JPH07140619A - Photographic processing solution having bleaching capability - Google Patents

Abstract

PURPOSE:To sufficiently desilverize in a short time and to improve color reproducibility by incorporating 1,3-diaminopropane triacetate-ferric salt complex. CONSTITUTION:This photographic bleachable processing solution contains 1,3- diaminopropane triacetate (1,3-PDTA)-ferric salt complex. The processing soln. having bleaching capability means concretely a bleaching soln. or a bleaching and fixing soln. The aminopolycarboxylic acid-ferric salt complex can be used in the form of a complex salt, or a ferric ion complex salt is formed in a soln. by using a ferric salt of an aminocarboxylic acid. When the soln. is used in the form of the complex salt, one kind of complex salt is used or >=2 kinds of complex salts are used. Meanwhile, one or >=2 kinds of ferric salts are used, when the complex salt is formed in the soln. by using the ferric salt and aminocarboxylic acid. Further, one or >=2 kinds of aminocarboxylic acids can be used.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a color photographic light-sensitive material, and more particularly to a method for processing a silver halide color photographic light-sensitive material capable of sufficiently desilvering in a short time to improve color reproduction. Regarding

[0002]

2. Description of the Related Art Generally, the basic steps of processing a color light-sensitive material are a color developing step and a desilvering step. In the color developing step, the exposed silver halide is reduced by the color developing agent to produce silver, and the oxidized color developing agent reacts with the color developing agent (coupler) to give a dye image.
The silver formed here is oxidized by a bleaching bath in the subsequent desilvering step, further converted into a soluble silver complex by the action of a fixing agent, and dissolved and removed. In addition to the above basic steps, the actual development processing includes various auxiliary steps in order to maintain the photographic and physical qualities of the image or to improve the storability of the image. For example, a hardening bath, a stopping bath, an image stabilizing bath, a washing bath and the like. In recent years, in particular, there has been a strong demand for speeding up the processing, that is, shortening the processing time, and there is a great need to shorten the desilvering step, which accounts for nearly half of the processing time in the above processing steps. As a means for shortening the desilvering process, German Patent No. 866,60 responds to such needs.
A bleach-fixing solution containing an aminopolycarboxylic acid (specifically, EDTA) ferric complex salt and a thiosulfate salt as described in JP-A No. 5 is known in one solution. When an aminopolycarboxylic acid ferric salt represented by EDTA having a weak bleaching power) is made to coexist with a thiosulfate having a reducing power, the bleaching power is remarkably weakened, and a high-sensitivity, high-silver amount color photosensitive material for photographing It is extremely difficult to sufficiently desilver the silver and it is a situation that cannot be put to practical use. On the other hand, as a method for increasing the bleaching power, for example, US Pat.
No. 93,858, etc., a method has been proposed in which a bleaching accelerator such as various mercapto compounds is added to a bleaching bath, a bleach-fixing bath or a pre-bath thereof, but all of these methods are used. The effect of the bleaching accelerator was not always sufficient in the processing using the conventional bleaching bath and fixing bath. Also, Japanese Patent Application Nos. 59-198197 and 59
The specification of -198197 describes a method for accelerating desilvering by a method of processing in a bleaching bath followed by a bleach-fixing bath.

[0003]

However, in order to accelerate the desilvering process, D contained in the light-sensitive material is required.
The IR coupler has caused a problem that the desilvering property is deteriorated. Therefore, even if an attempt is made to process a color light-sensitive material with a processing solution having a bleaching ability using only ethylenediaminetetraacetic acid iron (III) complex salt as a bleaching agent, the bleaching speed is remarkably slow,
Inadequate performance was obtained for particularly rapid processing. Therefore, a first object of the present invention is to provide a method suitable for accelerating desilvering of a color light-sensitive material and forming an excellent color image. A second object of the present invention is to provide a color light-sensitive material suitable for shortening the processing time.

[0004]

Means for Solving the Problems As a result of intensive studies by the inventors, the object of the present invention is that it contains 1,3 diaminopropanetetraacetic acid (1,3-PDTA) ferric iron complex salt. It has been found that this can be achieved by the photographic bleaching processing solution. The bleaching ability processing solution (processing solution having a bleaching ability) of the present invention specifically means a bleaching solution or a bleach-fixing solution. The ferric aminopolycarboxylic acid complex salt may be used in the form of a complex salt, or a ferric salt such as ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, ferric phosphate. Second in solution using iron and other aminopolycarboxylic acids
An iron ion complex salt may be formed. When used in the form of a complex salt, one type of complex salt may be used, or two or more types of complex salt may be used. On the other hand, when a complex salt is formed in a solution using a ferric salt and an aminopolycarboxylic acid, one or more ferric salts may be used. Furthermore, one or more aminopolycarboxylic acids may be used. Further, in any case, the aminopolycarboxylic acid may be used in excess to form the ferric ion complex salt.

Typical examples of these aminopolycarboxylic acids and salts thereof used in combination are: A-1 diethylenetriaminepentaacetic acid A-2 diethylenetriaminepentaacetic acid pentasodium salt A-3 ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid A-4 ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid trisodium salt A-5 ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid triammonium salt A-6 1,2-diaminopropane tetraacetic acid A-7 1,2-diaminopropane tetraacetic acid disodium salt A-8 nitrilotriacetic acid A-9 nitrilotriacetic acid tri Sodium salt A-10 Cyclohexanediaminetetraacetic acid A-11 Cyclohexanediaminetetraacetic acid disodium salt A-12 N-Methyl-iminodiacetic acid A-13 Iminodiacetic acid A-14 Dihydroxyethylglycine A-15 Ethyletherdiaminetetraacetic acid A-16 Glycol ether diamine tetraacetic acid A-17 ethylenediaminetetrapropionic acid A-18 ethylenediaminetetraacetic acid and the like can be mentioned, but they are not limited to these exemplified compounds. Preferably, 1,3-diaminopropanetetraacetic acid is used alone. Further, the treatment solution having the bleaching ability containing the above-mentioned ferric iron complex salt may contain a metal ion complex salt of cobalt, nickel, copper or the like other than iron ion. The amount of the bleaching agent per liter of the processing solution having a bleaching ability of the present invention is 0.1 mol to 1 mol,
It is preferably 0.2 mol to 0.5 mol. The pH of the bleaching solution is preferably 4.0 to 8.0, and more preferably 5.0 to 7.5.

