JP2747918B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter, also referred to as a light-sensitive material). And a processing method for preventing the rise.

[Prior Art] Generally, in order to obtain a color image by processing a photosensitive material which has been imagewise exposed, after a color development step, the generated metallic silver is desilvered and then washed with water, stable or replaced with water. A processing step is provided.

However, the photosensitive material is subjected to running processing by an automatic developing machine provided in a development facility. As a part of service improvement for users, development processing is performed within the day of development acceptance and returned to the user. In recent years, it has been even required to return the product within hours of reception, and the development of rapid processing technology is urgently required.

Recently, rapid processing of color paper called Process RA-4 (Developing time is 3 minutes, processing temperature is 35 ° C, and processing time is broken down into three steps: color development 45 seconds, bleach-fix 45 seconds, and stable 90 seconds ) Has also been proposed by Eastman Kodak Company.

Looking at the conventional techniques for rapid processing of these photosensitive materials, (1) techniques based on improvements in photosensitive materials, (2) techniques based on physical means during development processing, and (3) techniques based on improving the composition of processing solutions used in development processing Regarding the above (1), improvement of the silver halide composition (for example, a technique for forming fine particles of silver halide as described in JP-A-51-77223, JP-A-58-18142, and A technique for lowering silver bromide of silver halide as described in JP-B-56-18939) and the use of additives (for example, a 1-aryl-3-pyrazolidone having a specific structure as described in JP-A-56-64339) And JP-A-57-144547 and 58-50534
Nos. 58-50535 and 58-50536, in which 1-arylpyrazolidones are added to a light-sensitive material).
Technology using high-speed reactive coupler (for example, Japanese Patent Publication No. 51-107)
No. 83, Japanese Patent Application Laid-Open Nos. 50-123342 and 51-102636, and the technique of using a high-reactivity yellow coupler described in JP-A Nos. 50-123342 and 51-102636. (2) the processing liquid stirring technology (for example,
Japanese Patent Application No. 61-23334), and the above (3) relates to a technique using a development accelerator, a technique for enriching a color developing agent, a halogen ion, particularly a bromide ion. And the like are known.

In the above-mentioned rapid processing technology, a technology using a photosensitive material using a high concentration of silver chloride according to the technology (1) (for example, JP-A-58-95345, JP-A-60-19140, and JP-A-58-95736) Described in the specification) gives particularly excellent speeding performance.

However, even if the photosensitive material is improved and developed, the stopping property of the bleach-fix solution is considered to be reduced. Therefore, JP 62
As disclosed in JP-A-249151, a technique for lowering the pH of a bleach-fix solution is disclosed.

In Japanese Patent Application Laid-Open No. 62-196662, a technique for removing benzyl alcohol using a specific 2-equivalent coupler has been developed as a method for solving magenta stain. Even if the present invention is used, when color development and bleach-fixing are performed successively, magenta dye unevenness may occur in the color-developed portion even when using the technique disclosed in JP-A-62-196662. understood.

Therefore, an object of the present invention is to provide a light-sensitive material that can be processed quickly without causing unevenness of the magenta dye that occurs in the color-developed portion even if the bleach-fixing process is performed immediately after the color developing process, not only in the unexposed portion. It is to provide a processing method.

[Structure of the Invention] The present inventors have conducted intensive studies to achieve the above object, and as a result, have accomplished the present invention.

That is, the method for processing a light-sensitive material according to the present invention is a method for processing a silver halide color photographic light-sensitive material imagewise exposed to a color developing solution, followed by processing with a processing solution having a bleaching ability. In the material processing method, the silver halide color photographic light-sensitive material has a silver halide emulsion layer containing silver halide grains substantially consisting of silver chloride, and the color developing solution contains 0.03 mol of chloride. %
In addition to containing not containing benzyl alcohol,
In addition, the processing solution having the bleaching ability has a molecular weight of free acid of 30.
It is characterized by containing an iron complex salt of 0 or more.

 Hereinafter, the present invention will be described in detail.

The color developer used in the present invention has a chloride concentration of 0.03.
Mol / l or more.

As the chloride used in the present invention, KCl, NaCl, LiC
l, CsCl, RbCl, MgCl, NH ₄ Cl and the like.

As a color developing agent used in the color developing solution of the present invention, a p-pheninylenediamine compound having a water-soluble group is preferable from the viewpoint of achieving the effects of the present invention.

Such a water-soluble group has at least one on the amine group of the p-phenylenediamine compound or on the benzene nucleus. Specific examples of the water-soluble group include-(CH ₂ ) _n -CH ₂ OH,-(CH ₂ ) _m -NHSO _2- (CH ₂ ) _n -CH ₃ ,-(CH ₂ ) _m -O- (CH ₂ ) _n -CH ₃ ,-(CH ₂ CH ₂ O) _n C _m H _{2m + 1} ( m and n represent an integer of 0 or more, respectively), -. COOH group, be mentioned as -SO ₃ H group and the like.

Specific examples of the color developing agent preferably used in the invention are shown below.

[Exemplary color developing agent] Among the color developing agents exemplified above, those preferably used in the present invention are exemplified by Nos. (A-1), (A-2), and (A-
3), (A-4), (A-6), (A-7) and (A-
15), particularly preferably No. (A-
1).

