JPH06130604A - Method for processing direct positive silver halide color phographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the processing method superior in desilverability, even in the case of using a bleach-fixing solution after the lapse of time from continuous processing by incorporating at least one kind of a ferric complex salt of a specified compound in the bleach-fixing solution. CONSTITUTION:The color photosensitive material is processed with the color developing solution and then with the bleach-fixing solution containing at least one kind of ferric complex salt of the compound represented by formula I in which each of R1-R6 is H, an aliphatic or aromatic group or hydroxy; W is a bonding group of the formula; -(W1-Z)n-W2-; each of M1-M4 is H or a cation; W1 is alkylene or a simple bond; W. is alkylene or-COr; Z is a simple bond,-0-,- S-, -CO-, or-N(Rw); Rw is H or optionally substituted alkyl; Z and W1 are not a simple bond at the same time; and (n) is an integer of 1-3.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a method for processing a direct positive type silver halide color photographic light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION Photographic methods for obtaining direct positive images without the need for reversal processing steps or negative films are well known.
The conventionally used methods for producing a positive image using a direct positive silver halide photographic light-sensitive material, except for special ones, can be mainly classified into two types in consideration of practical usefulness. it can.

One type uses a fog-fogged silver halide emulsion in advance, and uses fog nuclei (latent image) in the exposed area by utilizing solarization or Herschel effect.
The positive image is obtained directly after development by destroying The other type is to directly obtain a positive image by using an unfogged internal latent image type silver halide emulsion and performing surface development after image exposure or after fog treatment or while performing fog treatment. .

The above-mentioned internal latent image type silver halide photographic emulsion is a type of halogen in which a silver halide grain has a photosensitive nucleus mainly inside and a latent image is mainly formed inside the grain by exposure. A silver halide photographic emulsion. This latter type of method, compared to the former type,
In general, it has high sensitivity and is suitable for applications requiring high sensitivity.

To form a direct positive color image, a direct positive silver halide light-sensitive material is subjected to imagewise exposure, followed by color development in the presence of a nucleating agent and / or fog light, followed by desilvering. A bleach-fixing solution containing a ferric aminopolycarboxylic acid complex salt and a thiosulfate salt in one solution is known as a means for the desilvering process. However, when a ferric aminopolycarboxylic acid salt, which originally has a weak oxidizing power (bleaching power), coexists with a thiosulfate having a reducing power, the bleaching power is remarkably weakened.

As a method for improving the drawbacks of such a bleach-fixing solution, for example, a method of adding iodide or bromide, a method of containing a high concentration of ferric aminopolycarboxylic acid complex salt with triethanolamine, and the like are available. is there. However, the effect of increasing the oxidizing power is insufficient. In addition to the lack of desilvering ability in the bleach-fixing solution, the cyan dye formed by color development can be used as a leuco dye (Leuco Dy).
There is a big drawback that it is reduced to e) and the color reproduction is impaired. It is known that this drawback can be ameliorated by increasing the pH of the bleach-fixing solution as described in U.S. Pat. No. 3,773,510, etc. However, increasing the pH conversely improves the bleaching power. This results in further weakening, which is an impractical condition. Moreover, the nucleating agent used for directly forming a positive color image is unstable under such a high pH condition because it is subject to air oxidation or the like.

On the other hand, those containing a bleaching accelerator to enhance the bleaching power, those containing sulfinic acid or a salt thereof in the bleach-fixing solution in order to improve the stability of the processing solution, etc. There is a technology.

[0008]

However, in the above technique, although the bleaching power or the stability of the solution can be improved, when the continuous processing is carried out and the bleach-fixing solution after the continuous processing is aged, it is removed. If the silver bleach-fixing solution after such time treatment is used, the resulting image will have a low image quality and will be difficult to use for a long period of time.

The reason for this is not clear, but in the direct positive system, the eluate from the light-sensitive material is accumulated in the bleach-fixing solution due to continuous processing, and the stability of the bleach-fixing solution is affected over time. It is presumed that the desilvering performance and the like are deteriorated as well. Therefore, an object of the present invention is to provide a method for processing a direct positive silver halide color photographic light-sensitive material which is excellent in desilvering property and stability even when the bleach-fixing solution after continuous processing is aged.

[0010]

The object of the present invention is to provide a direct positive type silver halide color photographic light-sensitive material having at least one internal latent image type silver halide emulsion layer which has not been fogged on a support. In the method of processing with a bleach-fixing solution subsequent to the processing with a color developing solution, the bleach-fixing solution contains at least one ferric complex salt of a compound represented by the following general formula (I). It can be achieved by a method of processing a type silver halide color photographic light-sensitive material.

[0011]

[Chemical 2]

(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆
Each represents a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group. W represents a linking group represented by the following general formula (W). M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) General formula _{(W) - (W 1 -Z} ) n -W 2 - (W 1 are .Z is .W ₂ representing an alkylene group or a single bond represents an alkylene group or -CO- represents a single bond, -O- , -S
-, - CO-, or -N (R _W) - represents the (R _W represents a hydrogen atom or an optionally substituted alkyl group.). However, Z and W ₁ are not a single bond at the same time. n is 1
Represents an integer of 3 to 3. That is, in the present invention, by using a ferric iron complex salt of the compound represented by the general formula (I) as a bleaching agent in the bleach-fixing solution (hereinafter sometimes referred to as the ferric iron complex salt of the present invention),
After the continuous processing, even if the bleach-fixing solution is aged, no precipitate is generated in the solution, and desilvering can be sufficiently performed even if the photographic material is treated with the aged bleach-fixing solution. In the present invention, even if the bleach-fixing solution after continuous processing is aged, the stability of the processing solution is good and the processing capacity can be maintained.

The ferric complex salt of the present invention has good biodegradability and is preferable in terms of environmental protection.

The compound represented by formula (I) which forms the ferric complex salt of the present invention will be described in more detail below.
The aliphatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group having 1 to 10 carbon atoms. Is preferred. The aliphatic group is more preferably an alkyl group, further preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group.

The aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group. ,
A phenyl group is more preferred. R ₁ , R ₂ , R ₃ , R ₄ ,
The aliphatic group and aromatic group represented by R ₅ and R ₆ may have a substituent, for example, an alkyl group (for example, methyl,
Ethyl), aralkyl groups (eg phenylmethyl), alkenyl groups (eg allyl), alkynyl groups, alkoxy groups (eg methoxy, ethoxy), aryl groups (eg phenyl, p-methylphenyl), amino groups (eg dimethylamino), Acylamino group (eg acetylamino), sulfonylamino group (eg methanesulfonylamino), ureido group, urethane group, aryloxy group (eg phenyloxy), sulfamoyl (eg methylsulfamoyl), carbamoyl group (eg carbamoyl, methylcarbamoyl) ), Alkylthio groups (eg methylthio), arylthio groups (eg phenylthio), sulfonyl groups (eg methanesulfonyl), sulfinyl groups (eg methanesulfinyl), hydroxy groups, halogen atoms ( For example, chlorine atom, bromine atom, fluorine atom, cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg phenyloxycarbonyl), acyl group (eg acetyl, benzoyl), alkoxycarbonyl group (eg methoxycarbonyl). ), An acyloxy group (eg acetoxy), a carbonamido group, a sulfonamide group, a nitro group, a hydroxamic acid group, and the like, and if possible, a dissociation product or a salt thereof.

