DE3635391C2 - Process for treating silver halide color photographic light-sensitive materials - Google Patents

Description

The present invention relates to a method of treating an exposed silver halide color photographic light-sensitive material (hereinafter sometimes referred to as "color-sensitive material"); it relates in particular to an improved treatment process with the help of which it is possible to carry out effective silver removal within a short period of time, to achieve sufficient color reproduction by preventing the reduction of the cyan ^{dye by Fe 2} ⁺ (leuco dye formation) and to achieve excellent photographic properties.

Process for the treatment of color-sensitive materialsi s basically comprise a color development stage and a Silver removal level. In the color development stage is an exposed silver halide by a Farbent winder connection reduced with the formation of silver and the oxidized color developing agent is mixed with a Couplers reacted to form a dye image. In the subsequent silver removal stage, the Silver formed in this stage of development with a Oxidizing agent (commonly referred to as "bleach" net) and then by means of a complexing agent dissolved out for silver ions. By removing the silver only one color image is obtained at this stage.

In the silver removal stage, there are usually two Baths, d. H. a bleach bath that contains a bleach, and a fixing bath containing a fixing agent det. In addition, a method in which a bleach-fix bad is used which is both a bleach as well contains a fixative, or a method in which a water wash between treatments in that Bleach bath and the treatment in the fixer leads will be applied depending on the one used photosensitive material. In the bleach treatment or bleach-fix treatment of highly sensitive color sensitive materials, especially light-sensitive reversal color photographic materials and light sensitive color photographic negative materials, Sufficient silver removal is often difficult and a long time is required for bleaching. Man therefore endeavored to shorten the treatment time. In addition, the bleach-fixing solution has the disadvantage that they the blue-green formed by the color development dye reduced to a leuco dye, whereby the color rendering is impaired. Under these In some circumstances, efforts were made to find a silver removal method drive to develop that free from the above Disadvantages is.

Couplers in the previous color photographic sensitive materials are contained, must be ver meet different conditions. You have to get one Excellent stability, excellent treatability developability and excellent color tones Have winding properties and the color image a give excellent shade and authenticity. In addition, it is necessary that the coupler be easy to open can be produced economically.

Under these circumstances, phenol and naphthol have hitherto been used coupler used as a cyan coupler. In particular 1-naphthol couplers are widely used in practice for the production of light-sensitive color negative media materials are used because they are cheap to produce can, many of them excellent color developing possess properties and the developed color Absorption maximum (max.) In a long-wave range and only an insignificant secondary absorption in the green Be rich and excellent color rendering have (see DE-A-21 29 201, DE-A-26 34 649 and DE-A-27 47 435).

But even with the process of developing the color sensitive material that this cyan coupler ent lasts, it takes a long time and the color like performance is impaired.

It has now been found that the above shortcomings be Can be reversed by treating a photosensitive lichen material that has a special cyan coupler contains, d. H. a 1-naphthol coupler with a mono substituted amino group in the 5-position, which also a color image fastness and a color reproducibility wise that are better than those more conventional Cyan couplers, and / or 1-naphthol couplers with an acylamino group in the 2-position, making it is possible after treatment in a bath with bleach and Fusing functions to provide excellent image density achieve. It has also been found that the above Problems can be solved more effectively by using a combination of a bleach bath and a fixer bath that has both bleaching and fixing effects.

The main aim of the present invention is therefore to provide a Method of treating a photosensitive color photographic material with excellent to create photographic properties from the the silver is effective within a short period of time can be removed and that has a good color rendering ability having.

This and other objectives, features and benefits of the Invention will emerge from the following description.

The invention relates to a process for the treatment of an exposed light-sensitive color photographic silver halide material, which is characterized in that a light-sensitive color photographic silver halide material which contains at least one cyan coupler of the general formula (I):

where mean:
R ₁ -CONR ₅ R ₆ , -NHCOR ₅ , -NHCOOR ₇ , -NHSO ₂ R ₇ , -NHCONR ₅ R ₆ or -NHSO ₂ NR ₅ R ₆ ,
R _{2 is} a substituent of the naphthol ring,
m is an integer from 0 to 3,
R _{3 is} a monovalent organic group,
X is a hydrogen atom or a group which can be split off by a coupling reaction with an oxidized primary aromatic amine developing agent,
R ₅ and R ₆ , which may be the same or different, each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
R _{7 is} an aliphatic group, an aromatic group or a heterocyclic group,
where, when the value for m 2, the groups R _{2 can be the} same or different from one another or can be connected to one another to form a ring and R ₂ and R ₃ or R ₃ and X together can form a ring,
is treated in a bath having bleaching and fixing effects and containing 0.04 to 1.0 moles of bleaching agent and 0.3 to 4 moles of fixing agent per liter of bleach-fixing solution.

The photosensitive materials to be treated according to the invention are characterized in that they contain a 1-naphthol cyan coupler of the general formula (I) given above and, if appropriate, additionally a 1-naphthol cyan coupler of the general formula (II):

where mean:
R _{4 is} a substituted or unsubstituted aryl group, and
X represents a hydrogen atom or a group which can be eliminated by the coupling reaction with an oxidized primary aromatic amine developer compound.

In the general formula (I) or (II), the term “aliphatic” is used Groups "for aliphatic hydrocarbon groups (these Definition also applies below), which include straight chain, branched or cyclic alkyl, alkenyl and Alkynyl groups that may be substituted or unsubstituted can. The aromatic groups stand for substituted or unsubstituted aryl groups, the condensed rings could be. The heterocyclic rings stand for sub substituted or unsubstituted, monocyclic or fused heterocyclic rings.

The following are the substituents of the compounds of general formulas (I) and (II) given above explained.

R ₁ has the meanings given above and R ₅ , R ₆ and R ₇ include aliphatic groups having 1 to 30 carbon atoms, aromatic groups having 6 to 30 carbon atoms and heterocyclic groups having 2 to 30 carbon atoms.

R ₂ is a substituent (including an atom, the same also applies to the following explanations) of the naphthol rings. Typical examples include halogen atoms and hydroxyl, amino, carboxyl, sulfonic acid, cyano, aromatic, heterocyclic, carbonamido, sulfonamido, carbamoyl, sulfamoyl, ureido, acyl, acyloxy, aliphatic oxy , aromatic oxy, aliphati cal thio, aromatic thio, aliphatic sulfonyl, aromatic sulfonyl, sulfamoylamino, nitro and imido groups. R ₂ contains 0 to 30 carbon atoms. When m = 2, the cyclic R _{2 is} , for example, the dioxymethylene group.

R ₃ is a monovalent organic group, which is preferably represented by the following general formula (III):

R ₈ (Y) _n - (III)

where mean:

n is the number 0 or 1 and
R _{8 is} a hydrogen atom, an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms,

wherein R ₉ , R ₁₀ and R _{11 have} the same meanings as given above for R ₅ , R ₆ and R ₇ .

In the definition of R ₁ and R ₈ , the groups R ₅ and R ₆ in

or the groups R ₉ and R ₁₀ in

together a nitrogen-containing hetero cyclic ring (for example a morpholine, Piperidine or pyrrolidine ring).

R ₄ is a substituted or unsubstituted aryl group or a condensed ring. Typical examples for the substituents of R ₄ include halogen atoms and cyano, nitro and trifluoromethyl groups,

R ₁₂ and R ₁₃ can be the same or different and each represent a hydrogen atom or an aliphatic, aromatic or heterocyclic group and R ₄ represents an aliphatic, aromatic or heterocyclic group. R ₄ contains 6 to 30 carbon atoms and preferably it is a phenyl group with the above-mentioned substituent.

X represents a hydrogen atom or a coupling eliminating group (including an eliminated atom, the same applies to the explanations below). Typical examples of the coupling eliminating groups include halogen atoms,

aromatic azo groups with 6 to 30 carbon atoms and heterocyclic groups with 1 to 30 carbon atoms and they are connected to the coupling active position of the coupler via a nitrogen atom (such as succinimide, phthalimide, hydantoinyl, pyrazolyl and 2- Benzotriazolyl groups). R ₁₅ in the above formulas represents an aliphatic group having 1 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a heterocyclic group having 2 to 30 carbon atoms.

As noted above, those described herein aliphatic groups saturated or unsaturated, substituted or unsubstituted and straight-chain, be branched or cyclic aliphatic groups. Typical examples include the methyl, ethyl, Butyl, cyclohexyl, allyl, propargyl, methoxyethyl, n-decyl, n-dodecyl, n-hexadecyl, trifluoromethyl, Heptafluoropropyl, dodecyloxypropyl, 2,4-di-tert-amyl phenoxypropyl- and 2,4-di-tert-amylphenoxy butyl groups.