The above color developing agents are usually used in the form of salts such as hydrochloride, sulfate, p-toluenesulfonate and the like.

The p-phenylenediamine compound having a water-soluble group used in the present invention is used in an amount of from 1.0 × 10 ^-2 to 1 per color developing solution.
It is preferably in the range of 2.0 × 10 ^-1 mol, more preferably in the range of 1.5 × 10 ^{-2 to} 2.0 × 10 ^-1 mol.

The color developer of the present invention preferably contains a triazinylstilbene-based fluorescent whitening agent.

The triazinylstilbene-based fluorescent whitening agent is preferably represented by the following general formula.

In the formula, X ₂ , X ₃ , Y ₁ and Y ₂ are each a hydroxyl group, a halogen atom such as chlorine or bromine, an alkyl group (eg, methyl, ethyl, etc.), an aryl group (eg, phenyl, methoxyphenyl, etc.), Or an -OR _25. Here, R ₂₁ and R ₂₂ each represent a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂₃ and R ₂₄ each have a substituent. R ₂₅ represents a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, and M represents a cation (eg, sodium, potassium, ammonium Etc.).

The alkyl group represented by R ₂₁ , R ₂₂ and R ₂₅ preferably has 1 to 6 carbon atoms, and the alkylene group represented by R ₂₃ and R ₂₄ preferably has 1 to 2 carbon atoms.

As the substituents of the alkyl group and the aryl group represented by the above R ₂₁ , R ₂₂ and R ₂₅ and the alkylene group represented by the above R ₂₃ and R ₂₄ , a hydroxy group, a sulfo group, a sulfoamino group and a carboxyamino group are preferable. .

Specific examples of the amino group include an amino group, an alkylamino group (eg, methylamino, ethylamino, propylamino, dimethylamino, cyclohexylamino, β-hydroxyethylamino, di (β-hydroxyethyl) amino, β-sulfoethylamino, N- (Β-sulfoethyl) -N′-
Methylamino, N- (β-hydroxyethyl) -N′-
Methylamino and the like, or an arylamino group (for example, anilino, o-, m-, p-sulfoanilino, o-, m
-, P-chloroanilino, o-, m-, p-toluidino, o-, m-, p-carboxyanilino, o-, m
-, P-hydroxyanilino, sulfonaphthylamino,
o-, m-, p-aminoanilino, o-, m-, p-anidino, etc.), Specific examples of include a morpholino group, and specific examples of —OR ₂₅ include an alkoxy group (eg, methoxy, ethoxy, methoxyethoxy, etc.) and an aryloxy group (eg, phenoxy, p-sulfophenoxy, etc.).

Among the optical brighteners represented by the above general formula, preferred compounds are those wherein X ₂ , X ₃ , Y ₁ and Y ₂ are all Or a compound that is -OR _25, and most preferred compounds X ₃ and one is -OR ₂₅ of Y _1, and the other And when one of X ₃ and Y ₂ is -OR ₂₅ , the other is Is a compound.

Specific examples include the following compounds, but are not limited thereto.

Triazinyl stilbene-based brighteners preferably used in the present invention include, for example, "Fluorescent Brightener" (edited by the Chemical Industry Association of Japan) (Showa
It can be synthesized by the usual method described on page 8).

The amount of the triazinylstilbene-based brightener is preferably in the range of 0.2 g to 6 g, more preferably 0.4 g to 3 g, per color developing solution.

The color developing solution of the present invention may contain the following developing solution components in addition to the above components.

As the alkaline agent, for example, sodium hydroxide, potassium hydroxide, silicate, sodium metaborate, potassium metaborate, trisodium phosphate, potassium triphosphate,
Borax and the like can be used alone or in combination as long as the above effect, that is, no precipitation occurs, and the pH stabilizing effect is maintained. Furthermore, various salts such as disodium hydrogen phosphate, dipotassium hydrogen phosphate, sodium bicarbonate, potassium bicarbonate, and borate are used for the purpose of preparation or for the purpose of increasing ionic strength. can do.

If necessary, inorganic and organic antifoggants can be added.

Furthermore, if necessary, a development accelerator can be used. U.S. Patent 2,648,604 as a development accelerator
No. 3,671,247, various pyridinium compounds represented by JP-B-44-9503, other cationic compounds, cationic dyes such as phenosafranine, neutral salts such as thallium nitrate, U.S. Pat. , Same 2,531,8
No. 32, No. 2,950,970, No. 2,577,127 and Japanese Patent Publication No. 44-950
No. 4 polyethylene glycol and derivatives thereof,
Nonionic compounds such as polythioethers, JP-B-44-9
The organic solvents and organic amines, ethanolamine, ethylenediamine, diethanolamine, triethanolamine and the like described in JP-A-509-509 are included. U.S. Patent 2,304,925
And acetylene glycol, methyl ethyl ketone, cyclohexanone, thioethers, pyridine, ammonia, hydrazine, amines and the like.

Benzyl alcohol is not used in the present invention, and for poorly soluble organic solvents represented by the above phenethyl alcohol, it is preferable to eliminate the use in order to effectively achieve the object of the present invention. . The use of the color developing solution for a long period of time, particularly in the running process in a low replenishment system, tends to generate tar, and the generation of such tar significantly impairs the commercial value due to adhesion to the processed paper photosensitive material. Even a serious failure.

