ A mixture of 70% by weight gelatin aqueous solution 1000f■ was dissolved in jjoC, and then heated to j50c in advance [F]
In addition, it was emulsified using a colloid mill.

C-10/ Emulsion (2) ■ A mixture of 70% by weight gelatin aqueous solution 1000 f■ After dissolving in iJj'c, the mixture was heated to 55°C in advance (added to D and emulsified in a colloid mill).

1) -/G layer Red-sensitive high-sensitivity halogen silver emulsion layer The following changes were made to the halogen silver emulsion liquid of the third layer.

The silver halide solution prepared in this way has a dry film thickness of λ, λμ.
I applied it to make it look like this.

5th layer Gelatin intermediate layer (dry film thickness o, rμ) 6th layer
A green-sensitive, low-sensitivity silver halide emulsion layer/kg of the silver iodobromide emulsion used in the third layer was added with a green-sensitive sensitizing dye to add 3.31-di(2-
sulfoethyl)-terethylbenzoxacarbocyanine pyridinium salt. /% methanol solution lzaocc
, s-methyl-7-hydroxy-λ, J, Hiro-) 20 cc of a 5% by weight aqueous solution of riazaindolizine was sequentially added, and then magenta coupler emulsion (3) according to the following formulation was prepared.
0g of emulsion (4) was added. Furthermore, a 2% by weight aqueous solution gjOcc of cohydroxy≠, A-dichlorotriazine sodium salt was added as a gelatin hardener to prepare a green-sensitive, low-sensitivity silver halide emulsion. Dry this liquid to a film thickness of 3
．． It was applied to a thickness of 2μ.

Layer 7: Green-sensitive high-sensitivity halogen pass emulsion layer The following changes were made to the silver halogen emulsion layer of the seventh layer.

The dry film thickness of the silver solution prepared in this way was 2.
Emulsion coated to give μ (3) ■ 10% gelatin aqueous solution Add to ■ heated to 1000 f and emulsify in a colloid mill.

N0 Emulsion (4) ■ A mixture of 70% by weight gelatin aqueous solution (iooogQ) was dissolved in a jt'c, then added to ■ that had been preheated to 5r0c, and emulsified in a colloid mill.

1st layer Yellow colloidal silver layer (dry film thickness/1μ) 1st layer Light-sensitive, low-sensitivity halogen silver emulsion layer Average grain size is o,
j-methyl-7-hydroxy-2,
3, Hiro - Triazaindolizine! Weight% water ff+g
, 20CC and yellow coupler emulsion (5) according to the following formulation were added. Furthermore, as a gelatin hardening agent, λ-hydroxyl 1. A 2% by weight aqueous solution jOcc of A-dichlorotriazine sodium salt was added to prepare a light-sensitive, low-sensitivity silver halide emulsion.

This liquid was applied to give a dry film thickness J of 117 μm.

Emulsion (5) ■ A mixture of 1000f of 1000f IO nail volume tizelatin aqueous solution was dissolved in 5j0 (:), added to ■ previously heated to jj°C, and milked in a colloid mill.

'1'-/ 1st O layer K-sensitive high sensitivity...Rogen silver emulsion The following changes were made to the 1st layer No. Rogen silver emulsion liquid.

The silver solution produced in this way was dried on a film J11.
It was applied so that it became jμ.

Eleventh Layer: Gelatin Preservation Layer [Dry 1 thickness/, jμ] The color negative film thus obtained was wedge exposed and developed according to the following development process. In the prebath, the thiourea compound and bleach accelerator of the present invention, and the thiourea compound other than the present invention (comparative compound) used in Examples/
were used with various additions.

Processing process Temperature Time Color development ≠/'CJ minute stop 31 0C 30 seconds water wash tt 30 seconds before bath tt 30 sections white 〃 3 minutes water wash 〃 1 minute fixation 〃 Solu water wash 〃 1 minute stabilization bath tt / 9 seconds The above development process was started using 21 of each of the mother liquors of each processing solution with the following composition, and then a replenisher with the following composition was applied to the film at 3jO.
For each tx2 process, add jOgo to the color developer replenisher, and add 1o to other replenishers continuously.
m processed.