In addition to the bleaching agent and the above-mentioned compounds, the treatment bath having a bleaching ability constituting the present invention contains bromide such as potassium bromide, sodium bromide, ammonium bromide or chloride such as potassium chloride and sodium chloride. , A rehalogenating agent such as ammonium chloride. In addition, pH buffers of nitrates such as sodium nitrate, ammonium nitrate, boric acid, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, etc. Additives known to be usually used in a bleaching solution, such as one or more inorganic acids, organic acids and salts thereof having ability, can be added. The treatment bath having a bleaching ability constituting the present invention includes sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate, thiosulfates such as potassium thiosulfate, ammonium thiocyanate, thiocyanates such as potassium thiocyanate, thiourea, A known compound as a fixing agent such as thioether can be contained. The amount of these fixing agents added is preferably 3 mol or less, and particularly preferably 2 mol or less, per liter of the processing solution having the bleaching ability. The treatment liquid having a bleaching ability of the present invention contains, for example, a so-called sulfite ion-releasing compound such as a sulfite or bisulfite such as sodium sulfite or ammonium sulfite, or an aldehyde and bisulfite adduct such as carbonyl bisulfite. Can be included. Furthermore, from A-1 to A-2
Aminopolycarboxylic acid salt as shown in 4, or
Ethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentakismethylenephosphonic acid, 1,
3-diaminopropane tetrakismethylenephosphonic acid,
Nitrilo-N, N, N-trimethylenephosphonic acid, 1-
Organic phosphonic acid compounds such as hydroxyethylidene-1,1'-diphosphonic acid can be included.

In the present invention, the treatment liquid having the bleaching ability is treated by adding at least one bleaching accelerator selected from a compound having a mercapto group or a disulfide bond, an isothiourea derivative and a thiazolidine derivative. You can also The amount of these compounds per liter having the bleaching ability is preferably 1 × 10 ^-5 to 1
× 10 ⁻¹ mol, particularly preferably 1 × 10 ^{−4 to} 5 ×
It is 10 ^-2 mol. In the present invention, the bleaching accelerator to be contained during the treatment having the bleaching ability is a compound having a mercapto group or a disulfide bond, a thiazolidine derivative,
It is selected from thiourea derivatives and isothiourea derivatives as long as they have a bleaching promoting effect, but those represented by the following general formulas (a) to (to) are preferable. General formula (a)

[0008]

[Chemical 1]

[0009] In the formula, R _'1, R' ₂ may be the same or different, a hydrogen atom, a substituted or unsubstituted lower alkyl group (preferably having from 1 to 5 carbon atoms, particularly a methyl group, an ethyl group, a propyl group Is preferred) or an acyl group (preferably having a carbon number of 1 to 3, such as an acetyl group and a propionyl group), and m is an integer of 1 to 3. R _'1 and R' ₂
May combine with each other to form a ring. R _'1, R' ₂
Of these, a substituted or unsubstituted lower alkyl group is particularly preferable. Here, as R _'1, R' _{substituent 2} has, a hydroxyl group, a carboxyl group, a sulfo group, and the like amino group. General formula (b)

[0010]

[Chemical 2]

[0011] In the formula, R _'3, R' ₄ is R _'1, R' ₂ and synonymous of formula (I). m is an integer of 1 to 3. R _'3 and R' ₄ may combine with each other to form a ring. R The _'3, R' _4, in particular a substituted or unsubstituted lower alkyl group is preferred. Examples of the R substituent _'3, R' ₄ have, a hydroxyl group, a carboxyl group, a sulfo group, and the like amino group.

[0012]

[Chemical 3]

[0013] formula, R _'5 represents a hydrogen atom, a halogen atom (e.g., chlorine atom, bromine atom), an amino group, a substituted or unsubstituted lower alkyl group (preferably having a carbon number of 1
To 5, particularly preferably a methyl group, an ethyl group, a propyl group), an amino group having an alkyl group (a methylamino group,
Ethylamino group, dimethylamino group, diethylamino group and the like). Examples of the substituent R _'5 have, a hydroxyl group, a carboxyl group, a sulfo group, and the like amino group. General formula (f)

[0014]

[Chemical 4]

[0015] wherein R _'6, R' _7, which may be the same or different, each represents a hydrogen atom, an optionally substituted alkyl group (preferably a lower alkyl group such as methyl group, ethyl group, propyl Group), a phenyl group which may have a substituent or a heterocyclic group which may have a substituent (more specifically, at least one hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom or the like). A heterocyclic group containing, for example, a pyridine ring,
Thiophene ring, thiazolidine ring, benzoxazole ring, benzotriazole ring, thiazole ring, imidazole ring, etc., and R ′ ₈ is a hydrogen atom or a lower alkyl group which may have a substituent (eg, methyl group, ethyl group). Etc., preferably having 1 to 3 carbon atoms. Here, the hydroxyl group as a substituent R _'6 ~R' ₈ has a carboxyl group, a sulfo group, an amino group, and the like lower alkyl group. R _'9 represents a hydrogen atom or a carboxyl group. General formula (g)