The aromatic groups can either be substituted or unsubstituted and typical examples these include the phenyl, tolyl and 2-tetradecyloxyphe nyl, pentafluorophenyl, 2-chloro-5-dodecyloxycarbo nylphenyl, 4-chlorophenyl, 4-cyanophenyl and 4-hydroxyphenyl groups.

The heterocyclic groups can either be substituted ated or unsubstituted and too typical games include the 2-pyridyl, 4-pyridyl, 2-furyl, 4-thienyl and quinolyl groups.

Preferred examples of the substituents are shown below ducks specified according to the present invention.

R ₁ is preferably a group of the formula -CONR ₅ R ₆ . Examples include the carbamoyl, ethylcarbamoyl, morpholinocarbonyl, dodecylcarbamoyl, hexadecylcarbamoyl, decyloxypropyl, dodecyloxypropyl, 2,4-di-tert-amylphenoxypropyl, and 2,4-di-tert-amylphenoxy butyl groups.

For R ₂ and m it is most preferred that m = 0, ie the compound of the general formula (I) has no substituent R ₂ . If the compound has the substituent R ₂ , it is preferably a halogen atom or an aliphatic group, a carbonamido group or a sulfonamido group.

In the general formula (III) of R ₃ , n is preferably 0. Examples of R ₈ include -COR ₉ (such as, for example, formyl, acetyl, trifluoroacetyl, chloroacetyl, benzoyl, pentafluorobenzoyl and p -Chlorobenzoyl groups), -COOR ₉ (e.g. methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, decyloxycarbonyl, methoxyethoxy carbonyl and phenoxycarbonyl groups), -SO ₂ R ₁₁ (e.g. methanesulfonyl, ethanesulfonyl, butanesulfonyl -, hexadecanesulfonyl, benzenesulfonyl, toluenesulfonyl and p-chlorobenzenesulfonyl groups), -CONR ₉ R ₁₀ (such as N, N-dimethylcarbamoyl-, N, N-diethylcarbamoyl-, N, N-dibutylcarbamoyl, morpholinocarbonyl- , Piperidino carbonyl, 4-cyanophenylcarbonyl, 3,4-dichlorophenylcarbamoyl and 4-methanesulfonylphenylcarbamoyl groups) and -SO ₂ NR ₉ R ₁₀ (such as, for example, N, N-dimethylsulfamo yl, N, N-Di -ethylsulfamoyl and N, N-dipropylsulfamoyl groups). Particularly preferred examples of R ₃ include -COOR ₉ , -COR ₉ and -SO ₂ R ₁₁ . Most preferred among them is -COOR _9.

Preferred examples of X include hydrogen atom, halogen atoms, aliphatic oxy groups with 1 to 30 Carbon atoms (such as methoxy, 2-methanesulfonami doethoxy, 2-methanesulfonylethoxy, carboxymethoxy, 3-carboxypropyloxy-, 2-carboxymethylthioethoxy-, 2-methoxyethoxy and 2-methoxyethylcarbamoylmethoxy groups), aromatic oxy groups (such as phenoxy, 4-chlorophenoxy, 4-methoxyphenoxy, 4-tert-octylphenoxy and 4-carboxyphenoxy groups), heterocyclic thio groups (such as 5-phenyl-1,2,3,4-tetrazolyl-1-thio- and 5-ethyl-1,2,3-tetrazolyl-1-thio groups) and aromatic Azo groups (such as 4-dimethylaminophenylazo, 4-acetamidophenylazo-, 1-naphthylazo-, 2-ethoxycarbonyl phenylazo and 2-methoxycarbonyl-4,5-dimethoxyphenylazo groups).

Examples of preferred R ₄ groups include the naphthyl group or phenyl group which are substituted by a halogen atom or an aliphatic oxy group in the 2-position (such as 2-chlorophenyl-, 2-ethoxyphenyl-, 2-propyloxyphenyl- , 2-butyloxyphenyl, 2-dodecyloxyphenyl, 2-tetradecyloxyphenyl, 2- (2-hexyl decyloxy) phenyl and 2-chloro-5-dodecyloxycarbonyl phenyl groups).

The couplers represented by the general formulas (I) and (II) may be in the form of a dimer, oligomer or polymer formed by connecting two or more molecules thereof through a divalent or higher valent group in the sub-substituent R ₁ , R ₂ , R ₃ or X (in the general formula (I)) or in the substituent X or R ₄ (in the general formula (II)). In such a case, the number of carbon atoms in the substituent may be beyond the above range.

When the coupler represented by the general formula (I) or (II) is in the form of the polymer, typical examples thereof include homopolymers or copolymers of addition-polymerizable, ethylenically unsaturated compounds having a coupler radical forming a cyan dye (cyan developing monomers ). These polymers comprise repeating units of the general formula (IV). The polymer contains one or more kinds of the cyan coupling repeating units represented by the general formula (IV). Alternatively, the polymer can be a copolymer containing one or more non-coupling ethylenic monomers used as comonomers:

where mean:
R is a hydrogen atom, an alkyl group with 1 to 4 carbon atoms or a chlorine atom,
A -CONH-, -COO- or a substituted or unsubstituted phenylene group,
B is a substituted or unsubstituted alkylene, phenylene or aralkylene group,
L -CONH-, -NHCONH-, -NHCOO-, -OCONH-, -NH-, -COO-, -OCO-, -CO-, -O-, -SO ₂ -, -NHSO ₂ - or -SO ₂ NH-,
a, b and c are each the number 0 or 1 and
Q is a cyan coupler residue remaining after the elimination of a hydrogen atom other than that of the hydroxyl group in the 1-position of the compound of the general formula (I) or (II).

The polymers are preferably copolymers of a blue green coupling monomers, which is the coupler unit of the general formula (IV) can form, and one not coupling ethylenic monomers.

Examples of the non-coupling ethylenic Monomers that do not interact with an oxidation product of a primary aromatic amine developing agent kup pels include acrylic acid, α-chloroacrylic acid, α-alkyl acrylic acid (such as methacrylic acid), the esters and amides, derived from these acrylic acids (such as Acrylamide, methacrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methyl acrylate, ethyl acryl lat, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate, Isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, Lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-hydroxymethacrylate), vinyl esters (such as vinyl acetate, vinyl propionate, and vinyl laurate), Acrylonitrile, methacrylonitrile, aromatic vinyl compounds compounds (such as styrene and its derivatives, e.g. vinyl toluene, Divinylbenzene, vinylacetophenone and sulfostyrene), Ita consic acid, citraconic acid, crotonic acid, vinylidene chloride, Vinyl alkyl ethers (e.g. vinyl ethyl ether), maleic acid esters, N-vinyl-2-pyrrolidone, N-vinylpyridine and 2- and 4-vinyl pyridines.

Among these are the acrylic acid esters, methacrylic acid esters and maleic acid esters are preferred. The non-coupling the ethylenic monomers can either be used alone or in the form of a mixture of two or more of them be used. For example, a mixture of methyl acrylate and butyl acrylate, a mixture of Butyl acrylate and styrene, a mixture of butyl meth acrylate and methacrylic acid and a mixture of methyl acrylate and diacetone acrylamide can be used.

As for those skilled in the art of polymer couplers known, that is with the vinyl monomers of the above given general formula (IV) to be copolymerized ethylenically unsaturated monomers as appropriate selected so that the copolymer obtained is excellent physical and / or chemical properties, such as B. excellent solubility, compatibility with a binder, such as. B. gelatin, in the photo graphic colloid composition, excellent Softening point, excellent flexibility and Has heat resistance.

The cyan polymer coupler used in the present invention can are made by dissolving an oleophilic polymer coupler made by polymerizing a vinyl mono meren that the coupler unit of the above general my formula (IV) forms in an organic solution medium and dispersing the resulting solution in a aqueous gelatin solution to form a latex or alternatively using the direct emulsion polymer sation procedure.

The first-mentioned procedure, in which the oleophilic buttocks lymer coupler dispersed in the aqueous gelatin solution is described in U.S. Patent 3,451,820 and that Emulsion polymerization process is in the U.S. Patents 4,080,211 and 3,370,952.

