DE69630419T2 - A method of processing a silver halide color photographic light-sensitive material - Google Patents

Description

FIELD OF THE INVENTION

The present invention relates a method of processing a color photographic light-sensitive Silver halide material (hereinafter sometimes referred to as "photosensitive Material "). In particular, the invention relates to a processing method with improved adhesion of the processed photosensitive material, improved moist warm bleaching a yellow dye and an improved magnetic reproduction capacity of a photosensitive material having a magnetic recording layer, even if the processing over for a long time using a bleach, excellent biodegradability (spontaneous decomposability) having.

BACKGROUND OF THE INVENTION:

In general, they are fundamental Components of the photographic processing of a color photographic photosensitive silver halide material, a color development step and a desilvering step, and the photosensitive material is through these fundamental steps and more additional Steps using a processing device known as Autoprozessor is called, processed. In the desilvering step becomes the silver developed in the color development step by exposure an oxidizing agent (a bleaching agent) used in a processing solution Bleaching power is contained, oxidized, causing it to become a silver salt is, and further, the silver salt from the photosensitive Material by a means of dissolving silver ions in the Location is (a fixative), which in a processing solution with Fixing effect is included, removed.

On the other hand, with regard to global environmental protection after using materials with Good biodegradability requires, as a step against Materials that are hardly biodegraded in nature, such as for example, ethylenediamine-N, N, N ', N'-tetraacetic acid and 1,3-propanediamine-N, N, N ', N'-tetraacetic acid, hitherto generally referred to as Bleaching agents were used. Materials with good biological Degradability include diamines type compounds as described in JP-A-313752/1992 ("JP-A" means an "unaudited published Japanese patent application ") as well as monoamino type compounds as disclosed in JP-A-265159/1993 and JP-A-161065/1994.

Since the nitrogen component in a processing solution an environmentally harmful Element is the monoamine compounds, the less nitrogen components contain, among these materials with good biodegradability preferred from the point of view of environmental protection. There were However, the following facts were found: When a photosensitive Material over a long time using a monoamine compound is processed with good biodegradability, the processed photosensitive material sometimes sticky and therefore the problems that occur Color negative film is difficult to remove from the envelope, the referred to as "nega sheet"; and further, such monoamine compounds tend to deteriorate the moist-warm bleaching of the yellow dye among the imaging Dyes.

Further, with respect to a photosensitive Material having a magnetic recording layer as in international publication WO 90/04205 discloses that such monoamine compounds the readout capacity significantly reduce the magnetic record. JP-A-95318/1994 describes the processing of the photosensitive material with a magnetic recording layer with a bleaching solution, the a ferric complex salt of an aminopolycarboxylic acid. Even though this publication the effects of change the density of the processed photosensitive material in the course the time under damp heat and storage stability the solution describes, it does not say anything about the influence on the readout capacity of the magnetic Recording.

In EP-A-611 990 is a photographic Fixative composition and a method of processing a silver halide photographic material using the same described. The photographic composition with fixing effect includes a specific sulfur-containing compound. Furthermore the composition also comprises a bleaching agent as the main component, the inorganic compounds or partially organic compounds could be, such as aminopolycarboxylic acid iron (III) complex salts and aminopolyphosphoric acid iron (III) complex salts.

JP-A-61050140 describes a method for processing a color photographic sensitive silver halide material using a bleach or bleach the one specific iron (III) complex salt an organic acid and contains a particular compound. The particular connection is selected from nicotinic acid and benzoic acid derivatives.

EP-A-588 289 discloses a process for processing an imagewise exposed photographic silver halide material comprising the use of a processing composition having a bleaching action which comprises as bleaching agent a metal chelate compound of a chelating compound and a metal lion contains.

The mechanisms of these phenomena were not yet clarified, However, it is believed that they are different Adherence of the components of the processing solution to the processed photosensitive Material could be caused.

SUMMARY OF THE INVENTION:

An object of the invention is the provision a process for processing a color photographic light-sensitive Silver halide material through which the adhesion of the processed photosensitive Material and the wet-warm bleaching of the dye does not deteriorate even if processing is taking place for a long time Use of a material with excellent biodegradability carried out becomes.

Another object of the invention is the provision of a method that the readout capacity of the magnetic Recording does not decrease when a photosensitive material is processed with a magnetic recording layer thereafter.

Other and more goals, characteristics and advantages of the invention will become apparent from the following description more clearly visible.

DETAILED DESCRIPTION THE INVENTION:

The above inventive objects are achieved by the subsequent processing method that represents:

worin R ein Wasserstoffatom, eine aliphatische Kohlenwasserstoffgruppe, eine Arylgruppe oder eine heterocyclische Gruppe ist; L₁ und L₂ sind jeweils eine Alkylengruppe; und M₁ und M₂ repräsentieren jeweils ein Wasserstoffatom oder ein Kation; Allgemeine Formeln (A) bis (I):

worin R₁, R₂, R₃, R₄, R₅, R₇ und R₈ jeweils ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe repräsentieren; R₆ ist ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Sulfogruppe, eine Sulfamoylgruppe, eine Hydroxylgruppe, ein Halogenatom, eine Alkoxygruppe oder eine Thiazolylgruppe; L₃ und L₄ repräsentieren jeweils eine Alkylengruppe oder eine Arylengruppe; R₉, R₁₀ und R₁₁ repräsentieren jeweils ein Halogenatom oder eine Alkylgruppe; R₁₂ und R₁₃ repräsentieren jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe oder einen stickstoffhaltigen heterocyclischen Rest; R₁₄ und R₁₅ repräsentieren jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe oder eine Arylgruppe, mit der Massgabe, dass R₁₄ und R₁₅ unter Bildung eines Benzolrings aneinander gebunden sein können; R₁₆ ist ein Wasserstoffatom oder eine Alkylgruppe; R₁₇ ist eine Alkylgruppe oder eine Arylgruppe; Y ist ein Halogenatom; Z₁ ist eine Gruppe von Nichtmetallatomen, die zur Vervollständigung eines Thiazolylrings erforderlich ist; Z₂ ist eine Gruppe von Nichtmetallatomen, die zur Vervollständigung eines 6-gliedrigen Kohlenwasserstoffrings erforderlich ist; n ist 0 oder 1; m ist 1 oder 2; und k ist eine ganze Zahl von 3–20;
und die Verarbeitungslösung mit Bleichwirkung enthält ferner mindestens eine Verbindung der allgemeinen Formel (J):

worin Q eine Gruppe von Nichtmetallatomen ist, die zur Vervollständigung eines heterocyclischen Rings erforderlich ist; p ist 0 oder 1; und Ma ist ein Wasserstoffatom oder ein Kation.A method of processing a silver halide color photographic light-sensitive material, the method comprising the steps of color development of a silver halide color photographic light-sensitive material, and then desilvering and further washing and / or stabilizing the same, wherein a bleaching-action processing solution in the desilvering step is a ferric complex salt of at least one compound of general formula (X) as shown below, and further a processing solution used in the desilvering step or subsequent steps, at least one compound of the general formulas (A) to (I) shown below or at least one aminoglycoside, selected from gentamicins, amikacin, tobramicin, dibekacin, albekacin, micronomicin, isepamicin, sisomicin, netilmicin and astromicin, contains: General formula (X):

wherein R is a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group; L ₁ and L ₂ are each an alkylene group; and M ₁ and M ₂ each represent a hydrogen atom or a cation; General formulas (A) to (I):

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ and R ₈ each represents a hydrogen atom, an alkyl group or an aryl group; R ₆ is a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxyl group, a halogen atom, an alkoxy group or a thiazolyl group; L ₃ and L ₄ each represent an alkylene group or an arylene group; R ₉ , R ₁₀ and R ₁₁ each represents a halogen atom or an alkyl group; R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an aryl group or a nitrogen-containing heterocyclic group; R ₁₄ and R ₁₅ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, with the proviso that R ₁₄ and R ₁₅ may be bonded to each other to form a benzene ring; R ₁₆ is a hydrogen atom or an alkyl group; R ₁₇ is an alkyl group or an aryl group; Y is a halogen atom; Z ₁ is a group of non-metal atoms required to complete a thiazolyl ring; Z ₂ is a group of non-metal atoms required to complete a 6-membered hydrocarbon ring; n is 0 or 1; m is 1 or 2; and k is an integer of 3-20;
and the processing solution having bleaching action further contains at least one compound of the general formula (J):

wherein Q is a group of non-metal atoms necessary to complete a heterocyclic ring; p is 0 or 1; and Ma is a hydrogen atom or a cation.

worin L₁ eine Alkylengruppe ist; M₁ ist ein Wasserstoffatom oder ein Kation; und Ma₁ und Ma₂ repräsentieren jeweils ein Wasserstoffatom oder ein Kation; Allgemeine Formeln (A) bis (I):

worin R₁, R₂, R₃, R₄, R₅, R₇ und R₈ jeweils ein Wasserstoffatom, eine Alkylgruppe oder eine Arylgruppe repräsentieren; R₆ ist ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe, eine Nitrogruppe, eine Carboxylgruppe, eine Sulfogruppe, eine Sulfamoylgruppe, eine Hydroxylgruppe, ein Halogenatom, eine Alkoxygruppe oder eine Thiazolylgruppe; L₃ und L₄ repräsentieren jeweils eine Alkylengruppe oder eine Arylengruppe; R₉, R₁₀ und R₁₁ repräsentieren jeweils ein Halogenatom oder eine Alkylgruppe; R₁₂ und R₁₃ repräsentieren jeweils ein Wasserstoffatom, eine Alkylgruppe, eine Arylgruppe oder einen stickstoffhaltigen heterocyclischen Rest; R₁₄ und R₁₅ repräsentieren jeweils ein Wasserstoffatom, ein Halogenatom, eine Alkylgruppe oder eine Arylgruppe, mit der Massgabe, dass R₁₄ und R₁₅ unter Bildung eines Benzolrings aneinander gebunden sein können; R₁₆ ist ein Wasserstoffatom oder eine Alkylgruppe; R₁₇ ist eine Alkylgruppe oder eine Arylgruppe; Y ist ein Halogenatom; Z₁ ist eine Gruppe von Nichtmetallatomen, die zur Vervollständigung eines Thiazolylrings erforderlich ist; Z₂ ist eine Gruppe von Nichtmetallatomen, die zur Vervollständigung eines 6-gliedrigen Kohlenwasserstoffrings erforderlich ist; n ist 0 oder 1; m ist 1 oder 2; und k ist eine ganze Zahl von 3–20.The present invention further relates to a process for processing a silver halide color photographic light-sensitive material, the process comprising the steps of color development of a silver halide color photographic light-sensitive material, and then desilvering, and further washing and / or stabilizing the same, wherein a bleaching-action processing solution in the desilvering step is an iron (III) Complex salt of at least one compound of the general formula (1-a) as shown below, and wherein a processing solution used in the desilvering step or subsequent steps, at least one compound of the general formulas (A) to (I) shown below or at least one aminoglycoside selected from gentamicins, amikacin, tobramicin, dibekacin, albekacin, micronomicin, isepamicin, sisomicin, netilmicin and astromicin, contains: General formula (1-a):

wherein L _{1 is} an alkylene group; M ₁ is a hydrogen atom or a cation; and Ma ₁ and Ma ₂ each represent a hydrogen atom or a cation; General formulas (A) to (I):

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ and R ₈ each represents a hydrogen atom, an alkyl group or an aryl group; R ₆ is a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxyl group, a halogen atom, an alkoxy group or a thiazolyl group; L ₃ and L ₄ each represent an alkylene group or an arylene group; R ₉ , R ₁₀ and R ₁₁ each represent a halogen atom or an alkyl group; R ₁₂ and R ₁₃ each represent a hydrogen atom, an alkyl group, an aryl group or a nitrogen-containing heterocyclic group; R ₁₄ and R ₁₅ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, with the proviso that R ₁₄ and R ₁₅ may be bonded to each other to form a benzene ring; R ₁₆ is a hydrogen atom or an alkyl group; R ₁₇ is an alkyl group or an aryl group; Y is a halogen atom; Z ₁ is a group of non-metal atoms required to complete a thiazolyl ring; Z ₂ is a group of non-metal atoms required to complete a 6-membered hydrocarbon ring; n is 0 or 1; m is 1 or 2; and k is an integer of 3-20.

According to the invention, the photosensitive Material developed with a color developing solution and then desilvered and is then further processed with a washing solution and / or a stabilizing solution.

In desilvering step becomes substantially with a processing solution, has the bleaching effect, the bleaching performed, and then the fixation is performed with a processing solution that Has fixing effect. The bleaching and fixation can be separated performed from each other can be as described above, or alternatively be carried out simultaneously with a bleach-fix solution, which has bleaching effect as well as fixing effect, what as Blixverarbeitung referred to as. These bleach, fix and blix processing can be done in a bath or in two or more baths.

• 1. Bleichen-Fixieren
• 2. Blix
• 3. Bleichen-Blix
• 4. Blix-Blix
• 5. Bleichen-Blix-Fixieren
• 6. Bleichen-Blix-Blix
• 7. Bleichen-Fixieren-Fixieren
• 8. Bleichen-Fixieren-Blix
• 9. Bleichen-Fixieren
• 10. Blix-Bleichen

According to the present invention, the bleaching-effect processing solution among the processing solutions used in the desilvering step means a processing solution containing a bleaching agent, and more specifically, both a bleaching solution and a blix solution. Hereinafter, specific embodiments are given for the desilvering processing applicable in the present invention, but the invention is not limited thereto.

• 1. bleach-fix
• 2. Blix
• 3. Bleaching Blix
• 4. Blix Blix
• 5. Bleaching-Blix fixation
• 6. Bleaching-Blix-Blix
• 7. Bleach-fix-fix
• 8. Bleach-Fix-Blix
• 9. bleach-fix
• 10. Blix bleaching

Between the above-described processes a washing step can be inserted his.

Hereinafter, the usable according to the invention Compound of the general formula (X) described in detail. The Number of carbon atoms as indicated below the carbon atoms of only one substituent.

Examples of those represented by R. aliphatic hydrocarbon group close an unbranched, branched or cyclic alkyl group preferably having 1-12, further preferably 1-10 and even more preferably 1-8 Carbon atoms, as well as an alkenyl group with preferably 2-12, on preferably 2-10 and even more preferred 2-7 Carbon atoms, and an alkynyl group preferably having 2-12, further preferably 2-10 and still more preferably 2-7 Carbon atoms, each substituted with a substituent could be.

