JPH06161063A - Processing method for direct positive type silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the processing method which forms good images with an excellent desilvering property and recolorability without increasing the density of the min. concn. part by continuous processing by using the ferrous complex salt of a specific compd. as a cleaning agent for a bleach-fixing bath. CONSTITUTION:Hydrophilic colloidal layers contg. colloidal silver and silver halide emulsion layers are provided by coating by holding only the nonphotosensitive hydrophilic colloidal layers. The bleach-fixing liq. contains at least one kind of the ferric complex salt of the compd. expressed by the formula as the bleaching agent. In the formula, R1 to R6 respectively denote a hydrogen atom, aliphat. group, arom. group or hydroxy group. W denotes the combination group expressed by -(W1-Z)n-W2-. M1 to M4 denote a hydrogen atom or cation. W1 denotes an alkylene group or single bond. W2 denotes an alkylene group or -CO-. Z denotes a single bond, -O-, -S-, -CO- or -N(Rw-. Rw denotes a hydrogen atom or alkyl group; n denotes an integer form 1 to 3. There is no case Z and W1 are simultaneously single bonds.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of processing a direct positive type silver halide color light-sensitive material using internal latent image type silver halide grains which have not been fogged in advance.

[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.

Various techniques have been heretofore known in this technical field. For example, US Pat.
6,957, 2,497,875, 2,58
6,982, 2,592,250, 3,76
Nos. 1,266, 3,761,276 and British Patent 1,151,363. By using these known methods, a relatively high-sensitivity light-sensitive material can be directly produced as a positive-working silver halide photographic light-sensitive material, but in order to apply these light-sensitive materials to various photographic fields, photographic performance There has been a demand for further improvement of the.

In a general silver halide color photographic light-sensitive material, colloidal silver is contained in the photographic constituent layers as an antihalation layer, a yellow filter layer and the like. When the colloidal silver layer is in direct contact with the internal latent image type silver halide emulsion layer, fog called contact fog occurs. As a measure against this, a method using an antifoggant or an antistain agent has been proposed. However, in actuality, not only a sufficient effect is not exhibited, but when used in a large amount to obtain the effect, development is suppressed and a color density is lowered, which is a drawback.

As a means for solving the above problems, it is improved by providing a non-photosensitive layer between the direct positive type silver halide emulsion grain layer and the colloidal silver layer described in JP-A-1-219732. However, it has been found that the increase in the minimum density in preventing fog cannot be solved when continuous processing is performed.

[0008]

As a result of intensive studies, it has been found that the above-mentioned problems are caused by a bleach-fixing solution which is carried out immediately after processing with a developing solution. This is because a new non-photosensitive layer is provided and continuous processing causes the eluate from the photographic material to accumulate in each processing solution, which deteriorates the washing out of the developing agent and changes the color developing bath to a bleach-fixing solution. It is presumed that bleaching fog occurred when the photosensitive material entered. Although this problem is improved to some extent by increasing the replenishing amount of the bleach-fixing solution, it does not meet the requirement of low replenishing treatment for environmental protection, and a technique for improving it without increasing the replenishing amount, There has been a demand for a technique for reducing the desilvering property, the color recoloring property and the increase in the minimum density even if the replenishment amount is reduced.

Therefore, a first object of the present invention is to process an internal latent image type direct positive silver halide color light-sensitive material which is excellent in desilvering property and color-recovery property and which is prevented from increasing in minimum density due to continuous processing. Is to provide a method. A second object of the present invention is to provide an environment-friendly internal latent image type direct positive silver halide color light-sensitive material processing method which can obtain excellent photographic performance even if the replenishment of the bleach-fixing solution is reduced. Is.