Some examples of couplers represented by general formula (I) are given below, but the invention is by no means restricted to the use of these couplers. In the structural formulas given below, (t) C ₅ H _{11 stands} for -C (CH ₃ ) ₂ C ₂ H ₅ and (t) C ₈ H ₁₇ stands for -C (CH ₃ ) ₂ CH ₂ C (CH ₃ ) ₃ :

Examples of couplers of the general formula (II) are as follows:

The couplers of the general formula (I) given above can be synthesized by methods as described in Japanese Examined Patent Publication 237 448/1985 and in Japanese Patent Applications 264277/1984 and 268 135/1984 are described.

The couplers of the general formula (II) given above can be synthesized by methods as described in U.S. Patent 3,488,193 and prepackaged Japanese Patent publications 15 529/1973, 117 422/1975, 18 315/1977, 90 932/1977, 52 423/1978, 48 237/1979, 66 129/1979, 32 071/1980, 65 957/1980, 105 226/1980, 1938/1981, 12 643/1981, 27 147/1981, 126 832/1981 and 95 346/1983.

The couplers used in the present invention and other couplers disclosed in Combination with these couplers can be used, can using various known dispersions process introduced into the photosensitive material will. For examples of suitable dispersion methods include the solid dispersion process, the alkali disperser sion process, preferably the latex dispersion process and in particular the o / w dispersion method. In which o / w dispersion process, the coupler is used in an orga niche solvents with a high boiling point of 175 ° C or higher, a cosolvent with a low boiling point or a mixture of these and the obtained solution is in an aqueous medium, such as. B. Water, or in an aqueous gelatin solution in the presence a surfactant dispersed, wherein one a fine dispersion is obtained. Examples of the organic Solvents with a high boiling point are in the U.S. Patent 2,322,027. The phase inversion can be in the Dispersion can be effected and if necessary Cosolvent removed or reduced in amount are made by distillation, by washing pasta or by Ultrafiltration before application.

Examples of organic solvents with a high Boiling point include phthalic acid esters, such as dibutyl phthalate, Dicyclohexyl phthalate, di-2-ethylhexyl phthalate and decyl phthalate; Phosphoric and phosphonic esters, such as Tri phenyl phosphate, tricresyl phosphate, 2-ethylhexyldiphenyl phosphate, tricyclohexyl phosphate, tri-2-ethylhexyl phosphate, Tridodecyl phosphate, tributoxyethyl phosphate, trichloro propyl phosphate and di-2-ethylhexyl phenyl phosphonate; Benzoin acid esters such as 2-ethylhexyl benzoate, dodecyl benzoate and 2-ethylhexyl p-hydroxybenzoate; Amides such as B. Diethyldo decanamid and N-tetradecylpyrrolidone; Alcohols and pheno oils such as isostearyl alcohol and 2,4-di-tert-amylphenol; aliphatic carboxylic acid esters, such as dioctyl azelate, glyce trioctyl citrate, isostearyl lactate and trioctyl citrate; Aniline derivatives such as N, N-dibutyl-2-butoxy-5-tert-octylane lin; and hydrocarbons such as paraffins, dodecylbenzene and diisopropylnaphthalene. The cosolvents include organic solvents with a boiling point of about 30 ° C or higher, preferably 50 ° C or higher, and less than about 160 ° C. Typical examples include Ethyl acetate, butyl acetate, ethyl propionate, methyl ethyl ketone, Cyclohexanone, 2-ethoxyethyl acetate and dimethylformamide.

The latex dispersion process, its effects and factors games for the latices used for impregnation are in US-PS 4,199,363 and in DE-OS 25 41 274 and 25 41 230.

According to the invention, different color couplers may have in common be used sam. Typical examples include Cyan, purple, and yellow color couplers, as used in a patent published in Research Disclo sure "(Dec. 1978), 17643 VII-D and November 1979, 18 717 is given. These couplers can preferably can be made resistant to dispersion by introducing a ballast group or by polymerizing it sized to form a dimer or higher polymer. The couplers can be 4-equivalent or 2-equivalent couplers be. In addition, couplers can also be used which have the Deficiency of graininess can be eliminated through dispersion ren of the dye formed, as well as DIR couplers, the a development retarder in the coupling reaction release so that an edge effect or an intermediate layer effect occurs.

Preferred examples of the ver according to the invention Yellow couplers used include α-pivaloyl or α-benzoyl acetanilide coupler. To particularly preferred examples for the two-equivalent couplers, yellow couplers belong to Oxygen atom elimination type as used in the U.S. Patents 3,408,194, 3,447,928, 3,933,501 and 4,022,620 ben, and yellow couplers from nitrogen atom elimination tion type, as described in U.S. Patents 3,973,968 and 4,314,023, Japanese Patent Publication 10 739/1983, in Japanese pre-examined patent publication 132 926/1975, and in DE-OS 22 19 917, 22 61 361, 23 29 587 and 24 33 812 are described. Ge to the purple couplers hear for example pyrazolo (5,1-c) (1,2,4) triazole, as described in U.S. Patent No. 3,725,067, and Pyrazolo (5,1-b) (1,2,4) triazoles as used in the European U.S. Patent 119,860. Purple coupler that with a detachable group attached to an active coupling part via a nitrogen or oxygen atom is bonded, made into two-equivalent couplers are also preferred.

The cyan coupler used in the present invention and the above called dye image forming couplers (main couplers), which can be used in combination with this coupler, is made using a high boiling organic Solvent, such as a phthalic acid ester with 16 to 32 Carbon atoms or a phosphoric acid ester and if necessary another organic solution by means of such as ethyl acetate in an aqueous medium dis pergates, an emulsion being obtained. The standard amount in which the main coupler is used preferably 0.01 to 0.5 mol (yellow coupler), 0.003 to 0.3 mole (magenta coupler) or 0.002 to 0.3 mole (blue green coupler) per mole of photosensitive silver halo genids.

The photographic emulsion layer that the invention according to used photographic sensitive material ent holds a silver halide that is selected from the Group silver bromide, silver bromide iodide, silver chloride bromide iodide, silver chlorobromide and silver chloride. A preferred silver halide is silver bromide iodide or silver chlorobromide iodide which is 30 mol% or less Contains silver iodide. Silver bro is particularly preferred midiodide, which contains 2 to 25 mol% silver iodide.

The shape of the silver halide particles in the photogra phical emulsion is not particularly critical. she can be called regular shaped crystalline particles with cubic, octahedral or tetradecahedral Shapes, irregularly shaped particles, e.g. B. kugelför moderate particles, particles with crystal defects or be a mixture of the same.

The diameter of the silver halide particles can be inner half of the range from 0.1 µm or less to 10 µm (Projection surface). The range of particles size distribution can either be narrow (monodisperse emul sion) or broad (polydisperse emulsion).

Two or more silver halide emulsions can be used are made separately and then mixed together.

In addition, tabular particles with one aspect can be used ratio of at least 5 can be used according to the invention. The tabular particles can easily after a Ver drive will be made as it is in Cleve, "Photo graphy Theory and Practice "(1930), page 131, Gutoff, "Photographic Science and Engineering" Vol. 14, 248 to 257 (1970), U.S. Patents 4,434,226, 4,414,310 and 4,434,048 and in GB-PS 2,112,157. If the tabular particles are used, that is Increased opacity and the degree of spectral sensitivity ization is also increased in an advantageous manner, such as in the aforementioned U.S. Patent 4,434,226.

As for the crystal structure, it can be uniform be the halogen composition in the inner section of the crystal may be different from that in its outer section or it can be a laminar structure ture are present. These emulsion particles are in British Patent 1,027,146, U.S. Patent 3,505,068 and 4,444,877 and in Japanese Examined Patent Publication 143 331/1985. In addition, different chemical silver halides through epitaxial bonding with one another which can be connected or the silver halide can be with a other connection, such as B. silver rhodanide or lead oxide.

The photographic emulsion used in the present invention can with a known photographic sensitization dye are spectrally sensitized. aside from that may be a known antifoggant or a known one Stabilizer can be used to prevent a Fogging in the course of the production of the light sensitive material, its storage or its photographic processing or development or for Stabilization of the properties of the same. Examples for antifoggants and stabilizers and their ver Usages are in U.S. Patents 3,954,474 and 3,982,947, in Japanese Patent Publication 28 660/1977, in "Research Disclosure" 17,643 (December 1978), VIA & VIM and E.J. Birr, "Stabilization of Photographic Silver Halide Emulsions ", Focal Press (1974), be wrote.