[0016]

[Chemical 5]

[0017] In the _{formula, R '10, R' 11} , R '12 may be the same or different, each a hydrogen atom or a lower alkyl group (e.g., methyl group, ethyl group. Preferably 1 carbon atoms
3. ) Is represented. R _'10 and R' ₁₁ or R _'12 may be bonded to each other to form a ring. Z is an amino group which may have a substituent (for example, a lower alkyl group such as a methyl group, an alkoxyalkyl group such as an acetoxymethyl group),
Represents a sulfonic acid group and a carboxyl group. R _'10 ~R'
Particularly, ₁₂ is preferably a hydrogen atom, a methyl group or an ethyl group, and Z is preferably an amino group or a dialkylamino group. Specific examples of the compounds represented by formulas (A) to (G) are shown below.

[0018]

[Chemical 6]

[0019]

[Chemical 7]

[0020]

[Chemical 8]

[0021]

[Chemical 9]

[0022]

[Chemical 10]

[0023]

[Chemical 11]

[0024]

[Chemical 12]

[0025]

[Chemical 13]

[0026]

[Chemical 14]

[0027]

[Chemical 15]

[0028]

[Chemical 16]

Although any of the above compounds can be synthesized by a known method, particularly for the compound of the general formula (a), US Pat. No. 4,285,984, G. Schwarzenba.
ch et al., Helv. Chim. Acta., 38, 1147 (1955), RO
Clinton et at., J. Am. Chem. Soc., 70, 950 (1948)
For compounds of the general formula (b), see JP-A-53-95.
No. 630, the compounds of the general formulas (c) and (d) are JP-A-54-52534, and the compounds of the general formula (e) are JP-A Nos. 51-68568 and 51-
No. 70763, No. 53-50169, and compounds having the general formula (f) are described in JP-B No. 53-9854, JP-A No. 59-214855, and general formula (G).
For the compound of JP-A-53-94927, reference can be made. To add these compounds to the treatment liquid, it is common to dissolve them in water, an alkali organic acid organic solvent or the like in advance, and add them directly as a powder to the bleaching bath. There is no effect on the bleaching promoting effect.

In the present invention, a processing bath or a washing bath may be provided between the color developing bath and the processing bath having the bleaching ability, and the above bleaching accelerator can be contained in the processing bath. The amount added at that time can be the same as that in the case of adding the bleaching accelerator to the bleach-fixing bath. Further, in the present invention, the bleaching accelerator can be contained in the light-sensitive material. In this case, the bleaching accelerator can be contained in any emulsion layer of blue, green and red sensitivities or a gelatin layer such as an uppermost layer, an intermediate layer or a lowermost layer. The treatment bath having a bleaching ability of the present invention may be a step consisting of one tank, but it may be a step consisting of two or more tanks, and in the tank group, the replenisher may be supplied in a multistage countercurrent system, Alternatively, the replenisher may be supplied to one of the tank groups as a replenisher by uniformly circulating the treatment solution in the tank group as a whole. The treatment bath subsequent to the treatment bath having the bleaching ability of the present invention is a washing bath or a fixing bath, and is disclosed in JP-A-61-75352 and JP-A-61-75352.
It may be the bleach-fixing bath described in 1-75353. In the fixing solution, a thiosulfate such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thiosulfate and potassium thiosulfate as a fixing agent,
Sodium thiocyanate, ammonium thiocyanate,
Thiocyanates such as potassium thiocyanate, thiourea, thioether and the like can be used. The amount of these fixing agents is 0.3 mol to 3 mol, preferably 0.5 mol to 2 mol, per liter of the fixing solution. If desired, the fixing bath may contain various additives.
For example, sulfites such as sodium sulfite and ammonium sulfite, and pH adjusting agents such as boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, acetic acid and sodium acetate, alone or in combination of two or more kinds. Can be included. Further, various antifoaming agents or surfactants may be contained, and alkali metal halides such as potassium iodide, potassium bromide and ammonium bromide, ammonium halides, and further hydroxylamine, hydrazine and aldehyde compounds. A bisulfite addition product or the like can also be included. The pH of the fixing bath is preferably 5-8, especially 6-
8 is preferable.

The primary aromatic amino-based color developing agent used as a color developing solution in the present invention includes known ones widely used in various color photographic processes. These developers are aminophenol-based and p-based.
-Includes phenylenediamine derivatives. Since these compounds are more stable than the free state, they are generally used in the form of salts, for example, hydrochlorides or sulfates. In addition, these compounds generally contain about 0.1 per 1 liter of color developer.
g-about 30 g, more preferably about 1 g-about 15 g per liter of color developer. Examples of the aminophenol-based developer include o-aminophenol, p-aminophenol, 5-amino-2-oxy-toluene, 2-amino-3-oxy-toluene,
2-oxy-3-amino-1,4-dimethyl-benzene and the like are included. A particularly useful primary aromatic amino-based color developing agent is an N, N-dialkyl-p-phenylenediamine-based compound in which the alkyl group and the phenyl group may or may not be substituted. Among them, examples of particularly useful compounds include N, N-diethyl-
p-phenylenediamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N, N-dimethyl-p-phenylenediamine hydrochloride, 2-amino-5- (N-ethyl-
N-dodecylamino) -toluene, N-ethyl-N-β
-Methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-β-hydroxyethylaminoaniline, 4-amino-3-methyl-N, N
-Diethylaniline, 4-amino-N- (2-methoxyethyl) -N-ethyl-3-methylaniline-p-toluenesulfonate and the like can be mentioned. The alkaline color developing solution which can be used in the present invention is, in addition to the first aromatic amino color developing agent, various components which are usually added to the color developing solution, such as sodium hydroxide, sodium carbonate and potassium carbonate. Alkaline agents, such as
Alkali metal sulfite, alkali metal bisulfite, alkali metal thiocyanate, alkali metal halide,
Benzyl alcohol, a water softening agent, a thickening agent and the like may be optionally contained. The pH value of the color developing solution is usually 7 or more, and most commonly about 9 to about 13.