Examples of such a substituent include an aryl group of preferably 6-12, more preferably 6-10 and more preferably 6-8 Carbon atoms (eg, phenyl, methylphenyl); an alkoxy group with preferably 1-8, more preferably 1-6 and more preferably 1-4 Carbon atoms (eg, methoxy, ethoxy); an aryloxy group with preferably 6-12, more preferably 6-10 and more preferably 6-8 Carbon atoms (eg phenyloxy); an acyl group with, preferably 1-12, more preferably 2-10 and particularly preferred 2-8 Carbon atoms (eg, acetyl); an alkoxycarbonyl group with preferably 2-12, more preferably 2-10 and more preferably 2-8 Carbon atoms (eg, methoxycarbonyl); an acyloxy group with preferably 1-12, more preferably 2-10 and more preferably 2-8 Carbon atoms (eg, acetoxy); an acylamino group with preferably 1-10, more preferably 2-6 and more preferably 2-4 Carbon atoms (eg, acetylamino); a sulfonylamino group with preferably 1-10, more preferably 1-6 and more preferably 1-4 Carbon atoms (eg, methanesulfonylamino); a sulfamoyl group with preferably 0-10, more preferably 0-6 and more preferably 0-4 Carbon atoms (eg, sulfamoyl and methylsulfamoyl); a carbamoyl group with preferably 1-10, more preferably 1-6 and more preferably 1-4 Carbon atoms (e.g., carbamoyl and methylcarbamoyl); an alkylthio group with preferably 1-8, more preferably 1-6 and more preferably 1-4 Carbon atoms (eg, methylthio and ethylthio); a sulfonyl group with preferably 1-8, more preferably 1-6 and more preferably 1-4 carbon atoms (eg, methanesulfonyl); a sulfinyl group of preferably 1-8, preferably 1-6 and especially preferably 1-4 Carbon atoms (eg, methanesulfinyl); a hydroxyl group Halogen atom (eg fluorine, chlorine, bromine and iodine), a cyano group, a sulfo group, a carboxyl group, a nitro group; and a heterocyclic group (eg, imidazolyl, pyridyl). These groups can further substituted. When two or more substituents exist are, they are identical or different.

Among the substituents listed above for the represented by R Aliphatic hydrocarbon groups are an alkoxy group, a Carboxyl group, a hydroxyl group and a sulfo group are preferred, and more preferred are a carboxyl group and a hydroxyl group.

Among those represented by R. aliphatic hydrocarbon groups, an alkyl group is preferred, more preferably a chain-shaped Alkyl group. Still further preferred examples include methyl, Ethyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1,2-dicarboxyethyl, 1-carboxy-2-hydroxyethyl, 2-carboxy-2-hydroxyethyl, 2-hydroxyethyl, 2-methoxyethyl, 2-sulfoethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2- (4-imidazolyl) ethyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl, 2-carbamoyl-1-carboxyethyl and 4-imidazolylmethyl; and especially preferred are methyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 1,2-dicarboxyethyl, 1-carboxy-2-hydroxyethyl, 2-carboxy-2-hydroxyethyl, 2-hydroxyethyl, 1-carboxypropyl, 1-carboxybutyl, 1,3-dicarboxypropyl, 1-carboxy-2-phenylethyl and 1-carboxy-3-methylthiopropyl.

Among those represented by R. Aryl groups are preferably an aryl group consisting of a single ring or a double ring each having 6-20 carbon atoms have (for example, phenyl and naphthyl); more preferred is a Phenyl group with 6-15 Carbon atoms and even more preferred is a phenyl group with 6-10 Carbon atoms.

The aryl group represented by R may have a substituent, and examples thereof include: an alkyl group having preferably 1-8, more preferably 1-6, and particularly preferably 1-4 carbon atoms (eg, methyl and ethyl); an alkenyl group having preferably 2-8, more preferably 2-6 and more preferably 2-4 carbon atoms (e.g., vinyl and allyl); and an alkynyl group having preferably 2-8, more preferably 2-6, and particularly preferably 2-4 carbon atoms (eg, propargyl) in addition to the above-listed groups as substituents for the aliphatic hydrocarbon group represented by R.

Among the substituents for by R represented Aryl group is an alkyl group, an alkoxy group, a hydroxyl group and a sulfo group is preferred, and more preferred are an alkyl group, a Carboxyl group and a hydroxyl group.

Specific examples of through R represented Aryl group include 2-carboxyphenyl and 2-carboxyphenyl.

The heterocyclic group represented by R is a residue of a 3- to 10-membered saturated or unsaturated heterocyclic compound containing at least one of N-, O- and Contains S atoms, and may be a single ring or a condensed ring.

Among the heterocyclic groups preferred is a 5- or 6-membered aromatic heterocyclic group, and a further preferred one Example is a 5- or 6-membered nitrogenous, aromatic, heterocyclic group. Even more preferred is a 5- or 6-membered one aromatic, heterocyclic group containing 1 or 2 nitrogen atoms contains.

Specific examples of the heterocyclic Group exclude pyrrolidinyl, piperidyl, piperazinyl, imidazolyl, Pyrazolyl, pyridyl and quinolyl. Preferred among these groups are an imidazolyl group and a pyridyl group.

The heterocyclic group represented by R may have a substituent, and examples thereof include an: an alkyl group having preferably 1-8, more preferably 1-6 and especially preferably 1-4 Carbon atoms (eg, methyl and ethyl); an alkenyl group with preferably 2-8, more preferably 2-6 and more preferably 2-4 Carbon atoms (eg, vinyl and allyl); and an alkynyl group with preferably 2-8, more preferably 2-6 and more preferably 2-4 Carbon atoms (eg propargyl), in addition to the groups listed above as substituents for which represented by R. aliphatic hydrocarbon group.

Among the substituents for by R represented heterocyclic group are an alkyl group, an alkoxy group, a hydroxyl group and a sulfo group are preferred; and more preferred are an alkyl group, a carboxyl group and a hydroxyl group.

R is preferably a hydrogen atom or an alkyl group with 1-8 Carbon atoms, and more preferably a hydrogen atom, a Methyl group, an ethyl group, a 1-carboxyethyl group, a 2-carboxyethyl group, a hydroxyethyl group or a 2-carboxy-2-hydroxyethyl group. Particularly preferred is a hydrogen atom.

The alkylene groups represented by L ₁ and L ₂ are the same or different and may be straight, branched or cyclic groups. Further, they may have a substituent, and examples thereof include: an alkenyl group having preferably 2-8, more preferably 2-6, and particularly preferably 2-4 carbon atoms (eg, vinyl and allyl); and an alkynyl group having preferably 2-8, more preferably 2-6, and particularly preferably 2-4 carbon atoms (eg, propargyl) in addition to the above-mentioned groups as substituents for the aliphatic hydrocarbon group represented by R.

Preferred among the substituents for the alkylene groups represented by L ₁ and L ₂ are an aryl group, an alkoxy group, a hydroxy group, a carboxyl group and a sulfo group; and further preferred are an aryl group, a carboxyl group and a hydroxyl group. Preferred alkylene groups represented by L ₁ and L ₂ are groups whose alkylene units have 1-6 carbon atoms and more preferably 1-4 carbon atoms. Even more preferred alkylene groups are substituted or unsubstituted methylene and ethylene groups.

Preferred specific examples for the Alkylene group include methylene, ethylene, trimethylene, methylmethylene, Ethylmethylene, n-propylmethylene, n-butylmethylene, 1,2-cyclohexylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethylmethylene, Hydroxymethylmethylene, 2-hydroxyethylmethylene, carbamoylmethylmethylene, Phenylmethylene, benzylmethylene, 4-imidazolylmethylmethylene and 2-methylthioethylmethylene; and more preferred are methylene, ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, Carboxyethylmethylene, hydroxymethylmethylene, benzylmethylene, 4-imidazolylmethylmethylene and 2-methylthioethylmethylene; and even more preferred are methylene, Ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, hydroxymethylmethylene and benzylmethylene.

The cation represented by M ₁ or M ₂ is an organic or inorganic cation, and examples thereof include: an alkali metal ion (eg, Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ ), an alkaline earth metal ion (e.g., Mg ²⁺ , Ca ²⁺ ), an ammonium ion (eg, ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-ethanediammonium), a pyridinium ion, an imidazolium ion and a phosphonium ion (eg, tetrabutylphosphonium). Preferred examples of M ₁ and M ₂ are an alkali metal ion and an ammonium ion, and more preferably Na ⁺ , K ⁺ and NH ₄ ⁺ .

If by the general formula (X) Compound has an asymmetric carbon atom in the molecule, is it preferable in view of the aspect of spontaneous decomposability that at least one asymmetric carbon atom of the L-type (L-form) is. When the compound has at least two asymmetric carbon atoms the more asymmetric the compound is, the more preferred it is Carbon atoms of the L-type are present in the molecule.

worin L₁ und M₁ die gleichen Bedeutungen haben wie in der allgemeinen Formel (X), und daher sind ihre bevorzugten Bedeutungen ebenfalls die gleichen; Ma₁ und Ma₂ haben jeweils die gleichen Bedeutungen wie M₂ in der allgemeinen Formel (X).Among the compounds of the general formula (X), those of the following general formula (1-a) are preferable: General formula (1-a):

wherein L ₁ and M _{1 have} the same meanings as in the general formula (X), and therefore their preferred meanings are also the same; Ma ₁ and Ma ₂ each have the same meanings as M ₂ in the general formula (X).

Among the compounds of the general formula (1-a), preferred are those wherein L _{1 is} a substituted or unsubstituted methylene or ethylene group, and M ₁ , Ma ₁ and Ma ₂ are any selected from a hydrogen atom, an alkali metal ion and an ammonium ion , More preferred compounds are those wherein L _{1 is} a substituted or unsubstituted methylene group having a total of 1-10 carbon atoms, including a substituent thereof, and M ₁ , Ma ₁ and Ma ₂ are any of a hydrogen atom, Na ⁺ , K ⁺ or NH ₄ ⁺ . Specific examples of the compound of the general formula (X) are shown below, but the examples are not limited to those shown.

The compounds marked therein with L indicate that the asymmetric carbon atom marked L. is of the L type. On the other hand, compounds without L mark one Mixture of D and L types.

The compounds listed above are those in which a hydrogen atom of the carboxyl group is substituted by a cation. In this case, the cation has the same meanings as M ₁ and M ₂ in the general formula (X).

The compounds represented by the general formula (X) represented, inventively used compound can be prepared by the methods as described, for example, in Journal of Inorganic and Nuclear Chemistry, Vol. 35, page 532 (1973), CH-PS 561 504, DE-A1-391 255, DE-A1-39 39 755, DE-A1-39 39 756, JP-A-265159/1993, JP-A-59422/1994 (Method for the preparation of the L-forms of the example compounds 1-42, 1-43, 1-46, 1-52 and 1-53 are in Synthesis Examples 1, 2, 3, 4 and 6), JP-A-95319/1994 (Process for the preparation of the L-forms of the example compounds 1-8, 1-11, 1-37, 1-38 and 1-40 are in Synthesis Examples 2 to 6), JP-A-161054/1994 and JP-A-161065/1994.

According to the invention, a ferric complex salt a compound of general formula (X) in the form of an isolated Compound are added. Alternatively, the connection may be of general formula (X) and an iron (III) salt (e.g., ferric nitrate and ferric chloride) in a solution side by side be added and these are used in the processing solution of Subjected to complex formation.

Furthermore, the invention used according to Compound of general formula (X) individually or in combination of two or more kinds thereof are used.

In the present invention, the compound of the general formula (X) may be used in slight excess over the amount necessary to form a complex salt of a ferric ion (e.g. In the 0.5, 1 or 2 times the molar amount per ferric ion). When the compound is used in such an excess amount, the excess amount is generally preferably controlled in the range of 0.01-15 mol%.

According to the invention, a ferric complex salt a compound of the general formula (X) in a processing solution, such as for example, a blix solution and a bleaching solution, be present, with a bleaching solution is preferred.

An iron (III) complex salt of a organic acid, that in an invention used processing solution is contained with bleaching action, may be in the form of an alkali metal salt or an ammonium salt. Exemplary alkali metal salts are a lithium salt, a sodium salt and a potassium salt. on the other hand are examples of Ammonium salts, an ammonium salt and a tetraethylammonium salt. According to the invention is the Concentration of ammonium ions in a processing solution with Bleaching effect preferably 0-0.4 mol / l and more preferably 0-0.2 minor.

According to the invention, as a bleaching agent the iron (III) complex salt a compound of the general formula (X) in combination with a Iron (III) complex salt of known compounds are used, such as ethylenediamine-N, N, N ', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, glycoletherdiaminetetraacetic acid and 1,3-propanediamine-N, N, N ', N'-tetraacetic acid and / or in combination with an inorganic oxidizing agent, such as potassium ferricyanide, a persulfonic acid salt, Hydrogen peroxide and a bromic acid salt. It is, however, in view on the environmental protection and handling safety according to the invention preferred that the compound of general formula (X) has a content of 70-100 mol%, more preferably 80-100 mol% and more preferably 100 mol% of the total bleaching agent.

The amount of the compound used according to the invention of the general formula (X) is generally 0.003-3 mol / l, preferably 0.02-2.0 mol / l, more preferably 0.05-1.0 mol / l and more preferably 0.08-0.5 mol / l. The total concentration the iron (III) complex salt in combination with the above however, inorganic oxidizing agent is preferably 0.005-0.030 minor.

A processing solution for the use according to the invention in the desilvering step or in the subsequent step contains at least one of the compounds of the general formulas described above (A) to (I), or at least one aminoglycoside selected from Gentamicins, amikacin, tobramicin, dibekacin, albekacin, micronomicin, Isepamicin, sisomicin, netilmicin and astromicin.

Gentamicins are preferred aminoglycosides.

The compounds of the general Formulas (A) to (I) are explained below.

Among the compounds of the general Formulas (A) to (I) are those of the general formulas (B), (G) and (H) are preferred; and more preferred are those of general formulas (G) and (H).

The alkyl groups R ₁ to R ₁₇ may be substituted with a substituent and are preferably straight, branched or cyclic alkyl groups having 1-30 carbon atoms, and specific examples include methyl, ethyl, octyl, dodecyl, tetradecyl and octadecyl.

The aryl groups for R ₁ to R ₈ may be substituted with a substituent and may have a single ring or a fused ring; and preferably they are groups of 6-20 carbon atoms, such as a phenyl group and a naphthyl group.

The sulfamoyl group for R ₆ may be substituted with a substituent, and preferably has 0 to 30 carbon atoms. Specific examples of the sulfamoyl group are sulfamoyl and N, N'-dimethylsulfamoyl. The alkoxy group for R ₆ may be substituted with one substituent and preferably has 1-30 carbon atoms. Specific examples of the alkoxy group are methoxy, ethoxy and octyloxy. The thiazolyl group for R ₆ may be substituted with a substituent in the 2-, 4- or 5-position.

