JPS61143755A - Treatment of color photographic sensitive material - Google Patents

Abstract

PURPOSE:To finish a silver removal step securely in a short time and to save a necessary amt. of processing soln. to be replenished, by forming the silver removal step composed of a bleaching bath specified in compsn., a bleach-fixing bath, and a fixing bath, and introducing the overflow solns. of the bleaching bath and the fixing bath into the bleach-fixing bath to use them for effective processing. CONSTITUTION:The silver removal step after a color development step is composed of the bleaching bath contg. ferric aminopolycarboxylate complex salt, the bleach-fixing bath contg. said salt and a fixing agent, and a fixing bath, and parts or all of the overflow solns. from the bleaching bath and the fixing bath are introduced into the bleach-fixing bath. These 3 baths may be optionally arranged, but the orders of bleaching, bleach-fixing, and fixing, and that of bleach-fixing, bleaching, and fixing are preferred. Such a combination of the 3 baths permits the functions of the bleaching bath and the fixing bath to be imparted, so that loads of both to be alleviated, and the overflows of them to be effectively used, replenishment of the processing solns. to be made only to the 2 baths, not to 3 baths, and sufficient silver removal to be finished in a shorter time that the conventional 3-bath process.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for processing silver halide color photographic materials (hereinafter referred to as color photographic materials), and in particular to a method for processing silver halide color photographic materials (hereinafter referred to as color photographic materials). The present invention relates to an improved treatment method 1C which is more complete and requires less replenisher volume.

(Prior art) In general, the basic steps in processing color photosensitive materials are a color developing agent and a desilvering step.In the color developing agent, exposed silver halide is reduced to produce silver, and oxidized silver halide is reduced by the color developing agent. The color developing agent reacts with the color former (coupler) to give a dye image.In the next desilvering step,
The silver produced in the color developing agent is oxidized by the action of an oxidizing agent (commonly known as a bleaching agent), and then dissolved by a silver ion complexing agent, commonly known as a fixing agent. As a result, only a dye image is created on the color photosensitive material.

The above desilvering process is carried out in a co-bath of a bleaching bath containing a bleaching agent and a fixing bath containing a fixing agent, or in a single bath using a bleach-fixing bath containing a bleaching agent and a fixing agent. There is.

In addition to the basic steps mentioned above, the actual development process includes various auxiliary steps to maintain the photographic and physical quality of the image, or to improve the preservation of the image. For example, hardening. These include a membrane bath, a stop bath, a stable temperature, and a water washing bath.

The above-mentioned in-situ processing of color photosensitive materials is generally carried out continuously in large quantities using an automatic imager.Such continuous processing is accompanied by the processing of color photosensitive materials. In order to compensate for consumption of each processing liquid portion, replenishing liquid is added as appropriate. Therefore, due to the addition of replenisher, a large amount of exhausted and used processing solution is discharged from each processing bath as overflow solution, but in order to protect the environment, these discharged solutions are collected and outsourced to specialized companies for disposal. is the reality.

In general, known bleaching agents include red blood salt, dichromate, ferric chloride, persulfate, and ferric noboricarmenic acid salt. However, as is well known, red blood salt and dichromate are difficult to use today from the viewpoint of environmental conservation, and ferrous chloride 1 produces iron hydroxide in the subsequent washing process, so washing with water is difficult. A washing step with an organic chelating agent must be performed before the process, which has the disadvantage of not being able to meet the recent demands for simplification and speeding up of processing in the industry.Also, regarding persulfates, Its bleaching action is very weak (it requires a significantly long bleaching time, so it cannot be put to practical use except for special purposes from the viewpoint of speeding up the bleaching process).

On the other hand, ferric aminopolycarboxylic acid complexes (e.g., ferric complex salts of ethylvindiaminetetraacetic acid, ferric complex salts of diethylenetriaminepentaacetic acid, etc.) have fewer environmental conservation problems, and ferric chlorides such as ferric chloride It is currently the most widely used bleaching agent because it does not have the problem of producing iron hydroxide and exhibits a faster bleaching action than persulfates.

However, the bleaching blade of the ferric aminopolycarboxylic acid complex salt is by no means sufficient (those using this as a bleaching agent are used for low-sensitivity silver halide color light-sensitive materials based on silver chlorobromide emulsions). In the case of bleaching or bleach-fixing processing, the desired purpose can be achieved to a certain extent, but high-sensitivity color photographic materials that are color-sensitized and that are based on silver iodide or silver iodobromide emulsions, especially When processing color reversal light-sensitive materials for photography and color negative light-sensitive materials for photography that use emulsions with a high silver content, there are disadvantages in that desilvering failure occurs and bleaching takes a long time.

For example, when bleaching a color negative light-sensitive material for photography using a bleaching solution of a ferrous aminopolycarboxylic acid complex salt, the bleaching time is at least longer than the necessary time, and in addition, Vcs is required to maintain the bleaching edge. ! It requires complicated management such as pH control of fi white f and implementation of aeration. Even if such management is implemented, the reality is that bleaching defects still often occur.

Furthermore, for desilvering, VC requires treatment with a fixing solution for at least 3 minutes following bleaching. There is.

On the other hand, as a means to speed up the desilvering process, a bleach-fix solution containing a ferric aminopolycarmenic acid complex salt and a thiosulfate as described in German Patent No. RTT, TOP is used. It is known that when aminopolycarboxylic acid ferric complex salts, which originally have a weak oxidizing power (bleaching blade), coexist with thiosulfate, which has a reducing power, the bleaching blade becomes significantly weakened, making it difficult to take photos with high sensitivity and high silver content. (1) It is extremely difficult to sufficiently desilver color photosensitive materials for commercial use, and it cannot be put to practical use.