The method of the present invention can also be used for color reversal processing. In the present invention, as the black and white developing solution used at this time, what is commonly known as a black and white first developing solution used for reversal processing of a color photographic light-sensitive material or one used for processing a black-and-white light-sensitive material can be used. Further, various well-known additives which are generally added to the black and white developer can be contained. Typical additives include 1-
Developers such as phenyl-3-pyrazolidone, methol and hydroquinone, preservatives such as sulfites, alkali accelerators such as sodium hydroxide, sodium carbonate, potassium carbonate, potassium bromide and 2-methylbenz Examples include inorganic or organic inhibitors such as imidazole and methylbenzthiazole, water softeners such as polyphosphates, trace iodides, and development inhibitors composed of mercapto compounds. The processing method of the present invention usually comprises processing steps such as color development, bleaching and bleach-fixing. Here, after the bleach-fixing step, a treatment step such as washing and stabilization is generally carried out. However, after the bleach-fixing step, the stabilizing treatment can be easily carried out without substantially washing with water. Treatment methods can also be used. The washing water used in the washing step may contain known additives, if necessary. For example, chelating agents such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, bactericides / antifungal agents that prevent the growth of various bacteria and algae, hardening agents such as magnesium salts and aluminum salts, drying load, unevenness It is possible to use a surfactant or the like for preventing the above. Or West (LEWest), Photographic Science and Engineering
(Phot. Sci. And Eng.), Vol.9 No.6 page 344 to 359 (19
The compounds described in 65) and the like can also be used. The washing step may be carried out using two or more tanks if necessary, and the washing water may be saved as multi-stage countercurrent water washing (for example, 2 to 9 steps). As the stabilizing solution used in the stabilization process,
A processing liquid that stabilizes the dye image is used. For example,
A liquid having a buffering capacity of pH 3 to 6, a liquid containing an aldehyde (for example, formalin), and the like can be used. If necessary, a fluorescent whitening agent, a chelating agent, a bactericidal agent, an antifungal agent, a hardener, a surfactant or the like can be used in the stabilizing solution. In addition, the stabilization step may be performed using two or more tanks if necessary, and multi-stage countercurrent stabilization (for example, 2 to
It is also possible to save the stabilizing solution (9 stages) and omit the water washing step.

In the photographic emulsion layer of the photographic light-sensitive material used in the present invention, any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride can be used. Good. A preferred silver halide is silver iodobromide or silver iodochlorobromide containing about 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from about 2 mol% to about 25 mol% silver iodide. The silver halide grains in the photographic emulsion may be so-called regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having an irregular crystal shape such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof. The grain size of the silver halide may be fine grains of about 0.1 micron or less, or large grains with a projected area diameter of up to about 10 microns, a monodisperse emulsion having a narrow distribution, or a polydisperse grain having a wide distribution. It may be an emulsion. The silver halide photographic emulsion which can be used in the present invention can be produced by a known method. The monodisperse emulsion is a silver halide grain having an average grain diameter of greater than about 0.1 micron, at least about 95
Emulsions are typically such that the weight percent is within ± 40% of the average grain diameter. Further, tabular grains having an aspect ratio of about 5 or more can be used in the present invention. When tabular grains are used, there are advantages such as improvement of color sensitization efficiency, improvement of graininess and increase of sharpness by a sensitizing dye, which is cited in US Pat. No. 4,434,226 cited above. In detail. The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with a compound other than silver halide such as silver rhodanide and lead oxide. The emulsion of the invention is
Usually, those which have been physically aged, chemically aged and spectrally sensitized are used. Additives used in such processes are Research Disclosure No. 17643 and No. 17643.
18716, and the relevant parts are summarized in the table below. Known photographic additives that can be used in the present invention are also described in the above two Research Disclosures, and the locations thereof are shown in the table below.

Additive type RD17643 RD18716 1 Chemical sensitizer, page 23, page 648, right column 2 Sensitivity enhancer, same as above 3 Spectral sensitizer, supersensitizer, page 23 to page 648, right column, page 649, right column 4 increase Whitening agent page 24 5 Antifoggants and stabilizers 24 to 25 pages 649 right column 6 Light absorbers, filter dyes 25 to 26 pages 649 right column to UV absorbers 650 pages left column 7 Stain inhibitors 25 pages right column Page 650 Left to right column 8 Dye image stabilizer page 25 9 Hardener 26 page 651 Page left column 10 Binder page 26 Same as above 11 Plasticizer, lubricant 27 page 650 Right column 12 Coating aids, surface active agents 26 to 27 Page Ibid. 13 Antistatic agent page 27 Ibid. Various color couplers can be used in the present invention, specific examples of which are described in Research Disclosure (RD) No. 17643, VII-CG. Described in the patent. Dye-forming couplers for subtractive primary colors (ie yellow, magenta and cyan)
The coupler which gives the color development by color development is important, and specific examples of the diffusion-resistant 4-equivalent or 2-equivalent coupler are described in RD1 above.
In addition to the couplers described in the patents described in 7643, VII-C and D, the following can be preferably used in the present invention.