The alkylene groups for L ₁ and L ₂ may be substituted with a substituent, and they are preferably straight, branched or cyclic groups having 1-10 carbon atoms, and specific examples include methylene, ethylene and propylene. The arylene groups for L ₁ and L ₂ may be substituted with one substituent, and they are preferably those having 6-10 carbon atoms, for example, phenylene and naphthylene.

The halogen atoms for R ₆ , R ₉ , R ₁₀ , R ₁₁ , R ₁₄ , R ₁₅ and Y are a chlorine atom, a fluorine atom and a bromine atom.

The nitrogen-containing heterocyclic radical groups for R ₁₂ and R ₁₃ are preferably 5 to 8-membered saturated or unsaturated groups, and preferred heteroatoms in addition to a nitrogen atom are an oxygen atom or a sulfur atom. Specific examples of the nitrogen-containing heterocyclic groups include 2-oxazolyl, 3-isoxazolyl, 3-pyrrolyl, 2-imidazolyl, 5-pyrazolyl, 5-isothiazolyl, 2-1,3,4-thiadiazolyl, 4-thiadiazolyl, 2-pyridyl and 2-pyrimidyl.

Z ₁ represents a group of non-metal atoms necessary to complete a thiazolyl ring which may be substituted with a substituent in the 2-, 4- or 5-position. Z ₂ is a group of non-metal atoms necessary to complete a 6-membered hydrocarbon ring, which may be saturated or unsaturated, such as a cyclohexane ring or a cyclohexene ring.

Examples of the above-mentioned substituents include the following: an alkyl group (eg, methyl, ethyl), an aralkyl group (e.g., phenylmethyl), an alkenyl group (e.g. Allyl), an alkynyl group, an alkoxy group (e.g., methoxy, Ethoxy), an aryl group (eg, phenyl, p-methylphenyl), an amino group (eg dimethylamino), an acylamino group (eg acetylamino), a sulfonylamino group (eg methanesulfonylamino), an ureido group, a urethane group, an aryloxy group (e.g., phenyloxy), a Sulfamoyl group (e.g., methylsulfamoyl), a carbamoyl group (e.g. Carbamoyl, methylcarbamoyl), an alkylthio group (e.g., methylthio), a Arylthio group (e.g., phenylthio), a sulfonyl group (e.g., methanesulfonyl), a Sulfinyl group (e.g., methanesulfinyl), a hydroxyl group Halogen atom (eg chlorine, bromine, fluorine), a cyano group, a sulfo group, a carboxyl group, a phosphono group, an aryloxycarbonyl group (eg phenyloxycarbonyl), an acyl group (eg acetyl, benzoyl), an alkoxycarbonyl group (e.g., methoxycarbonyl), an acyloxy group (eg, acetoxy), a carbonamido group, a sulfonamido group, and a nitro group.

In the general formula (A), R ₁ , R ₂ , R ₃ and R ₄ preferably each represent an alkyl group, and more preferably, at least one of R ₁ , R ₂ , R ₃ and R _{4 is} an alkyl group having 5-20 carbon atoms. Y is particularly preferably a chlorine atom.

In the general formula (B), R ₅ and R _{6 are} each preferably a hydrogen atom. n is preferably 0. Z ₁ is preferably a group of non-metal atoms necessary to complete an unsubstituted 4-thiazolyl ring.

In the general formula (C), R _{7 is} preferably a hydrogen atom, R ₈ is preferably an alkyl group, and more preferably an alkyl group having 5-20 carbon atoms.

In the general formula (D), L _{3 is} preferably an alkylene group having 5-10 carbon atoms. k is preferably 3-10.

In the general formula (E), R ₉ , R ₁₀ and R _{11 are} each preferably an alkyl group substituted with at least one halogen atom or a halogen atom.

Particularly preferably, R ₉ , R ₁₀ and R _{11 are} each a halogen atom. Z ₂ is preferably a group of non-metal atoms necessary to complete a cyclohexane ring.

In the general formula (F), R ₁₂ and R _{13 are} each preferably a hydrogen atom, an alkyl group or a nitrogen-containing heterocyclic residual group. R ₁₂ is more preferably a hydrogen atom and R ₁₃ is more preferably a hydrogen atom or a 5- or 6-membered, nitrogen-containing, unsaturated, heterocyclic residual group.

In the general formula (G), each of R ₁₄ and R ₁₅ is preferably a hydrogen atom, or they are combined together to form a benzene ring. The latter benzene ring combination is more preferred. R ₁₆ is preferably a hydrogen atom.

In the general formula (H), R _{17 is} preferably an unsaturated alkyl group having 1-4 carbon atoms.

In the general formula (I), L _{4 is} preferably an unsaturated alkylene group having 2-4 carbon atoms.

Specific examples of the compounds of the general formulas (A) to (I) as used according to the invention are shown below, but is the present Invention is not limited to the compounds shown.

The compounds of the general Formulas (A) to (I) include compounds described, for example, in U.S. Pat JP-A-263938/1985, JP-A-228247/1984, JP-A-27424/1979 and JP-A-211751/1989 are described, in addition to the compounds exemplified above.

The above-described used according to the invention Aminoglycosides are explained below.

The aminoglycosides used according to the invention are compounds known as antibiotics. For example, gentamicin may be referred to U.S. Patents 3,091,572 and 3,136,704, and correspondingly to amikacin, U.S. Patent 3,781,268 to Albekacin U.S. Patent 4,107,424 and DE-PS 23 50 169, for dibekacin on DE-PS 21 35 191, for Isepamicin on U.S. Patent 4,002,742 , for Micronomicin U.S. Patent No. 4,045 298 and DE-PS 23 26 781, for netilmicin on US Pat. Nos. 4,002,742 and 4,029,882 and DE-PS 24 37 160 and for sisomicin U.S. Patent 3,832,286 ,

According to the invention, the use of gentamicins particularly preferred among these aminoglycosides. Typical specific examples for the gentamicins are indicated below.

Compound No. (B-1) (gentamicin A ₂ )
(B-2) (Gentamicin A)
(B-3) (Gentamicin A ₁ )
(B-4) (Gentamicin B)
(B-5) (Gentamicin X ₂ )
(B-6) (Antibiotic JI-20A)
(B-7) (Gentamicin B ₁ )
(B-8) (antibiotic G418)
(B-9) (Antibiotic JI-20B)
(B-10) (Gentamicin C ₁ )
(B-11) (gentamicin C _1a )
(B-12) (Gentamicin C ₂ )
(B-13) (Gentamicin C _2a )
(B-14) (gentamicin C _2b )

The preparation of the invention usable Aminoglycosides is described in the patents listed above and these materials are also available on the market. About that In addition, the properties of these materials are in The Merck Index, to Encyclopedia of Chemicals, Drugs and Biologicals, 11th Ed. (1989), Merck & Co., Inc., described.

The compounds of the general Formulas (G) and (H) and gentamicins are preferred according to the invention. Particularly preferred are the compounds of the general formulas (G) and (H).

The compounds of the general Formulas (A) to (I) and the aminoglycosides according to the invention in a processing solution used in the desilvering step or subsequent thereto Steps is used as described above. Such a processing solution is preferably a processing solution with bleaching action (eg, a bleach solution, a blix solution) Washing water or a stabilizing solution, and a washing water or a bleach solution is further preferred.

The addition amount of these compounds is preferably 1 mg to 1 g, and more preferably 5-500 mg per Liter of the desilvering step or adjoining it Steps used processing solution. The addition of these compounds to the processing solutions described above can be performed by adding the compounds directly to the processing solution or by adding the compounds in a refreshing agent and / or a Reconditioner or by entering the compounds from a previous bath for incorporating them into the processing solution described above. Further can these compounds are added to the photosensitive material. About that can out these compounds individually or in combination of two or more Species can be used.

If these compounds in the processing solution bad soluble are, can various auxiliary solvents be added. Specific examples of the auxiliary solvent close methanol, ethanol, propanol, ethylene glycol, diethylene glycol, Monoethanolamine, diethanolamine, triethanolamine and ethylenediamine on.

It is preferred to use in the invention processing solution with bleaching action to incorporate a pH buffer. Preferred pH buffers are an odorless organic acid such as glycolic acid, succinic acid, maleic acid, malonic acid and glutaric and particularly preferred are glycolic acid, malonic acid and succinic acid. The Concentration of these buffers is preferably 0-3 mol / l, more preferably 0.2-1.5 minor.

A refreshing agent for a processing solution according to the invention Bleaching effect can be liquid or solid (a powder, a granule, a tablet). For a granular or tablet form of a booster is the use a polyethylene glycol type surfactant is preferable because such Compound also acts as a binder.

To solidify a photographic Processing agent can Various methods are used, such as in JP-A-29136/1992, JP-A-85535/1992, JP-A-85536/1992, JP-A-88533/1992, JP-A-85534/1992 and JP-A-172341/1992. For example the solidification can be effected by kneading a dense one liquid or a finely powdered or granular lithographic processing agent with a water-soluble Binder and subsequent shaping thereof, or by Atomize a water-soluble Binder on the surface a provisionally shaped photographic processing agent and then forming a coating layer thereon.

A tablet-form processing agent can be obtained according to a general production method as disclosed, for example, in JP-A-61837/1976, JP-A-155038/1979, JP-A-88025/1977 and GB-PS 1 213 808, and further, a granular processing agent can be obtained according to a general production method as disclosed, for example, in JP-A-109042/1990, JP-A-109043/1990, JP-A-39735/1991 and JP-A No. 39739/1991.

In addition, a powdered processing agent are obtained according to a general manufacturing process, such as for example, in JP-A-133332/1979, British Patent 725,892, British Patent 729 862 and DE-PS 3 733 861 is described.

When the processing solution replenisher with Bleaching effect from a liquid is composed, the liquid can a single liquid or a combination of liquids be with different components. With regard to such aspects, like the storage volume for the refreshing agent and handling at the time of chemical mixing is a single liquid or a set of two liquids preferred, and particularly preferred is a single liquid. In these cases For example, the density of the refreshing agent is preferably such that it corresponds to the 1.0 to 5 times the booster corresponds, and in particular preferably 1.5 to 3 times.

The pH of the inventive processing solution with Bleaching efficiency is generally in the range of 3.0-7.0. in the Case of a bleaching solution the pH is preferably 3.5-5.0. On the other hand, the pH is in the case of a blix solution preferably 4.0-6.5. In order to adjust the pH to these ranges, it is preferred according to the invention the above organic acid as a buffer. As an alkali to adjust the pH aqueous Ammonia, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like are preferable.

The pH of the invention used processing solution with bleaching effect can with the above-mentioned alkali and a known Acid (inorganic acids and organic acids) be adjusted to the above ranges.

Preferably, these processes become with an inventive used solution with bleaching action performed immediately after color development. in the However, in the case of reverse processing, they are usually over Compensating bath (or alternatively a bleach accelerating bath) or the like. This compensation bath may contain an image stabilizer, such as described below.

Furthermore, the invention used according to solution with bleaching effect in addition to a bleach a rehalogenizer, a pH buffer and known additives as described in JP-A-144446/1991, page 12, contain, and further, the solution aminopolycarboxylic and organic phosphonic acids contain. Preferred rehalogenants are sodium bromide, Potassium bromide, ammonium bromide, potassium chloride, etc. Their addition is preferably 0.1-1.5 mol, more preferably 0.1-1.0 mol, and particularly preferably 0.1-0.8 mol per liter of solution with bleaching effect.

Furthermore, the invention used according to solution with bleaching action further a nitric acid compound such as Ammonium nitrate and sodium nitrate. According to the invention, the concentration of nitric acid compound per liter of solution with bleaching effect preferably 0-0.3 mol and more preferably 0-0.2 mol.

Usually are used to prevent corrosion of stainless steel nitric acid compounds, such as ammonium nitrate and sodium nitrate. Prevented according to the invention even a small amount of nitric acid corrosion and the desilvering is good.

The replenishing amount of the solution having bleaching effect is preferably 30-600 ml, more preferably 50-400 ml per m ^{2 of} the photosensitive material.

The processing time during processing with a bleach solution is preferably 7 minutes or less, more preferably 10 seconds to 5 minutes and more preferably 15 seconds to 3 minutes.

Preferably, the total processing time is in the desilvering step in a shorter range where no Desilvering defect occurs. That is, the preferred processing time is 1-12 minutes, more preferably 1-8 Minutes. Further, the processing temperature is generally 25-50 ° C, and preferably 35-45 ° C. In this preferred temperature range is the desilvering rate improved and the occurrence of generated after processing Stains can be effectively prevented.

Particularly preferred is the invention used processing solution ventilated with bleaching action at the time of processing, since such ventilation the photographic properties are extremely stable. For the ventilation can be different in the present technical means known. For example There are several methods, such as blowing in Air in the processing solution with bleaching action and absorption by means of an ejector.

At the time of blowing in air, it is preferable to introduce the air into the solution through a gas-diffusing tube having fine pores. The air dispersing tube is commonly used for an activated sludge venting tube. For further peculiarities of aeration, reference is made to the articles described in Z-121, Using Process C-41, 3rd ed. (1982), published by Eastman Kodak Co., Ltd., pages BL-1 to BL-2, are described. It is preferable to vigorously stir the processing solution used in the present invention with bleaching action. For this purpose, a method may be used which is described in JP-A-33847/1991, page 8, right upper column, line 6 to left lower column, line 2 is described.

Further, according to the present invention, a bath preceding the bleaching-effect processing solution may contain various bleach-accelerating agents. Examples of these bleach accelerating agents to be used include compounds having a mercapto group or a disulfide group, as in U.S. Patent 3,893,858 DE-PS 1 290 821, GB-PS 1 138 842, JP-A-95630/1978 and Research Disclosure No. 17129 (July 1978); Thiazolidine derivatives as described in JP-A-140129/1975; Thiourea derivatives, as in U.S. Patent 3,706,561 described; Iodides as described in JP-A-16235/1983; Polyethylene oxides as described in DE-PS 2 748 430; and polyamine compounds as described in JP-B-8836/1970 ("JP-B" means an "examined published Japanese patent application"). Further, it is preferable to use the compounds described in U.S. Pat U.S. Patent 4,552,834 are described. These bleach accelerating agents may be added in a photosensitive material.

The photosensitive used in the invention Material is softened with a wash water and / or a stabilizing solution processed the desilvering step. The stabilizing solution, on the invention Reference is made to a stabilizing solution in the final processing step a color negative film and a color reversal film have hitherto been applied and includes a stabilizing solution in the stabilization step for a Bad, the last processing step or a rinsing step (previous bath). Preferably, however, the stabilizing solution becomes used as last bath.

The stabilizing solution used in the invention is capable of forming a color image formed by the color development before bleaching and discoloration to protect, over time due to the effect of a compound contained therein, which is capable of stabilizing a color image, z. B. aldehyde compounds, such as formalin, as described below becomes.