In addition, poorly soluble organic solvents have poor solubility in water, which not only complicates the necessity of using a stirrer to adjust the color developing solution itself, but also deteriorates the dissolution rate due to the use of such a stirrer. Therefore, the effect of accelerating the development is limited.

Furthermore, poorly soluble organic solvents have large pollution load values such as biochemical oxygen demand (BOD) and cannot be disposed of in sewers or rivers. Since it has problems such as requiring labor and cost, it is preferable to reduce or eliminate not only benzyl alcohol but also other poorly soluble organic solvents as much as possible.

Further, in the color developing solution of the present invention, if necessary, ethylene glycol, methyl cellosolve, methanol, acetone, dimethylformamide, β-cyclodextrin, and other JP-B-47-33378, JP-B-44-9509 Can be used as an organic solvent for increasing the solubility of the developing agent.

Further, an auxiliary developer can be used together with the developing agent. These auxiliary developers include, for example, N-methyl-p-aminophenol hexalfate (methol), phenidone, N, N'-diethyl-p-aminophenol hydrochloride, N, N, N ', N'-tetra Methyl-p-phenylenediamine hydrochloride and the like are known, and the amount of addition is usually preferably 0.01 g to 1.0 g / l.

In addition, various additives such as a stain inhibitor, a sludge inhibitor, and a layering effect promoter can be used.

Further, various chelating agents may be added to the color developing solution of the present invention, for example, diethylenetriaminepentaacetic acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid, ethylenediaminetetramethylenesulfonic acid, tripolyphosphoric acid, hexametaphosphoric acid, 1-hydroxyethylitene -1,1-Diphosphonic acid and the like may be added.

In the color developing solution of the present invention, it is preferable to use a compound represented by the general formula [I] in place of hydroxylamine conventionally used as a preservative from the viewpoint of rapidity.

General formula [1] In the formula, R ₁ and R ₂ each represent an alkyl group or a hydrogen atom. However, both R ₁ and R ₂ are not hydrogen atoms at the same time. R ₁ and R ₂ may form a ring.

In the general formula [I], represents R ₁ and R ₂ are each an alkyl group or a hydrogen atom are not hydrogen atoms at the same time, R ₁
And the alkyl groups represented by R ₂ may be the same or different, and are each preferably an alkyl group having 1 to 3 carbon atoms. R ₁
And the alkyl group of R ₂ includes those having a substituent, and R ₁ and R ₂ may combine to form a ring, for example, to form a heterocyclic ring such as piperidine or morpholine.

Specific examples of the hydroxylamine compound represented by the general formula [I] are described in U.S. Pat. Nos. 3,287,125 and 3,293,034.
No. 3,287,124, etc., and particularly preferred specific exemplary compounds are shown below.

These compounds are usually used in the form of free amine, hydrochloride, sulfate, p-toluenesulfonate, oxalate, phosphate, acetate and the like.

The concentration of the compound represented by the general formula [I] in the color developing solution is usually 0.2 g / l to 50 g / l, preferably 0.5 g / l to 30 g / l, more preferably 1 g / l to 15 g / l. is there.

Each component of the color developing solution is added to a certain amount of water sequentially,
It can be adjusted by stirring. In this case, the component having low solubility in water can be added by mixing with the above-mentioned organic solvent such as triethanolamine. Also more generally, a concentrated aqueous solution containing a plurality of components each of which can stably coexist, or a solution prepared in advance in a small container in a solid state is added to water and adjusted by stirring, and as a color developing solution of the present invention, Obtainable.

In the present invention, the above-mentioned color developing solution can be used in an arbitrary pH range, but is preferably from pH 9.5 to 13.0, more preferably from pH 9.8 to 12.0, from the viewpoint of rapid processing.

In the present invention, the processing temperature of the color development is 30 ° C. or higher and 50 ° C. or lower, and the higher the temperature, the faster the processing can be performed in a shorter time, which is preferable.On the other hand, it is better not to be too high from the image storage stability. Preferably, the treatment is carried out at a temperature of not less than 33 ° C. and not more than 45 ° C.

The processing solution having the bleaching ability of the present invention contains an iron complex salt having a free acid molecular weight of 300 or more (hereinafter, referred to as the iron complex salt of the present invention) as a bleaching agent.

Examples of the organic acid or a salt thereof used to constitute the iron complex salt of the present invention include the following compounds.