Of course, various attempts have been made in the past to improve the drawbacks of bleach-fix solutions.
A method of coexisting with a large amount of rogay compound described in Iμ publication, a method of containing a high concentration of aminopolycarboxylic acid second complex salt using triethanolamine described in JP-A No. Sho≠r-yztJGC publication, etc. However, all of these effects are insufficient and cannot have any practical value. Also, as described in U.S. Patent No. 31/3rzr and British Patent No. 1 Jr.
Various bleaching accelerators have been proposed for the purpose of increasing the silver source whiteness of bleach-fixing solutions, but their effects are not always satisfactory, and their stability is particularly poor in bleach-fixing solutions. , it loses its effectiveness in a short time and cannot be put to practical use11.Thus, great efforts have been made to shorten the time of the desilvering process, that is, speed up the process, but it still has sufficient practical value. The technology has not yet been developed. However, in recent years, the demand for faster processing in this industry has become even stronger, and there is an urgent need for the development of a technology that can meet the demand.

Furthermore, in recent years, from the perspective of environmental conservation, biochemical oxygen demand f
It is essential to collect and process photographic processing waste liquids with high (BOD) and chemical oxygen demand (COD), and in order to reduce the costs of recovery and processing, treatment methods that require a small amount of waste liquid, i.e., processing that requires a small amount of replenishment, are recommended. Development of a method is strongly desired. Of course, reducing the amount of replenishment does not only reduce the cost of waste liquid collection, but also reduces the amount of processing agent itself used, reduces the frequency of replenisher preparation, and reduces the space for storing replenisher, etc. It also leads to various cost savings and improvements in work efficiency. Therefore, in addition to speeding up the process, there is a strong demand for the development of technology to reduce the amount of replenishment.

(Object of the Invention) A first object of the present invention is to provide a rapid processing method that can sufficiently desilver a highly sensitive color light-sensitive material containing a high amount of silver in a short period of time. A first object of the present invention is to provide an economical processing method that can maintain excellent photographic performance even with small amounts of replenishment. Furthermore, a third object of the present invention is to provide a treatment method that causes fewer problems in terms of environmental protection.

(Structure of the Invention) The present inventors have proposed that in a processing method for desilvering an exposed silver halide color light-sensitive material after color development, the desilvering step includes a bleach bath containing a ferric aminopolycarboxylic acid complex salt, an amino It consists of three baths: a bleach-fix bath containing a ferric polycarboxylic acid complex salt and a fixing agent, and a fixing bath, and a part or all of the overflow liquid from the bleaching bath and the fixing bath is introduced into the bleach-fixing bath. It has been found that the above object can be achieved by making the method more effective.

Here, the arrangement and head pressure of the bleaching bath, bleach-fixing bath, and fixing bath may be arranged in any manner depending on the purpose, but it is preferable to arrange them in the order of (1) bleaching bath - constant loading of bleach-fixing bath, or (2) Bleach-fixing bath - bleach bath constant wearing bath or ■ fixing bath - bleach bath - bleach-fixing bath, and particularly preferably: ■ bleach bath - bleach-fixing bath constant wearing bath or ■ bleach-fixing bath - bleach bath constant wearing bath. In order.

In the present invention, overflow liquid refers to the used bleach solution that flows out of the bleach bath as a result of adding bleach replenisher to the bleach bath, and the used fixer solution that flows out of the fix bath as a result of adding fixer replenisher to the fix bath. means.

That is, the present inventors have developed a bleaching bath of an aminopolycarbonate orderly complex salt with a weak bleaching blade and a bleaching blade with a weak bleaching blade (particularly for color photosensitive materials with high sensitivity and high silver content (1), which have been considered to be impractical (1). By combining a bleach-fixing bath (composed of a ferric noboricarzenate ferric complex salt and a fixing agent) and a treatment with a fixing bath to this λ bath, a three-bath treatment is performed.9. The present inventors have discovered an unexpected effect in that silver can be sufficiently desilvered in a shorter time than when processing with a bleach-fixing bath or when processing with a bleach-fixing bath alone. The required capacity of the bleach-fix bath is maintained by introducing some or all of the overflow liquid of the white and fix baths into the bleach bath, and in most cases requires direct replenishment of the bleach-fix bath. Therefore, although the desilvering process of the present invention is composed of three baths, the replenisher required is only one bath, and it does not require an increase in the work for preparing the replenisher. There is.

Moreover, the present inventors have developed the present invention VC in which the desilvering process is performed in three baths.
According to the authors, it was discovered that the amount of replenishment solution to the bleaching bath and fixing bath can be reduced by nine times compared to conventional methods. Although it is difficult to clearly explain these reasons, in the present invention, a bleach bath,
Because the functions of the fixing bath are shared with the bleach-fixing bath, the load on the bleaching and fixing baths is significantly reduced, and the overflow liquid from both the bleaching and fixing towers, which was previously disposed of, is now It is believed that effective reuse as a bleach-fix bath made possible rapid desilvering and a reduction in the amount of replenisher.

The ferric aminopolycarboxylic acid complex salt used as a bleaching agent in the white bath and bleach-fixing bath in the present invention is a complex of ferrous ion and aminopolycarboxylic acid or a salt thereof.