A compound that helps stabilize of a color image (hereinafter referred to as image stabilizer may be added to the stabilizing solution. Examples for the Image stabilizer include: formalin; Benzaldehydes, such as m-hydroxybenzaldehyde; an adduct of formaldehyde and hydrogen sulfite; Hexamethylenetetramine and its derivatives; Hexahydrotriazine and its derivatives; N-methylol compounds such as dimethylolurea and N-methylolpyrazole; and azolylmethylamines, such as N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine. These image stabilizers are described, for example, in JP-A-153348/1990, JP-A-270344/1992; JP-A-313753/1992, corresponding to EP-A2-504 609; JP-A-359249/1992, corresponding to EP-A2-0 519,190; JP-A-34889/1993 and EP-A1-0 521 477.

According to the invention, the concentration (density) of free formaldehyde in a solution in the range of 0-0.1%, in particular from 0-0.005%, which shows a big effect.

Among these image stabilizers, which provide such a concentration (density) of free formaldehyde are m-hydroxybenzaldehyde, hexamethylenetetramine; N-methylolazoles, like in JP-A-270344/1992 (e.g., N-methylolpyrazole); and azolylmethylamines, as described in JP-A-313753/1992 (corresponding to EP-A2-0 504 609) (eg N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine) prefers. Particularly preferred is azoles as described in JP-A-359249/1992 (corresponding to EP-A2-0 519 190) (eg 1,2,4-triazole), and azolylmethylamine or its derivatives (eg 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine) in combination with each other.

K-23 Hexamethylentetramin
K-24 N-MethylolharnstoffPreferred examples of the image stabilizer are shown below, but the present invention is not limited to the stabilizers shown.

K-23 hexamethylenetetramine
K-24 N-methylolurea

According to the invention, the addition amount of Image stabilizer preferably 0.001-0.1 mol, more preferably 0.001-0.05 mol per liter of the stabilizing solution.

The stabilizing solution used according to the invention can an organic acid such as acetic acid or citric acid, and Sulfuric acid. For further reinforcement the effect of the inventive stabilizing solution For example, it is preferred to include a monobasic organic to the stabilizing solution Acid with to add a hydroxyl group. The monobasic organic acid with a hydroxyl group includes an unbranched or branched alkyl group, which contains both a hydroxyl group part and an organic one acid moiety having. The monobasic organic acid preferably has 2-6, more preferably 2-4 Carbon atoms. Preferred organic acid moieties are a carboxylic acid, a sulfonic acid and a phosphoric acid. A carboxylic acid is particularly preferred.

Examples of the above, monobasic, organic acids with a hydroxyl group are glycolic acid and butyric acid. A glycolic acid is particularly preferred.

The content of the organic acid in the inventively used stabilizing solution is preferably 0.00001-0.5 mol, more preferably 0.0001-0.1 mol per liter of the stabilizing solution.

Preferably, various surfactants in the washing water and / or the stabilizing solution used according to the invention. In particular, the use of a surfactant in a processing solution which is used immediately before the drying step (i.e. last bath), is effective for protecting the processed photosensitive Material from inequities, which are transmitted by water spots in the drying step. The last Bath may be a wash water or a stabilizing solution the latter being preferred.

worin W -CH₂CH₂O- oder -CH₂CH(OH)CH₂O- repräsentiert, R₁₈ und R₁₉ sind jeweils eine Alkylgruppe, n ist 0 oder 1 und m ist die Anzahl der zugegebenen Mole an -CH₂CH₂O-Gruppen oder -CH₂CH(OH)CH₂O-Gruppen.Examples of the surfactants include a polyalkylene glycol type nonionic surfactant, a polyhydric alcohol type nonionic surfactant, an alkylbenzene sulfonic acid salt type anionic surfactant, a higher alcohol / sulfuric acid ester salt type anionic surfactant, an anionic surfactant of Alkylnaphthalene-sulfonic acid salt type, quaternary ammonium salt cationic surfactant, amine salt type cationic surfactant, aminosalt type amphoteric surfactant and betaine type amphoteric surfactant. Preferred among these surfactants are polyalkylene glycol type nonionic surfactants, and particularly preferred are those of the general formula (W) shown below, such as alkylphenoxypolyethylene oxides and alkylphenoxypolyhydroxypropylene oxides. General formula (W):

wherein W represents -CH ₂ CH ₂ O- or -CH ₂ CH (OH) CH ₂ O-, R ₁₈ and R ₁₉ are each an alkyl group, n is 0 or 1 and m is the number of moles of -CH _{2 added} CH ₂ O groups or -CH ₂ CH (OH) CH ₂ O groups.

The alkyl groups represented by R ₁₈ and R ₁₉ have 3-20, preferably 6-12, carbon atoms. Among these alkyl groups, an octyl group, a nonyl group and a dodecyl group are particularly preferable. Further, m (the number of moles added) is preferably 6-14.

According to the invention, a nonionic surfactant of the polyhydroxypropylene oxide type, wherein W represents a -CH ₂ CH (OH) CH ₂ O group, is preferred, since this significantly enhances the effect according to the invention.

Further, the use of a surfactant of the silicone type, which has an excellent antifoaming effect shows, preferred. examples for these preferred surfactants are given below, but the the present invention is not limited to these.

The amount of addition of the surfactant is generally 0.005-3 g, preferably 0.02-0.3 g per liter of washing water and / or stabilizing solution.

The washing water and / or the stabilizing solution contains depending from the circumstances preferably other additives, such as Ammonium compounds (eg, ammonium chloride, ammonium sulfite), metal compounds (eg a bismuth compound, an aluminum compound), a fluorescent brightener, a hardener; Alkanolamines as described in U.S. Patent 4,786,583; and sulfinic acid compounds, as described in JP-A-231051/1989.

Furthermore, the invention used according to stabilizing solution water-soluble Contain cellulose derivatives. Preferred water-soluble cellulose derivatives are Hydroxycellulose and carboxymethylcellulose. Their content is preferably 0.01-5.0 g and more preferably 0.05-1.0 g per liter of stabilizing solution.

The stabilizing solution used in the present invention preferably contains various chelating agents, thereby improving the storage stability of the stabilizing solution and the staining can be reduced. Examples of preferred Chelating agents are organic carboxylic acid-based chelating agents, Chelating agents based on organic phosphoric acid, chelating agents inorganic phosphoric acid base and polyhydroxy compounds. Among these chelating agents, aminopolycarboxylic acids are particularly preferably, such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N'-disuccinic acid and iminodiacetic acid monopropionic acid; organic phosphonic, such as 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N'-trimethylenephosphonic acid and diethylenetriamine-N, N, N ', N'-tetramethylenephosphonic acid; and a hydrolysis product of an anhydrous maleic acid polymer as in EP-A1-0 345 172 described. The amount of addition of the chelating agent is preferably 0.00001-0.01 mol / l of the stabilizing agent.

The photosensitive material used in the present invention may be subjected to stabilization after desilvering through a washing step, or alternatively, the photosensitive material may be subjected to stabilization are directly stabilized by omitting the washing step.

The amount of in the washing step too used washing water will depend on the properties of the photosensitive material (e.g., the type of photographic Additives, such as couplers), the end use of photosensitive material, the temperature of the washing water, the Number of wash tanks (the number of stages) of the refresh system (eg countercurrent system or direct current system) and other various Conditions selected within a wide range. For example can the relationship between the number of washing tanks and the amount of water in one multi-stage countercurrent system can be obtained by the method the Journal of Society of Motion Picture and Television Engineers, Vol. 64, pages 248-253 (May 1955). According to the disclosed multistage countercurrent system can the needed Amount of water can be significantly reduced.

The washing water and the stabilizing solution, such as according to the invention used, each have a pH of usually 4-9, preferably 5-8. The processing conditions, although these are dependent from the properties or end use of the photosensitive Materials and the like are usually a temperature from 15-45 ° C and a Time from 20 seconds to 10 minutes, preferably a temperature from 25-40 ° C and a Time from 30 seconds to 2 minutes. Furthermore, the processing increases with the invention stabilizing solution clearly the stain-preventing effect when the stabilization with a stabilizing solution directly after the desilvering without washing is performed.

When the stabilization with the invention used stabilizing solution is carried out, can Furthermore, any stabilization techniques are used, such as for example, in JP-A-8543/1982, JP-A-14834/1983 and JP-A-220345/1985 are described.

The Auffrischmengen of the washing water and the stabilizing solution used according to the invention are respectively 50-3,000 mL, more preferably from 100 to 1200 ml, more preferably 100-900 ml, and most preferably 200-600 ml per m ² of the photosensitive material. Further, the total refresh amount of the washing water and the stabilizing solution is preferably 50-3,000 ml, more preferably 100-1,500 ml, still more preferably 100-900 ml, and particularly preferably 200-700 ml per m ^{2 of} the light-sensitive material.

The overflow solution of the above washing water and / or the stabilizing solution can be reused in other steps, such as in desilvering.

To reduce the amount of wash water is used an ion exchange or an ultrafiltration, wherein the latter is particularly preferred.

The washing water and the stabilizing solution, such as inventively used, can contain various ionic constituents, such as Calcium ions, magnesium ions, sodium ions and potassium ions, as a material consisting of a mixed chemical solution used to manufacture the Refreshment was used, or from a photosensitive Material comes from. According to the invention is the concentration of sodium ions in the last processing bath the washing and stabilizing steps preferably 0-50 mg / l and more preferably 0-20 mg / l.

According to the invention, the moist-warm bleaching of the yellow dye by incorporation of a compound of the general formula (J) into a processing solution having bleaching action (a Bleaching solution, one blix) further improved. About that In addition, the readout characteristics of a magnetic recording become especially reinforced, when a photosensitive material has a magnetic recording layer.

worin Q eine Gruppe von Nichtmetallatomen ist, die zur Vervollständigung eines heterocyclischen Rings erforderlich ist; p ist 0 oder 1; und Ma ist ein Wasserstoffatom oder ein Kation.The compounds of general formula (J) as used according to the invention are explained in detail below.

wherein Q is a group of non-metal atoms necessary to complete a heterocyclic ring; p is 0 or 1; and Ma is a hydrogen atom or a cation.

The completed by Q heterocyclic The radical is a 3- to 10-membered saturated or unsaturated heterocyclic radical having at least one N, O or S atom. The heterocyclic ring may be a single ring or a fused one Be a ring.

The heterocyclic ring is preferably a 5- or 6-membered aromatic heterocyclic radical, further preferably a 5- or 6-membered aromatic heterocyclic A radical containing a nitrogen atom, and even more preferred a 5- or 6-membered aromatic heterocyclic radical, the Contains 1 or 2 nitrogen atoms.

Specific examples of the heterocyclic group include 2-pyrrolidinyl, 3-pyrrolidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-piperadinyl, 2-morpholinyl, 3-morpholinyl, 2-thienyl, 2-furyl, 3 furyl, 2-pyrrolyl, 3-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 4-pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrazinyl, 3-pyrazinyl, 4-pyridazinyl, 3 (1,2,4-triazolyl), 4- (1,2,3-triazolyl), 2- (1,3,5-triazinyl), 3- (1,2,4-triazinyl), 5- (1 , 2,4-triazinyl), 6- (1,2,4-triazinyl), 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 3-indazolyl, 4- Indazolyl, 5-indazolyl, 6-indazolyl, 7-indazolyl, 2-purinyl, 6-purinyl, 8-purinyl, 2- (1,3,4-thiadiazolyl), 2- (1,3,4-oxadiazolyl), 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-phthalazinyl, 5-phthalazinyl, 6-phthalazinyl, 2-naphthylizinyl, 3-naphthylizinyl, 4- Naphthylizinyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 5-quinazolinyl, 6-quinazolinyl, 7-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 4-cinnolinyl, 5-cinnolinyl, 6-Cinnolinyl, 7-Cinnolinyl, 8-Cinnolinyl, 2-Puteridinyl, 4-Puteridinyl, 6-Puteridinyl, 7-Puteridinyl, 1-Acridinyl, 2-Acridinyl, 3-Acridinyl , 4-acridinyl, 9-acridinyl, 2- (1,10-phenanthrolinyl), 3- (1,10-phenanthrolinyl), 4- (1,10-phenanthrolinyl), 5- (1,10-phenanthrolinyl), 1 Phenazinyl, 2-phenazinyl, 5-tetrazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolidinyl, 4-thiazolidinyl and 5-thiazolidinyl.

Preferred heterocyclic radicals are 2-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrrazolyl, 2-pyridyl, 2-pyrazinyl, 3-pyridazinyl, 3- (1,2,4-triazolyl), 4- (1,2,3-triazolyl, 2- (1,3,5-triazinyl), 3- (1,2,4-triazinyl), 5- (1,2,4-triazinyl), 6- (1,2,4-triazinyl), 2-indolyl, 3-indazolyl, 7-indazolyl, 2-purinyl, 6-purinyl, 8-purinyl, 2- (1,3,4-thiadiazolyl), 2- (1,3,4-oxadiazolyl), 2-quinolyl, 8-quinolyl, 1-phthalazinyl, 2-quinoxalinyl, 5-quinoxalinyl, 2-quinazolinyl, 4-quinazolinyl, 8-quinazolinyl, 3-cinnolinyl, 8-cinnolinyl, 2- (1,10-phenanthrolinyl), 5-tetrazolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl and 4-oxazolyl; more preferred are 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 2-indolyl, 3-indazolyl, 7-indazolyl, 2- (1,3,4-tiadiazolyl), 2- (1,3,4-oxadiazolyl), 2-quinolyl, 8-quinolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl and 4-oxazolyl; and even more preferred are 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 2-quinolyl and 8-quinolyl; and are particularly preferred 2-imidazolyl, 4-imidazolyl, 2-pyridyl and 2-quinolyl. Most preferred is a 2-pyridyl group.

