JPS63104051A - Method for processing silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To permit quick desilvering process of a silver halide color photographic sensitive material by processing said material with a processing liquid having bleaching power in the presence of a specific compd. CONSTITUTION:The above-mentioned material is processed with the processing liquid having the bleaching power in the presence of the compd. expressed by the formula I. In the formula, Z denotes an atomic group necessary for forming a 5- and 6-membered heterocyclic rings together with a sulfur atom, which heterocycles may have a substituent, but there is not case in which said rings have a mercapto group as the substituent. The amt. of the compd. expressed by the formula I varies with the kind of photographic material to be processed, the processing temp., the time required for the objective processing, etc., and is preferably 1X10<-4>-5X10<-1>mol per l of processing liquid in the case of adding said compd. to the processing liquid having the bleaching power.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention relates to an exposed silver halide color photographic light-sensitive material (
The present invention relates to a method for developing (hereinafter simply referred to as "processing") for a color photosensitive material (hereinafter referred to as "color photosensitive material"), and particularly to a rapid processing method with improved desilvering performance.

(Prior Art) Generally, the basic steps in processing color photosensitive materials are a color development step and a desilvering step. In the color development step, the exposed silver halide is reduced by a color developing agent to produce silver, and the oxidized color developing agent reacts with a color former (coupler) to provide a dye image. The silver formed here is oxidized by a bleaching agent in the subsequent desilvering process, and then transformed into a soluble silver complex by the action of a fixing agent, which is dissolved and removed, thereby forming a dye image on the color photosensitive material. only is completed.

In addition to the above-mentioned basic steps, the actual processing includes various auxiliary steps in order to maintain the photographic and physical quality of the image, or to improve the storage stability of the image. Examples include a hardening bath, a stop bath, an image stabilization bath, and a water washing bath.

In recent years, there has been a strong demand in this industry for speeding up processing, that is, shortening the time required for processing, and in particular, shortening the desilvering step, which accounts for nearly half of the processing time, has become a major issue.

Commonly used bleaching agents include red blood salt dichromate, ferric chloride,
Iron, ferric aminopolycarboxylic acid complex salts, persulfates, and the like are known.

(Problems to be Solved by the Invention) However, red blood salts and dichromates have pollution problems related to cyanide compounds and hexavalent chromium, and their use requires special treatment equipment. Furthermore, ferric chloride has problems in the production of iron hydroxide and staining during the subsequent washing process, which poses some practical problems. Persulfates have the disadvantage that their bleaching action is very weak and that they require a significantly long bleaching time. In addition, persulfates themselves are regulated as dangerous substances under the Fire Service Act and require appropriate storage measures, making them generally difficult to put into practical use.

Aminopolycarboxylic acid ferric complex salts (especially ethylenediaminetetraacetic acid ferric complex salts) have few pollution problems and do not have storage problems like persulfates, so they are currently widely used in bleaching. However, the bleaching blade of the ferric aminopolycarboxylic acid complex salt is not necessarily sufficient.

A means of speeding up the desilvering process has previously been described in German Patent No. 866.605. A bleach-fix solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate in one solution is known. However, in this case 1
Since aminopolycarboxylic acid ferric complex salt, which originally has a weak oxidizing power (bleaching blade), coexists with thiosulfate, which has a reducing power, the bleaching blade is significantly weakened. It is extremely difficult to desilver the material sufficiently, and it has the disadvantage that it cannot be put to practical use.

On the other hand, as a method for increasing the bleaching strength, methods have been proposed in which various bleaching accelerators are added to bleaching baths, bleach-fixing baths, or their pre-baths. Such bleach accelerators are described, for example, in US Pat. No. 3,893,858, British Patent No. 1,13
8,842, various mercapto compounds as described in JP-A-53-141623, JP-A-53-95
Compounds having a disulfide bond as described in Japanese Patent Publication No. 630, thiazolidine derivatives as described in Japanese Patent Publication No. 53-9854, isothiourea derivatives as described in Japanese Patent Publication No. 53-94927, 8
506, thiourea derivatives as described in JP-A No. 49-26586, thioamide compounds as described in JP-A-49-42349, JP-A-49-42349; d55-2650
6, arylene diamine compounds as described in US Pat. No. 4,552,834, and the like. Some of these bleach accelerators do indeed exhibit a bleach accelerating effect, but they are expensive and have insufficient stability in baths that have bleaching ability, making them impractical. We have not yet reached the point where we are satisfied with the results.

Also, Research Tisflora 24023 ([84
(April 2013) and Japanese Patent Application Laid-open No. 60-230653, etc., treatment methods using two or more of various ferric aminopolycarboxylic acid complex salts are described, but these methods also do not sufficiently promote bleaching. It has not reached the point where it is effective.

Accordingly, a first object of the present invention is to provide a processing method for quickly desilvering color light-sensitive materials.

A second object of the present invention is to provide a rapid desilvering method with stable photographic performance.

A third object of the present invention is to provide a rapid desilvering method that causes fewer pollution problems.

A fourth object of the present invention is to provide an inexpensive, highly practical and rapid desilvering method.

(Means for solving the problems) The above object could be achieved by the method described below.

(1) A method of processing an exposed silver halide color photographic light-sensitive material with a processing solution having bleaching ability after color development, in the presence of a compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material, which is characterized by processing with a liquid.

General formula (1) % formula % (wherein Z represents an atomic group necessary to form a saturated or unsaturated 5- or 6-R heterocycle with a sulfur atom, and this heterocycle is a substituent (2) The processing liquid having bleaching ability contains an organic acid ferric complex as a bleaching agent. Component cylinder (1
) A method for processing a silver halide color photographic light-sensitive material.

When processing with a processing solution that has bleaching ability in the presence of a conventional heterocyclic mercapto compound, some compounds exhibit a bleaching accelerating effect, but if the amount added is too large or the processing is performed continuously with an automatic processor, In this case, depending on the composition of the photosensitive material, poor fixing often occurs, and furthermore, the bleaching reaction may be delayed. On the other hand, the compound of the present invention did not cause poor fixing, but a favorable promoting effect was obtained.

The compound represented by general formula (I) will be explained in more detail.

General formula (1) % formula % In the formula, 2 is saturated or unsaturated 5 along with the sulfur atom.
Represents a group of atoms necessary to form a shell or 6R heterocycle, and this heterocycle may have a substituent, but does not have a mercapto group as a substituent.

The atomic group represented by Z consists of a carbon atom, a nitrogen atom, an oxygen atom and/or a sulfur atom, and the heterocycle formed by this Z and a sulfur atom may be fused with another ring to form a fused ring. good.

Substituents of the heterocycle formed by Z and a sulfur atom include a hydrogen atom, a halogen atom (fluorine atom, chlorine atom,
bromine atom), substituted or unsubstituted aliphatic groups (preferably saturated or unsaturated, linear, branched or cyclic aliphatic groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, vinyl group, cyclohexenyl group, benzylidene group, hydroxycarbonylmethyl group, methoxycarbonylmethyl group, morpholinomethyl group, hydroxyethyl group, etc.), substituted or unsubstituted aryl group (preferably one with 6 to 20 carbon atoms, e.g. , phenyl group, etc.)
, an alkoxy group (preferably one having 1 to 20 carbon atoms, such as a methoxy group), an aryloxy group (preferably one having 6 to 20 carbon atoms, such as a phenoxy group), an alkylthio group (preferably one having 1 to 20 carbon atoms, such as a phenoxy group), -20, e.g., methylthio group), arylthio group (preferably one with 1 to 2° carbon atoms, e.g., phenylthio group, etc.),
An acyloxy group (preferably one with 2 to 20 carbon atoms, such as an acetyloxy group), an amino group (preferably an unsubstituted amino group, or an alkyl group with 1 to 20 carbon atoms or an aryl group with 6 to 20 carbon atoms) Substituted secondary or tertiary amino group (e.g., amino group, p-chlorophenylamino group, etc.), carbonamide group (preferably an alkylcarbonamide group having 1 to 20 carbon atoms, 6 to 20 carbon atoms)
(e.g., an acetamide group, a benzoylamide group, etc.), a ureido group (preferably a furkylureido group having 1 to 20 carbon atoms, an arylureido group having 6 to 20 carbon atoms), a carboxyl group, an oxycarbonyl group (preferably an alkyloxycarbonyl group having 1 to 20 carbon atoms, an aryloxycarbonyl group having 6 to 2 carbon atoms, such as an ethyloxycarbonyl group), a carbamoyl group (preferably an unsubstituted carbamoyl group, a carbon number 1
~20 alkylcarbamoyl groups, arylcarbamoyl groups having 6 to 20 carbon atoms, such as carbamoyl groups, dimethylcarbamoyl groups, etc.), acyl groups (preferably aliphatic carbonyl groups having 1 to 2 carbon atoms, and arylcarbamoyl groups having 6 to 20 carbon atoms). Arylcarbonyl group (e.g., formyl group), sulfo group, sulfonyl group (preferably an alkylsulfonyl group having 1 to 2 carbon atoms, arylsulfonyl group having 6 to 20 carbon atoms), sulfinyl group (preferably 1 to 20 carbon atoms) alkylsulfinyl group, arylsulfinyl group having 6 to 2 carbon atoms), sulfonamide group (preferably 1 to 2 carbon atoms),
20 alkylsulfonamide groups, C6-C20 arylsulfonamide groups, such as mertylsulfonamide groups), sulfamoyl groups (preferably unsubstituted sulfamoyl groups).

Alkylsulfamoyl group having 1 to 20 carbon atoms, 6 carbon atoms
~20 arylsulfamoyl groups, such as sulfamoyl groups), cyano groups, hydroxyl groups, nitro groups,
Oxo group, thioxo group, imino group.

Alkylimino group (preferably an alkylimino group having 1 to 20 carbon atoms, such as a methylimino group), =C<88
8■ group, heterocyclic group (e.g., pyridyl group,
(morpholino group, etc.).

Among the compounds represented by the general formula (I), preferred are compounds represented by the following general formulas (II) to (■) or compounds having a thiadiazole ring.

General formula (II),...Pa'°"'°'..., where Y is a compound necessary to form a 5- to 6-membered saturated or unsaturated heterocycle together with a sulfur atom and a carbon atom. Represents an atomic group, and this heterocycle may have a substituent,
It does not have a mercapto group as a substituent. X is o
, S or NH.