[0010]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a support having at least one layer of an internal latent image type silver halide grain which has not been previously fogged and at least one dye-forming coupler. A method of treating a direct positive type silver halide color light-sensitive material having a silver emulsion layer and at least one hydrophilic colloid layer containing colloidal silver with a bleach-fixing solution following the processing with a color developing solution, A hydrophilic colloid layer containing silver and the silver halide emulsion layer are coated so as to sandwich only a non-photosensitive hydrophilic colloid layer, and the bleach-fixing solution is represented by the following general formula (I) as a bleaching agent. This can be achieved by a method for processing a direct positive type silver halide color light-sensitive material characterized by containing at least one ferric complex salt of the compound. General formula (I)

[0011]

[Chemical 3]

(Wherein 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 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 is .W ₂ representing an alkylene group or a single bond represents an alkylene group or -CO- .Z represents a single bond, -O -, - S
-, - CO- or -N (R _W) - represents a. R _W represents a hydrogen atom or an alkyl group. n represents an integer of 1 to 3. However, Z and W ₁ are not a single bond at the same time. ) That is, the present invention, as a bleaching agent in the bleach-fixing solution,
By using the ferric iron complex salt of the compound represented by the general formula (I) (hereinafter sometimes referred to as the ferric iron complex salt of the present invention), the increase in the minimum concentration due to the continuous treatment can be reduced.

The compound represented by the general 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 methyl or ethyl.

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 phenyl and naphthyl. Is more preferable. The aliphatic group and aromatic group represented by R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ may have a substituent, for example, an alkyl group (eg methyl, ethyl), aralkyl. Group (eg phenylmethyl), alkenyl group (eg allyl), alkynyl group, alkoxy group (eg methoxy, ethoxy), aryl group (eg phenyl, p-methylphenyl), amino group (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 group (Eg methylthio), arylthio groups (eg phenyl Ruthio), sulfonyl group (eg methanesulfonyl), sulfinyl group (eg methanesulfinyl), hydroxy group, halogen atom (eg chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxy Carbonyl group (eg phenyloxycarbonyl), acyl group (eg acetyl, benzoyl), alkoxycarbonyl group (eg methoxycarbonyl), acyloxy group (eg acetoxy), carbonamide group, sulfonamide group, nitro group, hydroxamic acid group, etc. It may be a dissociation product or a salt thereof, if possible.

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 alkyl group. The alkyl group may be substituted, and 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.

The value of n is preferably 1 or 2, and more preferably 1. Specific examples of W include the following.

[0020]

[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.

[0023]

[Chemical 5]

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

[0027]

[Chemical 9]

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 10 seconds to 2 minutes, more preferably 15 seconds to 90 seconds, still more preferably 20 seconds to 60 seconds.

The replenishing amount of the bleach-fixing solution of the present invention is 20 to 4
00 ml / m ² , preferably 50-350 ml / m ² ,
More preferably, it is 75 to 300 ml / m ² .

It is particularly preferable to use various compounds as a bleaching accelerator in the bleach-fixing solution and / or the pre-bath thereof in order to reduce the increase in the minimum density in continuous processing. 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. 1712
No. 9 (July 1978), compounds having a mercapto group or a disulfide bond, and JP-B-45-85.
06, JP-A-52-20832, and JP-A-53-3273.
5, 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. The amount of these bleaching accelerators added is preferably 10 ⁻⁵ per liter of the bleach-fixing solution.
˜1 mol, more preferably 10 ^{−4 to} 0.1 mol.

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 in the present invention contains sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite, etc.) and bisulfites (eg, preservatives) 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, sulfite is generally added, but ascorbic acid, carbonyl bisulfite adduct, 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.

The light-sensitive material of the present invention is imagewise exposed and then processed with a color developing solution. The color developer of the present invention is
Contains an aromatic primary amine color developing agent. The amount of these color developing agents used is preferably 1 to 20 g, more preferably 2 g, per liter of color developing solution.
~ 8g. These color developing agents may be used alone or in combination of two or more kinds. 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 in the invention are D-4 and D-.
5 and 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). The following general formula (II)

[0042]

[Chemical 10]

In the general formula (II), R¹²And R¹³Are each
Represents a hydrogen atom or an alkyl group. Alkyl group has 1 carbon
-10, more preferably 1-5, substituted
Or may be unsubstituted. Substituent of alkyl group
As described below^Ten, R ¹¹It is the same as the substituent of.
Preferred substituents are hydroxy group and sulfonic acid group
Alternatively, it is a carboxyl group.