Representative examples of these aminopolycarboxylic acids and their salts include: A-/ Ethylenediaminetetraacetic acid A-co Ethylenediaminetetraacetic acid disodium salt A-J Ethylenediaminetetraacetic acid diammonium salt A-e Ethylenediaminetetraacetic acid tetra(trimethylammonium) Salt A-t Ethylenediaminetetraacetic acid tetrapotassium salt A-A Ethylenediaminetetraacetic acid tetrasodium salt A-7 Ethylenediaminetetraacetic acid trisodium salt A-r Diethylenetriamine pentaacetic acid intasodium salt A-io Ethylenediamine-N -(β-oxyethyl)-N,N',N'-triacetic acid A-ii Ethylenediamine-N-(β-oxyethyl-N,N'
, N'-Triacetic acid trisodium salt A-/J Ethylenediamine-N-(β-oxyethyl-N,N',N'-triacetic acid triammonium salt Human-73 Propylenediaminetetraacetic acid A-744 Propylenediaminetetraacetic acid Disodium salt A-/Jr Nitrilotriacetic acid -76 Nitrilotriacetic acid trisodium salt A-/7
Cyclohexanediaminetetraacetic acid A-/r Cyclohexanediaminetetraacetic acid disodium salt human-/F Iminodiacetic acid A-20 diethylglycine in dihydro-2/Ethyl ether diamine tetraacetic acid human-Coco Glycol ether diamine tetraacetic acid human- 13 Ethylenediaminetetrapropionic acid and the like can be mentioned, but of course the compounds are not limited to these exemplified compounds.

Among these compounds, A-/~A-J, A-r,
A-/7 to human-7 are preferred.

Aminopolycarmenic acid@ferric complex salts may be used in the form of complex salts, or may be used in the form of ferrous salts such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferrous phosphate, etc. A ferric ion complex salt may be formed in a solution using diiron or the like and an aminopolycarboxylic 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 a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, seven or more types of 8g coco salt may be used. Furthermore, one or more types of aminopolycarboxylic acids may be used. In any case, the aminopolycarboxylic acid may be used in excess of the amount required to form the ferrous ion complex.

Further, a bleaching solution containing the above-mentioned W1 iron ion complex or a metal ion complex salt of cobalt, steel, etc. other than bleach-fixing 1VCtt iron may be contained.

Bleach iK constituting the present invention contains, in addition to bleach and the above-mentioned compounds, bromides such as potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide or chlorides such as potassium chloride, sodium chloride, ammonium chloride can be included.

In addition, nitrates such as sodium nitrate and ammonium nitrate,
One or more inorganic acids having a pH buffering capacity such as boric acid, borax, sodium metaborate, hydrochloric acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Additives commonly known for use in bleaching solutions, such as organic acids and their salts, can be added.

In the present invention, the amount of bleach per liter of bleaching solution is 0.11
The amount is from mol to 1 mol, preferably from O1λ mol to 0.5 mol.

Also, the pH of the bleaching solution is 1t, μ, or when used.

O1 special Kj, 0-4. jVC is preferred.

In the present invention, the bleach-fix solution l! The amount of bleach used is 0.
01 mole~O0! mol, preferably (@0.1 mol to 0.3 mol).

In addition, the bleach-fixing solution contains fixing agents such as thiosulfate salts such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate, potassium thiocyanate, etc. Thiourea, thioether, etc. can be used. The responsibility of these fixing agents is 0.3 to 3 mol per liter of bleach-fix solution, preferably O0j
It is mole to comol.

In addition to the above-mentioned bleaching agents and fixing agents, the bleach-fixing solution according to the present invention contains compounds contained in the bleaching solution, sulfites, bisulfites, various buffering agents, intermediate rate agents, etc., which are commonly used in fixing solutions. Compounds may be included.

In the present invention, the bleach-fix solution (mother liquor) at the start of processing is
'U4 is prepared by dissolving the compounds used in the bleach-fixing solution described above in water, but it may also be prepared by mixing an appropriate amount of a separately prepared bleaching solution and a fixing solution described later. In addition, the pH of the bleach-fix solution was 411. G~! .

! is preferred, and a, tr, and o are more preferred.

The fixing solution constituting the present invention includes thiosulfates such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, potassium thiosulfate,
Sodium thiocyanate, ammonium thiocyanate,
Thiocyanates such as potassium thiocyanate, thioureas, thioethers, etc. can be used. These fixers have a concentration of 00j-≠ mol per liter of fixer, preferably 7
~3 moles. In addition, as a preservative for the fixing agent, sulfites such as ammonium sulfite, sodium sulfite, and potassium sulfite, and bisulfite salts such as sodium bisulfite and potassium bisulfite are used per 1 liter of the fixing solution.
It is preferable to use 000 mol to 002 mol. In addition, boric acid, sodium metaborate, acetic acid, sodium acetate, citric acid, sodium citrate, fJ,
Seven or more types of inorganic acids having pH buffering ability such as sodium chloride, carbonic acid, sodium carbonate, potassium carbonate, etc., gastric acid, and salts thereof can be used, and nitrates such as ammonium nitrate can also be used. In the present invention, p) (it≠, O~ri of the fixer).

It can be used within the range of O, but preferably t, or.

! , more preferably ≦,! ~r, O.

In the present invention, in order to introduce the overflow liquid of the bleach bath and the fixing bath into the bleach-fixing bath (i. the overflow pipes of the agitation bath and fixing bath A are directly connected to the bleach-fixing bath, the auger flow liquid is directly transferred to the bleach-fixing bath). Alternatively, the overflow liquid may be stored outside the tank and both overflow liquids may be separately injected into the bleach-fixing bath using a pump or the like.Alternatively, both overflow liquids may be pumped into the bleach-fixing bath. The mixture may be mixed outside and then injected into the bleach-fixing bath using a pump or the like.

In the present invention, the amount of replenishment solution to the bleaching bath is determined as per color photosensitive material/rPL processing/j Owl - r 0 Ow
l, preferably o out −+ o oMt
It is. Also, the replenisher i for the fixing bath is provided by KoOOt-too.
It is preferably JOOy+l to 700ml. All of the over-70 solution associated with these replenishments may be introduced into the bleach-fixing bath, or may be introduced in an amount necessary to bring the composition of the bleach-fixing bath into a preferred range VCtQn. In addition, the bleach-fix bath VC is
Normally, the performance is maintained simply by introducing the overflow liquid of the bleaching bath and fixing bath, but if necessary, necessary components may be added to the bleaching bath and the fixing bath separately.