The atomic group represented by Y consists of a carbon atom, a nitrogen atom, an oxygen atom, and/or a sulfur atom, and a compound ring formed by Y, a sulfur atom, and a carbon atom is fused with another ring to form a condensed ring. You may.

As the substituent for the heterocycle formed by Y, a sulfur atom, and a carbon atom, the same substituents as for the heterocycle in general formula (1) can be mentioned.

General formula (m) In the formula, Y and X have the same meanings as Y and Y in general formula (II), respectively.

Although the heterocycle in general formula (m) may have a substituent, it does not have a mercapto group as a substituent. Examples of this substituent include the same substituents as those for the heterocycle in general formula (I).

General formula (IV) General formula (V) In the formula, R is a hydrogen atom, a substituted or unsubstituted aliphatic group (
Saturated or unsaturated, preferably having 20 or less carbon atoms,
straight-chain, branched-chain, or cyclic aliphatic groups (e.g., methyl, vinyl, morpholinomethyl, etc.), substituted or unsubstituted aromatic groups (preferably those with 6 to 20 carbon atoms), e.g., phenyl, etc. ), an amino group (preferably an unsubstituted amino group, or a secondary or tertiary amino group substituted with an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, such as a p-chlorophenylamino group) ),
or an amide group (preferably an alkylcarbonamide group having 1 to 20 carbon atoms, an arylcarbonamide group having 6 to 20 carbon atoms, such as a benzoylamide group).

General Formula (VI) General Formula (■) The heterocycles represented by the above general formulas (IV) to (■) may have a substituent, but do not have a mercapto group as a substituent. Examples of these substituents include the same substituents mentioned in general formula (1).

Compounds having a thiadiazole ring include the following four isomers and derivatives thereof.

If the thiadiazole ring can be condensed with another ring, it may be condensed with another ring to form a condensed ring.

Further, the thiadiazole ring may have a substituent other than a mercapto group. Examples of these substituents include the same substituents mentioned in general formula (I).

In the present invention, compounds represented by general formulas (■) and (m) are particularly preferred.

Specific examples of the compound represented by the general formula (1) are listed below, but the present invention is not limited thereto.

I-(6) b Summer - (power) NH,・HCQ -I　-(11) NHCOCH.

I-(13)! -(15) ○ I I -(17) Vll I-(20) I=(26) ■ I-(27) I-(29) L' I-(31) I-(32) H3 Go b shi IJ 2shi2ni'i gl-(37
) I-(39) I-(40) 1N! -(45) I-(46) I-(48) Δ I-(50) Next, a specific synthesis example of the compound represented by the general formula (1) is shown below.

Synthesis of Compound 1-(1) Thiourea 38g and chloroacetic acid 47. Green water 100n+Q
and heated to reflux. After one hour, 10 d of concentrated hydrochloric acid was added and the mixture was further heated under reflux for 4 hours. The reaction mixture was cooled with water, and the crude crystals were collected by filtration. Recrystallized from 100 mQ of water, compound 1-
(1) was obtained. Yield 4.2g (72%).

Synthesis of Compound 1-(4) Add 22.8 g of thiourea and 37.5 g of ethyl chloroacetate to 150 ml of ethanol, and add 22.8 g of ethyl chloroacetate.
1.9 g was added and heated under reflux for 1 hour. Compound I-
(4) was obtained. Yield 25 g (72%).

Synthesis of compound [-(8) 76 g of Thiourine J and 86 g of γ-butyrolactone were dissolved in 310 ml of 47% hydrogen bromide, heated under reflux for 19 hours, and dissolved in 1 liter of
It was 1δ. After cooling, add 150 g of sodium hydroxide.
A solution prepared by dissolving .

While cooling on ice, 110 mQ of concentrated sulfuric acid was added little by little.

Compound 1-(8) was obtained by extraction with 1500n+Q ether and distillation under reduced pressure. b, p, 90~bm
mHg e yield 39g (38%).

Synthesis of compound 1-(12) Org, 5ynth, Co11. Vol, 4.
14 g of cyanamide synthesized by the method of No. 645 and 30 g of thiosalicylic acid were dissolved in 60 mQ of tetrahydrofuran and heated under reflux for 70 minutes. It was cooled to 0°C and yellow crystals were collected by filtration.

The crystals were dissolved in 30 mR of 6N hydrochloric acid and heated under reflux for 5 hours. After cooling, the obtained crystals were collected by filtration and recrystallized from ethanol to obtain compound 1-(12).

Yield 12.1 g (48%).

Other compounds can also be synthesized by a synthesis method similar to the above synthesis method.

In the present invention, the processing solution with bleaching ability is a processing solution (bath) that has the ability to bleach (oxidize) silver produced in the development process, and usually includes a bleaching solution (bleach bath), a bleach-fix solution (bleach-fixing solution), and a bleach-fixing solution (bleach-fixing solution). It includes both, which are called baths.

The bleaching accelerator represented by the general formula CI) used in the present invention is usually preferably added to the processing solution having the bleaching ability, but it is preferable that the bleaching accelerator is added to the processing solution having the bleaching ability. Add it in advance to the bath before the bath,
It can also be processed by impregnating a photosensitive material.

When adding the compound represented by the general formula (1) of the present invention to the processing solution having bleaching ability, the amount added will vary depending on the type of photographic material to be processed, the processing temperature, the time required for the intended processing, etc. However, IX 10 per treatment liquid IQ
-4 to 5 x 10-' mol is preferred, particularly preferably I x 10-3 to I x 10-1 mol. Further, when the compound of the present invention is added to the prebath, it is preferably added in an amount of IX 10-4 to IX 10-1 mol per IQ. Further, when the compound of the present invention is contained in a light-sensitive material, the content is I x 10 per 1 d of light-sensitive material.
-' to 1.0 mol is preferable, more preferably lX
10-'' to 0.5 mol.

In order to add the above compounds to a processing solution, it is common to dissolve them in water, alkali, organic acids, organic solvents, etc. in advance, but they can also be added directly as a powder to a processing solution such as a bleach bath. Even if it is added, its bleaching promoting effect is not affected in any way.

Bleaching agents in the bleach solution or bleach-fix solution used in the present invention include iron (■), cobalt (rV), and chromium (■).
, manganese (■), copper (II) and other polyvalent transition metal ion compounds, peroxides, quinones, etc. are used. For example, ferricyanide monodichromic acid, organic acid chelate compounds of iron (III) or cobalt (IV), ferric chloride, persulfates, hydrogen peroxide, permanganates, benzoquinone, etc. can be used.

Among these compounds, organic acid ferric complex salts are particularly preferred from the viewpoint of safety, ease of handling, and prevention of environmental pollution. Examples of such organic acids are:

The following compounds may be mentioned.

Ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N-(β-oxyethyl)-N,
N'.

N'-triacetic acid, 1.2-diaminopropanetetraacetic acid, triethylenetetraminehexaacetic acid, propylene diamine tetraacetic acid, Nitrilotriacetic acid.

Nitrilotripropionic acid, cyclohexanediaminetetraacetic acid, 1,3-diamino-2-propatoltetraacetic acid, methyliminodiacetic acid, ■, 3-diaminopropanetetraacetic acid acetic acid minoniacetic acid, hydroxyliminodiacetic acid, dihydroxyethylglycine ethyl ether diaminetetraacetic acid , glycol ether diamine tetraacetic acid, ethylenediaminetetrapropionic acid, ethylenediaminenipropionic acid, phenylenediaminetetraacetic acid, 2-phosphonobutane-1,2,4-triacetic acid, 1,3-diaminopropanol-N, N, N' , N'-tetramethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetramethylenephosphonic acid, 1,3-propylenediamine-N, N, N', N
'-tetramethylenephosphonic acid, 1-hydroxyethylidene-1,1'-diphosphonic acid,
Among these compounds, iron(m) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3-diaminopropanetetraacetic acid, and methyliminodiacetic acid are preferred because they have a high bleaching edge.

In the present invention, the amount of bleaching agent contained in the processing liquid having bleaching ability is 0.05 mol to 1 mol per IQ.

If the processing solution with bleaching ability is a bleaching solution, 0 per IQ
．． The amount is preferably 1 mol to 1 mol, particularly 0.2 mol to 0.2 mol.
5 mol is preferred. Further, when the processing solution having bleaching ability is a bleach-fixing solution, the amount is preferably 0.05 mol to 0.5 mol, particularly preferably 0.1 mol to 0.3 mol per IQ.

In order to include the bleaching agent in a processing liquid having bleaching ability,
It may be added in the form of the ferric complex salt, or the free acid or its alkali metal salt, ammonium salt and ferric sulfate,
The ferric complex salt may be formed in solution by separately adding ferric chloride, ferric nitrate, ferric ammonium nitrate, ferric phosphate, etc.

The effects of the present invention can be fully exhibited by incorporating one type of each of the bleaching agents used in the present invention into a processing liquid having bleaching ability, but if necessary, two or more types may be included. Also good.

Further, in the present invention, the treatment solution having bleaching ability may contain metal salts such as cobalt, nickel, copper, etc. In addition to the above-mentioned compounds, rehalogenating agents such as bromides, such as potassium bromide, sodium bromide, ammonium bromide, or chlorides, such as potassium chloride, sodium chloride, ammonium chloride, can also be included. In addition, nitrates such as sodium nitrate and ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate,
PL such as sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, and tartaric acid (inorganic acids with buffering capacity of 1a or higher, organic acids, and their salts, etc.) that can be normally used in bleaching solutions. Known additives can be added.

The processing solution having bleaching ability in the present invention includes thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, and potassium thiosulfate, and thiocyanic acids such as sodium thiocyanate, ammonium thiocyanate, and potassium thiocyanate as a fixing agent. salt, thiourea.

Thioether etc. can be used. The amount of these fixing agents is 0.3 mol to 3 mol per bleach-fix solution IQ.

Preferably it is 0.5 mol to 2 mol.

In addition to the bleaching agent and fixing agent mentioned above, the processing liquid having bleaching ability according to the present invention may contain various additives as required.