[Exemplary Compounds] [1] Ethylenediaminetetramethylenephosphonic acid [2] Diethylenetriaminepentamethyleneacetic acid [3] Diethylenetriaminepentamethylenephosphonic acid [4] Ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid [5] ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-trimethylenephosphonic acid [6] Propylenediaminetetraacetic acid [7] Propylenediaminetetramethylenephosphonic acid [8] Ethylenediaminedipropionic diacetic acid [9] Nitrilotrimethylenephosphonic acid [10] Cyclohexanediamine Tetraacetic acid [11] Cyclohexanediaminetetramethylenephosphonic acid [12] Dihydroxyethylglycine citric acid [13] Dihydroxyethylglycinemethylenephosphonic acid [14] Dihydroxyethylglycinetartaric acid [15] Ethyl ether diamine tetraacetic acid [16] Ethyl ether diamine tetra Methylene phosphonic acid [17] Glycol ether diamine tetraacetic acid [18] Glycol ether diamine tetramethylene phosphonic acid [19] Ethylene diamine tetrapropionic acid [20] Diamine monopropionic triacetic acid [21] Ethylenediaminetetramethylenephosphonic acid [22] Ethylenediaminetetraacetic acid disodium salt [23] Ethylenediaminetetraacetic acid tetra (trimethylammonium) salt [24] Ethylenediaminetetraacetic acid tetrasodium salt [25] Diethylenetriaminepenta Pentasodium acetate [26] ethylenediamine-N- (β-oxyethyl)
-N, N ', N'-triacetic acid sodium salt [27] 1,2-propylenediaminetetraacetic acid sodium salt [28] Nitrilotriacetic acid sodium salt [29] Cyclohexanediaminetetraacetic acid sodium salt [30] diaminopropanoltetraacetic acid 31] Diaminopropanol tetramethylene phosphonic acid [32] Ethylenediamine-diortho-hydroxyphenylacetic acid [33] Ethylenediamine-diortho-hydroxyphenylmethylenephosphonic acid [34] Ethylenediaminetetrakis (methylenephosphonic acid [35] Triethylenetetramine hexaacetic acid [36] Triethylenetetramine hexamethylenephosphonic acid [37] 1,3-propylenediaminetetraacetic acid [38] 1,3-butylenediaminetetraacetic acid [39] neopentanediaminetetraacetic acid [40] 1,4-butylenediaminetetra Acetic acid [41] 2,4-butylenediaminetetraacetic acid [42] Aminoethyl-1,3-propanediaminepentaacetic acid One or more of the above compounds may be used in combination.

The iron complex salt of the present invention is a compound in which iron is coordinated to the above-mentioned organic acid or its alkali salt, ammonium salt or the like.

These bleaching agents are 5 to 450 g / l, more preferably 20 to 450 g / l.
Use at 250g / l.

To the bleach-fixing solution, a solution having a composition containing a silver halide fixing agent in addition to the bleaching agent as described above and, if necessary, a sulfite as a preservative is applied. Further, a special bleach-fixing solution having a composition comprising a combination of an ethylenediaminetetraacetate (III) complex bleach and a large amount of a halide such as ammonium bromide can be used. As the halide, besides ammonium bromide, hydrochloric acid, hydrobromic acid, lithium bromide, sodium bromide, potassium bromide, sodium iodide, potassium iodide, ammonium iodide and the like can also be used. it can.

As the silver halide fixing agent contained in the bleach-fix solution, a compound capable of forming a water-soluble complex salt by reacting with silver halide as used in ordinary fixing processing, such as potassium thiosulfate, sodium thiosulfate, and ammonium thiosulfate And thiocyanates such as potassium thiocyanate, sodium thiocyanate and ammonium thiocyanate, thiourea, thioether and the like. These fixing agents are used in an amount of 5 g / l or more, which is within a dissolvable range, but generally used in an amount of 70 g to 250 g / l.

In addition, boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate,
Various pH buffers such as sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide can be used alone or in combination of two or more. Furthermore, various fluorescent whitening agents, antifoaming agents or surfactants can be added. Preservatives such as hydroxylamine, hydrazine, bisulfite adducts of aldehyde compounds, etc .; organic chelating agents such as aminopolycarboxylic acid or stabilizers such as nitro alcohol and nitrate; organic solvents such as methanol, dimethyl sulfamide and dimethyl sulfoxide. Etc. can be appropriately contained.

The bleach-fixing solution used in the present invention includes JP-A-46-280, JP-B-45-8506, JP-B-46-556, Belgian Patent 770,910,
Various bleaching accelerators described in JP-B-45-8836, JP-B-53-9854, JP-A-54-71634 and JP-A-49-42349 can be added.

Although the pH of the bleach-fixing solution is preferably used at 4.0 or higher, it is generally used at pH 4.0 or higher and pH 9.5 or lower, preferably at pH 4.5 or higher and pH 8.5 or lower. The preferred pH is between 5.0 and 8.0. The treatment is performed at a temperature of 80 ° C. or lower, preferably 55 ° C. or lower, while suppressing evaporation and the like. The processing time for bleach-fixing is preferably 120 seconds or less, more preferably 5 seconds to 9 seconds, from the viewpoint of the effects of the present invention.
0 seconds.

The fixing step or the processing step after the bleach-fixing step can be carried out by various treatments such as a washing treatment, a stabilizing treatment, a stabilizing treatment instead of washing, and rinsing.For example, JP-A-57-8542 and JP-A-59-8542 can be used. No. 126533, No. 60-200345, No. 62-754
No. 51, No. 63-85628, No. 63-138349, No. 6
Examples thereof include those disclosed in Japanese Patent Application Laid-Open No. 3-244036 and Japanese Patent Publication No. 87-1984.

The silver halide grains used in the light-sensitive material applied to the present invention are substantially silver chloride. Here, the term "substantially silver chloride" refers to a silver halide grain containing at least 80 mol% of silver chloride, preferably 90 mol% or more, more preferably 95 mol% or more, and most preferably 99 mol% or more. % Or more.