When the above substituent has a carbon atom, it preferably has 1 to 4 carbon atoms. R ₁ , R ₂ , R
₃ , R ₄ , R ₅ and R ₆ are preferably a hydrogen atom or a hydroxy group, more preferably a hydrogen atom.

The linking group represented by W is represented by the following general formula (W). Formula _{(W) - (W 1 -Z} ) n -W 2 - W 1 represents an alkylene group or a single bond. The alkylene group represented by W ₁ is preferably a linear or branched alkylene group having 1 to 8 carbon atoms (for example, a methylene group, an ethylene group, a propylene group), a cycloalkylene group having 5 to 10 carbon atoms (for example, 1, 2-cyclohexylene group).

W ₂ represents an alkylene group or --CO--.
The alkylene group represented by W ₂ has the same meaning as the alkylene group represented by W ₁ . The alkylene groups represented by W ₁ and W ₂ may be the same or different from each other, or may have a substituent. As the substituent, those mentioned as the substituent for R ₁ are applicable, but an alkyl group, a hydroxy group or a carboxy group is preferable. More preferably, W ₁ and W ₂ are alkylene groups having 1 to 3 carbon atoms,
A methylene group or an ethylene group is particularly preferable.

Z is a single bond, --O--, --S--, --CO--,
Or -N (R _W) - represents a. R _W represents a hydrogen atom or an optionally substituted alkyl group. As the substituent, those mentioned as the substituent for R ₁ can be applied, but a carboxy group, a phosphono group, a sulfo group, a hydroxy group or an amino group is preferable. Z is preferably a single bond.

As n, 1 or 2 is preferable, and 1 is more preferable. Specific examples of W include the following.

[0021]

[Chemical 3]

[0022]

[Chemical 4]

Examples of the cation represented by M ₁ , M ₂ , M ₃ and M ₄ include alkali metals (eg lithium, sodium, potassium), ammonium (eg ammonium, tetraethylammonium) and pyridinium. it can.

In the present invention, specific examples of the compound represented by the above general formula (I) are shown below, but the present invention is not limited thereto.

[0025]

[Chemical 5]

[0026]

[Chemical 6]

[0027]

[Chemical 7]

[0028]

[Chemical 8]

[0029]

[Chemical 9]

[0030]

[Chemical 10]

The compounds represented by formula (I) of the present invention are disclosed in JP-A-63-199295 and JP-A-3-17.
It can be synthesized according to the description in Japanese Patent No. 3857 or the like. As described in these documents, the compound represented by the general formula (I) of the present invention includes optical isomers ([R, R], [S, S], [S, R] , [R, S])
Exists. For example, the exemplary compound (I-1) of the compound represented by formula (I) of the present invention has three optical isomers ([R, R], [S, S], [S, R]). Exist and these can be synthesized individually or as a mixture. It goes without saying that the present invention includes these individual optical isomers and mixtures thereof.

In the present invention, a compound synthesized from an L-amino acid such as [S, S] -form as a starting material is preferable to other optical isomers. These compounds are described by Springer and Copecca in Chem. Zvesti. 20
(6): 414-422 (1966) and JP-A-3-
It can be synthesized based on the method described in No. 173857.

The ferric iron complex salt of the present invention can be prepared by mixing a trivalent iron ion with the compound of the general formula (I), or can be isolated and used as a ferric iron complex salt. Is also good. In this case, it can be isolated, for example, as an ammonium salt, a sodium salt, or a potassium salt. The amount of the ferric complex salt used in the present invention is 0.01 mol to 1.0 mol, preferably 0.05 mol to 1 liter, per liter of the bleach-fixing solution.
It is about 0.50 mol. Further, it is preferable that the free form is present in excess of about 10 to 20% in addition to the iron (III) complex. In the ferric complex salt of the compound of general formula (I), I
-1, I-2, I-3, I-15, I-16, I-17
A ferric complex salt of the compound of is particularly preferable.

In the bleach-fixing solution of the present invention, a known bleaching agent can be used in combination with the ferric complex salt of the present invention as a bleaching agent, but in order to exert the effects of the present invention sufficiently,
It is preferred to use only the bleaching agent of the present invention. The process time of the bleach-fixing process of the present invention is 2 minutes or less, more preferably 15 minutes.
Seconds to 90 seconds, more preferably 20 seconds to 60 seconds.

The replenishing amount of the bleach-fixing solution of the present invention is 400 m
It is 1 / m ² or less, preferably 50 to 350 ml / m ² , and more preferably 75 to 300 ml / m ² .

Various compounds can be used as a bleaching accelerator in the bleach-fixing solution and / or the pre-bath thereof. For example, U.S. Pat. No. 3,893,858, German Patent 1,290,812, and Japanese Patent Laid-Open No. 53-956.
Publication No. 30, Research Disclosure No. 17129
(July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-45-850.
6, JP-A-52-20832, and JP-A-53-32735.
And thiourea compounds described in U.S. Pat. No. 3,706,561 and the like, or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleach-fixing solution used in the present invention contains a bromide (eg, potassium bromide, sodium bromide,
Rehalogenating agents such as ammonium bromide) or chlorides (eg potassium chloride, sodium chloride, ammonium chloride) or iodides (eg ammonium iodide) can be included. As required, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate,
One or more inorganic acids having a pH buffering ability such as potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid and the like, and alkali metal or ammonium salts thereof, ammonium nitrate, guanidine, etc. A corrosion inhibitor or the like can be added.

The fixing agents used in the bleach-fixing solution according to the present invention are known fixing agents, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate; ethylene. Bisthioglycolic acid, 3,6-dithia-
It is a water-soluble silver halide solubilizer such as thioether compounds such as 1,8-octanediol and thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used.

In the present invention, it is preferable to use thiosulfate, particularly ammonium thiosulfate. The amount of the fixing agent per liter is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol. The pH range of the bleach-fixing solution is preferably 3 to 10, more preferably 4 to 9, and particularly preferably 5 to 8. Further, the bleach-fixing solution may contain various other fluorescent whitening agents, defoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol and the like.

The bleach-fixing solution according to the present invention contains a sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite) and a bisulfite (eg, preservative) as preservatives.
Sulfite ion-releasing compounds such as ammonium bisulfite, sodium bisulfite, potassium bisulfite, etc., metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite, etc.), and JP-A 1-22472. It is preferable to contain the sulfinic acids described. These compounds are 0.02-0.50 mol /
It is preferable to contain liter, more preferably,
It is 0.04 to 0.40 mol / liter.

As the preservative, a sulfite is generally added, but ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound or the like may be added. Furthermore, buffers, optical brighteners, chelating agents, defoamers,
A fungicide or the like may be added if necessary. Next, the color developer of the present invention will be described.