The photosensitive material used in the present invention can for example hydroquinones, aminophenols and sulfonamidophenols as a color antifoggant or as a color mixing inhibitor contain. The photosensitive ones used in the present invention Materials can contain various discoloration inhibitors, such as B. organic inhibitors such as 5-hydroxycoumarans and spirocoumarans, and metal complex inhibitors such as Bis- (N, N-dialkyldithiocarbamato) nickel complexes contain.

The photosensitive materials used in the present invention may in combination with an ultraviolet radiation Absorber, such as B. a benzotriazole compound, use be det. Typical examples are given in "Research Dis closure ", 24 239 (July 1984) properly used photosensitive materials can one Filter dye or a water soluble dye contained in their hydrophilic colloid layer for the purpose the radiation or halation in hibition.

As a binder can be used in the photographically sensitive Layer or gelatin in the back layer Gelatin, a synthetic hydrophilic polymer and Like. Be used. A hardener such as B. a vinyl sulfone derivative, can be in a hydrophilic colloid layer be incorporated or it can be a vinyl polymer with a sulfinic acid salt in its side chain as hardening accelerator can be used.

The photosensitive material used in the present invention may be a Coating aid, an antistatic agent and a or more surfactants as used in Verbes Improvement of the lubricity, to prevent adhesion and to improve photographic properties (for example to accelerate development, to er aiming for a high contrast and for sensitization) used, included.

The photosensitive materials used in the present invention can in addition to the additives mentioned above, there are also various Contain additives that are suitable for photographic sensitive materials such as B. a stabilizer, an anti-discoloration agent, a developing agent, or a precursor to it, a development accelerator or a precursor thereof, a lubricant (lubricant tel), a mordant, a matting agent, an anti static agent and a plasticizer. Typical examples of these additions are in "Research Disclosure" 17,643 (December 1978) and 18716 (November 1976).

The inventive method can preferably for Processing of a high sensitivity photographic Color film with at least two emulsion layers that are sensitive to the same color, but that have different sensitivities on the Carrier are applied. The order of arrangement of the layers is usually the following: carrier → red sensitive layer → green sensitive layer → blue sensitive layer. In addition, a vice versa can also be used returned layer arrangement, which is a highly sensitive layer between emulsion layers with different color has sensitivities.

The process according to the invention is characterized in that the photosensitive material which contains at least one naphthol coupler of the general formula (I) given above and optionally the general formula (II) is exposed to light, then color-developed using a known process, washed with water if necessary and is treated in a bath with bleaching and fixing functions. The term "bath having bleaching and fixing functions" (hereinafter referred to as "bleaching and fixing bath") means a bath containing both a bleaching agent and a fixing agent. Suitable bleaching agents include those as are known per se, such as. B. compounds of polyvalent metals such as cobalt (III), chromium (III), chromium (IV) and copper (II) (z. B. Ferricyanide), peroxides, quinones and nitroso compounds; Dichromates; organic complex salts (e.g. amino polycarboxylic acids, such as complex salts of ethylenediaminetetra acetic acid and diethylenetriaminepentaacetic acid, amino polyphosphonic acids, phosphonocarboxylic acids and organophosphonic acids) of iron (III) and cobalt (III); organic acids such as citric acid, tartaric acid and malic acid; Persulfates; Hydrogen peroxide; and permanganates. Among them, the organic complex salts and persulfates of ferric iron are preferred from the viewpoints of rapid development and prevention of environmental pollution. Examples of the aminopolycarboxylic acids and aminopolyphosphonic acids and their salts useful for the formation of the organic complex salts of ferric iron include the following compounds:
Ethylenediaminetetraacetic acid
Diethylenetriaminepentaacetic acid
Ethylenediamine-N- (β-oxyethyl) -N, N ', N'-triacetic acid
1,2-diaminopropanetetraacetic acid
Triethylenetetraminehexaacetic acid
1,3-diaminopropanetetraacetic acid
Nitrilotriacetic acid
Nitrilotripropic acid
Cyclohexanediaminotetraacetic acid
1,3-diamino-2-propanol tetraacetic acid
Methyliminodiacetic acid
Iminodiacetic acid
Hydroxyliminodiacetic acid
Dihydroxyethylglycine ethyl ether diaminotetraacetic acid
Glycol ether diaminotetraacetic acid
Ethylenediaminotetrapropionic acid
Ethylenediaminodipropionacetic acid
Phenylenediamino tetraacetic acid
2-phosphonobutane-1,2,4-triacetic acid
1,3-diaminopropanol-N, N, N ', N'-tetramethylene phosphonic acid
Ethylenediamine-N, N, N ', N'-tetramethylene phosphonic acid
1,3-propylenediamine-N, N, N ', N'-tetramethylene phosphonic acid and
1-hydroxyethylidene-1,1'-diphosphonic acid.

Iron (III) complexes are among these compounds salts of ethylenediaminotetraacetic acid, diethylenetri aminopentaacetic acid, cyclohexanediaminotetraacetic acid, 1,2-diaminopropanetetraacetic acid, 1,3-diaminopropane tetraacetic acid, iminodiacetic acid and methylimino diacetic acid preferred because of its high bleaching power. According to the invention, these bleaching agents can also be used in Com bination can be used.

The amount of bleach is 0.04 to 1.0 mol, preferably 0.08 to 0.5 moles per liter of the fiction according to the bleach-fix bath used.

Examples of fixing agents used in the bleach-fixer Bad included include thiosulfates, such as sodium thiosulfate, ammonium thiosulfate, sodium ammonium thio sulfate and potassium thiosulfate, thiocyanates such as sodium thiocyanate, ammonium thiocyanate and potassium thiocyanate, Thiourea and thioethers. The amount of fixative is 0.3 to 4 moles, preferably 0.5 to 3 moles, per Liters of the bleach-fix solution. These fixatives can can also be used in combination.

Although the above bleach-fix bath in a basic different embodiment of the invention is used, even better effects can be achieved by using preparation of a bleaching bath in a previous stage. The term "bleach bath" used here stands for a Bath, which contains the bleach, but which is free of the fixative.

The bleach-fixing solution used in the present invention may be required If necessary, various additives in addition to the bleach and Fixatives included. Also, the bleach bath can contain the following additives: sulfites, such as sodium and Ammonium sulfites and pH regulators such as boron acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, Acetic acid and sodium acetate. You can either alone or in the form of a mixture of two or more of them be used. The bleach-fixing solution can also be others known additives useful in common bleaching solutions are, such as B. antifoam agents, and one or more anor ganic acids, organic acids and salts thereof with a pH regulating function, such as B. Sodium ace tat, sodium carbonate, potassium carbonate, phosphorous acid, Phosphoric acid, sodium phosphate, citric acid, sodium citrate and tartaric acid.

The amount of bleaching agent is 0.1 to 1 mole, preferably wise 0.2 to 0.5 mol, per liter of the invention Bleach bath. The pH of the bleach solution used will be preferably set to 4.0 to 8.0.

For examinations in which one or more bleach faster, selected from the group of compounds having a mercapto group or a disulfide bond, the Isothiourea derivatives and the thiazolidine derivatives were added to the bleach bath, it was found that a surface-active agent to the bleach bath in the conven can be added to conventional bleaching and fixing stages and that also an alkali metal halide, such as. B. Potassium iodide, potassium bromide or ammonium bromide, an ammonium halide, hydroxylamine, hydrazine and bisulfite adduct of Aldehyde compounds can be added.

The pH of the bleach-fixer used in the present invention solution is 4 to 8, preferably 6 to 7.5.

According to the invention, the bleaching time is preferably 20 seconds up to 4 min formulas (V) to (XIII) as shown below are used, the bleaching time is 20 seconds to 2 min. If the bleach accelerator is not used, the bleaching time is particularly preferably 1 to 4 minutes.

The bleach-fixing time is preferably from 20 seconds to 15 minutes, in particular 30 seconds to 10 minutes.

Between the bleach stage (bleach bath) and the bleach-fix stage (bleach-fix bath) can have a washing stage with water be provided. Even when washing with water in a very small bath in which the The amount of water introduced is very small the effects of the present invention do not at all impaired. The bleach-fixing bath can be two or more Baths include. Baths that cascade in a countercurrent are arranged system are particularly preferred.

It is preferred in that used in the present invention Bleach-fix bath a supplementary solution (regenerating solution). The complementary solution is one Solution that includes the required components (such as the bleach and fixative).

An overflow from the bleach bath can flow into the bleach-fixer solution to be introduced. The term used here "Overflow" stands for the used bleach solution that leaks from the bleach tank when the bleacher supplement solution is added to the bleach bath.