In the present invention, the number of skins in each of the bleaching bath, bleach-fixing bath, and fixing bath may be 1. Even better results can be obtained by setting j[cl.

In addition, in the processing method of the present invention, in the case where a bleach bath is followed by a bleach-fix bath and/or a fix bath, the present inventors have proposed that the following general formulas (1) to (■) be selected from the following: 7
When two bleach accelerators were included in the bleach bath, the desilvering rate was further improved, and the bleach accelerating effect continued to be significantly superior to that known in the conventional bleach bath and fixing bath process. I found out what I can get. Moreover.

The use of bleach accelerators of this type in conventional processing methods often results in a delay in fixing speed (although in the processing method of the present invention, a delay in fixing due to the use of bleach accelerator 4j also occurs). I found the advantage of not having one.

General formula (1) In the formula, R1% and R2 may be the same or different (, hydrogen atom, substituted or unsubstituted lower alkyl group (preferably carbon number/-j, especially methyl group, ethyl group, propyl group Preferred or acyl group (preferably carbon number/~3, e.g. acetyl group, propionyl group, etc.), n11
It is an integer between 7 and 3.

R1 and R2 may be linked to each other to form a ring.

As R1 and R2, substituted or unsubstituted lower alkyl groups are particularly preferred.

Here, examples of the substituent that R2 has include a hydroxyl group, a carboxyl group, a sulfo group, and an amine group.In the formula (n), R3 and R4 are R1 and R2 of the general formula (1). is synonymous with n is an integer from / to 3.

R3 and R4 may be linked to each other to form a ring.

As R3 and R4, substituted or unsubstituted lower alkyl groups are particularly preferred.

Examples of the substituents R3 and R4 include a hydroxyl group, a carboxyl group, a sulfo group, and an amino group.

General formula (Itl) R5/C-8-CN3)l General formula (■) General formula (V) 51J In the formula, R5 is a hydrogen atom, a halogen atom (for example, a chlorine atom, a chlorine atom, etc.), an amino group, Substituted or unsubstituted lower alkyl groups (preferably 1-1 carbon atoms, methyl, ethyl, and propyl groups are particularly preferred), amino groups substituted with alkyl groups (methylamino groups, (ethylamino group, dimethylamino group, diethylamino group, etc.).

Here, the Ft substituent that R5 has is a hydroxyl group,
Examples include carboxyl group, sulfo group, and amino group.

General formula (■) In the formula, % 16 and R7 may be the same or different, and each represents a hydrogen atom, an alkyl group that may have a substituent (preferably a lower alkyl group, such as a methyl group, an ethyl group, a propyl group) etc.), a phenyl group that may have a substituent, or a heterocyclic group that may have a substituent (more specifically, at least one heteroatom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc.)
Represents a heterocyclic group containing at least one group, such as a pyridine ring, a thiophene ring, a thiazolidine ring, a benzoxazole ring, a benzotriazole ring, a thiazole ring, and an imidazole ring), and may have R611, a hydrogen atom, or a substituent. Lower alkyl groups (e.g. methyl, ethyl, etc.)

Preferably, the number of carbon atoms is 1 to 3°.

Here, the substituents that R6-R8 have include a hydroxyl group, a carboxyl group, a sulfo group, an amino group, and a lower alkyl group.

R9t! , represents a hydrogen atom or a carboxyl group.

General formula (ν■) In the formula, RI Os R11s R121! Each represents a hydrogen atom or a lower alkyl group (eg, methyl group, ethyl group, etc., preferably carbon number 1 to 3°), which may be the same or different.

RIO and R11 Matai! R12 may be linked to each other to form a ring.

X is a substituent (for example, a lower alkyl group such as a methyl group,
Represents an amine group, a sulfonic acid group, or a carboxyl group that may have an alkyl group such as an acetoxymethyl group.

R10'=R12 is particularly preferably a hydrogen atom, methyl group or ethyl group, and X is preferably a hydrogen atom, a methyl group or an ethyl group.

An az) group or a dialkylamino group is preferred.

In the present invention, as the bleach accelerator, bleach accelerators represented by general formulas (1) and (II) are preferable.

Preferred examples of the compounds of formulas (1) to (', 41) are shown below.

(I) -fx) CI) -(31 (I) -(4) (I) -(51 (I) -(61 (I) -(71 (I) -(8) (■n -(9) (II) -(]) (n) -+2) (ff) -(31 (n)-(4) (II) integral) (rl) -(6) ?1 H ([1)-(7) ( U) -(S) (II)-(93 (I[) -In) -(t) (l[[) -(21 ([) -(31 (iIl) -(4) (fli') -(1) NV) -(21 (■) -(31 (V) -(1) (V) -(2) R (■) -(1) (M) -(21 (■Two (3) ( ■) -(sl (■n -(6) (■) -(1) (■) -(2) (~M) -(31 (■) -+4) (■) -(51 (■) -( 6) (■) -(7) (■) -<8) (■) -+91 (■)-01 (■)-(11) All of the above compounds 11 can be synthesized by known methods,
In particular, compounds of general formula (I) are described in US Patent No. 211. (4c Specification, G.

Schwarzenbach et al., He
1v, Chim.

Acta,, Jr, //g7 (/ri!Jri, R60°C
11nton et al., J. Am., Chem.
,SOC,.