The color developer of the present invention contains an aromatic primary amine color developing agent. The amount of these color developing agents used is preferably 1 to 20 g, and more preferably 2 to 8 g, per liter of the color developing solution.
These color developing agents may be used alone,
You may use together 2 or more types. Specific compounds will be described below, but the invention is not limited thereto.

D-1 N, N-diethyl-p-phenylenediamine D-2 2-amino-5-diethylaminotoluene D-3 2-amino-5- (N-ethyl-N-laurylamino) toluene D-4 4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-5 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline D-6 4-amino- 3-methyl-N-ethyl-N-
[Β- (Methanesulfonamido) ethyl] aniline D-7 N- (2-amino-5-diethylaminophenylethyl) methanesulfonamide D-8 N, N-dimethyl-p-phenylenediamine D-9 4-amino- 3-Methyl-N-ethyl-N-methoxyethylaniline D-10 4-amino-3-methyl-N-ethyl-N-β
-Ethoxyethylaniline D-11 4-amino-3-methyl-N-ethyl-N-β
-Butoxyethylaniline Preferred color developing agents are D-4, D-5, D-6.

Next, the preservative for the color developing solution of the present invention will be described. Of these preservatives, hydroxyamines are particularly preferable in terms of liquid stability. Preferred hydroxylamines in the present invention are represented by the following general formula (II).

[0045]

[Chemical 11]

In the general formula (II), R ¹² and R ¹³ each represent a hydrogen atom or an alkyl group. Alkyl group has 1 carbon
-10, and more preferably 1-5, which may be substituted or unsubstituted. The substituent of the alkyl group is the same as the substituents of R ¹⁰ and R ¹¹ described later.
A preferable substituent is a hydroxy group, a sulfonic acid group or a carboxyl group.

Specific examples of the general formula (II) are shown below, but the invention is not limited thereto.

[0048]

[Chemical 12]

In particular, the compounds (II-1), (II-4),
(II-6) is preferred. The amount of the hydroxyamines added to the color developer is 1 g / liter to 30 g / liter, preferably 2 g / liter to 15 g / liter.

Further, the color developing solution requires sulfite salts such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite and potassium metasulfite, and carbonyl compound sulfite adducts as preservatives. It can be added accordingly. The preferred addition amount is 0.5 g to 20 per liter of color developing solution.
g, and more preferably 1 g to 10 g.

In the present invention, it is preferable to use hydroxylamines as a preservative. Other known preservatives may be used in combination. Examples of such preservatives include hydroxamic acids described in JP-A-63-43138, hydrazines described in JP-A-63-170642, hydrazine derivatives and hydroxylamine derivatives described in JP-A-2-64632. JP 63-
Phenols described in JP-A-44657 and JP-A-63-58443 and α-described in JP-A-63-44656.
Examples thereof include hydroxyketones, α-aminoketones, and / or various sugars described in JP-A-63-36244. Further, in combination with the above compound, JP-A Nos. 63-4235, 63-24254 and 63-
21647, 63-146040, 63-27
841 and 63-25654, and other monoamines described in JP-A-63-30845 and 63.
Nos. 146040, 63-43439 and the like, diamines described in JP-A-63-21647 and 63-26655, and polyamines described in JP-A-63-44655. Described polyamines, nitroxy radicals described in JP-A-63-53551, JP-A-63-43140, and JP-A-63-53.
Alcohols described in JP-A No. 549, JP-A-63-5
The oximes described in Japanese Patent No. 6654 and JP-A-63
The tertiary amines described in JP-A-239447 may be used.

Other preservatives are disclosed in JP-A-57-44.
148 and 57-53749, various metals, salicylic acids described in JP-A-59-180588, alkanolamines described in JP-A-54-3532, and JP-A-56-94349. Polyethyleneimines described in Japanese Patent Publication No. 3746544, aromatic polyhydroxy compounds described in U.S. Pat. No. 3,746,544, and the like may be contained as necessary.

These compounds may be present in the light-sensitive material. In addition to the color developing solution, even if it is present in a bleaching and bleach-fixing solution or a washing solution or a washing substitute stabilizer,
It can give good performance by acting on the color developing agent (incorporated from the color developing solution or the like) present in each solution and its oxidant.

The color developing solution used in the present invention preferably has a pH of 9 to 12, more preferably 9 to 11.0, and the color developing solution contains compounds of other known developing solution components. be able to. In order to maintain the above pH, it is preferable to use various buffers. As the buffering agent, carbonate, phosphate, tetraborate and hydroxybenzoate are particularly excellent in solubility and buffering ability in a high pH range of pH 9.0 or higher.

Specific examples of the buffering agent include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, dipotassium phosphate, sodium borate, potassium borate, and tetraborate. Sodium acid salt (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate),
Examples thereof include potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate), potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate), and the like. However, the present invention is not limited to these compounds.

The amount of the buffer added to the color developer is
It is preferably 0.1 mol / liter or more, and particularly preferably 0.1 mol / liter to 0.4 mol / liter.

In addition, various chelating agents can be used in the color developing solution as a precipitation preventing agent for calcium and magnesium, or for improving the stability of the color developing solution. The chelating agent is preferably an organic acid compound, and examples thereof include aminopolycarboxylic acids, organic phosphonic acids, and phosphonocarboxylic acids. Specific examples include nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N ', N'.
-Tetramethylenephosphonic acid, transcyclohexanediaminetetraacetic acid, 1,2-diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, glycol etherdiaminetetraacetic acid, ethylenediamineorhuman hydroxyphenylacetic acid, 1-phosphonobutane-1,2,4- Tricarboxylic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N'-bis (2-hydroxybenzyl) ethylenediamine-N, N'-diacetic acid, 1,2-dihydrooxybenzene-3,5-disulfone Acid etc. are mentioned. Two or more of these chelating agents may be used in combination, if necessary. The amount of these chelating agents added may be an amount sufficient to block the metal ions in the color developing solution.
For example, it is about 0.1 g to 10 g per liter.

If desired, an optional development accelerator can be added to the color developing solution. However, it is preferable that the color developing solution used in the present invention does not substantially contain benzyl alcohol, from the viewpoints of solution preparation and prevention of color contamination. Here, "substantially" means not more than 2 milliliters per liter of the developing solution, preferably not containing at all.

Other development accelerators include JP-B-37-
16088, 37-5987, 38-7826
Nos. 44-12380, 45-9019 and U.S. Pat. No. 3,813,247, and the like, thioether compounds, JP-A-52-49829 and JP-A-5-29829.
No. 0-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-
30074, JP-A-56-156826 and JP-A-56-156826.
2-43429 and the like, quaternary ammonium salts, U.S. Patent Nos. 2,494,903 and 3,128,
No. 182, No. 4,230,796, No. 3,253,9
19, Japanese Patent Publication No. 41-11431, U.S. Pat. No. 2,4
82,546, 2,596,926 and 3,
582,346 and other amine compounds, Japanese Examined Patent Publication No. 3
7-16088, 42-25201, U.S. Pat. No. 3,128,183, Japanese Patent Publications 41-11431, 42-23883, and U.S. Pat. No. 3,532,50.
Polyalkylene oxide represented by No. 1 and the like, other 1-phenyl-3-pyrazolidones, imidazoles and the like can be added if necessary.