For example, sulfites such as sodium sulfite and ammonium sulfite, pH adjusters such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, acetic acid, and sodium acetate may be used alone or in combination of two or more. It can be made to contain. It is also possible to contain various antifoaming agents or surfactants, and alkali metal halides such as potassium iodide, potassium bromide, and ammonium bromide, ammonium halides, and hydroxylamine, hydrazine, and aldehyde compounds. Bisulfite adducts can also be included. Among these, it is preferable to use Br and I ions in combination.

In the present invention, the pH of the bleaching solution is 4.0 to 8.0.

In particular, it is preferably 5.0 to 7.0. In addition, the pH of the bleach-fix solution and the fix solution is 5.0 to 9.0, especially 6.0 to 9.0.
．． It is preferably 0 to 7.5.

Various compounds can be used in combination as bleach accelerators in the bleaching solution, bleach-fixing solution and/or their pre-bath.

For example, U.S. Patent No. 3,893,858, German Patent No. 1,290,812, JP-A-53-95630,
Research Disclosure No. 17129 (1978
Compounds having a mercapto group or disulfide bond described in JP-A No. 50-140129, 3,706,56 Kitsuki, U.S. time
Isothiourea derivatives described in No. 1, JP-A-58-162
Iodide described in No. 35, German Patent No. 2,748,4
Polyethylene oxides described in No. 30, Special Publication No. 1973
The polyamine compound described in No.-8836 can be used in combination.

As bleaching accelerators that can be used in combination with these, those represented by the following general formulas (■) to (XIV) are preferred.

General formula (■) Here, A is an n-valent aliphatic linking group (preferably an alkylene group having 3 to 12 carbon atoms, such as trimethylene, hexamethylene, cyclohexylene, etc.).

Aromatic linking group (preferably an arylene group having 6 to 18 carbon atoms, such as phenylene, naphthalene, etc.).

or a heterocyclic linking group (preferably a heterocyclic group consisting of one or more heteroatoms (e.g., oxygen atom, nitrogen atom), such as butene, triazine, pyridine, piperidine, etc.), and when n=1 , A is a simple aliphatic group,
Represents an aromatic group or a heterocyclic group.

Here, the number of aliphatic linking groups, aromatic linking groups, and petrocyclic linking groups is usually one, but two or more may be linked, and the linking format may be direct or from a divalent linking group. It may be a linking group that can be formed, and R5 represents a lower alkyl group. ) may be connected via.

Further, the aliphatic linking group, aromatic linking group, and peterocyclic linking group may have a substituent. Examples of the substituent include an alkoxy group, a halogen atom, an alkyl group, a hydroxy group, a carboxy group, a sulfo group, a sulfonamide group, and a sulfamoyl group.

Represents a kill group (e.g. methyl group, ethyl group, etc.).

R" and R" are substituted or unsubstituted lower alkyl groups (e.g., methyl group, ethyl convex, propyl group, isopropyl group,
pentyl group, etc.), and substituents include hydroxy group, lower alkoxy group (e.g., methoxy group, methoxyethoxy group, hydroxyethoxy group, etc.), amino group (e.g., unsubstituted amino group, dimethylamino group, N- hydroxyethyl-N-methylamino group, etc.) are preferred. Here, when there are two or more substituents, they may be the same or different.

R3 represents a lower alkylene group having 1 to 5 carbon atoms (methylene, ethylene, trimethylene, methylmethylene, etc.), and Y is an anion (halide ion).

For example, it represents Cρe, Br@, θ, sulfate ion, acetate ion).

R'' (or R2) and A are connected via a carbon atom or a heteroatom (e.g., oxygen atom, nitrogen atom, sulfur atom), and form a 5- or 6-membered heterocycle (e.g., hydroxyquinoline ring, hydroxyindole ring). , isoindoline ring, etc.).

Furthermore, R1 (or RZ) and R3 are connected via a carbon atom or a heteroatom (e.g., an oxygen atom, a nitrogen atom, a sulfur atom), and a 5- or 6-membered heterocycle (e.g., a piperidine ring, a pyrrolidine ring) Ring 1 morpholine ring, etc.) may be formed.

Q is 0 or 1. m is O or 1, n is 1.2 or 3, p
represents O or 1, and q represents Oll, 2, or 3.

General formula (IX) R1□ In the formula, n = 1 and R1□ may be the same or different, and represent a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably 1 to 5 carbon atoms, especially a methyl group, an ethyl group) , a propyl group is preferred) or an acyl group (preferably a carbon number of 1 to 31
For example, an acetyl group, a propionyl group, etc.), and n is an integer of 1 to 3.

R, and n=2 may be connected to each other to form a ring.

R□□, n=2 is particularly preferably a substituted or unsubstituted lower alkyl group.

Here, examples of the substituent that R, □, and RL2 include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula (X) In the formula, n=8, R12 and n have the same meanings as in general formula (IX).

General formula (XI) General formula (X11) General formula (XIII) In the formula, R is a hydrogen atom, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), an amino group, a substituted or unsubstituted lower alkyl group ( (preferably 1 to 5 carbon atoms, particularly methyl, ethyl, and propyl groups);
dimethylamino group, diethylamino group, etc.).

Here, examples of the substituent that I(13 has) include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula (XIV) NR2□R2□ In the formula, R2°, R2□, and R2m may be the same or different, and each is a hydrogen atom or a lower alkyl group (for example.

It represents a methyl group, an ethyl group, etc., preferably having 1 to 3 carbon atoms.

R2° and R21 or R2□ may be linked to each other to form a ring.

or a substituent (for example, a lower alkyl group such as a methyl group,
represents an amino group, a sulfonic acid group, or a carboxyl group that may have an alkoxycarbonyl alkyl group such as an acetoxymethyl group.

R2° to R2□ are particularly preferably a hydrogen atom, a methyl group or an ethyl group, and X is preferably an amino group or a dialkylamino group.

The general formulas (■) to () that can be used in combination with the present invention are shown below.
Specific compounds represented by XIV) are listed below, but are not limited to these.

(■-1) CH2N (CH, CH, OH).

(■-2) ・ (■-3) (■-4) (■-5) (■-6) (■-7) (■-8) (■-9) (■-10) (■-11) Akira (■-12) TSe (■-14) n-C,H.

N-CH,CH,OH n-C4H.

(■-1) □′ (IK-2) H,C (■-3) H, C.

(IX-4) H,C (IX-5) \N-(CH,), -3H H.C.O.C. (IX-6) (IX-7) (IX-8) (IX-9) (X-1) (X-2) (X-3) (X-4) (X-5) (X-6) (X-7) (X-8) (X-9) (X-10) (X[-1) (XI-2) (XI-3) Go to h2 (XI-4) (X[l-1) (XI)-2) (X11-3) (XIII-1) (IIu-4) H (XIV-1) (XIV-2) (XIV-4) N.H. □. . . -(.H,)2-5-C' N.H.

(XIV-9) NH HOOC-CH2-5-C NH2 (XIV-10) (XIV-11) Any compound having more than one member can be synthesized by a known method, but in particular, the compound of general formula (■) are U.S. Patent Nos. 4 and 5
No. 52,834, Japanese Patent Publication No. 54-12,056, Japanese Patent Publication No. 192,953/1989; U.S. Patent No. 4,285,984, G. Schw.
Arzenbach et al.

He1v, Chim, Acta,, 38.114
7 (1955), R60°C11nton et al.
,, J, Am, Chen+, Soc,, 70
．． 950 (1948); JP-A-53-95630 for the compound of general formula (X); general formula (XI), (X
Regarding the compound [I), see JP-A No. 54-52534;
General formula (XIII) (7) The compound was originally published in JP-A No. 5
No. 1-68568, No. 51-70763, No. 53-5
No. 0169 (for compounds of the general formula
Reference may be made to No. 3-94927.

When a bleaching accelerator such as a compound having a mercapto group or a disulfide bond in the molecule, a thiazoline derivative, or an isothiourea derivative that can be used in combination in the present invention is included in a processing liquid such as a bleaching solution, the amount to be added is as follows: Although it varies depending on the type of material, processing temperature, time required for the intended processing, etc.,
10-1 mol is suitable, preferably I x 10-
'~5 x 10-'' moles.

In order to add the bleaching accelerators that can be used in combination with the above, it is common to dissolve them in water, alkali, organic acids, organic solvents, etc. in advance, and then add them directly in powder form. Even if it is added to a bleach bath, etc., it has no effect on its bleaching promotion effect. Furthermore, two or more of these known bleach accelerators may be added in combination.

When the bleach accelerator of the present invention and these known bleach accelerators are used in combination, the ratio of the two can be arbitrarily selected.

In addition to the compounds already mentioned, the bath having bleaching ability of the present invention may contain inorganic phosphoric acid, organic phosphonic acid, aminopolyphosphonic acid, or phosphonocarboxylic acid having chelating ability, depending on the purpose. .

These compounds having chelating ability can be used for purposes such as preventing precipitation of iron salts, calcium, and magnesium, preventing sulfurization, and preventing the generation of bacteria in a bath having bleaching ability.

In addition, thiazole-based, isothiazole-based, halogenated phenols, sulfanilamide, benzotriazole, etc. are used to prevent the generation of bacteria in baths with bleaching ability or subsequent baths, and to impart mold-preventing ability to processed sensitive materials. It can also contain a bactericide and a fungicide.

The bath having bleaching ability of the present invention may be composed of one bath or two or more baths. When the system is configured with two or more tanks, it is preferable to use a multi-stage cascade system in which the rear tank is replenished and the resulting overflow liquid flows into the front tank.

In addition, when configuring with two or more tanks, Japanese Patent Application Laid-Open No. 61-75352
As described in No. 61-75353, the front tank can be used as a bleach bath and the rear tank can be used as a bleach-fixing bath. In this case, the overflow liquid of the bleaching bath can also be allowed to flow into the bleach-fixing bath. Further, as described in JP-A-61-511435, the front tank may be used as a fixing bath and the rear tank may be used as a bleach-fixing bath. In this case, the overflow liquid of the fixing bath can also flow into the bleach-fixing bath.