The heterocyclic group may have a substituent in addition to the (CH ₂ ) _p CO ₂ Ma group. Examples of the substituent include: an alkyl group having preferably 1-12, more preferably 1-6, and particularly preferably 1-3 carbon atoms (eg, methyl and ethyl); an aralkyl group preferably having 7-20, more preferably 7-15, and most preferably 7-11 carbon atoms (eg, phenylmethyl and phenylethyl); an alkenyl group having preferably 2-12, more preferably 2-6, and most preferably 2-4 carbon atoms (eg, allyl); an alkynyl group having preferably 2-12, more preferably 2-6, and most preferably 2-4 carbon atoms (eg, propargyl); an aryl group of preferably 6-20, more preferably 6-15, and most preferably 6-10 carbon atoms (eg, phenyl and p-methylphenyl); an amino group preferably having 0-20, more preferably 0-10, and most preferably 0-6 carbon atoms (e.g., amino, methylamino, dimethylamino, and diethylamino); an alkoxy group having preferably 1-8, more preferably 1-6 and most preferably 1-4 carbon atoms (eg, methoxy and ethoxy); an aryloxy group having preferably 6-12, more preferably 6-10, and particularly preferably 6-8 carbon atoms (eg, phenyloxy); an acyl group having preferably 1-12, more preferably 2-10 and more preferably 2-8 carbon atoms (e.g., acetyl); an alkoxycarbonyl group having preferably 2-12, more preferably 2-10 and more preferably 2-8 carbon atoms (eg, methoxycarbonyl); an acyloxy group having preferably 1-12, preferably 2-10, and more preferably 2-8 carbon atoms (e.g., acetoxy); an acylamino group having preferably 1-10, more preferably 2-6, and particularly preferably 2-4 carbon atoms (e.g., acetylamino); a sulfonylamino group preferably having 1-10, more preferably 1-6, and most preferably 1-4 carbon atoms (eg, methanesulfonylamino); a sulfamoyl group having preferably 0-10, more preferably 0-6, and particularly preferably 0-4 carbon atoms (eg, sulfamoyl and methylsulfamoyl); a carbamoyl group having preferably 1-10, more preferably 1-6, and particularly preferably 1-4 carbon atoms (eg, carbamoyl and methylcarbamoyl); an alkylthio group having preferably 1-8, more preferably 1-6, and particularly preferably 1-4 carbon atoms (eg, methylthio and ethylthio); an arylthio group preferably having 6 to 20, more preferably 6 to 10, and particularly preferably 6 to 8 carbon atoms (eg, phenylthio); a sulfonyl group having preferably 1-8, more preferably 1-6, and most preferably 1-4 carbon atoms (eg, methanesulfonyl); a sulfinyl group having preferably 1-8, more preferably 1-6, and particularly preferably 1-4 carbon atoms (eg, methanesulfinyl), an ureido group, a hydroxyl group, a halogen atom (eg, fluorine, chlorine, bromine, and iodine), a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a mercapto group and a heterocyclic group (eg, imidazolyl and pyridyl).

These substituents may further be substituted with a substituent. When two or more substituents are present, they are identical or different.

Preferred substituents are one Alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxyl group, a halogen atom, a cyano group, a nitro group and a mercapto group; and more preferred are an alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxyl group and a halogen atom; and even more preferred are an amino group, a carboxyl group and a hydroxyl group. A carboxyl group is particularly preferred.

p is 0 or 1, preferably 0.

The cation represented by Ma is an organic or inorganic cation. Examples of the cation include an alkali metal ion (eg Li ⁺ , Na ⁺ , K ⁺ , Cs ⁺ ), an alkaline earth metal ion (eg Ca ²⁺ , Mg ²⁺ ), an ammonium ion (eg ammonium, Tetraethylammonium), a pyridium ion and a phosphonium ion (eg, tetrabutylphosphonium, tetraphenylphosphonium).

worin p und Ma die gleichen Bedeutungen haben wie in der allgemeinen Formel (J), und Q¹ ist eine Gruppe von Nichtmetallatomen, die zur Vervollständigung eines stickstoffhaltigen heterocyclischen Rings erforderlich sind.Among the compounds of the general formula (J), those of the following general formula (Yes) are preferred: General formula (Yes)

wherein p and Ma have the same meanings as in the general formula (J), and Q ¹ is a group of non-metal atoms necessary for completing a nitrogen-containing heterocyclic ring.

The nitrogen-containing heterocyclic ring completed by Q ¹ is a 3 to 10-membered, saturated or unsaturated, heterocyclic radical containing at least one nitrogen atom. These rings can be a single ring or a condensed ring.

The nitrogen-containing heterocyclic The radical is preferably a 5- or 6-membered, nitrogen-containing, aromatic, heterocyclic radical, and more preferably a 5- or 6-membered, nitrogen-containing, aromatic, heterocyclic radical containing or contains two nitrogen atoms.

Specific examples and preferred examples for these nitrogen-containing heterocyclic radicals are those which have been presented above with respect to the general formula (J).

The nitrogen-containing heterocyclic group may have a substituent in addition to the (CH ₂ ) _p CO ₂ Ma group.

Specific examples and preferred examples for the substituents are the same as above as substituents for the completed by Q. heterocyclic group in the general formula (J) by way of example were specified.

worin Ma die gleiche Bedeutung hat wie in Formel (J), und Q² ist eine Gruppe von Nichtmetallatomen zur Vervollständigung einer 5- oder 6-gliedrigen stickstoffhaltigen heterocyclischen Gruppe, die mit eine Alkylgruppe, einer Aminogruppe, einer Alkoxygruppe, einer Carboxylgruppe, einer Hydroxylgruppe, einem Halogenatom, einer Cyanogruppe, einer Nitrogruppe oder einer Mercaptogruppe substituiert sein kann.p and Ma each have the same meanings as defined in connection with the general formula (J). Preferred ranges thereof are also the same as in the general formula (J). More preferred among these compounds of the general formula (Yes) are compounds of the following general formula (Jb): General formula (Jb)

wherein Ma has the same meaning as in formula (J), and Q ² is a group of non-metal atoms for completing a 5- or 6-membered nitrogen-containing heterocyclic group having an alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxyl group , a halogen atom, a cyano group, a nitro group or a mercapto group.

worin Ma die gleiche Bedeutung hat wie in der Formel (J), und Q³ ist eine Gruppe von Atomen, die zur Vervollständigung eines Pyridinrings oder eines Imidazolrings erforderlich sind, die mit einer Alkylgruppe, einer Aminogruppe, einer Alkoxygruppe, einer Carboxylgruppe, einer Hydroxylgruppe, einem Halogenatom, einer Cyanogruppe, einer Nitrogruppe oder einer Mercaptogruppe substituiert sein können.Among these compounds of the general formula (Jb), those of the following general formula (Jc) are more preferable: General formula (Jc)

wherein Ma has the same meaning as in the formula (J), and Q ³ is a group of atoms necessary for completing a pyridine ring or imidazole ring having an alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxyl group , a halogen atom, a cyano group, a nitro group or a mercapto group.

Specific examples of the compound of the general formula (J) are shown below, but is the present invention is not limited to these.

The connections shown above can used in the form of an ammonium salt or an alkali metal salt become.

The compounds of the above-described general formula (J) can be prepared by the methods described in Organic Synthesis Collective, Vol. 3, page 740, and further, some available from them as commercially marketed products.

Among the above exemplified Compounds are preferred (J-6), (J-7), (J-8), (J-13), (J-14), (J-20), (J-22), (J-29) and (J-49), with (J-7) being particularly preferred is.

The addition amount of the invention used Compound of the general formula (J) is preferably 0.001-0.3 mol, more preferably 0.005-0.2 mol and more preferably 0.01-0.10 mol per liter of the processing solution Bleaching effect. Here you can the connections through transmission into the processing solution be incorporated from a previous bath. These connections can used singly or in combination of two or more species.

The processing solution with Fixative effect may contain preservatives, including Sulphite salts (eg sodium sulphite, potassium sulphite, ammonium sulphite), Hydroxylamines, hydrazines, aldehyde compound bisulfite salt adducts (eg, acetaldehyde-sodium bisulfite adduct; preferably compounds as described in particular in JP-A-158848/1991 described) and sulfinic acid compounds, as described in JP-A-231051/1989. Furthermore, the processing solution may be various Fluorescence brightener and defoamer or a surfactant and an organic solvent such as for example, polyvinylpyrrolidone and methanol.

Furthermore, the processing solution contains Fixing effect for stabilizing the processing solution preferably a chelating agent such as various aminopolycarboxylic acids and organic phosphonic acids. Preferred examples of such chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, ethylenediamine-N, N, N', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans- 1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid and 1,2-propylenediamine on.

Furthermore, to keep the pH of the blix solution or the fixing solution preferably a buffer is added. Examples of the buffer are phosphates; Imidazoles such as imidazole, 1-methylimidazole, 2-methylimidazole and 1-ethylimidazole; Triethanolamine, N-allylmorpholine and N-benzoylpiperazine.

In the desilvering step it is preferred that as hard as possible touched becomes. Specific examples of Procedure for forced stirring include a method wherein a jet of processing solution the surface the emulsion of the photosensitive material is irradiated, as in JP-A-183460/1987 and JP-A-33847/1991, page 8, upper right Column, line 6 to left lower column, line 2 disclosed; on Process in which the stirring action is increased by using a rotary device as disclosed in JP-A-183461/1987 disclosed; a method wherein the photosensitive material having one in the solution installed wiper blade is moved, with the sheet in contact with the surface is the emulsion, and the generated turbulent flow at the surface of Emulsion the stirring effect elevated; and a method wherein the circulation flow velocity of the entire processing solution elevated is. This the stirring effect improving processes are in any of the bleaching solution, the Blixläsung and the fixing solution effective. It is believed that the improvement of stirring the feed of the bleaching agent and the fixing agent in the emulsion layer accelerates, causing an increase the Desilverungsgeschwindigkeit leads. Furthermore, those described above, the stirring effect improving process more effectively if a bleach accelerator is used, whereby the acceleration effect is significantly increased, and the fixation-inhibiting effect by the bleaching accelerator can be reduced.

An automatic processing device, for processing a photosensitive material according to the invention is used, preferably comprises transport devices for the photosensitive material as in JP-A-191257/1985, JP-A-191258/1985 and JP-A-191259/1985 described. As described in the above-mentioned JP-A-191257/1985, these means of transport reduce the amount of a solution that from a previous bath is transferred to the next bath, so that the Effect of deterioration prevention of the processing solution to be strengthened can. Consequently, this effect is particularly advantageous for the shortening of Processing time in each of the steps and reduce the Refreshment of the processing solution.

The processing solution used according to the invention Bleaching action may be by recovery in the processing step the excess fluid after use and subsequent equilibration of the composition be reused by adding components. Such Use, commonly referred to as regeneration, is according to the invention preferably applied. In terms of the details of the regeneration is referred to the details in Fuji Film Processing Manual, Fuji Color Negative Film, CN-16 Process (revised August 1990), pages 39-40 (published by Fuji Photo Film Co., Ltd.).

Regarding the regeneration of the bleaching-effect processing solution, in addition to the aeration methods described above, the methods disclosed in Shashin Kogaku no Kiso-Ginn-en Shashin-Hen (The Fundamentals of Photographic Technology-Silver Salt Photography) (edited by Nippon Shashin Gakkai) can be used by Corona Co., 1979), etc. Specific examples of the regeneration methods for the bleaching solution include a regeneration method by electrolysis, and a regeneration method with a hydrogen peroxide, a bromic acid, ozone, etc. wherein a bromic acid, a chloric acid, bromine, a bromine precursor, a persulfate, a hydrogen peroxide and a catalyst are used.

In the regeneration process by Electrolysis is a regeneration process performed by an anode and a cathode are placed in the same bleaching bath, or by separating the anode bath from the cathode bath through a diaphragm, and further a bleach solution and a development solution and / or a fixing solution simultaneously also regenerated using a diaphragm become.

The regeneration processing of fixing and the blix solution be by electrolytic reduction of the accumulated silver ions carried out. About that In addition, the removal of the accumulated halogen ions by means of an anion exchange resin for maintaining fixability also preferred.

The bleaching-effect processing solution used in the present invention is preferably stored in a sealed container having an oxygen-permeation rate of 1 cm ³ / m ² · day · atm or more.

A replenisher solution for the bleaching-action processing solution contains substantially all components in a concentration as calculated by the following equation: C R = C T * (V 1 + V 2 ) / V 1 + C P C _R : concentration of a component in the replenisher,
C _T : concentration of a component in a mother liquor (processing tank solution),
C _P : concentration of a consumed ingredient during processing,
V ₁ : refreshing amount (ml) of the replenisher having a bleaching effect of 1 m ^{2 of} the photosensitive material,
V ₂ : Amount (ml) of the solution transferred per m ² of photosensitive material from a preceding bath to a subsequent bath.

In the above-described refresh solution each constituent concentration in the mother liquor kept constant become.

A color development solution will be explained below.

The compounds described in JP-A-121739/1992, Page 9, right upper column, line 1 to page 11, lower left Column, line 4 are described, can be used as a color development solution become. Preferred examples of the color developing agent suitable for rapid processing in particular 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline, 2-methyl-4- [N-ethyl-N- (3-hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline on.

The addition amount of the color developing agent is preferably 0.01-0.08 mol, more preferably 0.015-0.06 mol and more preferably 0.02-0.05 mol per liter of the color developing solution. It is preferred, the color developing agent in an amount of 1,1- to 3 times the amount described above to a refreshing solution of Color developing solution admit.

The color developing solution generally contains a pH buffer, such as a carbonate, borate or phosphate an alkali metal; and a development inhibitor or a Fogging inhibitor such as a chloride Bromide, an iodide, benzimidazole, benzothiazoles or a mercapto compound.

The color development solution can also contain various preservatives as needed, such as Hydroxylamines, including hydroxylamine, diethylhydroxylamine, N, N-bis (2-sulfonatoethyl) hydroxylamine and other hydroxylamines of general formula (I) according to JP-A-144446/1991; Sulfites, hydrazines (eg N, N-biscarboxymethylhydrazine), phenyl semicarbazide, Triethanolamine and catecholsulfonic acids; an organic solvent, such as ethylene glycol and diethylene glycol; a development accelerator, such as benzyl alcohol, polyethylene glycol, a quaternary ammonium salt and amines; a dye-forming coupler, a competitive coupler; an auxiliary developing agent such as 1-phenyl-3-pyrazolidone; a tackifier and various chelating agents such as aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid and phosphonocarboxylic (eg, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic cyclohexanediamine, hydroxyethyliminodiacetic, 1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and Salts of these acids.

The processing temperature of the color developing solution is generally 20-55 ° C and preferably 30-55 ° C. The processing time is generally 20 seconds to 10 minutes, preferably 30 seconds to 8 minutes, more preferably 1 to 6 minutes and most preferably 1 minute and 10 seconds to 3 minutes and 30 seconds in photosensitive Materials for the photograph, and generally 10 seconds to 1 minute and 20 seconds, preferably 10 to 60 seconds, and more preferably 10 to 40 seconds in a photosensitive material for printing.

In the case of carrying out a Color inversion development generally precedes color development by black and white development. A black and white development solution, the for the black and white development used contains an or several known black and white developing agents. Representative Black / white developing agents include dihydroxybenzenes such as hydroquinone and hydroquinone monosulfate, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; and aminophenols, such as N-methyl-p-aminophenol. Furthermore, the above called black and white development solution too used in the process of a photosensitive black / white material become.