In the present invention, any antifoggant (or development inhibitor) can be added, if desired. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide, and organic antifoggants can be used. Examples of the organic antifoggant include benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5
-Chloro-benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine,
A typical example is a nitrogen-containing heterocyclic compound such as adenine.

The color developer used in the present invention may contain a fluorescent whitening agent. The fluorescent whitening agent is preferably a 4,4'-diamino-2,2'-disulfostilbene compound. The addition amount is 0 to 5 g / liter, preferably 0.1 to 4 g / liter.

If necessary, alkyl sulfonic acid,
You may add various surfactants, such as an aryl phosphonic acid, an aliphatic carboxylic acid, and an aromatic carboxylic acid. The processing temperature of the color developer of the present invention is 20 to 50 ° C., preferably 30.
-40 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 2 minutes. Replenishing amount of color developer in the present invention is a photosensitive material 1 m ² per 80Ml～800ml, preferably 100ml~600ml / m ^2, more preferably ^{150ml / m 2 ~350ml / m 2} .

In the processing of the present invention, it is general to carry out washing and / or stabilizing processing after desilvering processing such as bleach-fixing. The amount of rinsing water in the rinsing process varies widely depending on the characteristics of the light-sensitive material (for example, depending on the material used such as couplers) and application, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent and forward flow, and various other conditions. Can be set. Among these, the relationship between the number of washing tanks and the amount of water in the multi-stage countercurrent system is described in the Journal of the Society of Motion Picture and Television Engineers (Jour.
nal of the Society of Motion Picture and Televisio
n Engineers) Volume 64, P248-253 (May 1955). Usually, the number of stages in the multi-stage countercurrent system is preferably 2 to 6, particularly 2 to 6.
4 is preferable.

According to the multi-stage countercurrent system, the amount of washing water can be greatly reduced, and for example, it can be 0.5 liter to 1 liter or less per 1 m ^{2 of the} light-sensitive material. Due to an increase in the residence time of water in the tank, bacteria grow and problems such as floating substances produced adhere to the photosensitive material. In the processing of the color light-sensitive material of the present invention, as a solution to such a problem, calcium described in JP-A-62-288838,
The method of reducing magnesium can be used very effectively. Further, isothiazolone compounds and siabendazoles described in JP-A-57-8542, and 61-1.
Chlorinated germicides such as chlorinated sodium isocyanurate described in No. 201445, benzotriazoles described in JP-A No. 61-267761, copper ions and others Hiroshi Horiguchi "Chemistry of antibacterial and antifungal agents", Hygiene Society Volume "Sterilization of microorganisms,
The sterilizing agents described in "Sterilization and Antifungal Technology" and "Encyclopedia of Antibacterial and Antifungal" edited by Japan Society for Antibacterial and Antifungal can also be used.

Further, for washing water, a surfactant as a draining agent and a chelating agent typified by EDTA as a water softening agent can be used. Continue with the above washing process,
Alternatively, it may be directly treated with a stabilizing solution without a water washing step. A compound having an image stabilizing function is added to the stabilizing solution, and examples thereof include an aldehyde compound typified by formalin, a buffering agent for adjusting a film pH suitable for stabilizing a dye, and an ammonium compound. Further, in order to prevent the growth of bacteria in the liquid and impart antifungal property to the processed light-sensitive material, the above-mentioned various bactericides and antifungal agents can be used.

Further, a surface active agent, an optical brightening agent and a hardener may be added. In the processing of the light-sensitive material of the present invention, when the stabilization is directly carried out without a washing step, JP-A-57-8543 and JP-A-58-14834,
All known methods described in JP-A No. 60-220345 can be used. In addition, it is also a preferred embodiment to use a chelating agent such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminotetramethylenephosphonic acid, or a magnesium or bismuth compound.

In the present invention, a so-called rinse solution is also used as a washing solution or a stabilizing solution used after the desilvering process. The pH of the washing step or stabilizing step is 4 to 10, preferably 5 to 8. Temperature is the application of the photosensitive material,
Although it can be set variously depending on the characteristics and the like, it is generally 15 to 45 ° C, preferably 20 to 40 ° C. The time can be set arbitrarily, but a shorter time is preferable. It is preferably 30 seconds to 3 minutes, more preferably 30 seconds to 2 minutes. The smaller the replenishment amount, the more preferable from the viewpoints of running cost, reduction of discharge amount, handleability and the like, and the effect of the present invention is great.

A specifically preferable replenishing amount is 0.5 to 50 times, preferably 3 to 40 times the amount carried from the prebath per unit area of the light-sensitive material. Alternatively, it is 1 liter or less, preferably 500 milliliters or less per 1 m ^{2 of the} light-sensitive material. The replenishment may be performed continuously or intermittently. The liquid used in the washing and / or stabilizing step can be further used in the previous step. As an example of this, it is possible to reduce the amount of waste liquid by causing the overflow of washing water reduced by the multi-stage countercurrent system to flow into the bleach-fixing bath which is the pre-bath thereof, and replenishing the bleaching stabilizing bath with a concentrated liquid.

The direct positive color photographic light-sensitive material of the present invention comprises
Although it has various uses, it is particularly suitable for making color copies and color proofs. Various exposure means can be used for exposing the light-sensitive material of the present invention. Any light source that emits radiation corresponding to the sensitivity wavelength of the photosensitive material can be used as the irradiation light source or the writing light source. Flash light sources such as natural light (sunlight), incandescent lamps, halogen atom filled lamps, mercury lamps, fluorescent lamps and strobes or metal burning flash bulbs are common. A gas, a dye solution or a semiconductor laser, a light emitting diode, or a plasma light source which emits light in a wavelength range from ultraviolet to infrared can also be used as the recording light source. In addition, a linear or planar micro-shutter array using a phosphor screen (CRT, etc.) emitted from a phosphor excited by an electron beam, liquid crystal (LCD), lanthanum-doped lead titan zirconate (PLZT), or the like. It is also possible to use an exposure means combining the above light sources. If necessary, the spectral distribution used for exposure can be adjusted with a color filter. It is also used in a color copying machine AP-5000 manufactured by Fuji Photo Film Co., Ltd. A scanning exposure method can be used.

The non-pre-fogged internal latent image type silver halide emulsion of the present invention forms a latent image mainly inside the silver halide grains.
No. 125142, page 27, upper left column, line 9 to page 28, upper left column, fourth line. The shape and size of silver halide grains in the light-sensitive material of the present invention, the composition of silver halide, chemical sensitization method, spectral sensitization method, additives, binders,
Protective colloid, anti-fogging agent, anti-fading agent, color development enhancer, dye, anti-UV agent, layer structure of photosensitive material, fogging method of support and photosensitive material (optical fogging method, chemical fogging method),
Regarding the nucleating agent, the nucleating accelerator, the coating method, etc., see Japanese Patent Laid-Open No.
-125142, page 28, upper left column, line 5 to page 35, upper right column, line 9 and JP-A-3-126032, page 12, lower right column, line 18 to page 21, lower right column, line 19 Described in the eye.