Typical examples of the yellow coupler which can be used in the present invention include a hydrophobic acylacetamide type coupler having a ballast group. Specific examples thereof are U.S. Pat. Nos. 2,407,210 and 2,875,05.
7 and 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat. Nos. 3,408,194 and 3,4.
No. 47,928, No. 3,933,501 and No. 4,022,620, or oxygen atom-releasing yellow couplers or JP-B-58-10739.
U.S. Pat. Nos. 4,401,752 and 4,32
6,024, RD18053 (April 1979), British Patent No. 1,425,020, West German Application Publication No. 2,2.
No. 19,917, No. 2,261,361, No. 2,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A Nos. 329,587 and 2,433,812. The α-pivaloyl acetanilide type couplers are excellent in the fastness of color forming dyes, especially the light fastness, while the α-benzoyl acetanilide type couplers can obtain a high color density.

Examples of the magenta coupler which can be used in the present invention include hydrophobic indazolone or cyanoacetyl, preferably 5-pyrazolone and pyrazoloazole couplers having a ballast group. 5-
The pyrazolone 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 typical examples thereof are US Pat. No. 2,311,082 and US Pat. 2,343,70
No. 3, No. 2,600,788, No. 2,908,5
No. 73, No. 3,062, 653, No. 3,152,
896 and 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. In addition, 5-containing the ballast group described in EP 73,636
The pyrazolone-based coupler provides high color density. As a pyrazoloazole-based coupler, US Pat. No. 3,063
1,432 pyrazolobenzimidazoles, preferably pyrazolo [5,1-c] [1,2,4] triazoles described in US Pat. No. 3,725,067, Research Disclosure 24220 ( 198
June 1994) and pyrazolotetrazoles described in JP-A-60-33552 and Research Disclosure 24230 (June 1984) and JP-A-60-
The pyrazolopyrazoles described in 43659 are mentioned. The imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630 are preferable from the viewpoint of low yellow sub-absorption of a color forming dye and light fastness, and U.S. Pat. No. 4,540,654. Pyrazolo [1,5-b] described in
[1,2,4] triazole is particularly preferred.

The cyan couplers usable in the present invention include hydrophobic and diffusion resistant naphthol-type and phenol-type couplers. 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.
Couplers capable of forming cyan dyes that are fast to humidity and temperature are preferably used in the present invention, typical examples of which are at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Phenolic cyan coupler having an alkyl group of ethyl group or more, US Pat. No. 2,
772, 162, 3,758,308, 4,126,396, 4,334,011, 4,327,173, West German Patent Publication 3,329,
2,5-diacylamino-substituted phenol-based couplers described in U.S. Pat. No. 729 and European Patent No. 121,365, and US Pat. Nos. 3,446,622 and 4,33.
3,999, 4,451,559 and 4,427,767, and the like, such as a phenolic coupler having a phenylureido group at the 2-position and an acylamino group at the 5-position. Is. European Patent No. 16
The cyan couplers described in JP-A No. 1,626A in which the 5-position of naphthol is substituted with a sulfonamide group, an amide group, etc. are also excellent in the fastness of a color image and can be preferably used in the present invention. To correct unnecessary absorption of chromophores,
Masking is preferably carried out by using a colored coupler in combination with a color photosensitive material for photographing. US Pat. No. 4,163,3
No. 670 and Japanese Patent Publication No. 57-39413, and yellow colored magenta couplers or U.S. Pat. No. 4,0.
Typical examples include magenta colored cyan couplers described in 04,929, 4,138,258 and British Patent 1,146,368. Other colored couplers are described in RD17643, paragraphs VII-G above.

The graininess can be improved by using a coupler in which the color forming dye has an appropriate diffusibility. Such couplers are exemplified by magenta couplers in U.S. Pat. No. 4,366,237 and British Patent No. 2,125,570, and also in European Patent No. 96,570 and West German Patent Application No. 3,234. No. 533 describes specific examples of yellow, magenta or cyan couplers. The dye-forming coupler and the above-mentioned special coupler may form a dimer or higher polymer. Typical examples of polymerized dye-forming couplers are described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,
102,173 and U.S. Pat. No. 4,367,282.
No. Couplers that release a photographically useful residue upon coupling are also preferably used in the present invention. As the DIR coupler releasing a development inhibitor, the couplers of the patents described in the above-mentioned RD17643, VII to F are useful. In addition, a developer inactivating type represented by JP-A-57-151944; U.S. Pat. No. 4,248,9
62 and the timing type represented by JP-A-57-154234; the reaction type represented by JP-A-60-184248, and particularly preferred is JP-A-57-1.
No. 51944, No. 58-217932, No. 60-21.
No. 8644, No. 60-225156, No. 60-221
No. 750 and 60-233650, and developer deactivating DIR couplers and JP-A-60-184.
No. 248, etc., and is a reactive DIR coupler.
In the light-sensitive material of the present invention, a coupler capable of releasing a nucleating agent or a development accelerator or a precursor thereof imagewise during development can be used. Specific examples of such compounds include British Patent Nos. 2,097,140 and 2,13.
No. 1,188. A coupler which releases a nucleating agent having an adsorbing action on silver halide is particularly preferable, and specific examples thereof are disclosed in JP-A-59-1576.
38 and 59-170840. Suitable supports that can be used in the present invention are described, for example, in RD. No. 17643, page 28 and the same, No. 18
716, right column, page 647 to left column, page 648.

[0039]

The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto. Example 1 On a subbed cellulose triacetate film support,
Multi-layer color light-sensitive material 101 was prepared by coating each layer having the following composition in multiple layers. (Photosensitive layer composition) The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye and the coupler, the coating amount is shown in mol unit per mol of silver halide in the same layer.