70, 9210 (/rit), the compound of general formula (II) is disclosed in JP-A-Sho! J-ta J430 publication, general formula C
Regarding the compound of m> (IV), please refer to JP-A-Sho! ≠−jko! Regarding the compound of general formula (V) in Jμ publication, JP-A-Sho! /-4rjtr issue, same! No. l-70763, same! !
-! Regarding the compound of general formula (Vl) in Publication No. 0/4, Special Publication Shoj3-2! ! ≠ Publication, special application Shojt-rr 3
Regarding the compound of general formula (■) in Specification No. I, please refer to JP-A-Sho! 3-2≠227 can be referred to.

In the present invention, the bleach accelerator is added to bleach bath C (the amount added varies depending on the type of color photosensitive material to be processed, the processing temperature, the time required for the intended processing, etc. /×l0-5~to-'' mole is suitable, preferably !X10'''''~jxi o
mol, more preferably 1×10 −2×10 mol.

These bleach accelerators need to be replenished with appropriate Vc in the bleach bath in order to maintain their effectiveness during processing, but as a replenishment method, VC may be added to the bleach replenisher solution. Alternatively, the bleach accelerator alone may be added as a solution or powder.

In the present invention, the bleaching time is carried out for 0 seconds to μ minutes, and when the bleaching accelerators of general formulas (1) to (■) are contained in the bleaching bath, the bleaching time is preferably 20 seconds to 2 minutes; ~(■)
When no bleaching accelerator is used, the preferred time is /min to qmin.

The bleaching and fixing time is 30 seconds to 1 minute, preferably 7 minutes to 3 minutes.

The fixing time is also 30 seconds to ψ minutes, preferably 1 minute to 3 minutes.

In the present invention, between the bleach bath, bleach-fix bath, and fix bath,
Normally, a water washing step is not required, but a step of washing the pre-bath components such as a water washing bath or a short rinse bath may be added as necessary.

The first aromatic back amino color developing agent used in the color developing solution of the present invention includes known ones that are widely used in various color photographic processes. These present! and p-phenylene diamine derivatives. These compounds are generally used in the form of salts, such as danates or sulfates, since they are more stable than in the free state. Additionally, these compounds are generally present in a concentration of about 0.1 g to about 30 g per color developer solution/IVc, more preferably about 1 g per color developer solution/l.
It is used at a concentration of about p-/jfi.

Examples of aminophenol-based developers include 〇-aminophenol, p-aminephenol,! -Amine-co-oxytoluene, co-amino-J-oxytoluene, co-oxy-3-amino-/, IA-dimethyl-
Contains benzene, etc.

A particularly useful primary aromatic amino color developer is N.

N-Sial is a p-phenylenediamine type compound, and the alkyl group and phenyl group may be substituted or unsubstituted.

Among them, examples of particularly useful compounds include N,N-diethyl-p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, and N-methyl-p-phenylenediamine hydrochloride.
-Phenylenediamine hydrochloride N.

N-dimethyl-p-phenylenediamine hydrochloride, -mono-amino-7-(N-ethyl-N-dobushilua(1)-)toluene, N-ethyl-N-β-methanesulfonide i-ethyl-3-methyl-≠ -aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, Hiro-amino-3-methyl-N,N-')ethylaniline, Hiro-
Amino-N-(λ-methoxyethyl)-N-ethyl-3
-Methylaniline-p-toluenesulfonate.

In addition to the first aromatic amino color developer, the alkaline color developer used in the present invention further contains various components normally added to color developers, such as sodium hydroxide, sodium carbonate, and carbonate. Alkaline agents such as potassium, alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali gold M/%
A halogenide, benzyl alcohol, a water softener, a thickening agent, and the like may optionally be included. This color development 1
The pH value of the liquid is usually above 7, most commonly 11.
It is about 2 to about 13.

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

In the present invention, the black-and-white developing solution used at this time can be a so-called black-and-white first developer used in 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 phenomenon liquids can be included.

Typical additives include l-phenyl-3-pyrazolidone, developing agents such as metol and hydroquinone, preservatives such as sulfites, and accelerators consisting of alkalis such as sodium hydroxide, sodium carbonate, and potassium carbonate. ,
Inorganic or organic inhibitors such as potassium bromide, λ-methylbenzimidazole, methylbenzthiazole, water softeners such as polyphosphates, trace amounts of iodide, and modern inhibitors consisting of mercapto compounds. can be given.

Processing method of the present invention 1, the above-mentioned color development fjl! It consists of processing steps such as , bleaching, bleach-fixing, and fixing.

Here, 1c after the fixing process is generally performed to perform treatment processes such as washing with water and stabilization, but after the fixing process, after a short rinsing bath without substantial washing with water, A simple stabilization treatment method may also be used.

The washing water or rinsing bath used in the washing process can contain known additives as necessary. For example, chelates such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid. A disinfectant, a bactericide to prevent the growth of various bacteria and algae, a hardening agent such as magnesium salt or aluminum salt, a surfactant to prevent drying load and unevenness, etc. can be used.Alternatively, L, E, West
, “WaterQuality Cr1teria”P
hot, Sci, andEng,, vol, Ta A6t
Compounds described in page 3g Hiro-3 (/ritat) etc. can also be used.

Further, the washing step may be carried out using more than one tank if necessary (or the washing water may be saved by carrying out multi-stage countercurrent washing (for example, λ to three stages).

As the stabilizing liquid used in the stabilizing step, a processing liquid that stabilizes the dye image is used. For example, it is possible to use a solution having a buffering capacity of pH J to O, a solution containing an aldehyde (for example, formalin), etc. In the stabilizing solution (on the other hand, if necessary, a fluorescent brightener, a chelating agent, a bactericide, etc.) can be used. antifungal agent,
A hardening agent, a surfactant, etc. can be used.

In addition, the stabilization process may be carried out using a tank with more than one tank of water (multi-stage countercurrent stabilization (e.g., 2 to 2 stages) to save the stabilizing solution and omit the water washing process. You can also do that.