Particularly as a nucleating agent, the above-mentioned JP-A 3-1 is used.
No. 25142, page 30, lower right column, line 11 to page 33, lower left column, line 12 (including amendment of procedure as of April 3, 1990). Quaternary heterocyclic or hydrazine nucleation Agents are preferred. Further, the nucleation accelerator is also disclosed in JP-A-3-12
No. 5142, page 33, lower left column, line 13 to page 34, lower left column, line 4 is preferable.

Examples of magenta couplers usable in the light-sensitive material of the present invention include hydrophobic indazolone type or cyanoacetyl type, preferably 5-pyrazolone type and pyrazoloazole type couplers having a ballast group. . The 5-pyrazolone-based coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group, from the viewpoint of the hue and color density of the color forming dye, and a typical example thereof is U.S. Pat. No. 2,311,082.
No. 2,343,703, No. 2,600,788
No. 2,908,573, No. 3,062,65
No. 3, No. 3,152,896 and No. 3,93
No. 6,015. As a leaving group for a 2-equivalent 5-pyrazolone-based coupler, US Pat.
The nitrogen atom leaving group described in 0,619 or the arylthio group described in U.S. Pat. No. 4,351,897 is particularly preferable. Further, the 5-pyrazolone-based coupler having a ballast group described in EP 73,636 provides a high color density.

The pyrazoloazole type couplers include pyrazolobenzimidazoles described in US Pat. No. 3,061,432 and pyrazolo [5,1-c] [described in US Pat. No. 3,725,067. 1,2,4] Triazoles, Research Disclosure No. 24220
(June 1984) and pyrazolotetrazoles described in JP-A-60-33552 and Research Disclosure, No. 24230 (June 1984) and JP-A-60-43659, 63-80250,
JP-A-2-1245068, JP-A-2-115183,
Examples include pyrazolopiazoles described in Japanese Patent Application No. 3-165039.

Particularly, in the present invention, JP-A 2-12
No. 4568, No. 2-115183, JP-A-63-80.
Particularly preferred are the pyrazolotriazole-based magenta couplers described in Japanese Patent Application No. 250 and Japanese Patent Application No. 3-165039.

The cyan couplers which can be used in the present invention include hydrophobic and diffusion resistant naphthol-type and phenol-type couplers, and the naphthol-type couplers described in US Pat. No. 2,474,293, preferably US Pat. Nos. 4,052,212, 4,146,396, 4,228,233 and 4,296,200.
As a representative example, the oxygen atom-releasing two-equivalent naphthol-based couplers described in JP-A No. 1994-242242 can be mentioned. Specific examples of the phenol-based coupler are described in US Pat. No. 2,369,929,
No. 2,801,171, No. 2,772,162
No. 2,895,826 and the like.

Cyan couplers which are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include an ethyl group at the meta-position of the phenol nucleus described in US Pat. No. 3,772,002. Phenolic cyan coupler having the above alkyl groups, US Pat.
No. 2,162, No. 3,758,308, No. 4,1
No. 26,396, No. 4,334,011, No. 4,
327,173, West German Patent Publication No. 3,329,729
2,5-diacylamino-substituted phenol couplers described in U.S. Pat.
999, 4,451,559 and 4,4
Nos. 27,767 and the like include phenol couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position.

In the present invention, in particular US Pat. No. 2,895
826, JP-A-51-6551 and JP-A-61-690.
The cyan coupler described in No. 65 is particularly preferable. Yellow couplers include, for example, U.S. Pat. No. 3,933,50.
No. 1, No. 4,022,620, No. 4,326,0
No. 24, No. 4,401,752, Japanese Patent Publication No. 58-10
739, British Patent Nos. 1,425,020 and 1,
476,760, JP-A-3-125142 and 3-
The yellow coupler described in 126032 is particularly preferable.

The coupler which can be used in the present invention can be introduced into a light-sensitive material by various known dispersion methods, is dissolved in a high-boiling organic solvent (if necessary, a low-boiling organic solvent is also used), and is emulsified and dispersed in a gelatin aqueous solution. The oil-in-water dispersion method, in which the silver halide emulsion is added to the silver halide emulsion, is preferred. Examples of the high boiling point solvent used in the oil-in-water dispersion method are described in US Pat. No. 2,322,027. Further, steps of latex dispersion method as one of polymer dispersion methods, effects, and specific examples of latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,274. , 2, 5
No. 41,230, Japanese Examined Patent Publication No. 53-41091, European Patent Publication No. 029104 and the like, and a dispersion method using an organic solvent-soluble polymer is described in PCT International Publication No. WO88 / 00723.

The high boiling point organic solvent for photographic additives such as couplers which can be used in the present invention has a melting point of 100 ° C. or less and a boiling point of 14
It is a compound that is immiscible with water at 0 ° C. or higher and can be used as long as it is a good solvent for the coupler. The melting point of the high boiling point organic solvent is preferably 80 ° C. or lower. The boiling point of the high boiling point organic solvent is preferably 160 ° C. or higher, more preferably 170 ° C. or higher.

Details of these high boiling point organic solvents are described in JP-A-62-215272, No. 137.
It is described in the lower right column of the page to the upper right column of page 144.

[0081]

【Example】

Example 1 Preparation of Sample 101 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following first to eleventh layers were applied to the front side, and the twelfth to thirteenth layers were applied to the back side to form a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g / g) are shown below.
m ² unit). However, the addition amount of the sensitizing dye is shown in mol per mol of silver. For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was prepared by changing the grain size by changing the temperature according to the method for producing emulsion EM-1 described below. However, as the emulsion for the 11th layer, a Lippmann emulsion which was not surface-chemically sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver ... 0.10 Color Mixing Inhibitor (Cpd-7) ... 0.05 Color Mixing Inhibitor Solvent [Solv-4, 5 Each Equivalent) ... 0.12 Gelatin ... 0.70

Second layer (intermediate layer) Gelatin: 0.70 Dye (Cpd-32): 0.005

Third Layer (Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3 equivalents 5.4 × 10 ⁻⁴ ) (average grain size 0.40 μm, Grain size distribution 10%, octahedron) 0.25 gelatin 0.70 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4, 30 etc.) Amount) 0.18 Anti-staining agent (Equivalent amounts of Cpd-5 and 15) 0.003 Coupler dispersion medium (Cpd-6) 0.30 Coupler solvent (Solv-1, 3, 5 Equivalent amounts) 0.12

Fourth Layer (Intermediate Layer) Gelatin ... 1.00 Color Mixing Inhibitor (Cpd-7) ... 0.08 Color Mixing Inhibitor Solvent (Solv-4, 5 Equivalent Amount) ... 0.16 Polymer Latex (Cpd-8) ... 0.10