(Sample 101) First Layer: Antihalation Layer Black Colloidal Silver ………………………… Silver 0.18 Gelatin …………………… 1.40 Second Layer: Intermediate Layer 2 , 5-di-t-pentadecylhydroquinone ...... 0.18 C-1 ………………………… 0.07 C-3 …………………… 0.02 U-1 …… ………………… 0.08 U-2 ……………………… 0.08 HBS-1 ……………………… 0.10 HBS-2 ………………… …… 0.02 Gelatin …………………… 1.04 Third layer; first red-sensitive emulsion layer Silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.8 µ)… Silver 0.50 Sensitizing dye IX ………………………… 6.9 × 10 ^-5 Sensitizing dye II …………………… 1.8 × 10 ^-5 Sensitizing dye III ………… ……………… 3.1 × 10 ^-4 Sensitization Dye IV ………………………… 4.0 × 10 ⁻⁵ C-2 …………………… 0.146 HBS-1 …………………… 0.005 The present invention Compound (35): 0.0050 Gelatin: 1.20 4th layer: 2nd red-sensitive emulsion layer Silver iodobromide emulsion (5 moles of silver iodide) %, Average particle size 0.85μ) ... Silver 1.15 Sensitizing dye IX ………………………… 5.1 × 10 ^-5 Sensitizing dye II …………………… 1.4 × 10 ^-5 Sensitizing dye III …………………… 2.3 × 10 ^-4 Sensitizing dye IV …………………… 3.0 × 10 ^-5 C-2 ………… ……………… 0.060 C-3 …………………… 0.008 Compound of the present invention (35) ……………… 0.004 HBS-1 ………… ……… 0.005 Gelatin ………………………… 1.50

Fifth Layer: Third Red Sensitive Emulsion Layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.5 μ) ... Silver 1.50 Sensitizing dye IX ………………………… 5.4 × 10 ⁻⁵ Sensitizing dye II ………………………… 1.4 × 10 ⁻⁵ Sensitizing dye III ………………… 2.4 × 10 ⁻⁴ Sensitizing dye IV ………………………… 3.1 × 10 ^-5 C-5 ……………………… 0.012 C-3 ……………………… 0.003 C-4 ………………………… 0.004 HBS-1 …………………… 0.32 Gelatin …………………… 1.63 6th layer; Intermediate layer Gelatin ………… ……………… 1.06 7th layer; 1st green sensitive emulsion layer Silver iodobromide emulsion (6 mol% silver iodide, average grain size 0.8 µ)… Silver 0.35 Sensitizing dye V ……… ……………… 3.0 × 10 ^-5 Sensitizing dye VI ………………………… 1.0 × 10 ^-4 Sensitizing dye VII ………………………… 3.8 × 10 ^-4 C-6 …………………… 0.120 C-1 …………………… 0.021 C-7 ………………………… 0.030 C-8 …………………… 0.025 HBS-1 …………………… 0.20 Gelatin ……………… ...... 0.70

Eighth layer: second green emulsion layer Silver iodobromide emulsion (silver iodide 5 mol%, average grain size 0.85 μ) ... Silver 0.75 Sensitizing dye V ..... 2.1 × 10 ⁻⁵ Sensitizing dye VI ………………………… 7.0 × 10 ⁻⁵ Sensitizing dye VII …………………… 2.6 × 10 ⁻⁴ C-6 ……………………… 0.021 C-8 …………………… 0.004 C-1 ……………………… 0.002 C-7 …………… ………… 0.003 HBS-1 …………………… 0.15 Gelatin …………………… 0.80 9th layer; 3rd green emulsion layer Silver iodobromide ( (Silver iodide 10 mol%, average particle size 1.5 μ) ……… Silver 1.80 Sensitizing dye V …………………… 3.5 × 10 ^-5 Sensitizing dye VI ……………… ………… 8.0 × 10 ^-5 Sensitizing dye VII ………………………… 3.0 × 10 ^-4 C-6 …………………… …… 0.011 C-1 …………………… 0.001 HBS-2 ……………… 0.69 Gelatin …………………… 1.74 10th Layer: Yellow filter layer Yellow colloidal silver …………………… Silver 0.05 2,5-di-t-pentadecylhydroquinone …… 0.03 Gelatin ……………… 0.95 Eleventh layer: First blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 6 mol%, average grain size 0.6 μ) ... Silver 0.24 Sensitizing dye VIII …………………… 3.5 × 10 ^-4 C-9 …………………… 0.27 C-8 …………………… 0.005 HBS-1 …………………… 0.28 Gelatin ……………………… 1.28

Twelfth layer: Second blue-sensitive emulsion layer Silver iodobromide emulsion (silver iodide 10 mol%, average grain size 1.0 μ) ... Silver 0.45 Sensitizing dye VIII .... 2.1 × 10 ^-4 C-9 ………………………… 0.098 HBS-1 …………………… 0.03 Gelatin …………………… 0.46 13th layer: 3rd blue-sensitive emulsion layer Silver iodobromide emulsion (10 mol% of silver iodide, average grain size: 1.8 μ) Silver 0.77 Sensitizing dye VIII …………………… 2.2 × 10 ^-4 C-9 …………………… 0.036 HBS-1 …………………… 0.07 Gelatin …………………… 0.69 14th layer First protective layer Silver iodobromide (silver iodide 1 mol%, average particle size 0.07 μ) ………… Silver 0.5 U-1 ……………………… 0.11 U-2 …… ………………… 0.17 HBS-1 ……………………… 0.90 15 layers; second protective layer Polymethylmethacrylate particles (diameter: about 1.5 μm) 0.54 S-1 …………………… 0.15 S-2 …………………… 0 ．10 Gelatin ………………………… 0.72

In addition to the above composition, a gelatin hardening agent H-1 and a surfactant were added to each layer. A tungsten light source is used for these photographic light-sensitive materials, and the color temperature is set to 48 with a filter.
After exposure of 25 CMS adjusted to 00 ° K, it was processed at 38 ° C according to the following processing steps. Process time Color development 3 minutes 15 seconds Bleaching 3 minutes Fixing 3 minutes 15 seconds Washing with water 1 minute 30 seconds Stable 45 seconds The composition of the processing solution used was as follows.