In the processing method of the present invention, the color developing solution used for developing the photosensitive material is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3
-Methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methoxyethylaniline and their sulfates, hydrochlorides, phosphorus acid salt or p-toluenesulfonate, tetraphenylborate, p-(t-
Examples include octyl)benzenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

Examples of aminophenol derivatives include 0-aminophenol, P-aminophenol, 4-amino-2-
These include methylphenol, 2-amino-3-methylphenol, 2-oxy-3-amino-1,4-dimethylbenzene, and the like.

In addition, "Photographic Processing Chemistry" by F. A. Meson, Focal Press (
1966) (L, F, A, Mason, ”
PhotographicProcessing Ch
emistry”, Focal Press) 226
-229 pages, U.S. Patent No. 2,193,015, 2,
592,364, JP-A No. 48-64933, etc. may be used.

If necessary, two or more color developing agents may be used in combination.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates; development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. ; hydroxylamine, triethanolamine, the compound described in West German patent application (OLS) No. 2,622°950;
Preservatives such as sulfites or bisulfites; organic solvents such as diethylene glycol; benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, thiocyanates, 3,6-thiaoctane-1,8-diol; development accelerators such as; dye-forming couplers; competitive couplers; nucleating agents such as sodium boron hydride; auxiliary developers such as 1-phenyl-3-pyrazolidone; viscosity-imparting agents; ethylenediaminetetraacetic acid, nitrilotriacetic acid, cyclohexane Diaminetetraacetic acid, iminodiacetic acid, N
-Hydroxymethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, and aminopolycarboxylic acids represented by the compounds described in Special Patent No. Pj 8-195845, l-hydroxyethylidene-1,1'-diphosphonic acid , Research Disclosure 18170 (May 1979), organic phosphonic acid, aminotris (methylenephosphonic acid), ethylenediamine-N, N.

Aminophosphonic acids such as N',N'-tetramethylenephosphonic acid, Research Disclosure 18170 (1
It can contain a chelating agent such as phosphonocarboxylic acid described in May 1979).

Color developing agents are generally used at a concentration of about 0.05% per color developer IQ.
Concentrations of 1 g to about 30 g, more preferably color developer I
Use at a concentration of about 1 g to about 15 g per Q.

Further, the pH of the color developing solution is usually 7 or more, and most commonly used at a pH of about 9 to about 13.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer includes known black and white developers such as dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate, 3-pyrazolidones such as -phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. Drugs can be used alone or in combination.

After the fixing process or bleach-fixing process, processing processes such as water washing and stabilization are generally performed. Processing methods can also be used. .

In the present invention, the washing bath refers to the processing liquid components absorbed or occluded in the color photosensitive material, the photographic performance after processing,
The main purpose of this bath is to wash out the constituent components of the color photosensitive material that should be removed in order to ensure image stability.

In addition, a stabilizing bath has the function of a washing bath mentioned above.

Further, it refers to a bath that has an image stabilizing function that cannot be obtained with a water washing bath, and for example, a bath containing formalin corresponds to this bath. In addition, the amount brought in from the prebath refers to the volume of the prebath that is attached to and occluded by the photosensitive material and mixed into the washing bath. It can be calculated by extracting the components and measuring the amount of pre-bath components in the extract.

In the present invention, the amount of replenishment to the washing bath or the stabilizing bath that replaces it is 2 to 50 times the amount brought in from the previous bath per unit area of the color photosensitive material to be processed, but preferably 3 to 5 times.
It is 0 times, more preferably 5 to 30 times.

Further, the pH of the water washing or stabilization bath is 4 to 10, preferably 5 to 9. More preferably, it is 6.5 to 8.5.

It is preferable to use softened water as the washing water or stabilizing liquid. Examples of the water softening treatment include using an ion exchange resin or a reverse osmosis device.

As the ion exchange resin, a sodium type strongly acidic cation exchange resin in which the counter ion of the exchange group is sodium is preferred, and H type strongly acidic cation exchange resins and ammonium type strongly acidic cation exchange resins can also be used. Furthermore, it is also preferable to use an H type strongly acidic cation exchange resin and an OH type strongly basic anion exchange resin together. As the resin base, a copolymer of styrene and divinylbenzene is preferred, especially when the amount of divinylbenzene charged during production is 4 to 16% of the total amount of monomers charged.
(w/w) is preferred.

As an example of such ion exchange resin, Mitsubishi Kasei Co., Ltd.
The product name Diaion SK-IB or PK-216 can be mentioned.

Various reverse osmosis attachments can be used, but those using cellulose acetate or polyethersulfone membranes are suitable. Pressures of 20 kg/a1 or less are less noisy and easier to use.

With these ion exchange resins and reverse osmosis treatment equipment,
Water with reduced calcium and magnesium content has less bacterial and mold growth, and when combined with the present invention, provides good results.

In addition, at least one of aminocarboxylic acid, aminophosphonic acid, phosphonic acid, phosphonocarboxylic acid, and salts thereof is added to the washing water or stabilizing liquid in a range of 5X10-' to IX10-
It is also a preferred embodiment to use it by adding 2 mol/Q.

These aminocarboxylic acids, aminophosphonic acids.

Specific examples of phosphonic acid and phosphonocarboxylic acid are shown below.

N(CH2C00H)3 HN(CLCOOH)z A-8 -1O N(CH,PO3H,):.

As salts of aminocarboxylic acids, aminobosphonic acids, phosphonic acids, and phosphonocarboxylic acids used in the present invention, sodium salts, potassium salts, calcium salts, ammonium salts, magnesium salts, etc. are used, and usually ammonium salts,
Sodium salts and potassium salts are preferred, but preferred compounds may differ depending on the liquid.

The amount of these aminocarboxylic acids, aminophosphonic acids, phosphonic acids, phosphonocarboxylic acids, and salts thereof contained in at least the final tank of the tanks constituting the water washing bath is 5.
X 10-s to I X 10-2 mol/Q, preferably I X 10-' to 5 X 10-3 mol IQ
It is.

If it is less than 5 x 10-' mol/Q, the use of these compounds has no effect at all, and if it is more than I x 10-' mol/Q, it may cause precipitates on the surface of the color photosensitive material after drying. This results in unfavorable results such as stickiness and scum build-up.

Further, it is preferable that the washing water or stabilizing liquid contains an isothiazoline antibacterial agent as described below.

(1) 2-methyl-4-inthiazolin-3-one (2
) 5-chloro-2-methyl-4-isothiazoline-3-
(3) 2-Methyl-5-phenyl-4-inthiazolin-3-one (4) 4-bromo-5-chloro-2-methyl-4-isothiazolin-3-one (5) 2-hydroxymethyl- 4-isothiazoline-3
-one (6) 2-(2-ethoxyedyl)-4-isothiazolin-3-one (7) 2-(N-methylcarbamoyl)-4-isothiazolin-3-one (8) 5-bromomethyl-2-(N -dichlorophenylcarbamoyl)-4-inthiazolin-3-one (9)
5-Chloro-2-(2-funinylethyl)-4-inthiazolin-3-one (10) 4-Methyl-2-(3,4-dichlorophenyl)-4-isothiazolin-3-one These antibacterial agents are 1 to 1 in washing water or stabilizing solution
Used in the range of 100 mg/Q, preferably 3 to 301
Used in 11gIQ.

By using a combination of water softening through ion exchange or reverse osmosis treatment, antibacterial agents such as isothiazoline, and chelating agents such as aminopolycarboxylic acids, the objectives can be achieved more effectively.

In addition, irradiating at least one side of the water washing or stabilization replenishment tank or treatment tank with ultraviolet rays can also prevent bacterial growth and
Jl-like is preferable in terms of mold suppression. The method of irradiating ultraviolet rays is not limited to irradiation from outside the liquid, but also irradiation into the liquid by installing a waterproof ultraviolet lamp in the replenishment tank or processing tank or in the circulation system thereof.

In addition to the above, various compounds can be added to the water washing or stabilizing column of the present invention. For example, pH can be adjusted using various buffers (such as 1f borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide,
(using a combination of ammonia water, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc.).

Furthermore, various additives such as surfactants, optical brighteners, hardener metal salts, etc. may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
Various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate can also be added.

When the prebath has fixing ability, fixing agent components such as thiosulfate are brought into the washing or stabilizing bath, but in order to prevent the sulfidation phenomenon caused by this, sodium sulfite, potassium sulfite, and Sulfites such as ammonium sulfate can also be added. Furthermore, sulfanilamide, to prevent bacterial growth in washing or stabilization baths,
The use of benzotriazoles and the like is also a preferred embodiment.

The processing time in the water washing or stabilizing bath varies depending on the purpose and the type of color photosensitive material, but is usually 10 seconds to IO minutes, preferably 20 seconds to 5 minutes. The temperature of the washing bath is usually 20
-45°C, preferably 25-40°C, particularly preferably 30-40°C.

In the present invention, it is also preferable that the water washing or stabilizing bath be configured in a multi-stage countercurrent treatment system with two or more tanks in order to reduce the amount of replenishment.

A component that imparts an image stabilizing effect that cannot be obtained by washing with water is further added to the stabilizing bath. Examples include aldehyde compounds such as formalin.

Specific processing steps of the present invention are shown below, but the steps of the present invention are not limited thereto.

1. Color development - bleaching - (washing with water) constant coloring - washing with water - (stable) 2. color development - bleach-fixing - washing with water - (stable) 3. color development - bleaching - bleach-fixing - washing with water - (stable) 4. color development - Bleach - Bleach fixing - Constant fixing - Washing - (stable) 5. Color development - Constant bleaching - Bleach fixing - Washing - (stable) 6. Black and white development - Washing - (reversal) - Color development - (adjustment)
-Constant bleaching-washing-(stable) 7. Black and white TfJ, image-washing (reversal)-color development-(
Adjustment) - Bleach fixing, washing with water - (stable) 8. Black and white development - washing with water - (reversal) - color development - (adjustment)
- bleaching - bleach-fixing - washing with water - (stable) In the above steps,
Steps marked in parentheses are steps that can be omitted depending on the type of sensitive material and purpose of use.

Further, the washing process may be a conventional method using a relatively large amount of water, or may be a water-saving method that reduces the amount of water.

The present invention can be applied to various color photosensitive materials. Typical examples include color negative film for general use or movies, color reversal film for slides or television, color paper, color positive film, color direct positive paper, and color reversal paper.

The silver halide emulsion used in the present invention is described in Research Disclosure, vol. 176, Item Na
17643, can be prepared using the method described in section (1).