The color developing solution or black-and-white developing solution generally has a pH in the range of 9-12. Further, the refresh rate for these developing solutions, although variable depending on the kind of color photographic light-sensitive material to be processed, is generally not more than 3 l / m ^{2 of} the photosensitive material. The refresh rate may be reduced to 500 ml or less when using a replenisher solution having a low bromide ion content. When the reduced refresh rate processing is performed, it is desirable to reduce the evaporation and air oxidation of the processing solution by reducing the contact area of the processing solution in the processing tank with air. The contact area of the processing solution in the processing tank with air is preferably 0.1-300 cm ^2, and more preferably 0.2-150 cm ² .

The contact area between the photographic processing solution and air in the processing tank, that is, the opening area in the processing apparatus can be expressed in units of the opening ratio as defined below: Opening ratio = [contact area (cm 2 ) of the processing solution with air] ÷ [volume (cm 3 ) of processing solution (tank volume of processing solution)]

The aperture ratio defined above is preferably 0.1 or less and more preferably 0.001-0.05. The opening ratio can for example, be reduced by a barrier, such as a floating lid, on the liquid surface of the Processing tanks using a movable lid, such as in JP-A-82033/1989, or by using slot development processing, as described in JP-A-216050/1988. Furthermore, the aperture ratio can be reduced be contacted by contacting the liquid surface of the processing solution with a liquid, the over cover the liquid surface suitable is, such as a liquid Paraffin, or with a badly oxidizing and / or non-oxidizing Gas. The reduction of the opening ratio is not only in color development and black and white development, but also in all subsequent steps, such as bleaching, the blix step, the fixation, the washing and the stabilization, desirable. The Refreshment may further be achieved by using a means for suppressing the Accumulation of bromide ions in the developing solution can be reduced.

In addition, it is in the case of Reduce the refresh rate or adjust the concentration Bromide ions to a high level are also preferred, a development accelerator to increase the photographic speed, including Pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone; Thioether compounds such as 3,6-dithia-1,8-octanediol; sodium thiosulfate and potassium thiosulfate.

These development accelerators will be also preferably used in the color developing solution.

Regarding the shape and structure the container, which contains a color developing agent as a component of the color developing solution are although these are dependent may be freely designed by the need, those preferred have a flexible structure, such as bellows, such as For example, in JP-A-97046/1983, JP-A-50839/1988, JP-A-235950/1989 and JP-A-U-45555/1988 (the term "JP-A-U" as used herein means an "unaudited published Japanese Utility Model Application "), containers with flexible compartments, which are capable of receiving waste, such as in JP-A-52065/1983, JP-A-246061/1987 and JP-A-134646/1987; and a structure wherein two or more containers, each one variable Inner volume, are interconnected, as in JP-A-264950/1990 described.

To fill a processing solution tank set in the processing device with a color developing agent from these containers For example, the color developing agent may initially be in a refresh solution tank stored and then automatically or manually in this tank for dilution with Water may be mixed, or alternatively, the above-mentioned liquid developing agent and water separately from each other directly into the processing solution tank be transported.

A structure wherein a lid of the container by touch open can be, is for prefers the above operation. Specific examples of such Structure are, for example, in JP-A-U-128646/1986, JP-A-265849/1991 and JP-A-240850/1992.

It is preferable to use a container made of a material having a permeability to carbon dioxide of not more than 25 ml / m ² with a permeability to carbon dioxide of not more than 25 ml / m ² .24 hrs · atm with the color developing agent described above a void fraction in the range of 0.15-0.05, to fill.

Preferred materials having such a permeability to carbon dioxide are polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, a laminated material of nylon and polyethylene or polypropylene, a laminated material of aluminum and polyethylene or polypropylene and glass each having a thickness of 300 to 2,000 μm. In particular, polyethylene terephthalate and a polyethylene-nylon laminated material each having a thickness of 500-1,000 μm are preferable in view of the balance between carbon dioxide permeability, mechanical strength and weight. Further, the material for the container used in the present invention preferably has an oxygen permeation rate of not more than 20 ml / m ² · 24 hr · atm.

The term "voids" as used herein means a value obtained according to the following formula: {[volume (ml) of the container to be filled with a color developing agent] - [volume (ml) of color developing agent]} ÷ [volume (ml) of the container]. The invention used liquid Color developing agent is preferably having a void fraction from 0.15 to 0.05 in the container described above filled.

The color developing agent described above can be used as it is as a color developing solution or refreshing solution However, it is preferably used as a mixture with water dilution used. When the color developing agent is used as a color developing solution it is preferred to add a starter containing a pH adjuster, a bromide and the like in addition to water.

When the color developing agent as Reconditioner is used, the color developing agent may further be mixed with water mixed and diluted and temporarily in a refreshing solution tank be stored so that the diluted solution from this tank is quantitative as a refresher can be transferred to a processing solution tank. alternative can do this the color developing agent and water separated from each other directly in a processing solution tank transferred in quantitative amount and then for dilution in the processing solution tank be mixed together. Furthermore, as an intermediate method, the invention can be applied, the color developing agent in a processing solution tank be transported while slowly add water for dilution supplied becomes. In this case, you can known methods are used, such as a method, wherein a mixing tank on the way to the processing solution tank is provided. In terms of the processing solution with fixing effect can the compounds and processing conditions are applied, as described in JP-A-135558/1992, page 7, left lower column, line 10 to page 8, right lower column, line 19 are described. In particular, you can one or more of the compounds of general formula (I) or (II), as described in JP-A-301169/1994, preferably to the processing solution Fixing effect can be added, whereby the preservation and the Fixation speed can be improved. Furthermore, the Use of p-toluenesulfinic acid salt and other sulfinic acids, as described in JP-A-224762/1989, to improve preservation prefers. In the processing solution with bleaching action and the processing solution with fixing action to improve the desilvering preferably ammonium ions as Cations used. To reduce pollution However, it is desirable to suppress the use of ammonium ions or these at all not to use.

In the steps of bleaching, the Blixverfahrens and fixation, it is particularly preferred, a beam mixing as described in JP-A-309059/1989.

The refreshing amount of the replenisher in the blixing and fixing step is generally 100-1,000 ml, preferably 150-700 ml, and more preferably 200-600 ml per m ^{2 of} the photosensitive material.

In the blix and fixation steps For example, it is preferred to use silver by various types of silver recovery devices recover, which are installed in-line or off-line. For in-line mounting, the Processing at a reduced silver concentration in the solution, which leads to a reduction of the refresh quantity. Furthermore, the remaining solution after the off-line silver separation treatment preferably as a refreshing solution reused.

In the blix step and in the fixing step can two or more processing tanks are used. Preferably For example, a countercurrent cascade system may be used in which these Tanks by a cascade pipe connection with each other stand. In terms of size The processing device is generally a 2-tank cascade system, and the relationship the processing time between the previous tank and the subsequent one Tank is preferably 0.5: 1-1 : 0.5, more preferably 0.8: 1-1: 0.8.

It is preferred that in the blix solution or the fixing solution free chelating agents are present which do not form a metal complex which improves the preservation of the solution. Regarding such Chelating agent is the use of at least one of the compounds according to the invention the general formula (X) is particularly preferred.

Particularly preferred is the inventive processing subjected to evaporation correction of the processing solution as in Kokai-giho, released by Hatsumei-kyokai, Kogi: No. 94-4992. In particular a method in which the correction according to formula-1 is carried out on page 2, based on information about the temperature and humidity in the environment in which the Processing device is placed. The water used for the evaporation correction is preferably used from a tank for refreshment taken from the wash water. In this case, it is preferable to deionized To use water as a refreshing water of the washing water.

The inventive processing can with different Types of processing devices are performed. Preferred examples for this Processing devices include cine type (motion picture film type) processing devices, manufactured by Fuji Photo Film Co., Ltd., such as the autoprocessors FNCP-300II, FNCP-600II and FNCP-900II, cine-type processing devices with a leadership transport system, which are called "mini-lab", manufactured by Fuji Photo Film Co., Ltd., such as the Autoprocessors FP-560B and FP-350; Hangar-type processing devices Noritsu Koki Co., Ltd. be prepared, such as the autoprocessors HM-55S, H8-440W-4, HM-60R and HR6-8360; and Processing devices with a roller transport system, the manufactured by Hope Company (USA), such as HOPE 138 and HOPE 2409V. Further, as a stirring method and materials for the Processing devices preferred are those described in JP-A-130432/1992 are described.

The following are preferred, used according to the invention, color photographic light-sensitive silver halide materials described.

Preferred examples of the color photographic Photosensitive silver halide material for the use according to the invention close color reversal and color negative films with one on top layered silver iodobromide emulsion. Color negative films are particularly preferred. A color photographic material, wherein one magnetic recording layer is coated on a support is most preferred.

Preferred for use according to the invention photosensitive materials having a magnetic recording layer are explained below.

The magnetic recording layer is formed by coating an aqueous or organic solvent coating solution having magnetic substance particles dispersed therein on a support in a binder. Examples of the magnetic substance include ferromagnetic iron oxide such as γFe ₂ O ₃ , Co-coated γFe ₂ O ₃ , Co-coated magnetite, Co-doped magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloys, hexagonal barium ferrite, Sr ferrite, Pb ferrite and Ca ferrite. Among these magnetic substances, Co-coated ferromagnetic iron oxides such as Co-coated γFe ₂ O _{3 are} preferable.

Any shape selected from acicular, rice-kernel, spherical, cubic or tabular may be used with respect to the shape. The specific surface area S _BET is preferably 20 m ² / g or more, more preferably 30 m ² / g or more. The saturation magnetization (σ _s ) of the ferromagnetic substance is preferably 3.0 × 10 ⁴ to 3.0 × 10 ⁵ A / m, particularly preferably 4.0 × 10 ⁴ to 2.5 × 10 ⁵ A / m.

The grain surfaces of the ferromagnetic Substance can treated with silica or alumina or with an organic material his. Furthermore, the grain surface the magnetic substance with a silane coupling agent or a Titanium coupling agents as described in JP-A-161032/1994. Furthermore, can grains be used of the magnetic substance whose surfaces with an inorganic material or an organic material as described in JP-A-259911/1992 and JP-A-81652/1993.

As a binder for the magnetic grains can following are used. Those described in JP-A-219569/1992, such as thermoplastic resins, thermosetting resins, radiation curing resins, Reactive resins, polymers with acid or alkali decomposability or biodegradability, natural polymers (eg, cellulose derivatives, sugar derivatives) and a mixture thereof. The glass transition temperature (Tg) of the above resins is usually -40 to 300 ° C and the weight average molecular weight is usually 2.000-1.000.00. examples for the ones listed above Materials close Vinyl-based copolymers; Cellulose derivatives, such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, Cellulose acetate butyrate and cellulose tripropionate; Acrylic resins and Polyvinylacetalharze. Also preferred is gelatin. In particular Cellulosedi (tri) acetate is preferred. The curing treatment of the binders listed above can by the addition of crosslinking agents on epoxy, aziridine or Isocyanate-based performed become. examples for the isocyanate-based crosslinkers include isocyanates, such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate and xylylene diisocyanate; Reaction products of these isocyanates with Polyalcohol (eg a reaction product of tolylene diisocyanate (3 mol) and trimethylolpropane (1 mol)); and polyisocyanates prepared be by condensation of these isocyanates, such as in JP-A-59357/1994.

For dispersing the above-mentioned magnetic substance in the above-mentioned binder For example, it is preferable to use one or more dispersing devices such as a kneader, a needle-type mill, and a ring-type mill as disclosed in JP-A-35092/1994. For the above purpose, dispersants as described in JP-A-88283/1993 and other known dispersants can be used.

The thickness of the magnetic recording layer is generally 0.1-10 μm, preferably 0.2-5 μm, and more preferably 0.3-3 μm. The weight ratio of the magnetic substance grains to the binder is preferably 0.5: 100-60: 100, more preferably 1: 100-30: 100. The coated amount of the magnetic substance grains is generally 0.005-3 g / m ² , preferably 0.01-2 g / m ² and more preferably 0.02-0.5 g / m ² .

An inventively used magnetic recording layer is as a striped pattern or on the entire surface on the side of the photographic support, the one on the the silver halide emulsion layer is piled up, opposite, applied by coating or printing a magnetic substance. For stacking the magnetic recording layer, various Methods, such as squeegee, blade, air knife, nip roll, impregnating, Reverse roll, transfer roll, gravure, stamp, pour, spray, dip bar and extrusion coatings be applied. Preferably, a coating solution, such as in JP-A-341436/1993.

The magnetic recording layer may be provided with functions such as slip improvement, waviness control, antistatic properties, adhesion prevention and head abrasion, or another layer may be provided which has these functions. It is preferable to use an abrasive comprising non-spherical inorganic particles of which at least one species has a Mohs hardness of not less than 5. Non-spherical inorganic grains are preferably composed of fine powders such as oxides (e.g., alumina, chromia, silica, titania), carbides (e.g., silicon carbide, titanium carbide) and diamond. The surface of these abrasives may be treated with a silane coupling agent or with a titanium coupling agent. These particles may be added to the magnetic recording layer or coated on the magnetic recording layer to form a coating (e.g., a protective layer, a lubricant-containing layer) containing them. As the binder used here, those described above can be used, and preferably, the same binder is used as in the magnetic recording layer. A photosensitive material having a magnetic recording layer is disclosed in U.S. Patent Nos. 5,336,589, 5,250,404, 5,229,259, and 5,215,874 EP 0 466 130 described.

The photosensitive used in the invention Material is preferably a photosensitive material for photography, and its carrier is preferably a polyester. Details of this material are in Kokai-giho, Kogi No. 94-6023 (Hatsumei-kyokai, 1994.3.15).

The polyester used in the invention is by a chemical reaction between a diol and an aromatic one dicarboxylic acid formed, which are both essential components. Examples of the aromatic dicarboxylic acid include 2,6-, 1,5-, 1,4- or 2,7-naphthalenedicarboxylic acid, terephthalic acid, isophthalic acid and phthalic on. examples for the thiol close diethylene glycol, triethylene glycol, cyclohexanedimethanol, Bisphenol A and bisphenol.

Examples of the thus polymerized polyester include homopolymers such as polyethylene terephthalate, Polyethylene naphthalate and polycyclohexanedimethanol terephthalate. A polyester containing 2,6-naphthalenedicarboxylic acid as the reaction component in an amount of 50-100 contains mol%, is particularly preferred. Of all, polyethylene 2,6-naphthalate most preferred. These polyesters each have an average Molecular weight of 5,000-200,000. The invention used polyesters have a Tg of 50 ° C or more, preferably 90 ° C or more.