This way the process can be extremely economical be carried out as the concentration of the bleach with means in the bleach-fix bath to any desired value can be kept by the overflow from the bleach bath in the previous stage.

To prevent pollution, it is him required the amount of photographic waste flow fluid with a high biochemical oxygen demand (BOD) or chemical oxygen demand (COD) gladly. When the amount of waste liquid decreases the cost of recovery is decreased sets and the process can be economically advantageous adherent way to be carried out.

In the embodiment of the present invention, where the make-up solution in the bleach-fix solution is introduced when the overflow from the bleach bath, which was previously discarded into the bleach-fixer bad is introduced, the overflow serves as a medium that the supplementary solution up to a desired concentration tion diluted. Therefore, the supplement solution that is introduced into the bleach-fix bath, a concentrate te solution and as a result, the amount of Waste liquid can be reduced.

In conventional processes, there is a washing stage with Place water between the bleach bath and the fixer bath to see if the fixer has been contaminated by the Prevent bleach bath as this will contaminate the Cyan dye converted into a leuco dye, the the photographic properties are severely impaired. It was therefore assumed that the introduction of bleach solution in the fixing solution is very undesirable. Of the Basic idea of the present invention, the overflow from to mix with the bleach bath with the fixative Formation of the bleach-fix bath is therefore essential different from the basic idea of the conventional Procedure.

The amount of overflow from the bleach bath to be introduced into the bleach-fix bath, and the amount of the fixer solution to be added to the bleach-fix bath as a supplement at the same time, are adjusted so that the concentrations of the bleaching agent and the fixing agent in the Bleach-fix in the above ranges are kept constant. The amount is preferably 150 to 900 ml per m ^{2 of} the light-sensitive material, although it varies depending on the concentration of the bleach in the overflow to be introduced and the concentration of the supplementary fixing agent.

The supplementary solution to the bleach used in the invention Fixing bath to be added can be a known one Fixing agents, such as. B. ammonium thiosulfate or sodium thiosulfate and any of the additives included in the fixing solution solution can be added, such as. B. sulfites, bisulfites, Buffers and chelating agents. The concentrations of the components in the supplementary solution can be such a be put that when they overflow with diluted from the bleach bath, the concentrations of the Components of the same are those that are responsible for bleaching Fixing bath are required. The concentrations are usually higher than those of usual supplementary solutions sings. As a result, the amount of carried out Fluid decreases and the recovery becomes it eases.

The concentration of the fixative in the in the bleach The supplementary solution to be introduced in the fixing bath is preferred wise 0.5 to 4 mol / l, in particular 1 to 3 mol / l.

The pH of the supplement solution is preferably 6 to 10, in particular 7 to 9. An addition, such as. B. a Iron (III) aminopolycarbonate complex salt, an ammonium halo genide or an alkali metal halide such as ammonium bromide, Sodium bromide or sodium iodide can also be added be practiced.

The overflow from the bleach bath can go into the bleach-fix bath be introduced by putting an overflow pipe of the bleach the bath tank directly with the bleach-fix tank ver binds to introduce the overflow into the bleach-fix bath or alternatively by saving the over run outside the container, mixing the same with the the solution containing the fixing agent and introducing the Mix in the bleach-fix tank. With another Procedure are the overflow and the fixative ge separated from each other.

The bleach accelerating agent added to the bleach bath or Bleach-fix bath added according to the present invention can be selected from the group that consists from compounds with a mercapto group or a Di sulfite bond, thiazolidine derivatives, thiourea derivatives Isothiourea derivatives, which have a bleaching accelerator have an effect. Among these are compounds of the General formulas (V) to (XII) given below preferred.

Compounds of the general formula (V)

where mean:
R ₂₁ and R ₂₂ , which can be the same or different, each represent a hydrogen atom, a substituted or unsubstituted lower alkyl group (with preferably 1 to 5 carbon atoms, in particular a methyl, ethyl or propyl group) or an acyl group (preferably with 1 to 3 carbon atoms, in particular an acetyl or propionyl group) and
n is an integer from 1 to 3
or in which R ₂₁ and R _{22 can} together form a ring.

R ₂₁ and R ₂₂ each particularly preferably represent a substituted or unsubstituted lower alkyl group.

Examples of the substituents of R ₂₁ and R ₂₂ include hydroxyl, carboxyl, sulfo and amino groups.

Compounds of the general formula (VI)

wherein R ₂₃ and R _{24 have} the same meanings as R ₂₁ and R ₂₂ in the above general formula (V) and n is an integer from 1 to 3. R ₂₃ and R ₂₄ can form a ring. R ₂₃ and R ₂₄ each particularly preferably represent a substituted or unsubstituted lower alkyl group.

Examples of the substituents of R ₂₃ and R ₂₄ include hydroxyl, carboxyl, sulfo and amino groups.

Compounds of the general formulas (VII), (VIII) and (IX)

wherein R _{25 is} a hydrogen atom, a halogen atom (e.g. a chlorine or bromine atom), an amino group, a substituted or unsubstituted lower alkyl group (preferably having 1 to 5 carbon atoms, especially a methyl, ethyl or propyl group) or an amino group with an alkyl group (e.g. a methylamino, ethylamino, dimethylamino or diethylamino group).

Examples of the substituents on R ₂₅ include hydroxyl, carboxyl, sulfo and amino groups.

Compounds of the general formula (X)

wherein R ₂₆ and R ₂₇ , which may be the same or different, each represent a hydrogen atom, a substituted or unsubstituted alkyl group (preferably a lower alkyl group such as a methyl, ethyl or propyl group), a substituted or unsubstituted one Phenyl group or a substituted or unsubstituted heterocyclic group (ie a heterocyclic group with one or more heteroatoms such as nitrogen, oxygen and sulfur atoms) (such as a pyridine, thiophene, thiazolidine, benzoxazole -, Benzotriazole, thiazole or imidazole ring), R _{28 is} a hydrogen atom or a substituted or unsubstituted lower alkyl group (with preferably 1 to 3 carbon atoms, such as, for example, a methyl or ethyl group) and R _{29 is} a hydrogen atom or a Mean carboxyl group.

Examples of the substituents from R ₂₆ to R ₂₈ are hydroxyl, carboxyl, sulfo, amino and lower alkyl groups.

Compounds of the general formula (XI)

wherein R ₃₀ , R ₃₁ and R ₃₂ , which can be the same or different, each represent a hydrogen atom or a lower alkyl group (preferably having 1 to 3 carbon atoms, such as, for example, a methyl or ethyl group) or wherein R ₃₀ and R ₃₁ or R _{32 can} together form a ring,
X is an amino, sulfo, sulfonic acid or carboxyl group which can be substituted by a lower alkyl group, such as. B. a methyl group, or an alkoxyalkyl group, such as. B. an acetoxymethyl group,
where R ₃₀ to R _{32 are} preferably a hydrogen atom or a methyl or ethyl group and X is preferably an amino or dialkylamino group.

Compounds of the general formula (XII)

wherein R ₄₁ and R ₄₂ each represent a hydrogen atom or a hydroxyl group, a substituted or unsubstituted amino group, carboxy group, sulfo group or substituted or unsubstituted alkyl group, R ₄₃ and R ₄₄ each represent a hydrogen atom or a substituted or unsubstituted alkyl group or a substituted or unsubstituted acyl group or wherein R ₄₃ and R ₄₄ together can form a ring, M represents a hydrogen atom, an alkali metal atom or an ammonium group and n represents an integer from 2 to 5.

Compounds of the general formula (XIII)

wherein XN or CR, R, R ₅₁ , R ₅₂ and R ₅₃ each represent a hydrogen atom or a halogen atom or an amino, hydroxyl, carboxyl, sulfo or substituted or unsubstituted alkyl group, R ₅₄ and R ₅₅ each represent a hydrogen atom or a substituted or unsubstituted alkyl or acyl group or in which R ₅₄ and R _{55 can} together form a ring, with the proviso that not both radicals R ₅₄ and R ₅₅ can be a hydrogen atom at the same time, and n is an integer from 0 to 5 represents.