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

[0045]

[Chemical 11]

In particular, 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 a sulfite salt such as sodium sulfite, potassium sulfite, sodium bisulfite, potassium bisulfite, sodium metasulfite, potassium metasulfite and the like, or a carbonyl compound sulfite adduct as a preservative. 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 an agent for preventing the precipitation of calcium or 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, in order to reduce bleaching fog, color development and bleach-fixing treatment are carried out in the presence of at least one compound represented by the following general formula (III), (IV) or (V). Are particularly preferable.

The compounds of the general formulas (III) and (IV) will be described in detail below. General formula (III)

[0059]

[Chemical 12]

Formula (IV)

[0061]

[Chemical 13]

(In the general formulas (III) and (IV), R ¹⁴ ,
R ¹⁵ , R ¹⁶ and R ¹⁷ are each a hydrogen atom, a hydroxy group,
Halogen atom, cyano group, carboxy group, alkyl group,
It represents an aryl group, an amino group, an alkoxy group, an alkylthio group, a carbamoyl group or a heterocyclic residue. R ¹⁴ and R
¹⁵ or R ¹⁵ and R ¹⁶ may combine with each other to form a 5- or 6-membered ring. However, at least one of R ¹⁴ and R ¹⁶ represents a hydroxy group. ) General formula (V)

[0063]

[Chemical 14]

(In the general formula (V), R ¹⁸ represents a group substitutable on the benzene ring, R ¹⁹ represents a group substitutable on a hydrogen atom or a nitrogen atom, and m is an integer of 0 to 4). Represents.)

In the formula, R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be the same or different and each is a hydrogen atom; it may have a ring having 1 to 20 carbon atoms or a branch, Substituted or substituted alkyl group; monocyclic or bicyclic, unsubstituted or substituted aryl group; unsubstituted or substituted amino group; hydroxy group; alkoxy group having 1 to 20 carbon atoms; 1 to 6 carbon atoms An alkylthio group; a carbamoyl group having 1 to 20 carbon atoms which may be substituted with an aliphatic group or an aromatic group; a halogen atom; a cyano group; a carboxy group; or a hetero atom such as a nitrogen atom, an oxygen atom or a sulfur atom. Represents a heterocyclic residue having a 5- or 6-membered ring. R
¹⁴ and R ¹⁵ or R ¹⁵ and R ¹⁶ may together form a 5- or 6-membered ring. However, at least one of R ¹⁴ and R ¹⁶ represents a hydroxy group.

Examples of the above-mentioned unsubstituted alkyl group are methyl, ethyl, n-propyl, i-propyl, n-butyl and t-.
Butyl, hexyl, cyclohexyl, cyclopentylmethyl, octyl, dodecyl, tridecyl, heptadecyl. Examples of the substituent in the substituted alkyl group include a monocyclic or bicyclic aryl group, a heterocyclic residue, a halogen atom, a carboxy group, an alkoxycarbonyl group having 2 to 6 carbon atoms, an alkoxy group having 20 or less carbon atoms, and a hydroxy group. And specific examples of the substituted alkyl group are benzyl, phenethyl, chloromethyl, 2-chloroethyl, trifluoromethyl, carboxymethyl, 2-carboxyethyl,
2- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2-methoxyethyl, hydroxymethyl, 2
-Hydroxyethyl and the like. Examples of the unsubstituted aryl group are phenyl and naphthyl, and examples of the substituent when the aryl group is substituted are an alkyl group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a carboxy group, and 2 carbon atoms. ~ 6 alkoxycarbonyl group, hydroxy group, C1-6 alkoxy group, etc., and specific examples of the substituted aryl group include p-tolyl, m-tolyl, p-chlorophenyl, p-bromophenyl, o-chlorophenyl, m-
Nitrophenyl, p-carboxyphenyl, o-carboxyphenyl, o- (methoxycarbonyl) phenyl,
p-hydroxyphenyl, p-methoxyphenyl, m-
Examples include ethoxyphenyl.