The polyester carrier is subjected to a heat treatment at a temperature of 40 ° C or more but less than Tg, preferably at Tg -20 ° C or more but less than Tg, to suppress corrugation formation. The heat treatment can be carried out at a constant temperature within the above range. Alternatively, the heat treatment may be carried out under cooling. The heat treatment time is 0.1-1,500 hours, more preferably 0.5-200 hours. The heat treatment of the carrier may be performed in the form of a roll or in the form of a propelled net. To improve the quality of the surface, the surface of a support may be provided with unevenness, for example, by coating with electrically conductive, inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ . Further, in the manufacture of a carrier, it is desirable to take measures for preventing the problem of deformation of the carrier by providing knurling (unfolding) at both ends along the width of the carrier (the right and left ends in the direction of propulsion), whereby the ends of the carrier become slightly higher than the middle part between the ends. The problem of deformation of the carrier means that when the carrier is wound on a core, the core follows the unevenness of the cut edge of the first turn in the second and further turns, thereby deforming a flat sheet shape. The above The above-mentioned heat treatment may be carried out at any stage after the preparation of the support (film), surface treatment, coating of a backcoat layer containing an antistatic agent, a lubricant and the like, or coating of a primer layer. A step following the stacking of the antistatic agent is preferred.

In the polyester can be a UV absorber be kneaded. Furthermore, the light pipe can be kneaded by kneading a dye or a pigment for the polyester in the polyester be prevented, and examples of this, the commercial products are diaresin (trade name, manufactured by Mitsubishi Chemicals Co., Ltd.) and Kayaset (trade name, manufactured by Nippon Kayaku Co., Ltd.).

The photosensitive used in the invention Material is then used to make the adhesion between the carrier and a photographic construction layer subjected to a surface treatment. Regarding this surface treatment can different surface-activating Treatment, such as a chemical treatment, a mechanical treatment, a corona discharge treatment, a Flame treatment, a UV treatment, a high-frequency treatment, a glow discharge treatment, an active plasma treatment, a Laser treatment, a mixed acid treatment and an ozone oxidation treatment; and preferred are a UV treatment, a flame treatment, a corona treatment and a glow treatment.

The following is a primer method described.

The primer layer may be a single layer or a multilayer. Examples of the binder used in the undercoat layer include copolymers prepared by using monomers selected from vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, maleic anhydride and the like as a starting material; and other examples are polyethyleneimine, an epoxy resin, a grafted gelatin, nitrocellulose and gelatin. Resorcinol and p-chlorophenol can be used to swell the support. As the gelatin hardener for the undercoat layer, there may be used a chromium salt (e.g., chromalum), aldehydes (e.g., formaldehyde, glutaraldehyde), isocyanates, active halogen compounds (e.g., 2,4-dichloro-6-hydroxy). S-triazine), epichlorohydrin resins and vinylsulfone active compounds. The undercoat layer may contain SiO ₂ , TiO ₂ , inorganic fine particles or fine particles of polymethyl methacrylate or its copolymer (0.01-10 μm) as a matting agent.

Furthermore, the invention used according to photosensitive material preferably an antistatic agent. On such antistatic agent may be a high molecular compound the one carboxylic acid or their salt contains, or a sulfonic acid salt, cationic high molecular compounds and ionic surfactants.

The most preferred examples of the antistatic agents include crystalline fine metal oxide grains having a volume resistivity of 10 ⁷ Ω · cm or less, more preferably 10 ⁵ Ω · cm or less, and a grain size of 0.001-1.0 μm, the metal having at least one is selected from ZnO, TiO ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , MgO, BaO, MoO ₃ and V ₂ O ₅ , or fine grains of composite oxides thereof (Sb, P, B, In, S, Si, C, etc.) and further fine grains of sol-like metal oxides or composite oxides thereof. The addition amount of the antistatic agent is preferably 5-500 mg, and more preferably 10-350 mg per m ^{2 of} the light-sensitive material. The ratio of the amount of electroconductive crystalline oxides or composite oxides thereof to the amount of the binder is preferably 1: 300-100: 1, more preferably 1: 100-100: 5.

Furthermore, has the photosensitive Material preferably lubricating properties. Preferably provided a lubricant-containing layer on the same side, on which the photosensitive layer is coated, as well on the opposite side Side (i.e., the back). The preferred lubricity is 0.01-0.25 in units of dynamic Coefficient of friction. This value means a value obtained is achieved by propelling the photosensitive material at a speed of 60 cm / min against a stainless steel ball of 5 mm diameter (at 25 ° C, 60% relative humidity). In this investigation procedure will be get almost the same results also with respect to the surface, on which the photosensitive layer is coated.

Close examples of available lubricants Polyorganosiloxanes, higher fatty acid amides, Metal salts higher fatty acids and esters higher fatty acids and higher Alcohols. As polyorganosiloxanes polydimethylsiloxane, polydiethylsiloxane, Polystyrylmethylsiloxane, polymethylphenylsiloxane and the like become. As the layers into which the lubricant is added are the outermost Layer on the same side on which the photographic emulsion layered, and the backside layer prefers. In particular, the addition of polydimethylsiloxane and / or an ester with a long-chain alkyl group to these layers prefers.

Further, the photosensitive material preferably contains a matting agent. The matting agent may be added to any layer on the same side on which the photographic emulsion is layered or on the back side, but the addition to the outermost layer on the side on which the photographic emulsion is coated is preferred. The matting agent may be soluble or insoluble in the processing solution. It is preferred to use both types of flatting agent in combination other to use. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9: 1 or 5: 5 (molar ratio)) and polystyrene grains are preferred. A preferred grain size is 0.8-10 μm. A narrower grain size distribution is preferred. In particular, it is preferable that not less than 90% of the total number of grains have 0.9 to 1.1 times the average grain size.

Further, it is also preferable to fine grains of not more than 0.8 μm add together with the larger grains mentioned above, whereby the Matting properties are improved. Examples of these Close fine grains Polymethylmethacrylate (0.2 μm), Poly (methyl methacrylate / methacrylic acid = 9: 1 (molar ratio), 0.3 μm), polystyrene beads (0.25 μm) and colloidal silica (0.03 μm) on.

Preferred, usable according to the invention, Photosensitive materials are disclosed in JP-A-125558/1992, page 14, left upper column, line 1 to page 18, left lower column, line 11 described. In particular, as the silver halide emulsion, silver iodobromide emulsions are disclosed with an average silver iodide content of 3-20 mol% preferred and preferred are those containing tabular grains an aspect ratio of not less than 5, and those having double structure grains a different halogen composition between indoor area and outdoor area. Furthermore, the double structure grains may have a Have layer structure, wherein the inner region with respect to the Halogen composition from the outside Area is clearly different. The aspect ratio is further preferred 5-20, even more preferred 6-12.

Further, it is preferred to be a monodisperse Emulsion, as described in US Pat. Nos. 3,574,628 and 3,655,394 described.

The photosensitive used in the invention Material preferably has a layer which is a light-insensitive fine-grained Silver halide with an average grain size of 0.02-0.2 μm. The fine-grained Silver halide is preferably a silver bromide, the silver iodide in an amount of 0.5-10 contains mol%.

Other additives used in the invention photosensitive material are used are described below.

In the inventive photosensitive Material can various types of dye-forming couplers can be used. The following couplers are particularly preferred.

Yellow coupler: coupler of formulas (I) and (II) of EP-A-502 424; Couplers of formulas (1) and (2) of EP-A-513 496 (in particular Y-28 on page 18); A coupler of formula (I) as described in claim 1 of EP-A-568,037; Coupler of the general formula (I) according to U.S. Patent No. 5,066,576 , Column 1, lines 45-55; Coupler of the general formula (I) of paragraph 008 of JP-A-274425/1992; Couplers described in claim 1 on page 40 of EP-A1-498 381 (especially D-35 on page 18); Coupler of formula (Y) on page 4 of EP-A1-447 969 [in particular Y-1 (page 17) and Y-54 (page 41)]; Couplers of formulas (II) to (IV) of U.S. Patent 4,476,219 , Column 7, lines 36-58 [in particular, (II-17), (II-19) (column 17) and (II-24) (column 19)].

Purple coupler: L-57 (page 11, right lower column), L-68 (page 12, right lower column) and L-77 (page 13, right lower column) of JP-A-39737/1991; ([A-4] -63 (page 134), [A-4] -73, -75 (page 139) of EP 456,257 ; M-4, -6 (page 26) and M-7 (page 27) of EP 486 565 ; M-45 (page 19) of EP-A-571 959; (M-1) (page 6) of JP-A-204106/1993; M-22 in paragraph 0237 of JP-A-362631/1992.

Teal coupler: CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14-16) from JP-A-204843/1992; C-7, 10 (page 35), 34, 35 (page 37), (I-1) and (I-17) (pages 42-43) from JP-A-43345/1992; Coupler of the general formula (Ia) or (Ib) in claim 1 of JP-A-67385/1994.

Polymer coupler: P-1 and P-5 (page 11) of JP-A-44345/1990.

Preferred couplers that develop a dye that has moderate diffusibility are those that are known in the art U.S. Patent 4,366,237 , GB-PS 2 125 570, EP-B-96 873 and DE-PS 32 34 533 are described.

Preferred examples of a coupler which can be used to correct for excessive absorption of a developed dye include yellow-colored cyan couplers of formulas (CI), (CII), (CIII) and (CIV) as described on page 5 of EP-A1 -456 257 (especially YC-86 on page 84); yellow colored magenta couplers ExM-7 (page 202), EX-1 (page 249) and EX-7 (page 251) of EP-A1-456 257; purple cyan couplers CC-9 (column 8) and CC-13 (column 10) of U.S. Patent 4,833,069 ; Coupler (2) (column 8) of U.S. Patent 4,837,136; and colorless masking couplers of the formula (A) according to claim 1 of WO 92/11575 (in particular the illustrative compounds on pages 36-45).

The packaging (cartridge, magazine), the according to the inventive Process to be processed, photosensitive material surrounds, is described below. A main material of the cartridge to be used may be a metal or a synthetic plastic, and preferred as such plastics are polystyrene, polyethylene, polypropylene and polyphenyl ether.

Further, the cartridge used in the present invention may contain various types of antistatic agents, and preferred are carbon black, metal oxide grains, nonionic, anionic, cationic or betaine type surfactants, polymers and the like. The cartridges containing these antistatic agents are described in JP-A-312537/1989 and JP-A-312538/1989. The resistance of the cartridge is preferably 10 ¹² Ω or less at 25 ° C and 25% relative humidity. The plastic cartridge is usually made of a plastic that contains soot or other pigments kneaded for light shielding. The size of the cartridge may be the usual 135 format. Further, due to the miniaturization of the cameras, it is advantageous to reduce the diameter of the 135 cartridge from 25 mm to 22 mm or less. The volume of the cartridge is not more than 30 cm ^3, and preferably not more than 25 cm ² . The weight of the plastic used for the cartridge and its housing is preferably 5-15 g.

Furthermore, the cartridge may have a structure wherein a film is released therefrom by rotation of a spur or a structure in which the end of a film in the body of the Cartridge is encapsulated, and the end of the film is made by rotation the spur axis in the same direction from the outlet of the cartridge issued. These structures are disclosed in U.S. Patents 4,834,306 and 5 226 613 discloses.

The processed photosensitive Material can be encapsulated in a cartridge again. In this Case, the cartridge to be used with that for the unprocessed photosensitive material is used, identical or thereof to be different.

According to the invention, a processing method not only in terms of adhesion properties and the wet-heat bleaching of the processed photosensitive Material is excellent, but also in terms of magnetic reproducibility of the photosensitive material comprising a magnetic recording layer having.

The present invention will become more detailed with reference to the following examples, however the present invention is not limited thereto.

EXAMPLE 1

Layers, each one below have been described on a cellulose triacetate film base (Carrier), which had a primer layer, multi-layered, whereby a Color negative film, Sample 101, was prepared.

Composition of the photosensitive Layers:

The essential materials used in each layer are classified as follows:
ExC: cyan coupler
ExM: Purple coupler
ExY: yellow coupler
ExS: sensitizing dye
UV: UV absorber
HBS: high boiling organic solvent
H: gelatin hardener

The numbers given for each component indicate the coating amount in units of g / m ² , and for silver halide in units of silver. With respect to the sensitizing dyes, the coating amount in moles per mole of silver halide is given in the same layer.

Furthermore, to improve the Conservability, processability, pressure resistance, the Anti-mold and antibacterial properties, anti-static properties and the coating properties, the compounds W-1 to W-3, B-4 to B-6 and F-1 to F-17, and salts of iron, lead, gold, platinum, Palladium, iridium and rhodium suitably to each layer added.

Details of this example used emulsions are given in Table 1.

• (1) die Emulsionen J bis L einer Reduktionssensibilisierung unter Verwendung von Thioharnstoffdioxid und Thiosulfonsäure bei der Herstellung der Körnern gemäss dem in JP-A-191938/1990 beschriebenen Beispiel unterzogen.
• (2) Die Emulsionen A bis I wurden einer Goldsensibilisierung, einer Schwefelsensibilisierung und einer Selensensibilisierung in Gegenwart entsprechender Sensibilisierungsfarbstoffe, wie sie bei jeder Schicht beschrieben sind, und Natriumthiocyanat gemäss dem Beispiel unterworfen, das in JP-A-237450/1991 beschrieben ist.
• (3) Bei der Herstellung von tafelförmigen Körnern wurde niedermolekulargewichtige Gelatine gemäss dem Beispiel verwendet, das in JP-A-158426/1989 beschrieben ist.
• (4) In den tafelförmigen Körnern wurden unter einem Hochspannungs-Elektronenmikroskop Dislokationslinien beobachtet, wie in JP-A-237450/1991 beschrieben.
• (5) Die Emulsion L enthielt Doppelstrukturkörner, wobei die Körner einen hohen Kerniodidgehalt aufwiesen, wie in JP-A-143331/1985 beschrieben.

In Table 1 were

• (1) The emulsions J to L are subjected to reduction sensitization using thiourea dioxide and thiosulfonic acid in the preparation of the grains according to the example described in JP-A-191938/1990.
• (2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of respective sensitizing dyes as described in each layer and sodium thiocyanate according to the example described in JP-A-237450/1991.
• (3) In the production of tabular grains, low molecular weight gelatin according to the example described in JP-A-158426/1989 was used.
• (4) Dislocation lines were observed in the tabular grains under a high voltage electron microscope as described in JP-A-237450/1991.
• (5) The emulsion L contained double structure grains, the grains having a high core iodide content as described in JP-A-143331/1985.

Preparation of a dispersion an organic solid disperse dye:

ExF-2, as described below dispersed by the following method. Water (21.7 ml) and one 5% aqueous solution of sodium p-octylphenoxyethoxyethane sulfonate (3 ml) and a 5% aqueous solution p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) (0.5 g) were placed in a pot mill (700 ml) and further the dye ExF-2 (5.0 g) and Zirconia beads (diameter: 1 mm) (500 ml) were added and then was the mix for 2 hours dispersed. For dispersion was a vibrating ball mill from BO type manufactured by Chuo Koki Co., Ltd. used. After Dispersing the mixture was removed and to 8 g of 12.5% aqueous gelatin solution and then the spheres were separated by filtration, whereby a gelatin dispersion of the dye was obtained. The average grain size of the dye in the form of fine grains was 0.44 μm.