The silver halide emulsion containing silver halide grains substantially consisting of silver chloride can contain silver bromide and / or silver iodide as a silver halide composition in addition to silver chloride. Silver is not more than 20 mol%, preferably not more than 10 mol%,
More preferably, it is 3 mol%, and when silver iodide is present, it is 1 mol% or less, preferably 0.5 mol% or less.

The crystal of the silver halide grains may be a normal crystal, a twin crystal or any other crystal, and any ratio of [1.0.0] plane to [1.1.1] plane can be used. Further, the crystal structure of these silver halide grains may be uniform from the inside to the outside, or may be a layered structure (core-shell type) in which the inside and the outside are different. These silver halides may be of a type in which a latent image is mainly formed on the surface or of a type in which a latent image is formed inside a grain. Further, tabular silver halide grains (see JP-A-58-113934 and JP-A-59-170070) can also be used.

Further, the silver halide grains may be obtained by any preparation method such as an acid method, a neutral method or an ammonia method.

Further, for example, a method may be used in which seed particles are formed by an acidic method and further grown by an ammonia method having a high growth rate to grow to a predetermined size. When growing silver halide grains, the pH in the reaction vessel, pAg, etc. are controlled, and for example, silver ions in an amount corresponding to the growth rate of silver halide grains as described in JP-A-54-48521 And halide ions are preferably sequentially and simultaneously injected and mixed.

The preparation of the silver halide grains is preferably performed as described above. The composition containing the silver halide grains is referred to herein as a silver halide emulsion.

These silver halide emulsions include active gelatin; sulfur sensitizers such as allyl thiocarbamide, thiourea, and cystine; selenium sensitizers; reduction sensitizers such as stannous salts and thiodioxide. Urea, polyamion and the like; noble metal sensitizers such as gold sensitizers, specifically, potassium aurithiocyanate, potassium chloroaurate, 2-aurothio-3-methylbenzothiazolium chloride and the like, or ruthenium, palladium, platinum, Sensitizers of water-soluble groups such as rhodium and iridium, specifically ammonium chloroparadate, potassium chloroplatinate and sodium chloroparadate (some of these may be sensitizers or antifoggants depending on the size of the sensitizers) Etc.) alone or in combination as appropriate (for example, a gold sensitizer and a sulfur sensitizer). Use, combined use of gold sensitizer and a selenium sensitizer) may be chemically sensitized with.

The silver halide emulsion according to the present invention is chemically ripened by adding a sulfur-containing compound, and before, during or after the chemical ripening, a nitrogen-containing heteroatom having at least one hydroxytetrazaindene and a mercapto group. At least one kind of a ring compound may be contained.

The silver halide used in the present invention may contain an appropriate sensitizing dye in an amount of from 5 × 10 ^{−3 to} 3 × 10 ⁻³ per mole of silver halide in order to impart photosensitivity to a desired photosensitive wavelength range. Optical sensitization may be performed by adding a mole. Various sensitizing dyes can be used, and one or a combination of two or more sensitizing dyes can be used. Examples of the sensitizing dye advantageously used in the present invention include the following.

That is, examples of sensitizing dyes used in blue-sensitive silver halide emulsions include, for example, West German Patent 929,080 and U.S. Pat.
No. 58, No. 2,493,748, No. 2,503,776, No. 2,519,001
Nos. 2,912,329, 3,656,959, 3,672,897,
Nos. 3,694,217, 4,025,034, 4,046,572, British Patent 1,242,588, JP-B-44-14030, and JP-A-52-24844. As sensitizing dyes used in green-sensitive silver halide emulsions, for example, U.S. Pat.Nos. 1,939,201, 2,072,908, and 2,739,149
No. 2,945,763, British Patent No. 505,979, and the like, there can be mentioned cyanine dyes, merocyanine dyes or complex cyanine dyes as typical examples. Further, as sensitizing dyes used in red-sensitive silver halide emulsions, for example, U.S. Patent Nos. 2,269,234 and 2,270,377
And cyanine dyes, merocyanine dyes and composite cyanine dyes described in JP-A Nos. 2,442,710, 2,454,629, and 2,776,280 can be mentioned as typical examples. Further, U.S. Pat.Nos. 2,213,995 and 2,4
Cyanine dyes, merocyanine dyes or composite cyanine dyes described in, for example, U.S. Pat. Nos. 93,749 and 2,519,001 and West German Patent 929,080 can be advantageously used in a green-sensitive silver halide emulsion or a red-sensitive silver halide emulsion.

These sensitizing dyes may be used alone or in combination.

The photographic light-sensitive material used in the present invention may be optically sensitized to a desired wavelength region by a spectral sensitization method using a cyanine or merocyanine dye alone or in combination, if necessary.

Representative examples of particularly preferred spectral sensitization methods include, for example, JP-B-43-4936, which relates to a combination of benzimidazolocarbocyanine and benzoxazolocarbocyanine,
43-22884, 45-18433, 47-37443, 48-282
No. 93, No. 49-6209, No. 53-12375, JP-A-52-23931
No. 52-51932, No. 54-80118, No. 58-153926, No. 5
9-116646, 59-116647 and the like.

As for the combination of carbocyanine having a benzimidazole nucleus with another cyanine or merocyanine, for example, JP-B-45-25831 and JP-B-47-11114
Nos. 47-25379, 48-38406, 48-38407, 54
-34535, 55-1569, JP-A-50-33220, 50-3852
No. 6, No. 51-107127, No. 51-115820, No. 51-135528,
Nos. 52-104916 and 52-104917.