The amino group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may be substituted, and examples of the substituent include an alkyl group (eg methyl, ethyl, butyl) or an aryl group (eg phenyl). ) Is given. Specific examples of the substituted amino group include a dimethylamino group, a diethylamino group,
Butylamino group.

Specific examples of the alkoxy group represented by R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ include methoxy, ethoxy, butoxy and heptadecyloxy.

The carbamoyl group represented by each of R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may have one or two alkyl groups having 1 to 20 carbon atoms and aryl groups having 2 or less rings as a substituent. . Specific examples of the substituted carbamoyl group include methylcarbamoyl, dimethylcarbamoyl, ethylcarbamoyl and phenylcarbamoyl.

Specific examples of the halogen atom represented by R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ include chlorine atom and bromine atom.

The heterocyclic residue represented by R ¹⁴ , R ¹⁵ , R ¹⁶ and R ¹⁷ may have a monocyclic ring or a condensed ring of 2 to 3 rings, and specific examples thereof include furyl, pyridyl and 2 Examples include-(3-methyl) benzothiazolyl and 1-benzotriazolyl.

Examples of the ring formed by R ¹⁴ and R ¹⁵ or R ¹⁵ and R ¹⁶ include a cyclopentane ring, a cyclohexane ring, a cyclohexene ring, a benzene ring, a furan ring, a pyrrolidine ring and a thiophene ring.

When R ¹⁷ represents a substituted alkyl group, the hetero ring may be a substituent or a substituted alkyl group represented by the following general formula (A). General formula (A)

[0074]

[Chemical 15]

R ¹⁴ , R ¹⁵ and R ¹⁶ have the same meanings as described above, and n represents 2 or 4.

Specific examples of the compound represented by formula (III) or (IV) are shown below.

[0077]

[Chemical 16]

[0078]

[Chemical 17]

[0079]

[Chemical 18]

[0080]

[Chemical 19]

[0081]

[Chemical 20]

The compounds represented by the general formulas (III) and (IV) are described in JP-A-3-288148 in addition to the above.

Next, details of the general formula (V) will be described. In the formula, R ¹⁸ represents a substitutable group on the benzene ring, and R ¹⁹ represents a substitutable group on a hydrogen atom or a nitrogen atom. Each substitutable group includes a halogen atom (chlorine atom,
A fluorine atom), an alkyl group, a substituted alkyl group, a hydroxyl group, an amino group, a nitro group, a carboxyl group or a sulfonic acid group, which may be the same or different. The alkyl group preferably has 1 to 1 carbon atoms.
0, more preferably 1 to 5, and the total number of carbon atoms of the substituted alkyl group is preferably 1 to 10, and the substituent here is a halogen atom, a hydroxyl group, an amino group, a sulfonic acid group, a nitro group or a carboxyl group. The group etc. can be mentioned.

R ¹⁸ is preferably a halogen atom, a lower alkyl group or a hydroxyl group, and R ¹⁹ is preferably a hydrogen atom, a halogen atom, a lower alkyl group or a hydroxyl group, and particularly m = 0, and It is preferred that R ¹⁹ is a hydrogen atom.

Specific examples of the compound represented by formula (V) are shown below, but the invention is not limited thereto.

[0086]

[Chemical 21]

[0087]

[Chemical formula 22]

Since the compound of the general formula (V) is a known compound, it can be easily obtained or synthesized.

The content of the compounds represented by the general formulas (III), (IV) and (V) in the color developer is 0.1 mg to
It is 1 g / liter, more preferably 1 mg to 500 mg / liter.

These compounds may be added to the color developing solution or may be eluted from the light-sensitive material to the above concentration.

The color developing solution 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, an 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 method, 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, a fluorescent whitening 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 rinsing solution is also used as a washing or 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 concretely preferable replenishing amount is 0.5 to 50 times, preferably 3 to 40 times the carrying amount per unit area of the light-sensitive material from the previous bath. 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.