The disinfectants and fungicides used in the water washing process, rinsing process, and stabilization process include halogenated phenol%'(''-isothiazolyl nobenzimidazole, further ICj-chlorocomethyl-Hiro-inthiazoline- 3
-one, inthiazolone derivatives such as 1,2-benzinotiazolin-3-one and Hiko (copromoethyl)
-/.

Benzointhiazolone derivatives such as cobenzisothiazoline, sulfaniladium, and the like are effective.

The photosensitive material processed according to the present invention is a known color photosensitive material, preferably a coupler-containing multilayer negative color photosensitive material or a color photosensitive material made for reversal color processing. It can be particularly advantageously used in cases where color X-ray photosensitive materials,
Single-layer special color photosensitive material, also the core of the US patent! /2ri No. 7 specification, 3ri No. 02201 specification, JP-A-Sho! t-6
≠Black-and-white phenomenon herbal medicines such as 3-pyrazolidones described in Japanese Patent Application Laid-Open No. 16-417μ, Japanese Patent Application Laid-open No. 66-1J7Ko2, and U.S. Patent No. 2μ7
t≠00 Specification, No. 33 μco J27 Specification, No. 33
μ Coj Tata Specification, No. 37/μ Taco No. Specification, No. μ
It is also possible to process color photosensitive materials in which precursors of color developing chemicals described in M21 Hiroo Kou No. 7 and Japanese Patent Application Laid-Open No. Sho S3-/3J6-1 are incorporated. Alternatively, there is nothing wrong with treating the coupler in the presence of the liquid.

The photographic emulsion layer VC of the photosensitive material of the great invention contains a color-forming coupler,
That is, in color development processing, compounds that can develop color by oxidative coupling with aromatic 7th class amine developers (for example, phenylenediamine cotton conductors, aminophenol derivatives, etc.), such as cyan couplers, phenol couplers, naphthol couplers, magenta couplers, j
- Pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, etc., and as yellow couplers, acylacetamide couplers (eg, hapenzoylacetanilides, pivaloylacetonilides) can be included.

As the cyan coupler, in particular, the following general formula (C-1)
Also, a coupler represented by (C-U) is preferred.

General formula (C-N General formula (C-■)) Zl In the formula, R1, R2 and R4 represent a substituted or unsubstituted aliphatic group, aryl group or heterocyclic group, R3 and R6 are hydrogen atoms, halogen Takako, is a substituted or unsubstituted aliphatic group, aryl group, annulamino group, or R is R
Along with nitrogen content! Represents a group of nonmetallic atoms forming a 6-membered ring, and R'! , ff represents an optionally substituted alkyl group, Zl and Zl represent a hydrogen atom or a group capable of releasing Kl during an oxidative coupling reaction with a developing drug, and represent nt-functional Q or /.

The cyan dye-forming coupler represented by the general formula (C-1) or (C-II) is usually used in silver halide emulsion '1ff (particularly in the red-sensitive emulsion layer) VC. The amount of addition is 1 = ko×lO~! ×/Q mol 1 mol-Ag, preferably /
×10 -jXlo-'mol 17 Ru Ag is used.

Furthermore, a method for synthesizing cyan dye-forming couplers represented by general formulas (C-1) and CC-■) is described in U.S. Pat.
02 issue, same≠, 3jltL, 0// issue.

It can be easily synthesized based on the method described in the specifications of M Hiromu, 3 Core, No. 173, Dohiro, Hiro λ7t717, etc.

When the cyan coupler represented by the above general formula is used, even when the bleaching time is short, the gradation of the cyan image does not become soft (good photographic properties can be obtained).

In addition, as for the color photosensitive materials used in the present invention, those having a high silver content per unit, for example, those having a silver content of 3 g/2 or more (preferably !-/19/nt) can be used effectively can. Further, the present invention can be effectively used for color light-sensitive materials having a high silver iodide content, for example, those having a silver iodide content of more than 70 mol.

(Examples) Example 1 Multilayer color photosensitive material samples having the compositions shown below were prepared on a triacetyl cellulose film support.

1st %; antihalation layer; gelatin layer containing black colloidal silver; first layer; middle layer;! - Gelatin layer 3rd layer containing an emulsified dispersion of di-t-octylhydroquinone; low-sensitivity red-sensitive emulsion layer silver iodobromide emulsion (silver iodide: j mol %)...silver coating ψ1,
≦11/m2 Sensitizing dye I......B x I for 1 mole of silver
O moles of sensitizing dye■・・・・・・・per mole of silver/
! X/ 0 mole coupler EX-/...O0O per mole of silver
μmol coupler EX-co...0.0 per mole of silver
03 mole coupler EX-J... o, o per mole of silver
oot mole layer; high sensitivity red-sensitive emulsion layer silver iodobromide emulsion (silver iodide; lO malt...silver coating amount
/ , Hiro y 7m2
Sensitizing dye I・・・・・・・・・3×10″′″ moles per 1 mol of silver Sensitizing dye 7.2XIO mole coupler EX-≠...000 per mole of silver
2 mole coupler EX-2...0.0 per mole of silver
0/Mole 2nd layer; 41st layer same as the second intermediate layer; Low-sensitivity green-sensitive emulsion layer Monodispersed silver iodobromide emulsion (Silver iodide; Hiromi %)...Amount of coated silver 1. Cog/rn2 sensitizing dye■
・・・・・・・・・J×10− for 1 mole of silver
1 mol sensitizing dye■・・・・・・・・・・・・/×10 mol coupler EX-J...@0.01 mol coupler EX-A... per 1 mol silver o per mole of silver, oot mole coupler EX-j...0.00/! per mole of silver!
Mole No. 7 j: High-sensitivity green-sensitive emulsion layer Silver iodobromide emulsion (Silver iodide; 70 moles...Amount of coated silver
/, 3g/yv+2 sensitizing dye ■・
・・・・・・・・・λ5jX10 for 1 mole of silver
-'molar sensitizing dye■・・・・・・・・・0, rx/0-5v for 1 mol of silver -Coupler EX-7...0.077 mol coupler for 1 mol of silver EX-4... o, ooi mole per mole of silver Coupler EX-4... 0.003 mole per mole of silver r@; Yellow filter with yellow colloidal silver in gelatin aqueous solution! -G-t-
Gelatin layer P layer containing an emulsified dispersion of octylhydroquinone; low-sensitivity blue-sensitive emulsion, refined silver iodobromide emulsion (silver iodide; 6 mol %)... coated silver q0.
7ji/m2 Coupler EX-2...0.2/mole for 1 mole of silver Coupler EX-3...0.0/mole for 1 mole of silver! High-sensitivity blue-sensitive emulsion layer silver iodobromide (silver iodide; t mole ratio)...Coated silver amount (),
6 y/-2 Coupler EX-2...0.01 mol to 1 mol of silver 1st/layer; First protective layer silver iodobromide (7 mol of silver iodide, average grain size 0.07 μm)・・・
・Amount of silver coated 0. jp Gelatin layer containing an emulsified dispersion of ultraviolet absorber Uv-/ First co-layer; Co-protective layer trimethylmethanoacrylate particles (diameter approx./.