Further, as for the combination of benzoxazolocarbocyanine (oxacarbocyanine) with other carbocyanines, see, for example, JP-B-44-32753 and JP-B-46-11627.
JP-A-57-1483 and those relating to merocyanine include, for example, JP-B-48-38408, JP-B-48-41204, and
No. 40662, JP-A-56-25728, JP-A-58-10753, JP-A-58-9144
No. 5, No. 59-116645 and No. 50-33828.

Further, as for the combination of thiacarbocyanine with other carbocyanine, for example, JP-B-43-4932
Nos. 43-4933, 45-26470, 46-18107, 47-
8741, JP-A-59-114533 and the like, and furthermore, JP-B-49-620 using zero methine or dimethine merocyanine, monomethine or trimethine cyanine and a styrene dye.
The method described in No. 7 can be advantageously used.

In order to add these sensitizing dyes to the silver halide emulsion according to the present invention, a dye solution such as methyl alcohol, ethyl alcohol, acetone, dimethylformamide, or a fluorinated alcohol described in JP-B-50-40659 is used in advance. Is used by dissolving in a hydrophilic organic solvent.

The timing of addition may be at any time at the start of chemical ripening of the silver halide emulsion, during ripening, or at the end of ripening. In some cases, it may be added to the step immediately before the emulsion coating.

To the photographic constituent layers of the silver halide color photographic light-sensitive material of the present invention, a dye (AI dye) capable of decolorizing with a water-soluble or color developing solution can be added. Examples of the AI dye include an oxonol dye and a hemioxonol. Dyes, merocyanine dyes and azo dyes are included. Among them, oxonol dyes,
Hemioxonol dyes and merocyanine dyes are useful. Examples of AI dyes that can be used include UK Patent 584,609
No. 1,277,419, JP-A-48-85130, 49-99620
No., No. 49-114420, No. 49-129537, No. 52-108115,
Nos. 59-25845, 59-111640, 59-111641, U.S. Pat.Nos. 2,274,782, 2,533,472, 2,956,079, 3,1
No. 25,448, No. 3,148,187, No. 3,177,078, No. 3,247,12
No. 7, 3,260,601, 3,540,887, 3,575,704,
Nos. 3,653,905, 3,718,472 and 4,070,352 can be mentioned.

These AI dyes are generally used in two moles per mole of silver in the emulsion layer.
It is preferable to use from 10 ^{-3 to} 5 x 10 ^-1 mol, more preferably from 1 x 10 ^-2 to 1 x 10 ^-1 mol.

The photographic coupler used in the present invention is preferably a phenolic compound or a naphthol compound as a cyan coupler, for example, US Pat. No. 2,369,929. Same 2,4
34,272, 2,474,293, 2,895,826, 3,253,92
No. 4, No. 3,034,892, No. 3,311,476, No. 3,386,301, No.
3,419,390, 3,458,315, 3,476,563, 3,53
The compounds can be selected from those described in 1,383 and the like, and methods for synthesizing those compounds are also described in the publication.

Examples of the magenta coupler for photography include pyrazolone-based, pyrazolotriazole-based, pyrazolinobenzimidazole-based, and indazolone-based compounds. As pyrazolone-based magenta couplers, U.S. Pat.No. 2,600,788,
3,062,653, 3,127,269, 3,311,476, 3,4
19,391, 3,519,429, 3,558,319, 3,684,51
No. 4, No. 3,888,680, JP-A-49-29639, No. 49-111631
No. 49-129538, No. 50-13041, Tokubo 53-47167
No. 54-10491, compounds described in No. 55-30615; Examples of pyrazolotriazole-based magenta couplers include couplers described in U.S. Pat. No. 1,247,493 and Belgian Patent 792,525. As the colored magenta coupler, a compound having an arylazo substituent at the coupling position of a colorless magenta coupler is generally used.For example, U.S. Pat.Nos. 2,801,171 and 2,983,608
Nos. 3,005,712 and 3,684,514, UK Patent 937,621
And compounds described in JP-A-49-123625 and JP-A-49-31448.

Further, a colored magenta coupler of the type described in U.S. Pat. No. 3,419,391 in which a dye flows out into a processing solution by reaction with an oxidized form of a developing agent can also be used.

As a photographic yellow coupler, an open-chain ketomethylene compound has been conventionally used, and a benzoylacetanilide-type yellow coupler generally used widely,
Bivaloylacetanilide type yellow couplers can be used. Further, 2-equivalent yellow couplers in which the carbon atom at the coupling position is substituted with a substituent capable of leaving during the coupling reaction are also advantageously used. These examples are described in U.S. Pat.Nos. 2,875,057 and 3,265,506.
No. 3,664,841, No. 3,408,194, No. 3,277,155,
3,447,928, 3,415,652, JP-B-49-13576,
JP-A-48-29432, JP-A-48-68834, JP-A-49-10736, and 49
No. -122335, No. 50-28834 and No. 50-132926 are described together with the synthesis method.

The amount of the diffusion-resistant coupler used in the present invention is generally from 0.05 to 0.05 per mol of silver in the photosensitive silver halide emulsion layer.
2.0 moles. In the present invention, a DIR compound is preferably used in addition to the above-mentioned diffusion-resistant coupler.