The hydrophilic colloid used in the non-photosensitive colloid layer, the silver halide emulsion layer containing a dye-forming coupler and the colloidal silver layer, which are applicable to the light-sensitive material of the present invention, are not particularly limited and are known. Are included. Cellulose derivatives such as gelatin, colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, carboxymethyl cellulose, hydroxyethyl cellulose and methyl cellulose;
Synthetic binders such as polyvinyl alcohol, partially saponified polyvinyl acetate, polyacrylamide, polyN, N-dimethylacrylamide, polyN-vinylpyrrolidone, US Pat. Nos. 3,847,620 and 3,655,389. , No. 3,341,332,
Water-soluble polymers such as those described in U.S. Pat. Nos. 3,615,424 and 3,860,428, and U.S. Pat. Nos. 2,614,928 and 2,525,753. Derivatives such as phenylcarbamylated gelatin, acylated gelatin, phthalated gelatin and the like, U.S. Pat. Nos. 2,548,520 and 2,83.
Examples thereof include those obtained by graft-copolymerizing a monomer having a polymerizable ethylene group such as acrylic acid (ester), methacrylic acid (ester), and acrylonitrile described in No. 1,767 with gelatin. These binders can optionally be used as a compatible mixture of two or more.

The non-photosensitive colloidal layer of the present invention preferably has a film thickness of 0.01 to 2.0 μm per layer. Further, the non-photosensitive colloidal layer of the present invention contains a non-photosensitive additive such as an ultraviolet absorber, a developer, a stabilizer, a silver halide solvent, a development inhibitor, a non-photosensitive silver halide and the like. good.

The total dry film thickness of the light-sensitive material of the present invention is the same as that of the present invention.
0.3g / m to exert the effect of ²2.0 g / m or more
²The following is preferable, and 0.5 g / m is more preferable.²
More than 1.5g / m²It is the following.

Various colloidal silver can be contained in the colloidal silver layer of the present invention. The method for preparing these colloidal silver is described in various documents and the like. For example, literature on the preparation of yellow colloidal silver by the dextrin reduction method (Wiley and Sons. Ne.
w York. Published 1933, by Welser, Col
(Loidal Elements), German Patent 1,0
96,193, U.S. Pat. No. 2,688,601 and the like. The yellow colloidal silver layer is preferably used as a yellow filter layer by coating on the green-sensitive layer under the blue-sensitive layer, and the dark-colored colloidal silver layer, for example, the black or brown colloidal silver layer is used as a support for the antihalation layer. It is preferably coated between the light-sensitive silver halide emulsion layer closest to the support. These embodiments are used for improving photographic performance, and either one of the yellow colloidal silver layer and the dark colloidal silver layer may be used, or both layers may be provided.

The colloidal silver used in the colloidal silver layer of the present invention is 0.01 g or more and 1.0 g or less, and more preferably 0.05 g or more and 0.5 g or less per 1 m ² of the light-sensitive material.

Examples of magenta couplers usable in the light-sensitive material of the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole 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 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.

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 (a low-boiling organic solvent is optionally used together), and is emulsified and dispersed in an aqueous gelatin 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 or less.
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 No. 62-215272, No. 137.
It is described in the lower right column of the page to the upper right column of page 144.

[0116]

【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 /
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 Equivalents] ... 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 μ, 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 equivalents) ... 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 spectrally sensitized with a blue sensitizing dye (ExS-5, 6 each equivalent weight 3.5 × 10 ⁻⁴ ) (average grain size 0.60 μ, grain size distribution) 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 (equal amounts of Cpd-2, 4, 16) 0.40 Color-mixing inhibitor (equal amounts 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-grained iodobromide (99 mol% of silver bromide, average size 0.05 μ) 0.03 Polyvinyl alcohol acryl-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 ... 0.05 Gelatin hardening agent (Equivalent for H-1 and H-2) ... 0.18

10th layer (back layer) Gelatin ... 2.50 UV 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 hardener (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. over 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 dry film thickness of this sample was 10.0 microns. The compounds used in the examples are shown below.