<Color developer> Mother solution Replenisher Sodium hydroxide 2g, 2f 11 [sodium acid λf, 2f Potassium prefecture /, II (10,79 Sodium chloride N/ /9 Borax iy t, iy Hydroxylamine sulfate 4′g 4′・″y Ethylene diamine tetraacetate λ sodium, 2f, 2..2p gouami/
3-Methyl-N-ethyl-N= (β-hydroxyethyl)aniline monosulfate μg ≠, φg Add water ig tl <Stop solution> Mother solution Replenishment solution Mother solution Replenishment solution Caustic soda i, tsy /, isy Water Add /4/l <Pre-bath> Mother solution Replenisher Anhydrous sodium sulfite /, 2'! /'If/ice vinegar m/
Omi 10tsl Bleach accelerator (3x10 in Table 3) 3.3x10
”) Mol Mol thiourea compound (listed in Table 3)
Amount of rQ battle Add the amount of water listed on RIC /e/4 <Wrong white liquor> Mother g, Replenisher Sodium persulfate 60g AAt Sodium chloride Co0 (120f/ Sodium dihydrogen phosphate isy it, s Datetrapolyline Sodium acid +2g 2.2f Mother solution Replenisher I-alanine 1/λ, 2f Phosphoric acid (rt%) 2.2wl 2.≠ Add water ll /1 <Fixer> Mother solution Replenisher il+sodium troy Hsg ``1
[Sodium sulfate (anhydrous) / If / lj9 Borax 12 g / 3 f Glacial acetic acid / j ll 11 At the start and end of the above development process (Film/2722
The amount of silver remaining in the highest density of the processed film sample (during processing) was measured by fluorescent X-ray analysis.

Furthermore, the same film sample was re-fixed for 30 minutes with an unused fixer solution (mother liquor) having the above composition, and then
The amount of residual silver was measured in the same manner.

The results are shown in Table-3.

From the results in Table 3, the bleaching accelerators selected from compounds with mercapto groups, disulfide bonds, thiazolidine derivatives, and isothiourea rust conductors have excellent bleaching accelerating effects, but as the film is processed. It can be seen that the fixing effect is delayed (Samples 2 to j).

On the other hand, the thiourea compound of the present invention exhibits an extremely excellent effect in preventing the delay in the fixing action caused by the bleach accelerator (sample g~/≠), but the thiourea compounds other than the present invention exhibit such an effect. It is shown that it does not show any effect and may promote a delay in fixing (Samples 6 to 7).

Example 4 A sample was obtained by coating an emulsion layer and an auxiliary layer in the following order on a triacetyl cellulose support provided with an undercoat layer.

1st layer Low red sensitivity pore 1111-ring cyan coupler λ-(hezotafluoroptylamido)-j-(coI-(2'', guti-t-amylphenoxy)butyramide 1-pheno- 100f,) 700 cc of licresyl phosphate and 100 cc of ethyl acetate
The emulsion jθOf obtained by dissolving in cc and stirring at high speed with a 10% gelatin aqueous solution/kg was converted into a red-sensitive low-iodophilic silver bromide emulsion/kg (silver 7017, gelatin toy, and the iodine content was 3. It was mixed into a mold and applied to a dry film thickness of λμ (silver amount: 0.5117 m2).

No. 1 - Highly sensitive red-sensitive emulsion layer A cyan coupler, co(heptafluorodatatelamide)-j-1λ/C2//, ≠〃-di-t-amylphenoxy)butyramide 1-phenol 100f, was added to tricresyl phosphate. /.

Emulsion 10 obtained by dissolving 100 ccK of Occ and ethyl acetate and stirring at high speed with /Q Tigelatin aqueous solution/kg
00f as a red-sensitive highly iodosilver bromide emulsion/kg (silver 70
f, gelatin tQy, iodine content I'i 3 mol%
) and coated to a dry film thickness of λμ (silver amount O1/1n2).

31st So Middle layer: J-T-octyl hydrogen was dissolved in 100 cc of dibutyl phthalate and 1 QOcc of ethyl acetate, and an emulsion obtained by stirring at high speed with an aqueous solution/kg of 10% gelatin was added. , 10% gelatin/kQ and coated to a dry film thickness of lμ.

Low-sensitivity green-sensitivity emulsion layer: 6/-(
z,≠,4-)lichlorophenyl)-3-(J-(,?
The emulsified proboscis obtained in the same manner as the emulsion of the first layer except that Keg--t-amylphenoxyacetamide) benzamide J-j-pyrazolone was used was treated with a green-sensitive, low-sensitivity odor. It was mixed with 1 kg of silveride emulsion (containing 70 f silver, toy gelatin, iodine content 0 μ, 5 mol%) and coated to a dry film thickness of θμ (silver amount 0.7 fl/m2).
.

s) Threat 11h Green-sensitive emulsion layer uses magenta coupler instead of cyan coupler /-(
J, Hiro, -trichlorophenyl)-3-(J-(2,
-≠-G-t-amylphenoxyacetate'') Besoi;k''l-1-S Lazoroso I The emulsion toooy obtained in the same manner as the emulsion of the seventh layer was added to the green-sensitive emulsion. Highly sensitive silver iodobromide emulsion lkQ (silver 701/, gelatin to
y and the iodine content was 2.5 mol%) and coated to a dry film thickness of Oμ (coated silver amount: 0.71
17m).