Preferred examples of compounds of the general formulas (V) to (XIII) given above are the following:

The above compounds can be prepared according to a known one Process to be synthesized. In particular, the Ver bonds of the general formula (V) by a process as described in U.S. Patent 4,285,954, in G. Schwarzenbach et al. "Helv. Chim. Acta", 38, 1147 (1955) or from R.O. Clinton et al. "J. Am. Chem. Soc.", 70, 950 (1948). The connections of the general Formula (VI) can be prepared by a process as disclosed in Japanese Patent Publication 95630/1978 is written. Compounds of the general formulas (VII) and (VIII) can be prepared by a process as disclosed in Japanese Patent Publication 52 534/1979 is written. The compounds of the general formula (IX) can be prepared by a process as described in Japanese Patent Publications 68 568/1976, 70 763/1976 and 50 169/1978. The connections of the general my formula (X) can be prepared by a process as disclosed in Japanese Patent Publication 9854/1978 or in Japanese Patent Application No. 88938/1983 be is written. The compounds of the general formula (XI) can be prepared by a process as described in Japanese Examined Patent Publication 94 927/1978 be is written. The compounds of the general formula (XII) can easily be prepared by alkylating 2,5-di mercapto-1,3,4-thiadiazole by a method as described in "Advanced in Heterocyclic Chemistry", 9, 165-209 (1968), is described. The compounds of the general formula (XIII) can be prepared by a process such as described by A. Wohl, W. Marchwald in "Ber." 22, 568 (1889), by M. Freund in "Ber.", 29, 2483 (1896), by A.P.T. Easson et al. in "J. Chem. Soc.", 1932, 1806 and by R.G. Jones et al. in "J. Am. Chem. Soc.", 71, 4000 (1949).

The amount of the compounds having a mercapto group or a disulfide bond in the molecule, the thiazoline derivatives or the isothiourea derivatives to be added to the solution having the bleaching function varies depending on the photographic material to be processed, the processing temperature and the time required for the processing . However, it is usual to 1 × 10⁻ ⁵ admit to 10⁻ ¹ mole, preferably 1 × 10⁻ ⁴ to 5 × 10⁻ ² moles per liter of the processing solution.

These compounds are usually the treatment solution added by putting them in water or in an alka dissolves in a mixture of organic acid solvents. The conn But applications can also be in the form of a powder directly to the Bleach bath can be added without affecting the bleach acceleration effects are impaired as a result.

According to the invention, a simple method can also be used be, that includes the treatment in the bleach bath, which is only washing with water follows, or it can be another Res procedure to be applied that only raises awareness treatment, the essential step being washing omitted with water.

In the step of washing with water, various be known compounds to prevent precipitation or to Stabilization of the wash water can be used. Too suitable th examples include chelating agents such. B. inorganic Phosphoric acids, aminopolycarboxylic acids and organic phosphonic acids, germicides and antifungal agents, e.g. B. such as see them in "J. Antibact. Antifung. Agents", Volume 11, No. 5, Sci th 207-223 (1983) and in Hiroshi Horiguchi, "Bokin Bobai no Kagaku (Antibacterial and Antifungal Chemistry) " are, metal salts, such as. B. Magnesium and aluminum salts, Alkali metal and ammonium salts and surfactants to prevent charging during drying or Ent stand of marks during drying. Besides, can also Compounds as described in "Phot. Sci. Eng.", Vol. 6, 344 bis 359 (1965), can be used. Among these are the chelating agents and the antibacterial and Antifungal agents particularly effective.

When washing with water, two or more containers (e.g. 2 to 9 containers) in a multi-stage countercurrent washing system used to contain water used for washing save. The step of washing with water can be substituted through a multi-stage countercurrent stabilization stage, such as it is described in Japanese Patent Publication 8543/1982 ben is. There are various compounds in the stabilization bath applications to stabilize the image. Too typical Examples include buffers for adjusting the pH of the Films to, for example, a value from 3 to 8 (such as Borates, metaborates, borax, phosphates, carbonates, potassium hydro xide, sodium hydroxide, aqueous ammonia, monocarboxylic acids, Dicarboxylic acids and polycarboxylic acids, which are in the form of a Mi can be used) and aldehydes, such as. B. Forma lin. Examples of other suitable additives include Chelating agents (such as inorganic phosphoric acids, amino polycarboxylic acids, organic phosphonic acids, aminopolyphosphonic acids and polyphosphonocarboxylic acids), germicides (such as Thiazole compounds, isothiazole compounds, halogenated Phenols, sulfanylamide and benzotriazole), surface-active Medium, fluorescent brightener and hardener. You can alone or in the form of a mixture of two or more who are used those that have the same or different effects on point.

After the treatment, an ammonium salt, such as. B. ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium phosphate, Ammonium sulfite or ammonium thiosulfate, as a pH regulator used to improve image retention.

When treating a color photographically sensitive Materials can usually run through after fixing performed stages (i.e. water washing and stabili sieren) can be replaced by the stabilization mentioned above level and the washing level (the water-saving washing level). When a 2-equivalent magenta coupler is used, can in such a case formalin in from the stabilizing bath removed.

The treatment solutions are according to the invention at a Temperature used from 10 to 50 ° C. Although the standard temperature is within the range of 33 to 38 ° C, a higher temperature can be applied to the treat to accelerate treatment and to shorten the duration of treatment zen or, on the contrary, it can have a lower temperature be turned to the quality of the image or the stabilization to improve the quality of the treatment solution. To save of silver in the photographic material may be a cobalt ver stronger or a hydrogen peroxide booster like him in DE-PS 22 26 770 or in US-PS 3,674,499 ben is to be used.

The treatment time in each treatment stage can be shortened be compared to the standard time, if necessary, to the extent that this does not cause any disturbances.

The color photographic silver used in the present invention halide material can be a color developing agent or a Precursors of it are incorporated so as to treatment facilitate or speed up. The forerunner is in one such a case from the standpoint of the stability of the photographi preferred from the point of view of the material. For examples of Precursors of the developer compounds according to the invention usable include indoaniline compounds as described in U.S. Patent 3,342,597, Schiff bases such as see them in U.S. Patent 3,342,599 and Research Disclosure 14,850 (August 1976) and 15 159 (November 1976), Aldol compounds, as they are in "Research Disclosure" 13 924, are described, metal salt complexes, as they are in the U.S. Patent No. 3,719,492, urethane compounds as described in U.S. Pat Japanese Examined Patent Publication 135 628/1978 and various salts as described in the above Japanese Examined Patent Publications 6235/1981, 16 133/1981, 59 232/1981, 67 842/1981, 83 734/1981, 83 735/1981, 83 736/1981, 89 735/1981, 81 837/1981, 54 430/1981, 106 241/1981, 107 236/1981, 97 531/1982 and 83 565/1982 are described.

The color photographic silver used in the present invention halide materials may contain 1-phenyl-3-pyrazolidones, to speed up color development. Typical examples for these compounds are pre-checked in Japanese Patent publications 64 339/1981, 144 547/1982, 211 147/1982, 50 532/1983, 50 536/1983, 50 533/1983, 50 534/1983, 50 535/1983 and 115 438/1983.

In the case of continuous treatment, a stable, one uniform finish can be obtained by the fact that the together composition of the treatment solutions keeps stable through ver application of the respective supplementary solutions. The amount of Complementary solutions can be reduced to half or less Standard quantity can be reduced in order to reduce costs wrestle.

If necessary, a heating device can be installed in each bathroom. a temperature sensor, a liquid level sensor, a Circulation pump, a filter, an overflow cover, a rubber dryer and the like. Be provided.

The present invention can be used to treat various apply light-sensitive color photographic materials can be used, for example for general and cinema color negatives films, reversal color films for slide and television, color papers, color positive films, and reversal color papers. The present The invention can be used for the treatment of photosensitivity lichen black and white materials are applied in which a three-color coupler mixture is used, as in Research Disclosure 17123 (July 1978). Among them, it is particularly preferred to use the present Er application for the treatment of negative color films.

The invention is further illustrated by the following examples purifies, but is not limited to it.

example 1

Multilayer color negative film samples were made the layers having the composition given below genes on a triacetyl cellulose film support included:

First layer Antihalation layer (antihalation layer)

A layer of gelatin, the black colloidal silver contains.

Second shift Intermediate layer

A gelatin layer that is dispersed and emulsified Contains 2,5-di-t-octylhydroquinone.

Third layer Red sensitive emulsion layer with a low sensitivity Silver bromide iodide emulsion (with 5 mol% silver iodide)

Amount of silver applied: 1.6 g / m ² Sensitizing Dye I: 6 x 10⁻ ⁴ mol per mol of silver Sensitizing dye II: 1.5 x 10⁻ ⁴ mol per mol of silver Coupler (see Table I): 0.04 moles per mole of silver Coupler EX-1: 0.003 moles per mole of silver Coupler EX-2: 0.0006 moles per mole of silver

Fourth layer Red sensitive emulsion layer with a high sensitivity Silver bromide iodide emulsion (with 10 mol% silver iodide)

Amount of silver applied: 1.4 g / m ² Sensitizing Dye I: 3 x 10⁻ ⁴ mol per mol of silver Sensitizing dye II: 1.2 x 10⁻ ⁴ mol per mol of silver Coupler (see Table I): 0.02 moles per mole of silver Coupler EX-1: 0.0016 moles per mole of silver

Fifth layer Intermediate layer

The same as the second layer.