In the silver halide color photographic light-sensitive material used in the present invention, any silver halide including silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride may be used. For high-sensitivity photosensitive materials, silver iodobromide (3 to 20 mol% silver iodide) is preferable, and for photosensitive materials for printing, silver chlorobromide (silver chloride 90 mol% or more or 10 to 30 mol%) is preferable. ), silver iodochlorobromide (silver iodide 1 mol% or less, silver chloride 10-30 mol%)
and silver chloride are preferred.

The silver halide grains in photographic emulsions may be so-called regular grains having regular crystal bodies such as cubes, octahedrons, dodecahedrons, and rhombidodecahedrons, or irregular crystals such as spherical shapes. It may be shaped, have crystal defects such as twin planes, or a combination thereof.

The grain size of silver halide may be fine grains of 0.1 micron or less, or large grains with a projected area diameter of up to 10 microns, and may be a monodisperse emulsion with a narrow distribution or a polydisperse emulsion with a wide distribution. But that's fine.

A typical monodisperse emulsion is an emulsion in which silver halide grains have an average grain diameter of greater than about 0.1 micron, and at least about 95% by weight of the silver halide grains are within ±40% of the average grain diameter. The average grain diameter is between about 0.25 and 2 microns, and at least about 95% by weight or at least about 95% by number of silver halide grains have an average grain diameter of ±20 microns.
% can be used in the present invention.

The crystal structure may be uniform, the inside and outside may have different halogen compositions, or it may have a layered structure. These emulsion grains are described in British Patent No. 1,027,1
No. 46, U.S. Pat. No. 3,505,068, U.S. Patent No. 4.44
No. 4,877 and Japanese Unexamined Patent Publication No. 143331/1984. Further, silver halides having different compositions may be joined by epitaxial joining.

By using tabular grains in the silver halide photographic emulsion used in the present invention, it is possible to improve sensitivity including improvement in color sensitization efficiency by sensitizing dyes, improve the relationship between sensitivity and graininess, improve sharpness, and improve development progress. Improvements in performance, covering power, crossover, etc. can be achieved. Here, tabular silver halide grains are those whose diameter/thickness ratio is 5 or more, such as 1 or more than 8, or 5 or more and 8 or more.
There are the following:

The tabular grains may have a uniform halogen composition or may consist of two or more phases having different halogen compositions. For example, when silver iodobromide is used, the silver iodobromide tabular grains may have a layered structure consisting of a plurality of phases each having a different iodide content. JP-A-58-113928 or JP-A-59
Preferred examples of the halogen composition of tabular silver halide grains and the intragrain distribution of halogen are described in No. 99433 and the like.

A preferred method of using the tabular silver halide grains in the present invention is as follows: Research Disclosure Nα22
534 (January 1983), same Nα25330 (19
(May 1985), which discloses, for example, a method of use based on the relationship between the thickness of tabular grains and optical properties.

Silver halide solvents are then useful in promoting ripening of silver halide grain formation. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. As ripening agents other than halogen ions, ammonia, amine compounds, thiocyanate salts, thioether ripening agents, and thione compounds can also be used.

The properties of silver halide grains can be controlled by allowing various compounds to be present during the silver halide precipitate formation process. For example, by making compounds such as copper, iridium, lead, bismuth, cadmium, zinc, (chalcogenic compounds such as sulfur, selenium and tellurium), gold and compounds of group II noble metals present during the silver halide precipitation process. The properties of silver halide can be controlled.

Silver halide emulsions are usually chemically sensitized.

Chemical sensitization is described by T. H. James,
The Photographic Process, 4th edition, Macmillan Publishing, 1977, (The Theory of
the Photo-graphic Process
, 4th ed, Macmillan, 1977
) 67-76 using activated gelatin. Also, sulfur, selenium, tellurium,
This can be done using gold, platinum, palladium, iridium or a combination of these sensitizers.

Chemical sensitization is optimally performed in the presence of a gold compound and a thiocyanate compound, or in U.S. Pat.
It is carried out in the presence of a sulfur-containing compound such as a sulfur-containing compound or a hypo-, thiourea-based compound, or rhodanine-based compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine.

The silver halide photographic emulsion used in the present invention is:

It may also be spectrally sensitized by methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization.

These dyes are listed in Research Disclosure, vol. 176, Item Nn17643.
．． The one described in rV (December 1978) can be used.

Spectral sensitization of the silver halide emulsion used in the present invention can be carried out at any stage of emulsion preparation.

Spectral sensitizing dyes are generally added to chemically sensitized emulsions before coating. US Pat. No. 4,425,426 and others disclose a method of adding it to an emulsion before or during chemical sensitization. Further, US Pat. No. 2,735,766 discloses a method in which a spectral sensitizing dye is added to an emulsion before the formation of silver halide grains is completed.

U.S. Patent No. 3,628,960, U.S. Patent No. 4,183,
No. 756, and US Pat. No. 4,225,666.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, 3-pyrazolidones, and the like.

The silver halide photographic emulsion used in the present invention includes:

Various compounds can be contained for the purpose of preventing fogging during the manufacturing process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. For example, Research Disclosure Item N (11
Compounds described in Section 7643VI (December 1978) can be used.

Various color couplers can be used in the present invention, specific examples of which can be found in the above-mentioned Research Disclosure (
RD) Nα17643. ■It is described in the patent described in -C-G. As dye-forming couplers, the three subtractive primary colors (i.e. yellow, magenta and cyan)
It is important to have a coupler that gives a 4-equivalent or 2-equivalent coupler during color development, and a specific example of a diffusion-resistant 4-equivalent or 2-equivalent coupler is the above-mentioned RD17.
643. In addition to the couplers described in the patents described in 1-C and 0, the following can be preferably used in the present invention.

Typical examples of yellow couplers that can be used include known oxygen atom elimination type yellow couplers and nitrogen atom elimination type yellow couplers. α-pivaloylacetanilide couplers have excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include hydrophobic 5-pyrazolone and pyrazoloazole couplers that have a ballast group.

As the 5-pyrazolone coupler, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the hue and coloring density of the coloring dye.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol couplers and phenol couplers, and representative examples include preferably oxygen atom-eliminating two-equivalent naphthol couplers. Couplers that can also form cyan dyes that are stable against humidity and temperature are
Typical examples of preferred examples include phenolic cyan couplers having an alkyl group of ethyl group or higher at the meta-position of the phenol nucleus, 2,5-diacylamino-substituted as described in U.S. Patent No. 3,772゜002. These include phenolic couplers, phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, and 5-amidonaphthol cyan couplers described in European Patent No. 161,626A''.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such a coupler is
Examples of magenta couplers are described in US Pat. No. 4,366,237, and examples of yellow, magenta or cyan couplers are described in European Patent No. 96,570.

Dye-forming couplers and special couplers listed above.

A typical example of a polymerized dye-forming coupler that may form a dimer or more polymer is U.S. Pat. No. 3,451
, No. 820, etc. Specific examples of polymerized magenta couplers are described in U.S. Pat. No. 4,367.282 and elsewhere.

Couplers that release photographically useful residues upon coupling are also preferably used in the present invention. The DIR coupler releasing the development inhibitor is the aforementioned RD17643,
The patent couplers listed in Sections .-F. are useful.

In the light-sensitive material of the present invention, a coupler that releases a nucleating agent, a development accelerator, or a precursor thereof in an image form during development can be used. Specific examples of such compounds include British Patent Nos. 2,097,140, 2,131,
It is described in No. 188. Others, JP-A-60-18
DIR redox compound releasing couplers such as those described in US Pat. No. 5,950, couplers that release dyes that turn yellow after separation as described in European Patent No. 173,302A, and the like can be used.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods. An example of a high boiling point organic solvent used in the oil-in-water dispersion method is U.S. Pat. No. 2,322,027.
It is written in the number etc. Further, the process of latex dispersion method, effects, and specific examples of latex for impregnation are described in U.S. Patent No. 4,199,363 and West German Patent Application (OLS) No.
, No. 541,274 and No. 2,541,230.

The photosensitive material used in the present invention contains hydroquinone derivatives, aminophenol derivatives, amines, gallic acid derivatives, catechol derivatives, ascorbic acid derivatives, colorless couplers, sulfonamidophenol derivatives, etc. as color fogging inhibitors or color mixing inhibitors. May contain.

Known anti-fading agents can be used in the photosensitive material used in the present invention. Known anti-fading agents include hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols, hindered phenols including bisphenols, gallic acid derivatives, and methylenedioxy. Representative examples include benzenes, aminophenols, hindered amines, and ether or ester derivatives obtained by silylating or alkylating the phenolic hydroxyl group of each of these compounds. Further, metal complexes represented by (bissalicylaldoximado)nickel complex and (bis-N,N-dialkyldithiocarbamado)nickel complex can also be used.

In the photosensitive material used in the present invention, an ultraviolet absorber can be added to the hydrophilic colloid layer. For example, US Patent No. 3,553,794 and European Patent No.
Benzotriazoles substituted with aryl groups as described in US Pat. No. 7,160, etc., U.S. Pat. No. 4,450.229
Butadines, as described in U.S. Patent No. 3.705,
Cinnamic acid esters described in No. 805, U.S. Pat.
, 215,530, and polymer compounds having ultraviolet absorbing residues such as those described in US Pat. No. 3,761,272 can be used.

Ultraviolet absorbing optical brighteners described in US Pat. No. 3,499,762 may also be used.

A typical example of an ultraviolet absorber is RD24239 (June 1984).
month) etc.

The photosensitive material used in the present invention is used as a coating aid, antistatic, improves sliding properties, emulsification and dispersion, prevents adhesion, and improves photographic properties (
For example, one or more known surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

The photosensitive material used in the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for various purposes such as preventing irradiation or halation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, and merocyanine dyes.

Anthraquinone dyes and azo dyes are preferably used, and in addition, cyanine dyes, azomethine dyes, triazolemethane dyes, and phthalocyanine dyes are also useful. An oil-soluble dye can also be emulsified by an oil-in-water dispersion method and added to the hydrophilic colloid layer.

In the present invention, in the silver halide color photosensitive material,
Preferably, p-hydroxybenzoic acid ester is included.