In the same way were solid dispersions obtained from ExF-3, ExF-4 and ExF-6. The average grain size of this Dyes in the form of fine grains was 0.24 μm, 0.45 μm or 0.52 μm. On the other hand, ExF-5 was subjected to the micro-precipitation dispersion method which is described in Example 1 of EP-A1-549 489. The average grain size of the dye was 0.06 μm.

Sample 101 above was cut to 135 film size (equivalent to International Standard ISO 1007) and the cut film was exposed through a wedge. Then, with the exposed photosensitive film material in an amount of 9 m ² / day for two months, the processing was carried out under the conditions shown below. The processing apparatus used was an autoprocessor FNCP-300 II manufactured by Fuji Photo Film Co., Ltd. The temperature of the processing solutions was adjusted to and maintained at the following processing temperatures during the test period.

The composition of the processing solutions was as follows:

For the photosensitive material thus processed by the method described above, the adhesion properties of the photosensitive material were evaluated by the method described below. Further, the light bleaching was evaluated. adhesion: The samples were cut into strips of 23 cm in length after completion of the entire processing, and each strip was coated in Fuji Color-Nega sheets [solid color (plain)) / brand name manufactured by Fuji Color Hanbai Co., Ltd .] shrouded. Subsequently, two frame sheets were put on both surfaces of the Nega Sheet, and then, under a humid condition (60 ° C / 60%), a weight of 1 kg per 25 cm ^{2 was} applied. These conditions were maintained for 4 weeks and then the adhesion between the samples and nega sheets was evaluated. O: The sample can be quickly removed from the Nega Sheet and no scratching is found on the sample. Δ: Slight adhesion between sample and Nega Sheet is observed, but the sample can be removed. x: Strong adhesion between sample and Nega Sheet, and adhesion marks are observed on the sample taken. Wet Warmausbleichung: For each of the processed samples, a density measurement was made and the _Dmax value measured with blue light (B light) was read from the respective curve. Subsequently, the photosensitive material thus measured was stored under the conditions described above, and _Dmax was measured in the same manner over time. A change in _{Dmax of} the yellow dye over time was determined according to the following formula: Storage Condition: Temperature 60 ° C; relative humidity 80%; 2 weeks [change of D _max over time (ΔD _max (B))] = (D _max before storage) - (D _max after storage)

The results thus obtained are in Table 2.

As from the results in table 2, it has been found that the process according to the invention processed samples had a minimized adhesion and in terms of the moist-warm bleaching were excellent.

EXAMPLE 2

The carrier of the photosensitive Materials and the backsheet were prepared as described below and those in Example 1 of the present application, photosensitive layers were on the carrier layered, causing the photosensitive materials of the sample 102 were made.

(1) Carrier:

The one used in the present example carrier was prepared as follows:

100 parts by weight of polyethylene-2,6-naphthalene polymer and 2 parts by weight of Tinuvin P. 326 (trade name, manufactured by Ciba-Geigy Co.) as a UV absorber were dried and then melted at 300 ° C. Subsequently, they were extruded through a T-die, stretched at 140 ° C in the longitudinal direction 3.3 times and then at 130 ° C in the width of 3.3 times, and then thermally fixed at 250 ° C for 6 seconds, whereby a PEN film having a thickness of 90 microns was obtained. To the PEN sheet were added suitable amounts of a blue dye, a magenta dye, and a yellow dye (I-1, I-4, I-24, I-26, I-27, II-5 as disclosed in Kokai Giho: Kogi No 94-6023). Further, this film was wound on a 20 cm diameter stainless steel core (coil) and then thermally annealed at 110 ° C for 48 hours to obtain a support having suppressed coring nucleation.

(2) stratification of a Primer layer:

An undercoat layer having the composition mentioned below was coated on each side of the above carrier, after both surfaces of the support of a corona discharge, UV discharge and glow discharge treatment were subjected (10 cm ³ / m ^2, there was a bar coater used). The primer layer was provided on the side which was heated to a higher temperature at the time of stretching. The drying was carried out at 115 ° C for 6 minutes (the roller and the advancing device in the drying zone were all set to 115 ° C).

(3) Stratification of a Backside layer:

On the other side of the above support which was coated with the primer layer were used as the backsheet layer an antistatic layer, a magnetic recording layer and a lubricant layer, each having the below-mentioned compositions show, piled up.

(3-1) Stratification of a Antistatic layer:

A layer with the following composition was piled up.

(3-2) Stratification of a magnetic recording layer:

3-poly (degree of polymerization: 15) -oxyethylenepropyloxytrimethoxysilane (15% by weight) - coated CO-γ-Fe ₂ O ₃ (specific surface area: 43 m ² / g, major axis: 0.14 μm, minor axis: 0.03 μm Saturation magnetization: 89 emu / g, Fe ²⁺ / Fe ³⁺ = 6:94, the surface was treated with 2% by weight each, based on Fe ₂ O ₃ , alumina and silica, the dispersion of the iron oxide was in an open kneader and carried out with a sand mill) (0.06 g / m ² ), diacetylcellulose (1.2 g / m ² ) and the hardener C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (CH ₃ ) NO) ₃ ( 0.3 g / m ² ) were coated using acetone, methyl ethyl ketone and cyclohexanone as a solvent by means of a bar coater, whereby a magnetic recording layer having a thickness of 1.2 μm was obtained. Silica grains (0.3 μm) as a matting agent and 3-poly (polymerization degree: 15) -oxyethylenepropyloxytrimethoxysilane (15% by weight) coated aluminum oxide (0.15 μm) as an abrasive were added thereto, thereby providing a coverage of 10 mg / m ² was obtained. It was dried at 115 ° C for 6 minutes (the roller and the advancing device in the drying zone were all set to 115 ° C). The increment of the color density DB of the magnetic recording layer was about 0.1 when X-light (blue filter) was used. The saturation magnetization of the magnetic recording layer was 4.2 emu / g, the coercive force was 7.3 × 10 ⁴ A / m, and the squareness ratio was 65%.

(3-3) Preparation of a lubricant:

A lubricant layer was prepared by coating the following composition so that the solids content the coating amount of the following amount corresponded, and the layer was at 115 ° C for 6 minutes dried, whereby a lubricant layer was prepared (the The roller and the conveyor in the drying zone were all at 115 ° C ) Is set.

The mixture of compound (a) / compound (b) (6: 9) was dissolved in a solution of xylene and propylene glycol monomethyl ether (1: 1) at 105 ° C and this solution was added to 10 times the volume of propylene glycol monomethyl ether (25 ° C ) and finely dispersed. This was further dispersed in acetone, and the obtained dispersion (average grain diameter: 0.01 μm) was added to the coating solution. Silica grains (0.3 μm) as a matting agent and 3-poly (polymerization degree: 15) -oxyethylenepropyloxytrimethoxysilane (15% by weight) coated aluminum oxide (0.15 μm) as an abrasive were added thereto, whereby a coverage of 15 mg / m ² was obtained. The lubricant layer showed excellent quality of dynamic friction coefficient: 0.06 (5 mm diameter stainless steel ball, load: 100 g, speed: 6 cm / min) and the static friction coefficient: 0.07 (clip method). The sliding properties of the lubricant layer having the surface of the emulsion described below were also excellent, so that the dynamic friction coefficient was 0.12.

The sample 102 thus prepared was cut into a strip having a length of 160 cm and a width of 24 mm. Two perforations of 2 mm edge length were made at intervals of 5.8 mm, which were located in a position of 0.7 mm in the widthwise direction and on one side in the longitudinal direction of the photosensitive material. Furthermore, sets of such two perforations were placed at intervals of 32 mm. The sample was encapsulated in a plastic film cartridge as in the 1 to 7 from U.S. Patent 5,296,887 shown.

The sample 102 was with a wedge and then into a camera with a built-in magnetic recording device with a head gap of 5 μm, a speed of 50, made of permalloy used. Under Application of a recording wavelength of 50 μm became a digital saturation recording carried out.

The sample 102 with as described above, recorded magnetic information was recorded with the sample 101, cut in the same manner as in Example 1, processed and exposed according to the same procedure as in Example 1 described except that the development solution, the bleach solution and the fixing solution through the following solutions have been replaced. Here was the ratio of processing amounts between sample 101 and sample 102 5: 1.

After completion of processing under the respective conditions, the adhesion properties became and the wet heat bleaching of Sample 101 in the same manner as examined in Example 1. Further, based on the sample 102 on a 150 m section from the point at the end of processing to the appropriate point before completion of processing the reproduced signal level of the isolated frequency by means of a Magnetic playback head with a head gap of 2.5 microns and a 2,000 rpm, made from Sendust. The results obtained are shown in Table 3. Regarding the Results of the magnetic reproduction became the average Output power defined at the beginning of the measurement to 1 m as 100, and the average playback power of the last 1 m section to the above value of 100, was given in%.

As shown in Table 3, the present invention also in terms of magnetic output power excellent.

EXAMPLE 3

The processing and the evaluation the samples were carried out in the same manner as in Example 2, except that the bleaching and stabilizing solutions by the below have been replaced.

After completion of processing under the respective conditions, the light bleaching and the magnetic output in the same way as in example 2 measured. It was confirmed that excellent effects can be achieved by the present invention.

EXAMPLE 4

The sample 102 described in Example 2 was cut and exposed, and then magnetic information was recorded on the sample 102. Thereafter, the sample was mixed with Sample 101 as described in Example 1. A total of 6 m ² per day of the photosensitive materials were processed under the conditions described below for three (3) months. Here, the ratio of the processed amounts between the samples 101 and 102 was 5: 2. As the processing apparatus, an autoprocessor FP-560B (manufactured by Fuji Photo Film Co., Ltd.) was used, but it was modified so that the overflow solution from the Bleach did not drain into the next bath but was dumped into a waste tank. Further, the autoprocessor FP-560B had means for correcting the evaporation, as described in Kokai-goho No. 94-4992 (Hatsumei-Kyokai).

The processing steps and the Composition of the processing solutions used in this example are shown below.

Stabilization and fixation were carried out in countercurrent mode from tank (2) to tank (1). The excess solutions from the washing step were all introduced into the fixer (2). Further, the carry amount of the color developer in the bleaching step, the carry amount of the bleaching solution in the fixing step, the carry amount of the fixing solution in the washing step and the carry amount of washing water in the stabilizing step were 65 ml, 50 ml, 50 ml and 50 ml per m ² of photosensitive, respectively Material of 35 mm width. Each transfer time was 6 seconds and included in the processing time of the previous step.

Each opening area in the processor was 100 cm ² for the color developer, 120 cm ² for the bleaching solution and about 100 cm ² for other processing solutions.

Using the tank volumes and the opening areas in the processing device can the opening ratios for every processing solution as defined in the above description. The composition the processing solutions was like this.

As a result of processing has been approved, that the inventive Processing methods have excellent effects on the adhesion property, the moist-warm bleaching and the magnetic reproducibility of the processed photosensitive Provides materials as shown in Example 2.

Claims (9)

A method of processing a silver halide color photographic light-sensitive material, the method comprising the steps of color development of a silver halide color photographic light-sensitive material and then desilvering and further washing and / or stabilizing it, wherein a bleaching-action processing solution in the desilvering step is a ferric complex salt of at least one compound of general Formula (X) contains:

wherein R is a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group; L ₁ and L ₂ are each an alkylene group; and M ₁ and M ₂ each represent a hydrogen atom or a cation; characterized in that a processing solution used in the desilvering step or steps subsequent thereto contains at least one compound of the general formulas (A) to (I):

wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ and R ₈ each represents a hydrogen atom, an alkyl group or an aryl group; R ₆ is a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxyl group, a sulfo group, a sulfamoyl group, a hydroxyl group, a halogen atom, an alkoxy group or a thiazolyl group; L ₃ and L ₄ each represent an alkylene group or an arylene group; R ₉ , R ₁₀ and R ₁₁ each represent a halogen atom or an alkyl group; R ₁₂ and R ₁₃ each represent a What a hydrogen atom, an alkyl group, an aryl group or a nitrogen-containing heterocyclic radical; R ₁₄ and R ₁₅ each represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, with the proviso that R ₁₄ and R ₁₅ may be bonded to each other to form a benzene ring; R ₁₆ is a hydrogen atom or an alkyl group; R ₁₇ is an alkyl group or an aryl group; Y is a halogen atom; Z ₁ is a group of non-metal atoms required to complete a thiazolyl ring; Z ₂ is a group of non-metal atoms required to complete a 6-membered hydrocarbon ring; n is 0 or 1; m is 1 or 2; and k is an integer of 3-20; or at least one aminoglycoside selected from gentamycins, amikacin, tobramicin, dibekacin, albekacin, micronomicin, isepamicin, sisomicin, netilmicin and astromicin; and the processing solution having bleaching action further contains at least one compound of the general formula (J)

wherein Q is a group of non-metal atoms necessary to complete a heterocyclic ring; p is 0 or 1; and Ma is a hydrogen atom or a cation. Process for processing a photosensitive The silver halide color photographic material of claim 1, wherein the processing solution, the at least one compound of the general formula (A), (B), (C), (D), (E), (F), (G), (H) or (I) or at least one aminoglycoside contains a processing solution with bleaching action, a washing water or a stabilizing solution. Process for processing a photosensitive color photographic silver halide material according to claim 1, wherein R in the general formula (X) represents a hydrogen atom or an alkyl group with 1-8 carbon atoms is. Process for processing a photosensitive color photographic silver halide material according to claim 3, wherein R in the general formula (X) is a hydrogen atom. A method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the compound of the general formula (X) is a compound of the general formula (1-a):

wherein L _{1 is} an alkylene group; M ₁ is a hydrogen atom or a cation; and Ma ₁ and Ma ₂ each represent a hydrogen atom or a cation. Process for processing a photosensitive The silver halide color photographic material of claim 1, wherein the ferric complex salt at least one compound of the general formula (X) in one bleach solution is included. Process for processing a photosensitive color photographic silver halide material according to claim 1, 2, 3, 4, 5 or 6, wherein the silver halide color photographic light-sensitive material is a color negative film. Process for processing a photosensitive color photographic silver halide material according to claim 1, 2, 3, 4, 5, 6 or 7, wherein the silver halide color photographic light-sensitive material has a having magnetic recording layer. Process for processing a photosensitive color photographic silver halide material according to claim 8, wherein the magnetic Recording layer Co-coated ferromagnetic iron oxide contains.