Layer 1 kg of the emulsion used in the 3rd intermediate layer, 1 kg of -10% gelatin
g and applied to give a dry film thickness/μ.

7th Layer Yellow Filter Layer An emulsion containing yellow colloidal silver was coated to a dry film thickness/μ.

Layer 2 Low-sensitivity blue-sensitivity emulsion layer Yellow coupler is used instead of cyan coupler, α-
(pivaloyl)-α-(/-benzyl-!-ethoxy-3-hydantoinyl)-λ-chloro-1-dodecyloxycarbonylacetanilide was used, but the emulsion obtained in the same manner as the emulsion of the first layer, iooog , low-sensitivity silver bromide emulsion / kg (70g silver, gelatin to
y and the iodine content is 1.5 mol%), and the dry film thickness is λ.

It was coated so that θμ (coated silver amount o, tf//11
12).

The second layer is a highly blue-sensitive emulsion layer containing a yellow coupler instead of a cyan coupler.
(pivaloyl)-α-(/-benzyl-j-ethoxy-
Emulsion 1000fi obtained in the same manner as the emulsion of the first layer except that 3-hydantoinyl)-2-chloro-j-dodecyloxycarbonylacetanilide was used was converted into H-sensitive highly sensitive silver iodobromide emulsion/kt. 1 (containing Vd47θv1 gelatin 609, iodine content d, 5 mol%) and dry film thickness.

It was coated so that it was θμ (coated silver amount i, oy7〃12
).

70th layer 2nd protective layer Emulsion used in 3rd layer/kgf, 10 chigelatin/k
g and applied to give a dry film thickness of λμ.

117th warning 1st protective layer Fine grain emulsion without chemical sensitization (grain size 0, /
An aqueous solution of 10 thigelatin containing 7.1 molar silver iodobromide emulsion) was coated with silver θ, J 9/7722,
The thus obtained color reversal film coated to a dry film thickness of lμ was exposed to light using a wedge and developed according to the following development process. The bleaching solution contains the thiourea compound and bleach accelerator of the present invention, as well as the thiourea compound other than the present invention used in Examples/λ (of course).
Comparative compounds) were used in various amounts.

Processing process Temperature Time 1st developing bath 3g 'C7 water washing 〃 λ outer inversion bath 〃 2 minutes color developing bath 〃 4-minute tone bath 〃 λ fractional distillation white bath 〃 λ min 30 seconds fixing bath 〃 ≠ water separation Washing 〃 Koubun stable bath cloth hood 7 minutes The development process in the above step was started using G21 of each processing solution having the following composition, and after that, 3 sets of film were used.
Every time m2 is processed, the replenisher is 0tnl for @l development and color development, and 1m is continuously replenished with each replenisher gllO,l for other processing reasons.
2 treatments.

<First phenomenon (shallow)> Mother solution Replenisher water 700 shoulders/700 tan Sodium tetrapolyphosphate, 2p 2f tl [Sodium sulfate 20f Mu Hydroquinone monosulfone) 3017 3 f Sodium carbonate (l hydrate) 30 f , / 30f l-phenyl V-methyl Hatake l-hydroxymethyl-3 pyrazolidone 2 ( / 29 Megumi potassium 2-!Q Of / mother solution replenisher potassium thiocyanate /0.2f /,, 21 potassium iodide (o.