Fifth Layer (Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4 2.6 × 10 ⁻⁴ ) (average particle size 0.40 μ, particle size distribution 10%, octahedron) 0.20 Gelatin 1.00 Magenta coupler (ExM-1, 2 each equivalent) 0.11 Yellow coupler (ExY-1) 0.03 Anti-fading agent (Cpd-9, 26, 30, 31 equivalents) 0.15 Stain prevention Agent (Cpd-10, 11, 12, 13 in 10: 7: 7: 1 ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupling solvent (Solv-4, 6 equivalents) 0.15

6th layer (intermediate layer) Same as 4th layer

Seventh Layer (Blue Sensitive Layer) Silver bromide (average grain size 0.60 μ, grain size distribution) spectrally sensitized with a blue sensitizing dye (ExS-5, 6 each equivalent weight 3.5 × 10 ⁻⁴ ). 11%, octahedron) 0.32 Gelatin 0.80 Yellow coupler (ExY-2, 3 equivalents) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd) -5, 15 in a ratio of 1: 5) 0.007 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ... 0.10.

Eighth layer (ultraviolet absorber-containing layer) Gelatin ... 0.60 Ultraviolet absorber (Equivalent amounts of Cpd-2, 4, 16) ... 0.40 Color mixing inhibitor (Equivalent amount of Cpd-7, 17) ... 0.03 Dispersion medium (Cpd-6) ... 0.02 UV absorber solvent (Solv-2, 7 each equivalent amount) ... 0.08 Irradiation prevention dye (Cpd-18, 19, 20, 21, 27 in 10: 10: 13: 15: 20 ratio) So)… 0.05

Ninth layer (protective layer) Fine-grain iodobromide (99 mol% of silver bromide, average size: 0.05μ) 0.03 Polyvinyl alcohol acrylic modified copolymer (molecular weight: 50,000) 0.01 Polymethylmethacrylate particles (average Particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent ... 0.05 Gelatin ... 0.05 Gelatin hardening agent (Equivalent for H-1 and H-2) ... 0.18

10th layer (back layer) Gelatin ... 2.50 Ultraviolet absorber (Equivalent amount of Cpd-2, 4, 16) 0.50 Dye (Equivalent amount of Cpd-18, 19, 20, 21, 27) 0.06

Eleventh Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardening agent (H-1, H- 2 Equivalent amount)… 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 65 ° C. for 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.23 μm were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was performed by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles were further grown in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / average particle size of 0.4 μ /
A shell silver bromide emulsion was obtained. Coefficient of variation of particle size is about 1
It was 0%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to perform internal latent image type halogenation. A silver emulsion was obtained.

ExZK-1 is used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
10 ^-2 % by weight, Cpd-22, 28 as a nucleation accelerator,
29 were used at 10 ^-2 wt% each. Further, in each layer, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as emulsifying and dispersing aids, and succinic acid ester and Magefac F-120 were used as coating aids.
(Manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, a stabilizer (Cpd-23, 24,
25 equal amounts) were used. This sample was designated as sample number 101. The compounds used in the examples are shown below.

[0096]

[Chemical 13]

[0097]

[Chemical 14]

[0098]

[Chemical 15]

[0099]

[Chemical 16]

[0100]

[Chemical 17]

[0101]

[Chemical 18]

[0102]

[Chemical 19]

[0103]

[Chemical 20]

[0104]

[Chemical 21]

Solv-1 Di (2-ethylhexyl) sebacate Solv-2 Trinonyl phosphate Solv-3 Di (3-methylhexyl) phthalate Solv-4 Torquerelyl phosphate Solv-5 Dibutyl phthalate Solv-6 Trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt

ExZK-17- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) Carbamoyl] -4-hydroxy-1
-Naphthylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formylhydrazine The sample 101 prepared as described above was contact-exposed with R, G, and B light under the following exposure conditions 1 to 3 through halftone positives of cyan, magenta, and yellow plates. (Exposure condition 1) Specimen with red filter (Ratten No. 2
6) and through the ND filter, when the white light was exposed, the ND filter density was adjusted to perform the exposure for 0.1 seconds with the minimum exposure amount that minimizes the red density after the development processing described below. (Exposure condition 2) Use a green filter (Ratten No. 5) for the sample.
8) and the white light is exposed through the ND filter, the ND filter density is adjusted to perform the exposure for 0.1 seconds with the minimum exposure amount that minimizes the green density after the development processing described below. (Exposure condition 3) Use a blue filter (Ratten No. 4) for the sample.
7B) and the white light was exposed through the ND filter, the ND filter density was adjusted to perform the exposure for 0.1 second with the minimum exposure amount that minimizes the blue density after the development processing described below.

However, a daylight fluorescent lamp was used as the light source under the exposure conditions 1 to 3.

These exposed samples were continuously processed by the following method using an automatic processor. (Continuous processing was carried out until the tank was replenished with a bleach-fixing solution having a capacity of 3 times.)

Treatment process time Temperature Tank capacity Replenishment amount Color development 135 seconds 38 ° C 28 liters 240 ml / m ² Bleach fixing 40 seconds 35 ° C 11 liters 320 ml / m ² Washing with water (1) 40 seconds 35 ° C 7 liters-washing ( 2) 40 seconds 35 ° C 7 liters 320 ml / m ² dry 30 seconds 80 ° C The replenishing method of washing water is to replenish the washing bath (2) and the overflow solution of the washing bath (2) into the washing bath (1). The so-called countercurrent replenishment method was adopted. At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each processing liquid was as follows. [Color developer] [Tank solution] [Replenisher] D-sorbit 0.15 g 0.20 g Sodium naphthalenesulfonate / formalin condensate 0.15 g 0.20 g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8 g 1.8 g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 14.0 ml 18.5 ml potassium bromide 0.70 g-benzotriazole 0.005 g 0.007 g sodium sulfite 5.6 g 7.4 g hydroxylamine 1/2 Sulfate 4.5 g 6.0 g Triethanolamine 6.0 g 8.0 g 4- [N-Ethyl-N- (β-hydroxyethyl) amino] aniline Sulfuric Acid / 1/2 Hydrochloride 4.2 g 5.6 g Potassium Carbonate 30.0 g 25.0 g Optical brightener ( Added amino stilbene based) 1.3 g 1.7 g Water 1000 ml 1000 ml pH (25 ℃) (pH adjusted with KOH or sulfuric acid) 10.25 10.75

[Bleach-fixing solution] [Tank solution] [Replenishing solution] Fe (III) ammonium salt of compound shown in Table 1 0.14 mol Same as tank solution Ammonium thiosulfate (750 g / l) 168 ml sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water was added to 1000 ml pH (25 ° C.) (pH adjustment with ammonia water or acetic acid) 6.20

[Washing Water] [Both Tank Solution and Replenisher Solution] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 The opening ratio of the bleach-fix solution continuously treated as described above. 0.01
Change the pH in a container of cm ^-1 as shown in Table A, and
Aged at 10 ° C for 10 days. The portion evaporated and concentrated over time was corrected by adding distilled water, and the bleach-fix solution was used to process the light-sensitive material again in the above-mentioned processing step. The amount of residual silver in the highest density part (unexposed part) was measured using fluorescent X-ray. In addition, the presence or absence of precipitates in the bleach-fix solution over time was visually confirmed. The results are shown in Table A.