As the p-hydroxybenzoic acid ester, one represented by the following general formula (PH8) is used.

General Formula (PHB) Here, R represents an alkyl group, a substituted alkyl group, an aralkyl group, or a substituted aralkyl group having 1 to 18 carbon atoms in total.

Preferred groups as R are unsubstituted alkyl, among which methyl group, ethyl group, n-propyl group, and n-
Butyl group is preferred, most preferred is n-butyl group.

These P-oxybenzoic acid esters are easily available commercially. P-oxybenzoic acid ester may be added to any layer in the photosensitive material. The amount of p-oxybenzoic acid ester added is 0.001 to 0.05 g per io+" of the photosensitive material, preferably 0.005 to 0. ．．
02g. The method of addition is based on solvents that do not affect photographic performance (e.g., water, methanol, ethanol,
It may be added in any step of producing a photosensitive material, either dissolved in ethyl acetate, etc.) or as a powder.

(Example) The present invention will be described below with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of silver halide emulsion: Silver halide emulsion (1) used in this example was prepared as follows.

(1 liquid) H, 01000rtrQ NaCQ 5.
5g gelatin 32g (2 liquids) Sulfuric acid (IN) 20mM (3
Liquid) The following compound (lvt% aqueous solution) 3 mQH3 CH.

(4 liquids) KBr 2.80gNaC
Add Q O, 34g H2O and 140 mQ (5 liquids) AgNO35g Add H, 0 and make 140 mΩ (6
Liquid) KBr 67.24gNa
Cf1 8,
26gK, Ir(4, (0,001wt% aqueous solution)
Add 0.7 rmQ■20
320 mQ (7 liquids) AgNOz 120
Add gH20 320 m
Q (liquid 1) was heated to 75°C, and (liquid 2) and (liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were allowed to stand for 9 minutes and added simultaneously. After another 10 minutes, (liquid 6) and (liquid 7) were added simultaneously over a period of 45 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, add pi (6.
2, the average particle size was 1.01μI, the coefficient of variation (
Standard deviation divided by average particle size; s/d) 0.0
8. A monodispersed cubic silver chlorobromide emulsion containing 80 mol % of silver bromide was obtained. Sodium thiosulfate was added to this emulsion to optimally chemically sensitize it.

Next, silver halide emulsion (2) was prepared as follows.

(8 liquids) Same as (1 liquid).

(9 liquids) Sulfuric acid (IN) 24 mQ (1
0 liquid) Same as (3 liquid).

(11 liquids) KBr 17.92gNa
Add CQ 2.20gH2O"'C220mQ (12 liquids) AgN0.32 gH20
Add 200 mQ (13 liquids) KBr 71.68 gNa
1j2 8.81gKzIr
CQs (0,001wt% aqueous solution) 4.5
Add mQH20 and test 00 mQ (14 liquids) AgN0. 128 gH,
600 m (1 (8 liquids) was heated to 56 °C, and (9 liquids) and (10 liquids) were added. Then, (11 liquids) and (12 liquids) were heated for 30 minutes. 10 minutes after the addition, (liquid 13) and (liquid 1) were added simultaneously.
4 liquids) were simultaneously added over a period of 20 minutes. 5 minutes after addition,
The temperature was lowered and desalted. Add water and dispersed gelatin, pH
6.2 to obtain a monodisperse cubic silver chlorobromide emulsion with an average grain size of 0.45 μm, a coefficient of variation of 0.08, and 80 mol % of silver bromide. Sodium thiosulfate was added to this emulsion to optimally chemically sensitize it.

Subsequently, a series of emulsions with a low silver bromide content were prepared. The silver bromide content was adjusted to 20% by changing the addition time and the amounts of KBr and NaCQ in the same manner as in emulsions (1) and (2).
1 and 0 mol% silver chlorobromide and silver chloride emulsions were prepared and designated as emulsions (3) to (8). Table A shows the average grain size and coefficient of variation of the emulsion obtained.

Table A Preparation of color photosensitive material: Table B is placed on a paper support laminated on both sides with polyethylene.
A color photographic paper with the layer structure shown below was prepared.

The coating solution was prepared as follows.

First layer coating solution preparation: Yellow coupler (a) Log and Buddha statue stabilizer (b)
Ethyl acetate lomM and 4 mQ of solvent (c) were added to and dissolved in 23 g, and this solution was emulsified and dispersed in 90 mfl of a 10% aqueous gelatin solution containing a 10% aqueous solution of sodium dodecylbenzenesulfonate 5a+Q. On the other hand, the silver chlorobromide emulsion (1) (silver bromide 80 mol%, silver content 70 g/kg
), the following blue-sensitive sensitizing dye was added to 7 moles of silver chlorobromide.
A blue-sensitive emulsion was prepared by adding 10-' mol of X. The emulsified dispersion and the emulsion were mixed and dissolved, and the concentration was adjusted with gelatin so that the composition shown in Table B was obtained, thereby preparing a coating solution for the first layer.

The coating solutions for the second to seventh M layers were also prepared in the same manner as the first layer coating solution.

The gelatin hardening agent for each layer is 1-oxy-3,5-
Cycloro s-triazine sodium salt was used.

The following sensitizing dyes were used.

Sensitizing dyes for blue-sensitive layers (7 x 10-' moles added per mole of silver halide) Sensitizing dyes for green-sensitive layers (4 x 10-' moles added per mole of silver halide) Sensitizing dyes for red-sensitive layers (added 4 x 10-' moles per mole of silver halide) The following anti-irradiation dyes were used (2×10-' moles added per mole of silver halide).

Anti-irradiation dye for the green sensitive layer (2,IX 10-' mole used) Anti-irradiation dye for the red-sensitive layer (2,OX 10-' mole/n image) Compounds used in this example, such as couplers The structural formula is as follows.

Yellow coupler (a) Yellow coupler (b) Magenta coupler (a) and 0 Magenta coupler (b) Magenta coupler (c) Magenta coupler (d) Cyan coupler (,) ShiU Cyan coupler (C) Color image stabilizer (a) Color image stabilizer (b) Shii-1, Ui-1゜ Color image stabilizer (c) Color image stabilizer (d) Color image stabilizer (e) UV absorber (a) UV absorber (b) UV absorber (c) Color mixing inhibitor (a) Color mixing inhibitor (b) Suh Solvent (a) Solvent (b) Solvent (c) (C9H1−○′+rP=0 Solvent (d) (cs　H□70hp　=.

Sample 101 was prepared by coating the coating liquids of the first to seventh layers on a paper support laminated on both sides with polyethylene while adjusting the balance of surface tension and viscosity.

Next, Samples 102 to 132 were prepared in exactly the same manner except for the changes shown in Table C.

Table C Table C (Continued) 32 pieces of 108 samples were prepared as above.
Samples were prepared by irradiating light through a blue filter using a light source at 00° (IOCMS) to develop a gray color and each density of yellow, magenta, and cyan was 2.0. These samples were processed according to the following processing steps.

■'' □ Time color development 33℃ 3 minutes 15 seconds bleach fixing
Rinse at 33℃ for 60 seconds■ 33
℃ 20 seconds rinse■ 33℃
Rinse for 20 seconds■ 33℃
Dry for 20 seconds 70℃ 50 seconds Rinse ■ to rinse ■ 3 from rinse ■ to rinse ■
A stage countercurrent replenishment system was used.

The composition of each treatment liquid is as follows.

Mitsutsugu Suiashi diethylenetriaminepentaacetic acid 3.0g
Benzyl alcohol 15 m
m diethylene glycol 10
mQ sodium sulfite 2
．． 0g potassium bromide
0.6g potassium carbonate
30 g hydroxylamine sulfate
4.0g optical brightener
Add 1.0g water
1000 mQp)l
to, 20 bleach-fix solution ammonium thiosulfate 110
g Sodium bisulfite 10
g Iron diaminetetraacetate (m)
40 g ammonium monohydrate bleach accelerator (compounds and amounts added are listed in Table 1) Add water 10001
00O7,2 Rinse liquid ■-■ Bismuth chloride 0.3
5g polyvinylpyrrolidone 0
・25g nitrilotriacetic acid trisodium salt
1.0g 2-octyl-4-isothiazolin-3-one 50mg Optical brightener (4,4'-diaminostilbene type) 1.0g Add water
100 axis Q pH 7.50 The residual silver amount of the obtained sample was measured by fluorescent X-ray method. The results are shown in Table 1. The amount of the bleach accelerator used in the present invention was determined by selecting the amount that showed the most preferable accelerating effect, except for Nos. 2 to 5, in which the amount was changed.

As is clear from Table 1, when processed with the bleach-fix solution of the present invention, favorable images with a small amount of residual silver were obtained. Furthermore, the effects of the present invention were also obtained with light-sensitive materials in which the coupler and the method of emulsifying the coupler were changed.

The comparative compounds shown in Table 1 are as follows.

Comparative compounds: 2-mercapto 1.3, 4. -Triazole comparison compound ■: 2-mercapto-4-amino-1
, 3,4-Thiadiazole Table 1 Table 10) Table 1 Seki) SuJ1'λ Materials 109 to 116 prepared in Example 1 were exposed in the same manner as in Example 1, and the color developing solution of Example 1 was used. at 33℃ for 1 minute 30
It was then treated with the bleach-fix solution of Example 1 modified as below at 33° C. for 45 seconds, and then with the rinse solution of Example 1. The residual silver amount of the treated sample was measured in the same manner as in Example 1. The results are shown in Table 2. The bleach-fix solution is made by mixing ethylenediaminetetraacetic acid Fe(m)/ammonium monohydrate with diethylenetriaminetetraacetic acid Fe(m)/ammonium monohydrate.
m) Ammonium and ethylenediaminetetraacetic acid disodium dihydrate were changed to diethylenetriaminetetraacetic acid. The amount added was equivalent to the equivalent molar amount.

As is clear from Table 2, the results obtained were obtained even when the silver bromide content of the silver halide emulsion was changed to 20 mol %.

It was the same as Example 1.

Table 2 (Table 20 sold) Example 3 Samples 117 to 124 prepared in Example 1 were exposed in the same manner as in Example 1 and processed in the following steps. Regarding the obtained sample, the amount of residual silver was measured by fluorescent X-ray spectroscopy.