Add water and invert the bath at 4/4> Mother solution Replenisher water 700 liters 700 tons of scraps Nitrilo・N,N,N-trimethylenefoscinic acid・4Na salt 3(/ 3(/Stannic chloride (dihydrate) /f //1p-amidium/phenol 0./f /f Sodium hydroxide Htry Ice vinegar p /3ml /j, 1 Add water /l /1 Color development Developing bath〉 Mother solution Replenisher water 7001ttl 700ml Tet-2-polysodium phosphate mother solution Replenisher lium 2f Sodium triphosphate 71 Iff Sodium triphosphate (/dihydrate) 349 361 Potassium bromide 1g O+39 Potassium iodide (o, i solution) TaOtant Otgl Sodium hydroxide 39 39 Citrazine /,!y/,if N・Ethyl-N+β-Methanesulfonamidoethyl)-3・Methyl-Hiroshi・Aminoaniline/4Jk acid resistant //l/ /Koichi Vundiamine 3f 3g Add water /IJ /1 <Adjustment bath> Mother solution Replenishment solution Water 700ml 700@1 Mother solution Replenishment solution Sodium sulfate 1 liter / /29 Sodium ethylenediaminetetraacetate (dihydrate) ry try Add 3ml of glacial acetic acid 3* to water ll /1 Bleach bath> Mother solution Brightening solution water tooM (too, l Sodium ethylenediaminetetraacetate (λ hydrate) ) 2.0/ 2.0 (/ ethylenediaminetetraacetic acid iron (river) ammonium (2 water L4) lxo, oy 1tro, op
Potassium bromide 10θ, o (1iro, op bleach accelerator (JXlo-34X#) listed in Table-μ) Mol Mol Mother solution Replenisher Thiourea compound (listed in Table-≠) Table-Hiro Table-≠ Description Add the stated amount of water 1 g <Fixing bath> Mother solution Replenisher water 10011 100 ml Thiosulfur 277 Mo=tsuA to, o (1to, oI/Sodium sulfate IOf 3.09 g iJM Sodium sulfate !r, Of 3-1Of water added /, 071 / (1 stable bath) 1 is liquid replenisher water too7 too phantom formalin (37 heavy weight%) s, o shoulder 1 j, 0 歭l Hatashi A film sample developed as described above was measured by fluorescent X-ray analysis.

Furthermore, the same film sample was re-fixed for 30 minutes with an unused fixer solution (mother liquor) having the above composition, and then
The amount of remaining silver was measured in the same manner.

The results are shown in Table-≠.

Note that the comparative compounds (1) and (4) used as thiourea compounds were those of Examples 1 and 2.

From the results of Omote-Hiroshi, bleach accelerators selected from compounds with mercapto groups, disulfide bonds, thiazolidine derivatives, and isothiourea derivatives have excellent bleach accelerating effects; It can be seen that the action is delayed (Samples 2-6).

On the other hand, the thiourea compounds of the present invention exhibit extremely excellent effects in preventing the delay in the fixing action caused by bleach accelerators (Samples 2 to 13), but the thiourea compounds other than the present invention exhibit such excellent effects. It is shown that there are cases where it does not show any effect and promotes a delay in fixing (Samples 7 to g).

Special C゛"Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment July 7, 1939 Mr. Commissioner of the Patent Office 1, Indication of the Case Showa! Year 1 Special Training 1 "7-22 No. 2,
Title of the invention Processing method for color photographic light-sensitive materials 3, Relationship with the case of the person making the amendment Patent applicant contact information Address: 2-26-30-4 Nishiazabu, Minato-ku, Tokyo 106, Subject of amendment ``Details of the invention'' in the specification The description in Column 5 of "Detailed Explanation of the Invention" and "Detailed Explanation of the Invention" in the Description of Contents of the Amendment is amended as follows.

+1) Page 7/7th line "thiosulfate ion" "Thiosulfate" and correct it.

(2) Page 30, line 3 ``What is called or'' “What is called, make it happen.” and correct it.

(3) Page j, line j [Thin? I:) See you next time. "Measurement. See you on the second railway." and correct it.

(4) st page, it line "17Ag" "lyA,Ofl" and correct it.

(5) Page j6, line 16 ``1jrnjJ [/j, Ome, J and correct it.

(6) Page 56, line 76 1゛1lI3! j” [l≠3.0gJ and correct it.

Claims (1)

[Scope of Claims] A processing method for desilvering an exposed silver halide color photographic light-sensitive material after color development, comprising: a compound having a mercapto group or a disulfide bond in a bleach bath, a bleach-fix bath, or a pre-bath thereof; at least one chain promoter selected from thiazolidine derivatives and isothiourea derivatives;
1. A method for processing a photographic light-sensitive material, which comprises containing at least one compound represented by the following general formula (I). General formula (summer) (In the formula, R1, R2, and 几 may be the same or different, and each may be a hydrogen atom, a lower alkyl group that may have a substituent, an amino group that may have a substituent, or Represents an allyl group. However, at least one of 几1, 几2, and fL3 is a hydrogen atom, and 几4, 几2, and R+3 are connected to each other to form 3J!
j may be formed. )