Further, in addition to the DIR compound, a compound which releases a development inhibitor upon development can be used in the present invention. For example, US Pat. Nos. 3,297,445 and 3,379,529, West German Patent Application (OLS) 2,417,914, No. 15271, 53-9116
And Nos. 59-123838 and 59-127038.

The DIR compound used in the present invention is a compound capable of reacting with an oxidized form of a color developing agent to release a development inhibitor.

A typical example of such a DIR compound is a DIR coupler in which a group capable of forming a compound having a development inhibiting action when released from the active site is introduced into the active site of the coupler, for example, British Patent 935,454. U.S. Patent 3,22
Nos. 7,554, 4,095,984 and 4,149,886.

When the above DIR coupler is subjected to a coupling reaction with an oxidized form of a color developing agent, the coupler nucleus forms a dye,
On the other hand, it has the property of releasing a development inhibitor. In the present invention, U.S. Patent Nos. 3,652,345, 3,928,041, 3,958,99
No. 3, 3,961,959, 4,052,213, JP-A-53-110529
Nos. 54-13333, 55-161237, etc. include a compound that releases a development inhibitor when subjected to a coupling reaction with an oxidized form of a color developing agent, but does not form a dye. It is.

Furthermore, Japanese Patent Application Laid-Open Nos. 54-145135, 56-114946 and
When reacted with an oxidized form of a color developing agent as described in 57-154234, the mother nucleus forms a dye or a colorless compound, while the released timing group is an intramolecular nucleophilic substitution reaction or elimination reaction. A so-called timing DIR compound which releases a development inhibitor by the above method can also be used in the present invention.

JP-A-58-160954 and JP-A-58-162949, the timing group as described above is present in a coupler nucleus which generates a completely diffusible dye when reacted with an oxidized form of a color developing agent. Bound timing DIR compounds can also be used.

The amount of the DIR compound contained in the light-sensitive material is preferably in the range of 1 × 10 ^-4 mol to 10 × 10 ^-1 mol per mol of silver.

The silver halide color photographic light-sensitive material used in the present invention may further contain various photographic additives. For example, antifoggants, stabilizers, ultraviolet absorbers, color stain inhibitors, fluorescent whitening agents, color image browning inhibitors, antistatic agents, hardeners, surfactants described in Research Disclosure No. 17643 Agents, plasticizers, wetting agents and the like can be used.

In the silver halide color photographic light-sensitive material used in the present invention, hydrophilic colloids used for preparing emulsions include gelatin, derivative gelatin, graft polymers of gelatin and other polymers, proteins such as albumin and casein. , Hydroxyethyl cellulose derivatives, cellulose derivatives such as carboxymethyl cellulose, starch derivatives, polyvinyl alcohol, polyvinyl imidazole,
Any material such as a single or copolymer synthetic hydrophilic polymer such as polyacrylamide is included.

Examples of the support of the silver halide color photographic light-sensitive material used in the present invention include, for example, baryta paper, polyethylene-coated paper, polypropylene synthetic paper, a transparent support having a reflective layer, or a combined use of a reflector, for example, a glass plate, Cellulose acetate, cellulose nitrate or polyester film such as polyethylene terephthalate,
Examples thereof include a polyamide film, a polycarbonate film, and a polystyrene film, and other ordinary transparent supports may be used.

These supports are appropriately selected according to the purpose of use of the light-sensitive material.

Various coating methods such as dipping coating, air doctor coating, curtain coating, and hopper coating can be used for coating the silver halide emulsion layer and other photographic constituent layers used in the present invention. U.S. Patent 2,761,791
No. 2,941,898, a simultaneous coating method of two or more layers can be used.

In the present invention, the coating position of each emulsion layer can be arbitrarily determined. For example, in the case of a full-color photographic paper light-sensitive material, an arrangement of a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, and a red-sensitive silver halide emulsion layer in this order from the support side is preferred. . Each of these photosensitive silver halide emulsion layers may be composed of two or more layers.

In the light-sensitive material of the present invention, it is optional to provide an intermediate layer having an appropriate thickness according to the purpose. Further, various layers such as a filter layer, an anti-curl layer, a protective layer, and an anti-allation layer are used as constituent layers. They can be used in appropriate combinations. In these constituent layers, hydrophilic colloids which can be used in the above-mentioned emulsion layers as binders can be used in the same manner, and the layers can be contained in the above-mentioned emulsion layers. Various photographic additives can be included.

In the method for processing a silver halide color photographic light-sensitive material of the present invention,
If the photosensitive material is processed by a so-called internal developing method containing a coupler in the photosensitive material, color paper, color negative film, color positive film, color reversal film for slide, color reversal film for movie, color reversal film for TV, It can be applied to any silver halide color photographic light-sensitive material such as reversal color paper.

[Effects of the Invention] According to the present invention, even if bleach-fixing processing is performed immediately after color development processing as well as unexposed areas, magenta dye unevenness that occurs in color development areas does not occur, and rapid processing is possible. Thus, a method for processing a light-sensitive material can be provided.

[Examples] Hereinafter, the present invention will be described in detail with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 On a paper support laminated with polyethylene, the following layers were sequentially applied from the support side to prepare a photosensitive material sample.