[0131]

[Chemical formula 23]

[0132]

[Chemical formula 24]

[0133]

[Chemical 25]

[0134]

[Chemical formula 26]

[0135]

[Chemical 27]

[0136]

[Chemical 28]

[0137]

[Chemical 29]

[0138]

[Chemical 30]

[0139]

[Chemical 31]

[0140]

[Chemical 32]

[0141]

[Chemical 33]

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-1 7- (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) When the sample is exposed to white light through a red filter (Ratten No. 26) and an ND filter, the ND filter density is adjusted to minimize the red density after the development processing described below. With a limited exposure amount.
It was exposed for 1 second. (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.

The exposed sample was 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 39 ° C 28 liters 320 ml / m ² Bleach fixing 60 seconds 35 ° C 11 liters 320 ml / m ² Rinse (1) 40 seconds 35 ° C 7 liters-rinse ( 2) 40 seconds 35 ° C 7 liters 320 ml / m ² dry 30 seconds 80 ° C Wash water is replenished in the rinse bath (2) and the overflow solution of the rinse bath (2) into the rinse bath (1). Lead,
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 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 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] [Both tank solution and replenisher] Fe (III) ammonium salt of the compound shown in Table 0.14 mol Ammonium thiosulfate (750 g / l) 168 ml 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

[Rinse Solution] [Both Tank Solution and Replenisher] Orthophenylphenol 0.5 g Ethylene glycol 10.0 g Potassium sulfite 5.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Bismuth chloride 0.1 g Zinc sulfate · 7H ₂ O 0.8 g Polyvinylpyrrolidone 2.0 g Optical brightening agent (diaminostilbene type) 2.0 g pH (25 ° C.) (pH adjusted with aqueous ammonia or acetic acid) 7.50 Continuous treatment was performed by changing the bleaching agent as shown in Table 1. The wedge-shaped exposed sample 101 was processed at the beginning and the end of each of these continuous processes to obtain the minimum density (Δ
Dmin) was measured with a Macbeth densitometer. The results are shown in Table 1.
It was shown to.

[0151]

[Table 1]

From the results, in the bleach-fixing solution using the bleaching agent of the present invention, there is little increase in the minimum density in continuous processing,
It showed excellent photographic performance. Further, the color recovery and desilvering property were also measured using a wedge-shaped exposed sample, and the treatment with the bleaching agent of the present invention showed excellent color recovery and desilvering property.

Example 2 Using the sample 101 prepared in Example 1, the same exposure as in Example 1 was applied and the following processing was performed.

The exposed sample was 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 Immersion (color developer) 12 seconds 38 ° C Fog exposure 12 seconds --- Color development 95 seconds 38 ° C 20 liters 320 ml / m ² Bleach fixing 45 seconds 35 ° C 8 liters 280 ml / M ² Washing with water (1) 45 seconds 35 ° C 8 liters-Washing with water (2) 45 seconds 35 ° C 8 liters 500 ml / m ² Drying 45 seconds 80 ° C Washing water is replenished in the washing bath (2). The so-called countercurrent replenishment system was used in which the overflow liquid of the washing bath (2) was introduced into the washing bath (1). At this time, the carry-out amount of each processing solution by the light-sensitive material was 35 ml / m ² . The steps from dipping to color development processing were performed in the same tank, and fog exposure was performed by irradiating light of 1 lux.

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-See Table 2 See Table 2 See Table 2 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 hydrate 4.2 g 5.6 g Potassium carbonate 30.0 g 25.0 g Fluorescent whitening (PH adjusted with KOH or sulfuric acid) (diaminostilbene type) 1.3 g 1.7 g Water to make 1000 ml 1000 ml pH (25 ° C.) 10.25 10.75

[Bleach-fixing solution] [Both tank solution and replenishing solution] Fe (III) ammonium salt of the compound shown in Table 2 0.11 mol Ammonium thiosulfate (750 g / l) 150 ml 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] Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μs / cm or less) 1000 ml pH 6.5 As shown in Table 2, the bleaching agent in the bleach-fixing solution and Continuous processing was carried out in the same manner as in Example 1 except that the additives in the color developing solution were changed. The wedge-shaped exposed sample 101 was processed at the beginning and end of each of these continuous processes, and the minimum density (ΔDmin) of the white background portion was measured by a Macbeth densitometer. The results are shown in Table 2.