Color developer Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine Sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulfate 4.5 g Water was added to 1.0 liter pH 10.0 Bleaching solution Bleach (A) ( Compounds and addition amount are shown in Table 1) Bleach (B) (Same as above) Chelate compound (A) (Same as above) Chelate compound (B) (Same as above) Ammonium bromide 150 g Ammonium nitrate 10 g Bleach accelerator (See Table 1) Description) 5 × 10 ⁻³ mol Water added to 1 liter pH 6.0

Here, the chelate compound (A) represents the same aminopolycarboxylic acid as the ferric aminopolycarboxylic acid ammonium salt used in the bleaching agent (A). The same applies to the chelate compound (B). Fixing solution Ethylenediaminetetraacetic acid disodium salt 1.0 g Sodium sulfite 4.0 g Ammonium thiosulfate aqueous solution (70%) 250.0 ml Sodium bisulfite 4.6 g Water was added to 1 liter pH 6.6 Washing solution Ethylenediaminetetraacetic acid disodium salt 0.4 g / liter Water added 1000 ml pH 7.5 Stabilizer Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization ≈10) 0.3 g Water added 1000 ml

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

With respect to each photographic light-sensitive material subjected to the above processing, the amount of residual silver in the highest color density portion was measured by fluorescent X-ray analysis. As is clear from the results shown in Tables 2-1 and 2-2, the case of treatment with the bleaching solution containing the compound of the present invention is better than the case of treatment with the conventional bleaching solution containing EDTA / Fe complex salt. However, the amount of residual silver is small, and this tendency is increased when a bleaching accelerator is used in combination.

Example 2 In the same manner as in Example 1, a multilayer color light-sensitive material 201 having the composition shown below was prepared. (Composition of photosensitive layer) The numbers corresponding to the respective components are shown by the same notation as that shown in Example 1. (Sample 201) First layer; antihalation layer Black colloidal silver ………………………… Silver 0.15 U-1 ……………………… 0.5 U-2 …………… ………… 0.2 HBS-3 …………………… 0.4 Gelatin ……………… 1.5 Second layer; Intermediate layer C-7 ………… ………… 0.10 C-3 …………………… 0.11 2,5-di-t-octylhydroquinone ………… 0.05 HBS-1 …………………… 0.10 Gelatin 1.50 3rd layer; 1st red-sensitive emulsion layer Silver iodobromide emulsion (5 mol% of silver iodide, monodisperse coefficient of variation of 17% concerning grain size) Average emulsion size 0.4 μm emulsion) ……………… 0.9 C-12 …………………… 0.35 C-13 …………………… 0.37 C -3 ………………………… 0.1 Compound (30) of the present invention 0.052 HBS-3 …………………… 0.30 Sensitizing dye I …………………… 4.5 × 10 ^-4 Same II ………………………… 1.4 × 10 ^-5 Same III ……………………… 2.3 × 10 ^-4 Same IV ………………………… … 3.0 × 10 ^-5 Gelatin ………………………… 1.50

Fourth Layer: Second Red-Sensitive Emulsion Layer Silver iodobromide emulsion (6 mol% silver iodide, monodisperse average grain size 1.0 μ emulsion with 16% variation coefficient regarding grain size) .... ………… 1.0 Sensitizing dye I ………………………… 3.0 × 10 ^-4 Same II …………………… 1.0 × 10 ^-5 Same III ……… ……………… 1.5 × 10 ^-4 Same IV ………………………… 2.0 × 10 ^-5 C-4 …………………… 0.078 C-3…. ………………………… 0.045 HBS-1 …………………… 0.010 Gelatin …………………… 0.80 Fifth layer; Intermediate layer 2,5-di -T-octylhydroquinone ……………… 0.12 HBS-1 …………………… 0.20 Gelatin …………………… 1.0 6th layer; 1st green emulsion Layer Silver iodobromide emulsion (silver iodide 6 mol%, variation coefficient for grain size 17% With an average grain size of 0.4 μ) ………………………… 0.5 Sensitizing dye V ………………………… 6.0 × 10 ^-5 Same VI ………………………… …… 2.0 × 10 ^-4 Same VII ………………………… 4.0 × 10 ^-4 C-6 ……………………… 0.27 C-1 …………… ………… 0.072 C-7 …………………… 0.12 C-8 …………………… 0.010 HBS-1 …………………… 0 ．15 Gelatin ………………………… 0.70

Seventh layer: second green-sensitive emulsion layer Silver iodobromide emulsion (7 mol% silver iodobromide, emulsion having an average grain size of 0.9 μ with a variation coefficient of 18% regarding grain size) ..... …… 0.80 Sensitizing dye V ………………………… 4.0 × 10 ^-5 Same VI ………………………… 1.5 × 10 ^-4 Same VII ……………… ………… 3.0 × 10 ^-4 C-6 …………………… 0.071 C-1 …………………… 0.021 C-7 ……………… ………… 0.016 HBS-2 …………………… 0.10 Gelatin …………………… 0.91 8th layer; Intermediate layer 2,5-di-t-octylhydroquinone ……………… 0.05 HBS-2 …………………… 0.10 Gelatin …………………… 0.70 9th layer; emulsion layer Silver iodobromide (silver iodide) 4 mol%, coefficient of variation of particle size of 15% and average particle size of 0.4 μ Agents) ........................... 0.40 Sensitizing dye ^{X ........................... 5.0 × 10 -4 C-} 8 ........................... 0.051 C -14 ………………………… 0.095 HBS-1 ……………………… 0.15 HBS-2 ………………… 0.15 Gelatin …………… ………… 0.60