Gelatin layers ^{1 ... 1.2g / m 2, 0.46g} / m 2 ( in terms of silver, hereinafter the same) (99.5 mol% as AgCl) blue-sensitive silver chlorobromide emulsion
And 1.0 × 1 dissolved in 0.48 g / m ² dioctyl phthalate
A layer containing 0 to ³ mol g / m ² of the following yellow coupler (Y-1).

Layer 2: an intermediate layer composed of 0.6 g / m ² of gelatin; Layer 3: 1.2 g / m ² of gelatin, 0.25 g / m ² of a green-sensitive silver chlorobromide emulsion (99.6 mol% as AgCl) and 0.25 g / m ² A layer containing 0.9 × 10 ⁻³ mol g / m ² of the following magenta coupler (M-1) dissolved in m ² dioctyl phthalate.

Intermediate layer of gelatin layers ^{4 ... 1.3g / m 2, (} 99.5 mol% as silver chloride) layer 5 ... 1.4g / m ² of gelatin, 0.28 g / m ² of red-sensitive silver chlorobromide emulsion and 0.18g / m ² of dibutyl phthalate 1.5 × 10 ^-3 mol g / m ² of the following comparative cyan coupler dissolved in (C-1) a layer containing.

Layer 6: Layer containing 1.0 g / m ² of gelatin and 0.21 of tinuvin 328 (ultraviolet adsorbent manufactured by Ciba Geigy) dissolved in 0.20 g / m ² of dioctyl phthalate.

Layer 7: a layer containing 0.48 g / m ² of gelatin. In addition, sodium 2,4-dichloro-6-hydroxy-s-triazine was used as a hardening agent in Layer 2, Layer 4 and Layer 7, respectively. It was added so as to be 0.015 g per 1 g.

Next, after exposing these samples, the following development processing was performed.

Processing process Processing temperature Processing time (1) Color development 35 ° C 45 seconds (2) Bleaching and fixing 35 ° C 45 seconds (3) Rinse 30 ° C 90 seconds (4) Drying 60 to 80 ° C 60 seconds Color developing solution used The blix solution used had the following composition.

[Color developing solution] Potassium chloride 0.03 mol Potassium sulfite 0.02 g DTPA / 5Na 3.0 g Color developing agent (Exemplified compound A-1) 5.5 g Diethylhydroxylamine 5 g Potassium carbonate 30 g Water is added to make 1 to make potassium hydroxide and 50% PH with sulfuric acid
Adjust to 10.15.

[Bleaching-fixing solution] Iron complex salt described in Table 1 0.15 mol / l Ethylenediaminetetraacetic acid 3.0 g Ammonium thiosulfate (70% solution) 100.0 ml Ammonium sulfite (40% solution) 27.5 ml Water was added to make the total amount 1 and potassium carbonate or Adjust to pH 5.5 with glacial acetic acid.

However, in the bleach-fix solution, the color developing solution is 200 m
After mixing and storage for 2 days, development processing was performed.

The sample was exposed to a magenta density of 0.8 using a Konica photoelectric densitometer PDA-65 (manufactured by Konica Corporation), and the color development of the magenta portion was measured to determine the increase in magenta density.

 The results are summarized in Table 1.

From the above table, it is found that magenta is reduced by using an iron complex salt having a molecular weight of free acid of 300 or more.

Example 2 EDTA in bleach-fix solution in Experiment No. 1-1 of Example 1
-Fe was replaced with the composition and concentration shown in Table 2, and treated in the same manner.
The increase in magenta density was measured.

 Table 2 shows the results.

From the above table, it was found that the increase in magenta concentration was even smaller when DTPA.Fe exceeded 20 mol% in combination with an iron salt having a molecular weight of 300 or less, rather than using an iron complex salt having a molecular weight of 300 or more alone.

Example 3 In Example 2, the total Fe concentration was changed to 0.1, 0.13, 0.15, 0.25, 0.3.
When the same processing experiment was performed in place of mol / l, 0.1 mol / l
Although the magenta concentration was increased by 5 to 10%, almost the same results were obtained in other cases.

Example 4 An increase in magenta density was measured in the same manner as in Experiment No. 1-1 of Example 1, except that the concentration of potassium chloride in the color developing solution was changed as shown in Table 3.

As is clear from Table 3, the KCl concentration in the color developer is
When it is in the range of 0.03 mol / l or more, the color development time is
It can be seen that the magenta density increases evenly despite the extremely short time of 45 seconds. However, when the bleach-fix solution of the present invention was used, the increase in magenta density was suppressed, and it was found that the effect was remarkably large.

In Experiment No. 6, KCl was replaced with NaCl, LiCl, MgCl ₂ ,
When similar experiments were performed in place of CsCl, RbCl, and NH ₄ Cl, similar results were obtained.

Claims (1)

(57) [Claims] 1. A method for processing a silver halide color photographic light-sensitive material, wherein the imagewise exposed silver halide color photographic light-sensitive material is processed with a color developing solution and subsequently processed with a processing solution having a bleaching ability. The silver halide color photographic light-sensitive material has a silver halide emulsion layer containing silver halide grains substantially consisting of silver chloride, and the color developer contains 0.03 mol / l or more of chloride and benzyl alcohol. And the processing solution having bleaching ability contains an iron complex salt having a free acid molecular weight of 300 or more.