Nie birch, Choo-wadan, Gaisei Kenpei, color development
35℃ 45 seconds bleach fixing 33℃
Washing for 45 seconds ■ Washing for 20 seconds at 33°C ■ Washing for 20 seconds at 33°C Drying for 20 seconds at 70°C The formulation of the treatment solution was as follows.

Triethanolamine 8.0
gN,N-diethylhydroxylamine 4
．． 2g sodium sulfite 0
．． 1g potassium carbonate 2
5゜Sodium chloride 1.
5g optical brightener (4,4'-diaminostilbene type)
Add 3.0g water
1000m APH10.05 Drifting A (Treatment A) Ferric ethylenediaminetetraacetate 55g Ammonium monohydrate ethylenediaminetetraacetic acid disodium 10g Ammonium thiosulfate (70ε/Q liquid) 1
00 mQ Sodium Sulfite
17g bleach accelerator (compound, amount added is listed in Table 3) Add water
1000mΩp8
6.00 Bleach-Fix Solution B (Processing B) 40 g/Ω of ammonium bromide was added to bleach-fix solution A.

Rinse five-fold tap water with H-type strongly acidic cation exchange resin (Mitsubishi Kasei Corporation)
Diaion 5K-III) and OH-type strong basic anion exchange resin (Diaion 5A-10A) were passed through a heated bed column to obtain the following water quality. After that, isocyanuric dichloride was added as a disinfectant. sodium acid 20mg
/Q was added.

Calcium ion 1, 1r
ng/Q magnesium ion O
-Sag/ρp+16.9 Here, for treatment A, bleach-fix solution A was used, and for treatment B, bleach-fix solution B was used. Example 1 The amount of residual silver in the sample after processing
It was measured by fluorescent X-ray analysis in the same manner as above. The results obtained are shown in Table 3.

As is clear from Table 3, the same results as in Example 1 were obtained (Processing A). Furthermore, when ammonium bromide was added to the bleach-fix solution, favorable results with a smaller amount of residual silver were obtained (Processing B).

Table 3 Table 30) Example 4 Samples 125 to 132 prepared in Example 1 were exposed and processed in the same manner as in Example 3. The residual silver amount of the obtained sample was measured by the fluorescent X-ray spectroscopy method in the same manner as in Example 1. Here, the bleaching agents in bleach-fix solutions A and B are changed from ferric ammonium ethylenediaminetetraacetate monohydrate to ferric ammonium cyclohexanediaminetetraacetate, and from ethylenediaminetetraacetic acid disodium dihydrate to cyclohexanediaminetetraacetic acid. Bleach-fix solutions C and D were obtained by adjusting the molar equivalents of each solution.

The results obtained are shown in Table 4. The results were similar to Example 3.

Table 4 Table 4 (1) (1) Table 4 Rinsing) Example 5 Sample 117 prepared in Example 1 was continuously replenished at a rate of 3M per day in the following treatment process until three times the tank capacity of the bleach-fix solution was replenished. processed.

Process Lay down Time Tank capacity Compensation ≧ Castle color development 35℃ 45 seconds
10 Q 160mL'rrr bleach fixing 3
3℃ 30 seconds IQ 100mQ
/m water washing■ 33℃ 20 seconds 4Q -water washing■ 33℃ 20 seconds 4Q -water washing■
33℃ 20 seconds 4 Q 3
00 m (1/rd drying 80° C. 60 seconds The water washing was carried out in 3-tank countercurrent water washing from washing (① to washing②).

The processing liquid used is as follows.

Diethylenetriaminetetraacetic acid 2.0g
2.0gN, N-diethylhydroxylamine 4.2
g 4.2g triethanolamine
8.0g 8. ．． 0g sodium sulfite 0.1. , 0.1g potassium carbonate 25g25g sodium chloride 1.5g - add water 1000m Q
1000m QpH10,0510,45 Ethylenediaminetetraacetic acid disodium dihydrate 10
gAmmonium thiosulfate (70g/Q liquid)
100mQ Sodium Sulfite
17g ammonium bromide
40g bleach accelerator (compound, amount added is listed in Table 5) Add water
1000m100O6,00; ■-■ (both tank and tank) tap water was mixed with H-type strongly acidic cation exchange resin (Diaion 5K-IB manufactured by Mitsubishi Kasei Corporation) and OH-type strongly basic anion exchange resin (Diaion 5A manufactured by Mitsubishi Chemical Corporation). The water was passed through a hot bed column filled with -1OA) to obtain the following water quality, and then 20 mg/Q of isocyanuric acid dichloride was added as a disinfectant.

Calcium ion 1, 1 mg/fl Magnesium ion 0.5 mg #tpH 6,9 Using each treatment solution after continuous treatment, exposed sample 117 was treated in the same manner as in Example 1, and the amount of residual silver was determined by fluorescent X-ray analysis. It was measured. The results obtained are shown in Table 5.

Table 5 As is clear from Table 5, when the bleach-fix solution of the present invention was used for continuous processing, favorable images with a small amount of residual silver were obtained.

Example 6 On a subbed cellulose triacetate film support,
A multilayer color photosensitive material 201 was prepared by coating layers having the compositions shown below.

(Photosensitive layer composition) The numbers corresponding to each component indicate the coating amount expressed in g/m, and for silver halide, the coating amount is expressed in terms of silver. However, for sensitizing dyes and couplers, the coating amounts are expressed in moles per mole of silver halide in the same layer.

(Sample 201) 1st layer; antihalation layer black colloidal silver silver 0.18
Gelatin 0.40
2nd layer; Intermediate layer coupler C-10,07 coupler C-30,02 ultraviolet absorber U-10,08 ultraviolet absorber U -20,08 organic solvent HBS-10,10 organic solvent HB S-20,02 gelatin 1.04
3rd layer: 1st red-sensitive emulsion layer sensitizing dye IK 6.9
X10-'sensitizing dye II
1.8X10-' sensitizing dye III
3. I X 10m' sensitized color sensitized V
4. OX 10-s coupler C-20,146 organic solvent HB S-10,40 coupler C-100,008 gelatin 1.20
4th layer; 2nd red-sensitive emulsion layer sensitizing dye IX 5. I
X 10-' Sensitizing dye II
1.4 x 10-' sensitizing dye m
2.3X10-' sensitizing dye IV
3.0X10-' Coupler C-20.060 Coupler C-30,008 Coupler C-100,004 Organic solvent HB S -20,40 Gelatin 1.50
5th layer; 3rd red-sensitive emulsion layer sensitizing dye IK 5.4
X IFs sensitizing dye ■1.4 X 10-S sensitizing dye m 2.4
X 10-'sensitizing dye IV
3. I
6th layer; middle layer gelatin 1.06
7th layer; first green-sensitive emulsion layer sensitizing dye V3. OX
lo-5 sensitizing dye VI
1. OX 10-'sensitizing dye■
3.8X10'' Coupler C-60,120 Coupler C-10,021 Coupler C-70,030 Coupler C-80,025 Organic solvent HBS-10,20 Gelatin 0.70
8th layer; 2nd green-sensitive emulsion layer sensitizing dye V 2.1
X 10-' 74-color MVI
7. OX 10-5 sensitizing dye■
2.6X10-'Coupler C-60.
021 Coupler C-80,004 Coupler C-10,002 Coupler C-70,003 Organic solvent HBS-10,15 Gelatin 0.80
9th layer; 3rd green-sensitive emulsion layer Sensitizing dye V3.5XlO-s Sensitizing dye VI 8. O
X 10-'sensitizing dye■
3.0XIO-'Coupler C-60,011 Coupler C-10,001 Organic solvent HB S -20,69 Gelatin 1.74
10th layer: yellow filter layer yellow colloidal silver silver 0.05
Gelatin 0.95
11th layer; 1st blue-sensitive emulsion layer sensitizing dye■ 3.5X1
0-'Coupler C-90,27 Coupler C-80,005 Organic solvent HBS-10,28 Gelatin 1.28
12th layer; 2nd blue-sensitive emulsion layer sensitizing dye ■ 2. I
X 10-'Coupler C-90,098 Organic solvent HBS-10,03 Gelatin 0.46
13th layer; 3rd blue-sensitive emulsion layer increased IB color MVm 2.
2 x 10-' coupler C-90,036 organic solvent HB S-10,07 gelatin 0.69
14th layer; 1st protective layer Ultraviolet absorber U-10,11 Ultraviolet absorber U-20,17 Organic solvent HBS-1 0.90
Gelatin 0.95
15th M; Second protective layer Scavenger 5-10.15 Scavenger S -20.05 Gelatin 0.72
In addition to the above composition, gelatin hardener H-1 and a surfactant were added to each layer.

The chemical structural formulas or chemical names of the compounds used in the above examples are shown below.

C-3 H 51J, iNa S) U, iNa'C-10 N HBS-1 )-Liclesyl phosphate HBS
-2 Dibutyl phthalate 1- Sensitizing dye■ hi2 -1-1° After exposing this light-sensitive material to 25 CMS using a tungsten light source and adjusting the color temperature to 4800°K with a filter, the following Development processing was performed at 38° C. according to the processing steps.

Process Time color development 3 minutes 15 seconds bleach 45 seconds bleach fixing
Washing with water for 2 minutes and 45 seconds Stability for 1 minute and 40 seconds The composition of the treatment solution used was as follows.

Color current 9-string diethylenetriaminepentaacetic acid 1.0
g1-hydroxyethylidene-1,1-diphosphonic acid
2.0 Sodium Sulfite
4.0g potassium carbonate
30.0g potassium bromide
1.4g potassium iodide
1.3mg hydroxylamine sulfate
2.4g4-(N-ethyl-N-β-
Add 4.5g of water (hydroxyethylamino)-2-methylaniline sulfate
1.0Qp8
10.0 Ammonium bromide 150.0 g Ammonium nitrate IQ, 0 g Bleach accelerator 1 (Compound name, described in Addition - 6) - Bleach accelerator 2 (Described in Addition - 6) Add water
1.0Qp8
6.0-Bleach accelerator 2: Bleach-fix solution 2ηQ group ammonium thiosulfate (70g/Q solution)
100 mQ sodium sulfite
17g bleach accelerator (compound, amount added is listed in Table 6) Add water
1000 pH 6,00 Washing liquid tap water to H-type strongly acidic cation exchange resin (Mitsubishi Kasei Corporation)
After passing water through a hot bed column filled with Diaion SK-IB) and OH-type strongly basic anion exchange resin (Diaion SA-1OA) to obtain the following water quality,
Sodium isocyanurate dichloride 20m as a disinfectant
g/Q was added.