Sixth layer Green-sensitive emulsion layer with a low sensitivity Monodisperse silver bromide iodide emulsion (with 4 mol% silver iodide)

Amount of silver applied: 1.2 g / m ² Sensitizing Dye III: 3 x 10⁻ ⁴ mol per mol of silver Sensitizing Dye IV: 1 × 10⁻ ⁴ mol per mol of silver Coupler EX-3: 0.05 moles per mole of silver Coupler EX-4: 0.008 moles per mole of silver Coupler EX-2: 0.0015 moles per mole of silver

Seventh layer Green-sensitive emulsion layer with a high sensitivity Silver bromide iodide emulsion (with 10 mol% silver iodide)

Amount of silver applied: 1.3 g / m ² Sensitizing Dye III: 2.5 × 10⁻ ⁵ mol per mol of silver Sensitizing Dye IV: 0.8 × 10⁻ ⁵ mol per mol of silver Coupler EX-5: 0.017 moles per mole of silver Coupler EX-4: 0.003 moles per mole of silver Coupler EX-6: 0.003 moles per mole of silver

Eighth shift Yellow filter layer

A gelatin layer consisting of an aqueous gelatin solution containing yellow colloidal silver and 2,5-di-tert-octyl contains hydroquinone dispersed and emulsified therein.

Ninth shift Blue-sensitive emulsion layer with a low sensitivity Silver bromide iodide emulsion (with 6 mol% silver iodide)

Amount of silver applied: 0.7 g / m ² Coupler EX-7: 0.25 moles per mole of silver Coupler EX-2: 0.015 moles per mole of silver

Tenth shift Blue-sensitive emulsion layer with a high sensitivity Silver bromide iodide emulsion (with 6 mol% silver iodide)

Amount of silver applied: 0.6 g / m ² Coupler EX-7: 0.06 moles per mole of silver

Eleventh shift First protective layer Silver bromide iodide emulsion (with 1 mol% silver iodide, average particle diameter 0.07 µm)

Amount of silver applied: 0.5 g / m ² a gelatin layer containing the UV absorber UV-1, which is dispersed and emulsified therein.

Twelfth layer Second protective layer

A gelatin layer containing trimethyl methacrylate part Chen (diameter about 1.5 µm).

The compositions making up the respective layers became the gelatin hardener A-1 and a surfactant Agent added.

Compounds used to prepare the samples Sensitizing Dye I

Pyridinium salt of anhydro-5,5'-dichlo ro-3,3'-di- (γ-sulfopropyl) -9-ethylthiacarbocyanine hydroxide

Sensitizing dye II

Triethylamine salt of anhydro-9-ethyl-3,3'-di- (γ-sul fopropyl) -4,5,4 ', 5'-dibenzothiacarbocyanine hydroxide

Sensitizing Dye III

Sodium salt of anhydro-9-ethyl-5,5'-dichlo ro-3,3'-di- (γ-sulfopropyl) oxacarbocyanine

Sensitizing Dye IV

Sodium salt of anhydro-5,6,5 ', 6'-tetrachloro-1,1'-diethyl-3,3'-di- (β- [β- (γ-sulfopropyl) ethoxy] ethylimidazolocarbocyanine hydroxide)

The thus prepared color photographic light-sensitive material was subjected to gray wedge (step wedge) exposure (25 CMS) using a tungsten light source at a color temperature set at 4,800 ° C. with a filter, and then it was subjected to the processing conditions shown below 38 ° C developed:

Color developing: 3 min 15 sec Bleach-fix: see Table I. Washing with water: 1 min 40 sec Stabilize: 40 min

The compositions of those used in the respective stages Treatment solutions were as follows:

Color developer

Diethylenetriaminepentaacetic acid: 1.0 g 1-hydroxyethylene-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: ad 1 l PH value: 10.00

Bleach-fix solution

Iron (III) ammonium ethylenediaminetetraacetate: 80.0 g Disodium ethylenediaminetetraacetate: 5.0 g Sodium sulfite: 12.0 g aqueous ammonium thiosulphate solution (70%): 240 ml aqueous ammonia (28%): 10.0 ml Water: ad 1 l PH value: see table

stabilizer

Formalin (37% w / v): 2.0 ml Polyoxyethylene-p-monononylphenyl ether (average degree of polymerization 10): 0.3 g Water: ad 1 l

The gradations of the above treated or ent wrapped samples examined.

In addition, these samples were made CN-16 using the Fuji Color process treated (this procedure includes color developing (3 min 15 sec), bleaching (6 min 30 sec), washing with water (2 min 10 sec), fixing (4 min 20 sec), washing with Water (3 min 15 sec), stabilizing (1 min 5 sec) and drying; Treatment temperature 38 ° C) and their gradations were also examined. The results obtained were compared with the results of the above samples.

The results of the comparison are given as the difference between the results obtained after treatment were, and those who were after standard treatment (CN-16 treatment) as shown in Table I. If the difference between the table I specified gradient and 0 greater is, the deviation from that according to the standard procedure is he keep gradients large and the photographic properties are bad.

The gradient was determined as follows:
Gradient: the amount of exposure was determined which was required for the sample treated according to the standard method in order to increase the density by 0.2 compared to the minimum density. The gradient was given as the difference between the density obtained in this exposure and the density obtained in this exposure + such an exposure that its logarithm was 1.5.

Table I shows the comparison compounds A, B and C to form the following a cyan dye the coupler:

Comparison compound A

Comparison compound B

Comparison compound C

From Table I it can be seen that when the erfindungsge a blue-green dye-forming coupler (the gen mean formulas (I) and, if necessary, additionally (II)), the cyan dyes are not converted into leuco dyes and that excellent photographic properties are obtained, while with the conventional, a blue-green dye forming couplers the gradient of the R-layer decreases when the pH of the bleach-fix solution drops, as from the samples 5 and 6 can be seen.

Table I.

Example 2

The procedure described in Example 1 was repeated where this time iron (III) ammonium methylenediamine tetraacetate in the Bleach solution was used and the bleach-fix solution through Iron (III) ammonium diethylenetriamine pentaacetate was replaced. The results were similar to those obtained in Example 1 had been held.

Example 3

The same color photographic light-sensitive material as in Example 1 was exposed to light in the same manner as in Example 1 and treated under the following conditions:

Color developing: 3 min 15 sec Bleach-fix: 4 min Washing with water: 1 min 40 sec Stabilize: 40 sec

The compositions of those used in the respective stages Treatment solutions were as follows:

Color developer

The same color developer as in Example 1 was used.

Bleach-fix solution

Iron (III) ammonium ethylenediaminetetraacetate: 80.0 g Disodium ethylenediaminetetraacetate: 5.0 g Sodium sulfite: 12.0 g aqueous ammonium thiosulphate solution (70%): 240 ml aqueous ammonia (28%): 10.0 ml Bleach accelerator *): 1 × 10⁻ mole of ² Water: ad 1 l PH value: vl. Table II

*) Compound VI- (1) was used as a bleach accelerator.

stabilizer

The same stabilizer as in Example 1 was used.

The gradients of the samples treated as above are expressed as differences rence to one obtained by the standard method Gradient indicated. From Table II it can be seen that then, when the cyan couplers of the invention (general formulas (I) if necessary together with (II)), the blue-green dyes were not converted into leuco dyes and excellent photo graphic properties could be obtained even if the bleach accelerator was used or the bleach-fixer time has been shortened.

The same test as above was repeated, this time with as a bleach accelerator the compounds VII- (2) and VIII- (2) ver were applied. Similar results were obtained.

Example 4

The procedure described in Example 1 was repeated where at this time the composition of the bleach-fix solution as after has been changed. The results are in the given in Table III below.

As is apparent from Table III, the same effects as in Example 1 can be obtained even if the Fe ² ⁺ concentration in the bleach-fixing solution increases.