Apply a gelatin layer containing jμ).

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer.

Compound sensitizing dye I used to prepare the sample: anhydro-j, j'-Schiff*CX
-3,3'-di(r-sulfopropyl)-terethylthiacali cyanine hydroxide pyridinium salt sensitizing dye II: anhydride coater ethyl-3,3'-di(r-sulfopropyl)-r j l ”'61-
Dibenzothiacarbocyanine hydroxide/triethylamine salt sensitizing dye ■: Anhydrote? A/-! ,! '-dichloro-3.3'-di(r-sulfopropylnooxacalzecyanine sodium salt sensitizing dye ■: anhydro!, t, j', t'-tetrachloro-1,/'-diethyl-3.31- C(β-[β-(r-sulfopropyl)2°toxy]ethylimidazolocarbocyanine hydroxide sodium salt EX-/EX-CoEX-J EX-蓼(n)H31CI5 EX-1 EX-7 2Hs OC4H .

EX-2 CH2=C x / y = 7 / J (ratio of w) After cutting this photographic element into a width of 3 j rnlrn, the color temperature is μro o' with a filter using a tungsten light source.
After applying wedge exposure of 2tcMs adjusted by K VC, Fuji Color Process CN-/4 processing of Fuji Photo Film ■ was performed using an automatic processor (color development 3 minutes/j seconds, bleaching for 30 seconds, washing with water for 2 minutes 70 seconds). , fixing μ minutes - 0 seconds, washing with water for 3 minutes lj seconds, and stabilizing for 1 minute! seconds, followed by drying.The treatment temperature was 3 r'c), and this was used as a standard sample.

Next, the photographic element subjected to the wedge exposure (hereinafter referred to as the sample) was processed using an automatic developing machine at a processing temperature of 3t0C through the seven treatments listed in Table 7 (1) and (2) below. did.

The amount of liquid brought into each bath from the previous bath in this automatic development @ is approximately 2 to j ml/m.

Table-7 (2) The composition of the treatment liquid used in the above treatment is as follows.

Color development solution (common to I to ■) Nitrilotriacetic acid trisodium salt 1. Sodium sulfite Hiroshi, 0g Potassium carbonate 30.0g Potassium bromide
1. da9 potassium iodide
1.3.Dahydroxylamine sulfate μ-(N-ethyl-N-β- and diethylaminofoucault methylaniline sulfate in slurry ≠, jI water added /, 071 pH/0,
0 Bleach solution (common to treatments ■, ■, v~■) Ethylenediaminetetraacetic acid ferric ammonium salt 100.0g Ethylenediaminetetraacetic acid disodium salt r, op ammonium bromide izo, op aqueous ammonia (cor) 7.0ml add water
/, 0ml pH 4, 0 Bleach-fix solution A (both processing ■ and ■ A) Ethylenediaminetetraacetic acid ferric ammonium salt / 00, 0:j Ethylenediaminetetraacetic acid disodium salt Hiroshi, Oyf Oa (R ammonium water soluble, λ (70 %) /7j, Oml Sodium sulfate 10.0g Aqueous ammonia (λleg,) /!r Add water /・01pH4,r Bleach-fixing QB (Processing V~■) Ethylenediaminetetraacetic acid ferric ammonium salt !0 .09 Ethylenediaminetetraacetic acid disodium salt Hiro, 09 Ammonium thiosulfate aqueous solution (70%) loo, omt Sodium sulfite 10,0 g ammonia water (λ! 壬) !, Orr, 1 Add water i, oxpHA, r Fixation Solution (Common to Treatments I, ■, V ~ ■) Sodium tetraheptalysate 2.0 g Sodium sulfite / 6.0 ammonium sothiosulfate aqueous solution (7o%) 200.0 mi Sodium bisulfite μ, Q water added
/, O/pH7, j Stabilizing solution (common to treatments I to ■) Holfsu7 (410%) 2.0mi Fuji Drywell! , add Omi water / , examine the gradation and relative sensitivity of the O1 standard sample and the famous sample *=+ subjected to the above treatment, and further calculate the amount of silver remaining in the highest color density part
Measured by fluorescence analysis.

Here, the relative sensitivity and gradation may be determined as follows: Relative sensitivity: lowest density in the standard sample,! The exposure amount at which the O9-density increased was determined from the above, and the difference between the density at this exposure amount and the lowest f&degree for each sample was defined as the relative sensitivity.