[0114]

[Table 1]

From the results, the bleach-fixing solution using the bleaching agent of the present invention shows excellent solution stability without generation of precipitates with the passage of time after continuous processing, and it is sufficient even if the light-sensitive material is processed again. It exhibited desilvering properties. The effect is particularly great at low pH.

Example 2 A paper support (thickness 10) laminated on both sides with polyethylene.
(0 micron), the following 1st to 14th layers were multilayer-coated and the 15th to 16th layers were coated on the back side to prepare a color photographic light-sensitive material. The polyethylene coated on the first layer contains titanium oxide (4 g / m ² ) as a white pigment and a trace amount (0.003 g / m ² ) of ultramarine as a bluing dye (the chromaticity of the surface of the support is L 88 in the ^* , a ^* , and b ^* systems.
It was 0, -0.20, -0.75. ).

(Photosensitive layer composition) The components and coating amount (g /
m ² unit). For silver halide, the coating amount in terms of silver is shown. The emulsion used for each layer was produced according to the production method of Emulsion EM1. However, as the emulsion of the 14th layer, a Lippmann emulsion which was not surface-sensitized was used.

First Layer (Antihalation Layer) Black Colloidal Silver ... 0.10 Color Mixing Inhibitor (Cpd-7) ... 0.05 Gelatin ... 0.70

Second layer (intermediate layer) Gelatin ... 0.70

Third Layer (Low Sensitivity Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.25 μ, grain size distribution [variation coefficient] 8 %, Octahedron) 0.04 Silver chlorobromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (5 mol% silver chloride, average grain size 0.40 μ, grain size distribution 10%, octane) 0.08 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Anti-stain ( Cpd-5) 0.003 Coupler dispersion medium (Cpd-6) 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) 0.12

Fourth Layer (Highly Sensitive Red Sensitive Layer) Silver bromide spectrally sensitized with a red sensitizing dye (ExS-1, 2, 3) (average grain size 0.60 μ, grain size distribution 15%, octahedron) ) 0.14 Gelatin 1.00 Cyan coupler (ExC-1, 2, 3 1: 1: 0.2) 0.30 Anti-fading agent (Cpd-1, 2, 3, 4, 30 equivalents) 0.18 Coupler dispersion medium (Cpd) -6) ... 0.03 Coupler solvent (Solv-1, 2, 3 equivalents) ... 0.12

Fifth layer (intermediate layer) Gelatin ... 1.00 Color mixing inhibitor (Cpd-7) ... 0.08 Color mixing inhibitor solvent (Solv-4, 5 equivalents) ... 0.16 Polymer latex (Cpd-8) ... 0.10

Sixth Layer (Low Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.25 μ, grain size distribution 8%, octahedron) ... 0.04 green Silver chlorobromide spectrally sensitized with a sensitizing dye (ExS-4) (silver chloride 5 mol%, average grain size 0.40 μ, grain size distribution 10%, octahedron) ... 0.06 Gelatin ... 0.80 Magenta coupler (ExM- 0.12 Anti-fading agent (equal amount of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 at 10: 7: 7: 1: ratio) 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

Seventh Layer (High-Sensitivity Green Sensitive Layer) Silver bromide spectrally sensitized with a green sensitizing dye (ExS-4) (average grain size 0.65μ, grain size distribution 16%, octahedron) ... 0.10 gelatin 0.80 Magenta coupler (ExM-1, 2, 3 equivalents) 0.11 Anti-fading agent (equal amounts of Cpd-9, 26, 30) 0.15 Anti-staining agent (Cpd-10, 11, 12, 13 10: 0.025 Coupler dispersion medium (Cpd-6) 0.05 Coupler solvent (Solv-4, 6 equivalents) 0.15

8th layer (intermediate layer) Same as 5th layer

Ninth layer (yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixing inhibitor (Cpd-7) 0.03 Color mixing inhibitor solvent (Solv-4, 5 equivalents) 0.10 Polymer Latex (Cpd-8) 0.07

10th layer (middle layer) Same as 5th layer

Eleventh Layer (Low Sensitivity Blue Sensitive Layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.40 μ, grain size distribution 8%, octahedron). ... 0.07 Silver chlorobromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (8 mol% silver chloride, average particle size 0.60 µ, particle size distribution 11%, octahedron) ... 0.14 gelatin ... 0.80 Yellow coupler (ExY-1, 2, 3 equivalents) 0.35 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15 in 1: 5 ratio) ) ... 0.007 Coupler dispersion medium (Cpd-6) ... 0.05 Coupler solvent (Solv-2) ... 0.10.

12th layer (high-sensitivity blue-sensitive layer) Silver bromide spectrally sensitized with a blue sensitizing dye (ExS-5, 6) (average grain size 0.85μ, grain size distribution 18%, octahedron) 0.15 Gelatin 0.60 Yellow coupler (ExY-1, 2, 3 equivalents) 0.30 Anti-fading agent (Cpd-14) 0.10 Anti-fading agent (Cpd-30) 0.05 Anti-staining agent (Cpd-5, 15) 0.007 coupler dispersion medium (Cpd-6) 0.05 coupler solvent (Solv-2) 0.10

13th layer (ultraviolet absorbing layer) Gelatin: 1.00 Ultraviolet absorber (Cpd-2, 4, 16 equivalents): 0.50 Color mixing inhibitor (Cpd-7, 17 equivalents): 0.03 Dispersion medium (Cpd-6) 0.02 UV absorber solvent (Solv-2, 7 equivalents) 0.08 Anti-irradiation dye (Cpd-18, 19, 20, 21, 27 in 10: 10: 13: 15: 20 ratio) ... 0.05

Fourteenth Layer (Protective Layer) Fine-grain silver chlorobromide (97 mol% silver chloride, average particle size 0.1 μ) 0.03 Polyvinyl alcohol acrylic modified copolymer (molecular weight 50,000) 0.01 0.01 Polymethylmethacrylate particles (average Particle size 2.4μ) and silicon oxide (average particle size 5μ) Equivalent… 0.05 Gelatin… 1.80 Gelatin hardening agent (H-1, H-2 equivalent)… 0.18

Fifteenth layer (back layer) Gelatin 2.50 UV absorber (Cpd-2, 4, 16 equivalents) 0.50 Dye (Cpd-18, 19, 20, 21, 27 equivalents) 0.06

16th Layer (Back Layer Protective Layer) Polymethylmethacrylate particles (average particle size 2.4 μ) and silicon oxide (average particle size 5 μ) Equivalent ... 0.05 Gelatin ... 2.00 Gelatin hardener (H-1, H- 2 equivalents)… 0.14

Preparation of Emulsion EM-1 An aqueous solution of potassium bromide and silver nitrate was simultaneously added to an aqueous gelatin solution at 75 ° C. over 15 minutes with vigorous stirring,
Octahedral silver bromide grains having an average grain size of 0.35μ were obtained. At this time, 0.3 g of 3,4-dimethyl-1,3 per mol of silver was used.
-Thiazolin-2-thione was added. 1 silver in this emulsion
Chemical sensitization was performed by sequentially adding 6 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mol and heating at 75 ° C. for 80 minutes. Using the particles thus obtained as a core, the particles were further grown in the same precipitation environment as in the first time, and finally an octahedral monodisperse core / average particle size of 0.7 μ /
A shell silver bromide emulsion was obtained. Coefficient of variation of particle size is about 1
It was 0%. To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mol of silver, and the mixture was heated at 60 ° C. for 60 minutes for chemical sensitization to perform internal latent image type halogenation. A silver emulsion was obtained.