Bleach-fix solution

Iron (III) ammonium ethylenediaminetetraacetate: 64.0 g Iron (II) ammonium ethylenediaminetetraacetate: 16.0 g Disodium ethylenediaminetetraacetate: 5.0 g Sodium sulfite: 12.0 g aqueous ammonium thiosulphate solution (70%): 240 ml aqueous ammonia (28%): 11 ml Water: ad 1 l PH value: see Table III

The above bleach-fixing solution was made assuming the Operating conditions formulated.

Table III

Example 5

The procedure described in Example 1 was repeated where this time a bleach bath with the addition given below composition was provided before the bleach-fix bath and the Treatment conditions changed as indicated in Table IV became. The results are given in Table IV.

Bleach solution

Iron (III) ammonium ethylenediaminetetraacetate: 120 g Disodium ethylenediaminetetraacetate: 10.0 g aqueous ammonia (28%): 17.0 ml Ammonium nitrate: 10.0 g Ammonium bromide: 100 g Water: ad 1 l PH value: 6.5

From Table IV it can be seen that if the silver removal time to 4 minutes (1 min 30 sec for bleaching and 2 min 30 sec for the bleach-fixing) was decreased, the gradient of the R-layer as indicated in samples 1 and 2 has been reduced. However, if the cyan according to the invention dye couplers (general formulas (I), if appropriate together with (II)) are used the filter removal was accelerated, the blue-green Dyes were not converted to leuco dyes and it could obtain excellent photographic properties will.

Example 6

The procedure described in Example 5 was repeated where this time iron (III) ammonium ethylenediamine tetraacetate in the Bleach solution and in the bleach-fix solution by ferric ammonium diethylenetriamine pentaacetate was replaced. The result Nits were similar to those obtained in Example 5 had been.

Example 7

The same color-sensitive material as in Example 1 was exposed to light in the same manner as in Example 1 and then treated under the following conditions:

Color developing 3 min 15 sec bleaching 50 sec Bleach-fix 2 min 30 sec Wash with water 1 min 40 sec Stabilize 40 sec

The compositions of those used in the respective stages Treatment solutions were as follows:

Color developer

The same color developer as in Example 1 was used det.

Bleach solution

Iron (III) ammonium ethylenediaminetetraacetate: 120 g Disodium ethylenediaminetetraacetate: 10.0 g aqueous ammonia: 17.0 ml Ammonium nitrate: 10.0 g Ammonium bromide: 100 g (1.02 moles) Bleach accelerator VI- (1): 5 × 10 ^-3 moles Water: ad 1 l PH value: 6.5

Bleach-fix solution

Iron (III) ammonium ethylenediaminetetraacetate: 50.0 g Disodium ethylenediaminetetraacetate: 5.0 g Sodium sulfite: 12.0 g aqueous ammonium thiosulphate solution (70%): 240 ml aqueous ammonia (28%): 10.0 ml Ammonium bromide: 40 g PH value: 7.3

stabilizer

The same stabilizer as in Example 1 was used.

The gradients of the samples treated as above were below and the one in the highest density part of each sample the amount of remaining silver was determined by fluorescent X-ray lysis determined. The results are in Table V below specified.

From Table V it can be seen that when the bleaching The faster the bleaching solution was added, the bleaching time could be further shortened and the gradient of the R-layer was not decreased. The same test as above was done again fetches, this time the compound VII- (2) or VIII- (2) as Bleach was used. The gradient of the R layer was not degraded, although the silver removing effect was inferior to that of the compound VI- (1).

Example 8

The procedure described in Example 7 was repeated fetches, this time the composition of the bleach solution has been changed as indicated below. The results were the same as in Example 7.

Bleach solution

Iron (III) ammonium ethylenediaminetetraacetate: 120 g Disodium ethylenediaminetetraacetate: 12 g aqueous ammonia (28%): 10 ml Sodium sulfite: 2 g aqueous ammonium thiosulphate solution (70%): 10 ml Ammonium nitrate: 11g Ammonium bromide: 100 g Accelerator (IV) - (1). 5 × 10 ^-3 moles Water: ad 1 l PH value: 6.4

Example 9

The procedure described in Example 4 was repeated except that the compositions of the bleaching solution and the bleach-fixing solution were changed as shown below. The results are given in Table VI. It can be seen from Table VI that even when the concentration of Fe ² ⁺ in the bleaching solution and the bleach-fixing solution was increased, effects similar to those in Example 4 were obtained. (The silver removal effects were excellent and the blue-green dye was not converted to a leuco dye).

Bleach solution

Iron (III) ammonium ethylenediaminetetraacetate: 102 g Iron (II) ammonium ethylenediaminetetraacetate: 18.0 g Disodium ethylenediaminetetraacetate: 10.0 g aqueous ammonia (28%): 18.0 ml Ammonium nitrate: 10.0 g Ammonium bromide: 100 g Water: ad 1 l pH value (25 ° C): 6.5

Bleach-fix solution

Iron (III) ammonium ethylenediaminetetraacetate: 35.0 g Iron (II) ammonium ethylenediaminetetraacetate: 15.0 g Disodium ethylenediaminetetraacetate: 5.0 g Sodium sulfite: 12.0 g aqueous ammonium thiosulphate solution (70%): 240 ml aqueous ammonia (28%): 11.0 ml Water: ad 1 l pH value (25 ° C): 7.3

The above bleaching solution and the above bleach fixing solution were prepared assuming the Operating conditions.

Example 10

It became the same multilayer color negative film as made in Example 1, this time the coupler EX-1 was replaced by the coupler EX-10, and the right resulting film was the same procedure as in Example 1 described subject. The results were similar to those obtained in Example 1 was.

Example 11

The procedure described in Example 5 was repeated fetches, this time the one prepared in Example 10 Multilayer color negative film was used, and the results obtained were similar to those obtained in Example 5 had been obtained.

Example 12

The procedure described in Example 1 was repeated, this time the iron (III) ammonium ethylenediamine tetra acetate in the bleach-fix solution by the same molmen ge of iron (III) ammonium cyclohexanediamine tetraacetate was set. The results obtained are in the table VII indicated.

As is apparent from Table VII, the results were of Example 12 similar to those used in Example 1 had been received.

Example 13

The procedure described in Example 5 was repeated, this time the iron (III) ammonium ethylenediamine tetra acetate in the bleach solution and in the bleach-fix solution by the same molar amount of iron (III) ammonium cyclohexane diamine tetraacetate was replaced. The results obtained are given in Table VIII.

As is apparent from Table VIII, the results were se of Example 13 similar to those in Example 5 had been received.

Claims (7)

1. A process for the treatment of an exposed light-sensitive color photographic silver halide material, characterized in that a light-sensitive color photographic silver halide material which contains at least one cyan coupler of the general formula (I):
where mean:
R ₁ -CONR ₅ R ₆ , -NHCOR ₅ , -NHCOOR ₇ , -NHSO ₂ R ₇ , -NHCONR ₅ R ₆ or -NHSO ₂ NR ₅ R ₆ ,
R _{2 is} a substituent of the naphthol ring,
m is an integer from 0 to 3,
R _{3 is} a monovalent organic group,
X is a hydrogen atom or a group which can be split off by a coupling reaction with an oxidized primary aromatic amine developing agent,
R ₅ and R ₆ , which may be the same or different, each represent a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group,
R _{7 is} an aliphatic group, an aromatic group or a heterocyclic group,
where, when the value for m 2, the groups R _{2 can be the} same or different from one another or can be connected to one another to form a ring and R ₂ and R ₃ or R ₃ and X together can form a ring,
is treated in a bath having bleaching and fixing effects and containing 0.04 to 1.0 moles of bleaching agent and 0.3 to 4 moles of fixing agent per liter of bleach-fixing solution. 2. The method according to claim 1, characterized in that a Fixing and bleaching solution with a pH between 4.0 and 8.0 is used. 3. The method according to claim 1 and / or 2, characterized characterized that the color photographic Silver halide material the bath with a bleach and Fixing solution in a bleach-fixing time of 20 s to 15 min passes through. 4. The method according to at least one of claims 1 to 3, characterized in that the color photographic Silver halide material before bath with a bleach and Fixing effect going through a bleach bath. 5. The method according to claim 4, characterized in that the Bath with the bleaching and fixing effects of a fixer is formed in which the bleach solution from a bleach bath in a previous stage has been introduced. 6. The method according to claim 1, characterized in that an accelerator in an amount of 1 × 10⁻ × 10⁻ ^{5-1 1} mole per liter of the bleach-fixing solution is used. 7. The method according to at least one of claims 1 to 6, characterized in that the color photographic Silver halide material after bathing with a bleaching and fixing action, a washing step or a Through stabilization stage.