Gradation level: The difference between the density value in the above 4-light beak and the density value at the point where 14 light beaks, which is the logarithm value/j, was added to the above-mentioned exposure amount was defined as the gradation.

Next, process -■ and v~! , Ill, the photographic element (width: 3j'y) was removed from the outside 100 m every day and then continuously processed for 70 days while replenishing the processing solution as described below. At the same time, samples given wedge dawn were also processed every day. In treatments v to were connected with a pipe so that all the overflow liquid generated by supplying replenisher to the bleaching and fixing baths was flowed into the bleach-fixing bath. In Processes-V to 1, no direct replenishment of the bleach-fix bath was performed.

Replenishment top> Color replenisher for the photographic element (width 3!χ) per meter, holiday replenisher for the photographic element (width j j z) / per meter /! m
l Fixing replenisher per 1 m of the photographic element (width 3! paper) /zmt Stable replenisher per 1 m of the photographic element (width! j%) ～■Common) Sodium nitrilotriacetate i, ip Sodium sulfite
Hiro, Hiroi Sodium carbonate
32.09 Potassium Bromide
0.79 and Dorogygylamine sulfate,
6y≠-(N-Ethyl-N-β-hydrokeytylamino-111 methylaniline sulfate r,oy Add water /lpH/17.Bleach replenisher (processing-■, V~~1 common Ammonium dibromide /7j, Oi ammonia water (ur%)
ψ, Omi ethylene cyanotetraacetic acid ferric ammonium salt / 10.09 ethylenediaminetetraacetic acid disodium salt 109 sulfur ammonium iog water added
/1 pHt, 7 Fixing replenisher (common to processing -■, V~■) Ammonium thiosulfate aqueous solution (70%) 2uOml sodium sulfite 7.0g ammonia water (21%) 10ml sodium bisulfite /co, λy sodium tetrapolyphosphate g, <zy Add water
/1 pH7, j Stable replenisher (processing-■, V to ■-jyI) Formalin (Hiroo%) 3.0ml Fuji Drywell 7.0 Add water
/・01 The results of the above treatments are shown in Table 1.

In A-2, the relative sensitivity difference and gradation difference are calculated using standard processing (C
It shows the difference in relative sensitivity and gradation with N-/4 processing). The amount of residual silver in the standard treated sample is J, jμso/cr
According to the processing method (V to ■) of the present invention, sufficient desilvering can be achieved in a short time and less replenishment is required.
It can be seen that excellent desilvering properties and photographic properties are maintained at m. On the other hand, it can be seen that treatments I, ■, and ■ exhibited poor desilvering at the beginning, and that even treatment H could not maintain the original performance with the same amount of replenisher as in the present invention.

Example 2 The photographic element described in Example-1 was cut to a width of 3×, and then a wedge was exposed in the same manner as described in Example-11C and processed using an automatic phenol machine to process CN-/ A standard sample was obtained by processing. Subsequently, the treatments listed in Table jTK were carried out.

Table J, (21) The treatment liquids used in the above treatments were the same as those used in treatments ① to ν■ of Example 1, except for those described below.

In addition, in processing-I, ■, V~\Mvc, the bleaching solution was
In Process-III,
I) - The holiday promotion MI of (1) was added to Jxlo Mo at a ratio of 1/1.

Furthermore, in Treatment-I and V~\1, yL, Example-IVC
A 10-day continuous treatment similar to that described was carried out.

The replenisher composition and replenishment λ in this case were the same as in Example 1 except for the rinsing solution, but the bleach accelerator was added to the bleach replenisher at a concentration of txio-3 mol/l.

Rinse liquid (processing 1 to 1)! -Chlorokomethyl-≠-ifthiazolin-3-one 0.0! i Ethylenediaminetetraacetic acid disodium trilam salt 0. Add 9 sulfanilamide 001g water
/1 pH7, (:l (adjusted with sodium hydroxide) rinse replenisher (processed [, V~'V
1 common)! -Chlorokomethyl-Hiro-ifthiazolin-3-one o, ozg Ethylenediaminetetraacetic acid dinatrilam salt 0.39 Sulfanilamide O12 Add water
/1 pH 7,0 (adjusted with sodium hydroxide) Amount of rinse replenisher per photographic element (Jjx width)/m The results of the above treatments are shown in Table-μ.

In Table 44, the relative sensitivity difference and gradation difference are the same as in Example-1. In addition, the amount of residual silver in the standard processed sample is J
, rμg/c, 2.

From the results in Table-≠, the treatment of the present invention (V～～・■) l/c
It can be seen that sufficient desilvering can be achieved in a short period of time, and that photographic properties can be maintained even with a small amount of replenishment.

Example 3 In the treatment-■ of Example-2, the bleaching accelerator (yoxio-3 mol/l) added to the bleaching solution and the mulberry white replenisher is shown in the table.
(changed and performed the same process. Also, the same 1cc
The photographic properties were compared with a standard sample processed by N-/4 processing, and the results are listed in Table-Jilt.

From the results in Table j, it can be seen that according to the treatment of the present invention (/%/~6), sufficient desilvering can be achieved in a short time and excellent photographic properties can be maintained with a small amount of replenishment.

Patent Applicant: Fuji Photo Film Co., Ltd. Procedural Amendment

Claims (1)

[Claims] In a processing method for desilvering an exposed silver halide color photographic light-sensitive material after color development, the desilvering step includes a bleaching bath containing a ferric aminopolycarboxylic acid complex salt, a ferrous aminopolycarboxylic acid complex salt, and a fixing agent. A silver halide color photographic sensitizer comprising a bleach-fixing bath and a fixing bath containing the above, and a part or all of the overflow liquid from the bleaching bath and the fixing bath is introduced into the bleach-fixing bath for processing. How materials are processed.