[0159]

[Table 2]

Only the constitution of the present invention showed excellent photographic performance. Further, when the compounds shown in Table 2 are added to the color developing solution, more excellent photographic performance can be obtained.

Example 3 Samples 102 and 103 were prepared in the same manner as sample 101 except that the following points were changed in the sample 101 prepared in Example 1. The samples 102 and 103 were exposed and processed in the same manner as in Example 1.

First Layer (Antihalation Layer) to Fifth Layer (Green Sensitive Layer) Similar to Sample 101 6-1 Layer (Intermediate Layer) Similar to Sample 101 6th Layer (Intermediate Layer) 6-2 Layer (Yellow filter layer) Yellow colloidal silver (particle size 100Å) 0.12 Gelatin 0.70 Color mixture inhibitor (Cpd-7) 0.03 Color mixture inhibitor solvent (Solv-4, 5 equivalents) 0.10 Polymer latex (Cpd-8) )… 0.07

6th-3rd Layer (Intermediate Layer) Similar to 6th Layer (Intermediate Layer) of Sample 101 7th Layer (Blue Sensitive Layer) to 11th Layer (Back Layer Protection Layer) Similar to Sample 101 Sample 103 Black Colloid Similar to sample 102 except that silver was removed, the bleaching agent was changed as shown in Table 3, and continuous treatment was performed. The wedge-shaped exposed sample was processed at the beginning and the end of each of these continuous processes to obtain the minimum density (ΔDmi
n) was measured with a Macbeth densitometer. The results are shown in Table 3.

[0164]

[Table 3]

Similar to Example 1, the bleach-fixing solution using the bleaching agent of the present invention showed little increase in the minimum density in continuous processing, and showed excellent photographic performance. In particular, the increase in the minimum concentration of the adjacent layer of colloidal silver is small.

[0166]

INDUSTRIAL APPLICABILITY The present invention is a method for processing a direct positive type silver halide color photographic light-sensitive material which is free from the increase in density in the minimum density portion due to continuous processing, is excellent in desilvering property and color recovery property, and can obtain a good image. Can be provided.

Claims (2)

[Claims] 1. A support containing at least one silver halide emulsion layer containing unfogged internal latent image type silver halide grains and at least one dye-forming coupler, and at least colloidal silver. A method of treating a direct positive type silver halide color light-sensitive material having one hydrophilic colloid layer with a bleach-fixing solution following the treatment with a color developing solution, wherein the hydrophilic colloid layer containing colloidal silver and A silver halide emulsion layer is coated so as to sandwich only a non-photosensitive hydrophilic colloid layer, and the bleach-fixing solution contains at least one ferric complex salt of a compound represented by the following general formula (I) as a bleaching agent. A method for processing a direct positive type silver halide color light-sensitive material, comprising: General formula (I) (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 is represented by the following general formula (W). Represents a linking group.
M ₁ , M ₂ , M ₃ and M ₄ each represent a hydrogen atom or a cation. 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- single bond, -O-, -S
-, - CO- or -N (R _W) - represents a. R _W represents a hydrogen atom or an alkyl group. n represents an integer of 1 to 3. However, Z and W ₁ are not a single bond at the same time. )) 2. The color developing solution according to the following general formula (III):
Containing a compound represented by (IV) or (V)
A direct positive type silver halide color as claimed in claim 1.
-Method of processing photosensitive material. [Chemical 2](In the general formulas (III), (IV) and (V), R¹⁴, R¹⁵, R
¹⁶And R¹⁷Are hydrogen atom, hydroxy group, halogen
Atom, cyano group, carboxy group, alkyl group, aryl
Group, amino group, alkoxy group, alkylthio group, carba
It represents a moyl group or a heterocyclic residue. R¹⁴And R¹⁵Or R¹⁵
And R¹⁶May combine with each other to form a 5- or 6-membered ring.
However, R¹⁴And R¹⁶At least one of the
Represent R ¹⁸Represents a substitutable group on the benzene ring, R
¹⁹Represents a group capable of substituting on a hydrogen atom or a nitrogen atom, and m
Represents an integer of 0 to 4. )