Calcium ion 1.1
mg/12 magnesium ion
0.5mg/QP8
6.9 Formalin (40wt% aqueous solution)
Add 2.0+J water
1000 mA The amount of residual silver in the most packed part of the sample thus obtained was measured by X-ray fluorescence analysis. The results obtained are shown in Table 6.

Table 6 (Compare Table 6) Note 1) The compound and amount added of Bleach Accelerator 1 are based on the bleaching solution.

Also shown is the bleach-fix solution.

Note 2) The amount of bleach accelerator 2 added is shown for the bleach solution.

As is clear from Table 6, when processed with the bleaching solution and bleach-fixing solution of the present invention, preferable images with a smaller amount of residual silver were obtained than in the comparative example. Furthermore, when the bleach accelerator of the present invention and bleach accelerator 2 are used together in a bleach solution,
A preferable image with a smaller amount of residual silver was obtained.

Color photographic light-sensitive material 3, in which two layers from the first layer are coated on a paper support laminated on both sides with Sueo ■Yu polyethylene.
01 was created. The first coated polyethylene layer contains titanium white as a white pigment and a trace amount of ultramarine as a bluish dye.

(Photosensitive layer composition) Below are the ingredients and girt? Indicates the coating amount in units.

Regarding silver halide, the coating amount is shown in terms of silver.

1st layer (gelatin layer) Gelatin 1.3
0 2nd layer (antihalation layer) Black colloidal silver 0.10
Gelatin 0.70
3rd layer (low sensitivity red sensitivity layer) Gelatin 1.00
Cyan coupler (umbrella 3) 0
．． 14 cyan coupler (middle school 4)
0.07 anti-fading agent ($5, vomit *7)
o, t.

Coupler solvent (see 8 and 9)
0.06 4th layer (high sensitivity red sensitive layer) Gelatin 1.00
Cyan coupler (middle school 3) 0
．． 20 cyan coupler (umbrella 4)
0.10 anti-fading agent (115, Chin 6 and Umbrella 7)
0.15 coupler solvent (Umbrella 8 and Umbrella 9)
0.10 5th layer (middle layer) Magenta colloid silver 0.02
gelatin 1.0
0 color mixture prevention agent ($10)
0.08 color mixing inhibitor solvent (*11 and $12)
0.16 volume latex ($13)
0.10 6th layer (low sensitivity green sensitive layer) Gelatin 0.80
Magenta coupler (umbrella 15)
0.10 anti-fading agent (-16)
0.10 Stain inhibitor (1117) 0.01 Stain inhibitor ($18) 0
．． 001 coupler solvent (Umbrella 11 and Umbrella 19)
0.15 7th layer (high sensitivity green sensitive layer) Gelatin 0.80
Magenta coupler ($15) 0
．． 10 Anti-fading agent (*16)
o, 1° stain inhibitor (*17)
o, o1 stain inhibitor (*18)
o, oo1 coupler solvent (mono 11 and -
19) 0.15 8th layer (yellow filter single layer) Yellow colloidal silver 0.2
0 gelatin 1.0
0 color mixture prevention agent ($10)
0.06 color mixing inhibitor solvent (Sin 11 and $12)
0.15 polymer latex (*13)
0.10 9th layer (low sensitivity blue sensitive layer) Gelatin 0.50
Yellow coupler (umbrella 21)
0.20 stain inhibitor (fist 18)
0.001 coupler solvent (*9)
o, os 10th layer (high sensitivity blue sensitive layer) Gelatin 1.00
Yellow coupler (umbrella 21)
0.40 stain inhibitor ($18)
0.002 coupler solvent (-9)
0.10 11th M (ultraviolet absorption layer) Gelatin 1.50
UV absorber (Fist 22.-6 and $7)
1.00 color mixture prevention agent (Umbrella 23)
0.06 color mixing inhibitor solvent (*9)
o, Is Anti-irradiation dye (medium 24) 0.02 Anti-irradiation dye (medium 25) 0.02 12th layer (protective layer) Gelatin 1.50
Gelatin hardener ($26) 0
．． 17-1 5.5'-dichloro-3,3'-di(3-
Sulfobutyl)-9-ethylthiacarbonyl cyanine N
a salt $2 Triethylammonium-3-(2-(2-
[3-(3-sulfopropyl)naphtho(1,2-d)thiazoline-2-indenmethyl]-1-butenyl)-3
-naphtho-(1゜2-d)thiazolino]propanesulfonate-32-Cα-(2,4-di-t-amylphenoxy)hexanamide]-4,6-dichloro-5-ethylphenol $42-(2 -chlorobenzoylamide)-4-chloro-5-[α-(2-chloro-4-t-amylphenoxy)octaneamitocophenol 5 2-(2-hydroxy-3-see, 5-t-
butylphenyl)benzotriazole-62-(2-hydroxy-5-t-butylphenyl)
Benzotriazole-7 2-(2-hydroxy-3,5-di-t-butylphenyl)-6-chlorobenztriazole-8 Dioctyl phthalate umbrella 9 Trinonyl phosphate-10 2,5-di-t-octylhydroquinone 11
Tricresyl phosphate $12 Dibutyl phthalate umbrella 13 Polyethyl acrylate-145,5'-diphenyl-9-ethyl-3,3'-
Disulfopropyl oxacarbocyanine Na salt 157-chloro-6-methyl-2-0-(2-octyloxy-5-(2-octyloxy-5-t-octyl)benzene-suldinamide) 2-propyl ]-1 topirazolo[1,5-b co[1,2,4 cotriazole*
t63.3.3', 3'-tetramethyl-5,6,5
', 6'-tetrapropoxy-1,1'-bisspiroindane 17 3-(2-ethylhexyloxycarbonyloxy)-1-(3-hexadecyloxyphenyl)-2
-Pyrazoline-182-methyl-5-t-octylhydroquinone $
19 trioctyl phosphate 20 triethylammonium-3-[2-(3-benzylrhodanin-5-ylidene)-3-penzoxazolinyl copropane sulfonate umbrella 21 α-pivaloyl-α-[(2,4-dioxo -1-benzyl-5-ethoxyhydantoin-3-yl)-2-chloro-5-(α-2,4-di-t-amylphenoxy)butanamido]acetanilide umbrella 225-chloro-2-(2-hydroxy- 3-t-butyl-5-t-octyl)phenylbenztriazole 23 2,5-di-5ec-octylhydroquinone-26 1.4-bis(vinylsulfonylacetamido)ethane The obtained sample 301 was exposed to white wedge light, The treatment was carried out according to the following steps.

Processing process First development (black and white development) 38℃ 45 seconds water wash 38℃ 45 seconds reverse exposure 500 lux or more 15 seconds or more Color development 38℃ 60 seconds water wash 38℃ 15 seconds bleach-fix 38℃ 45 seconds water wash
Dry at 38℃ for 60 seconds [First developer] Potassium sulfite 30.0g
Potassium thiocyanate 1.2g
Potassium carbonate 35.0g
Dinitylene glycol 15.0m
Q Potassium bromide 5.0m
g Add water 1000
mQ (pH 9,7) [Color developer] Triethanolamine 8.0g
N,N-diethylhydroxylamine 4.
0g3.6-cythia 1,8-octanediol
0.2g sodium sulfite
0.2g potassium carbonate
25.0g potassium bromide
0.5g potassium iodide
Add 1.0mg water
1000 mQ (PH1, 0, 4) [Bleach-fix solution/bleach accelerator (compound name and amount added are listed in Table 7)2
-Mercapto-1,3,4-triazole (Additional amount is listed in Table 7) Sodium sulfite 15.0g
Sodium thiosulfate (700g/Q liquid)
160 rnn glacial acetic acid
Add 6.0mn water
1000 mQ (pH 6,0) [Washing liquid] Same as the washing liquid of Example 3.

Table 7 shows the amount of residual silver in the white portion of the obtained sample.

Table 7 Table 7 (a) As is clear from Table 7, when processed with the bleach-fix solution of the present invention, preferable images with a smaller amount of residual silver were obtained than in the comparative example. Further, when the bleach accelerator of the present invention and 2-mercapto-1,3,4-triazole were used together, a preferable image with a smaller amount of residual @I silver was obtained.

(Effects of the Invention) According to the present invention, a bleaching accelerating effect that allows a color light-sensitive material to be sufficiently desilvered in a short period of time without impairing its photographic properties has been obtained.

(3 others anti-Mayo) Procedure 7 City official document 1986 Patent Application No. 249424 2. Name of the invention

Claims (3)

[Claims] (1) A method of processing an exposed silver halide color photographic light-sensitive material with a processing solution having bleaching ability after color development, in the presence of a compound represented by the following general formula (I). A method for processing a silver halide color photographic light-sensitive material, which is characterized by processing with a liquid. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. may have a substituent, but it does not have a mercapto group as a substituent.) (2) The processing method according to claim (1), wherein the processing liquid having bleaching ability contains an organic acid ferric complex as a bleaching agent. (3) The compound represented by the general formula (I) is at least one compound selected from the group of compounds consisting of compounds represented by the following general formulas (II) to (VII) and compounds having a thiadiazole ring. A processing method according to claim (1). General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y is 5 to 6 along with sulfur and carbon atoms.
Represents a group of atoms necessary to form a membered heterocycle, and this heterocycle may have a substituent, but does not have a mercapto group as a substituent. X represents O, S or NH. ) General formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, Y is 5 to 6, along with sulfur and carbon atoms.
Represents a group of atoms necessary to form a membered heterocycle, and this heterocycle may have a substituent, but does not have a mercapto group as a substituent. X represents O, S or NH. ) General formula (IV) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (V) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R is a hydrogen atom, an aliphatic group, an aromatic group, an amino group , or an amide group.) General formula (VI) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ General formula (VII) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the above general formulas (IV) to (VII) The represented heterocycle and thiadiazole ring may have a substituent, but they do not have a mercapto group as a substituent.)