10th layer: Yellow filter layer Yellow colloidal silver ………………………… 0.85 2,5-di-t-octylhydroquinone ………… 0.15 HBS-1 ………… ………… 0.20 Gelatin …………………… 0.80 11th layer; 1st blue-sensitive emulsion layer Silver iodobromide emulsion (4 mol% silver iodide, variation coefficient 16% regarding grain size) With an average grain size of 0.3 μ) ………………………… 0.45 Sensitizing dye VIII ………………………… 7.0 × 10 ^-4 C-9 ………… ……… 1.10 Compound of the present invention (30) …………………… 0.050 HBS-1 ……………………… 0.40 Gelatin ………………………… 1 .. 12th layer; 2nd blue-sensitive emulsion layer Silver iodobromide emulsion (emulsion having an average grain size of 0.7 µ with a variation coefficient of 19% of grain size of 19%). 0.5 sensitization Containing ^{VIII ........................... 1.5 × 10 -4 C-} 9 ........................... 0.31 HBS-1 ........................... 0.12 Gelatin ... …………………… 0.88 13th layer; Intermediate layer U-1 …………………… 0.12 U-2 …………………… 0.16 HBS-3 ……………………… 0.12 Gelatin …………………… 0.75

Fourteenth Layer; Protective Layer Silver iodobromide emulsion (4 mol% silver iodide, average grain size 0.08 μ with a variation coefficient of 10% regarding grain size) …………………… 0.15 Polymethyl Methacrylate particles (diameter 1.5 μ) S-1 ………………………… 0.05 S-2 ……………………… 0.15 Gelatin …………………… 0.80 In addition to the above composition, a surfactant and a gelatin hardening agent H-1 were added to each layer.

[0056]

[Chemical 17]

[0057]

[Chemical 18]

[0058]

[Chemical 19]

[0059]

[Chemical 20]

[0060]

[Chemical 21]

[0061]

[Chemical formula 22]

[0062]

[Chemical formula 23]

[0063]

[Chemical formula 24]

[0064]

[Chemical 25]

The light-sensitive material prepared as described above was processed using the same bleaching solution as in Example 1. As the color developing solution and the fixing solution, the same solutions as in Example 1 were used, but the washing solution was changed to the following formulation for processing. Water-washing solution Ethylenediaminetetraacetic acid disodium salt 0.4 g 5-Chloro-2-methyl-4-isothiazolin-3-one 50 mg Water was added to 1000 ml pH 7.5

[0066]

[Table 4]

As shown in Tables 3-1 and 3-2, the same effects as in Example 1 were obtained.

Example 3 The multilayer color photographic light-sensitive material 101 prepared in Example 1 was processed according to the following steps. Process time Color development 3 minutes 15 seconds Bleaching fixing 4 minutes Washing with water 1 minute 30 seconds Stable 45 seconds The composition of the processing solution used for processing was as follows.

Color developer Diethylenetriamine pentaacetic acid 1.0 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 g Sodium sulfite 4.0 g Potassium carbonate 30.0 g Potassium bromide 1.4 g Potassium iodide 1.3 mg Hydroxylamine Sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino) -2-methylaniline sulphate 4.5 g Water was added to 1.0 liter pH 10.0 Bleach-fixer Bleach (D) (Compound name and addition amount are described in Table 4) Bleaching agent (E) (Same as above) Chelate compound (D) (Same as above) Chelate compound (E) (Same as above) Bleaching accelerator (Listed in Table 4) 5 × 10 ^-3 mol / liter Sodium sulfite 15.0 g Ammonium thiosulfate (70% aqueous solution) 250.0 g Water was added to 1.0 liter pH 6.8

The chelate compound (D) is an aminopolycarboxylic acid of the same type as the ferric aminocarboxylic acid ammonium salt used in the bleaching agent (D). The same applies to the chelate compound (E). Water washing solution Ethylenediaminetetraacetic acid disodium salt 0.4 g / liter Water is added to 1000 ml pH 7.5 Stabilizing solution Formalin (40%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization ≈10) 0 For each photographic light-sensitive material that had been subjected to the above processing, fluorescence X was added.
The amount of residual silver in the highest color density portion was measured by line analysis.
As is clear from the results of Tables 5-1 and 5-2, the bleach-fix solution containing the compound of the present invention was treated as compared with the case of the conventional bleach-fix solution containing the EDTA.Fe complex salt. In this case, the residual silver amount was smaller, and this tendency was smaller when the bleaching accelerator was used in combination.

[0071]

[Table 5]

[0072]

[Table 6]

[0073]

[Table 7]

Example 4 The multilayer color light-sensitive material 201 prepared in Example 2 was processed using the same bleach-fixing solution as in Example 3. The same color developing solution as in Example 1 was used, but the washing solution was changed to the following formulation for processing. Water washing solution Ethylenediaminetetraacetic acid disodium salt 0.4 g / liter 5-chloro-2-methyl-4-isothiazolin-3-one 50 mg / liter Water was added to 1000 ml pH 7.5 Table 6-1 and Table 6-2. As shown, the same results as in Example 3 were obtained.

[0075]

[Table 8]

[0076]

By using the compound of the present invention in a bleaching solution or the like, the desilvering property can be remarkably improved.

Claims (1)

[Claims] 1. A photographic bleaching processing solution containing 1,3 diaminopropanetetraacetic acid ferric iron complex salt.