ExZK-1 was used as a nucleating agent in each photosensitive layer.
And ExZK-2 are 10 ^-3 for silver halide,
10 ^-2 % by weight, Cpd-22, 28 as a nucleation accelerator,
29 were used at 10 ^-2 wt% each. Further, in each layer, alkanol XC (Du Pont) and sodium alkylbenzene sulfonate were used as emulsifying and dispersing aids, and succinic acid ester and Magefac F-120 were used as coating aids.
(Manufactured by Dainippon Ink and Chemicals, Inc.) was used. For the layer containing silver halide and colloidal silver, a stabilizer (Cpd-23, 24,
25) was used. This sample has a sample number of 101.
The compounds used in the examples are shown below.

[0136]

[Chemical formula 22]

[0137]

[Chemical formula 23]

[0138]

[Chemical formula 24]

[0139]

[Chemical 25]

[0140]

[Chemical formula 26]

[0141]

[Chemical 27]

[0142]

[Chemical 28]

[0143]

[Chemical 29]

[0144]

[Chemical 30]

Solv-1 di (2-ethylhexyl) sebacate Solv-2 trinonyl phosphate Solv-3 di (3-methylhexyl) phthalate Solv-4 tricresyl phosphate Solv-5 dibutyl phthalate Solv-6 trioctyl phosphate Solv- 7 Di (2-ethylhexyl) phthalate

H-1 1,2-bis (vinylsulfonylacetamido) ethane H-2 4,6-dichloro-2-hydroxy-1,3,5-triazine Na salt

ExZK-17- (3-ethoxythiocarbonylaminobenzamido) -9-methyl-10-propargyl-1,2,3,3
4-Tetrahydroacridinium trifluoromethanesulfonate ExZK-2 2- [4- {3- [3- {3- [5- {3- [2-chloro-5- (1-dodecyloxycarbonylethoxycarbonyl) phenyl) phenyl Carbamoyl] -4-hydroxy-1
-Naphtylthio} tetrazol-1-yl] phenyl}
Ureido] benzenesulfonamide} phenyl] -1-
Formyl hydrazine

After imagewise exposure of the silver halide color photographic light-sensitive material prepared as described above, the cumulative replenishment amount of the solution was determined by the method described below using an automatic processor so that the tank capacity of the bleach-fixing solution was It was continuously processed until it became 3 times. Step Time Temperature Tank Capacity replenishment rate color developing 135 seconds 38 ° C. 11 liters 350 ml / m ² bleach-fixing 40 seconds 34 ° C. 3 liters 300 ml / m ² water washing (1) 40 sec 32 ° C. 3 liters - washing (2) 40 Second 32 ℃ 3 liter 350 ml / m ² dry 30 s 80 ℃ The replenishing method of the washing water is to replenish the washing bath (2) and guide the overflow liquid of the washing bath (2) to the washing bath (1), A countercurrent replenishment method was adopted. At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² .

The composition of each treatment liquid was as follows. [Color developer] [Tank solution] [Replenisher] D-sorbit 0.15 g 0.20 g Sodium naphthalenesulfonate / formalin condensate 0.15 g 0.20 g Nitrilotris (methylenephosphonic acid) pentasodium salt 1.8 g 1.8 g Diethylenetriaminepentaacetic acid 0.5 g 0.5 g 1-hydroxyethylidene-1,1-diphosphonic acid 0.15 g 0.15 g diethylene glycol 12.0 ml 16.0 ml benzyl alcohol 13.5 ml 18.0 ml potassium bromide 0.70 g-benzotriazole 0.003 g 0.004 g sodium sulfite 2.4 g 3.2 g disodium- N, N-bis (sulfonate ethyl) hydroxylamine 8.0 g 10.6 g triethanolamine 6.0 g 8.0 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline.3 / 2 Sulfur Acid / monohydrate 6.0 g 8.0 g Potassium carbonate 30.0 g 25.0 g Optical brightener (diaminostilbene type) 1.3 g 1.7 g Water is added to 1000 ml 1000 ml pH (25 ° C) (pH adjusted with KOH or sulfuric acid) 10.30 10.79

[Bleach-fixing solution] [tank solution] [replenishing solution] Fe (III) ammonium salt of compound shown in Table 2 0.14 mol Same as tank solution Ammonium thiosulfate (750 g / l) 168 ml sodium p-toluenesulfinate 30.0 g Ammonium sulfite 35.0 g 5-Mercapto-1,3,4-triazole 0.5 g Ammonium nitrate 10.0 g Water added 1000 ml pH (25 ° C.) (pH adjustment with ammonia water or acetic acid) 6.5

[Washing water] [Both tank solution and replenisher] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 After continuous treatment, in the same manner as in Example 1. The bleach-fixing solution was aged and examined for desilvering property of the bleach-fixing solution after the aged time and for the occurrence of precipitates. The results are shown in Table B. Similar to Example 1, excellent effects were obtained only in the structure of the present invention.

[0152]

[Table 2]

[0153]

The present invention provides a method for processing a direct positive type silver halide color photographic light-sensitive material, which is excellent in desilvering property and liquid stability even after lapse of time after continuous processing and can obtain a good image. You can

Claims (1)

[Claims] 1. A direct positive type silver halide color light-sensitive material having at least one internal latent image type silver halide emulsion layer which has not been previously fogged on a support, and is bleach-fixed following the processing with a color developing solution. A method of processing a direct positive type silver halide photographic light-sensitive material, characterized in that the bleach-fixing solution contains at least one ferric complex salt of a compound represented by the following general formula (I). [Chemical 1] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ each represent a hydrogen atom, an aliphatic group, an aromatic group or a hydroxy group.
W represents a linking group represented by the following general formula (W). M ₁ ,
M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. ) General formula _{(W) - (W 1 -Z} ) n -W 2 - (W 1 are .Z is .W ₂ representing an alkylene group or a single bond represents an alkylene group or -CO- represents a single bond, -O- , -S
-, - CO-, or -N (R _W) - represents the (R _W represents a hydrogen atom or an optionally substituted alkyl group.). However, Z and W ₁ are not a single bond at the same time. n is 1
Represents an integer of 3 to 3. )