JP3544245B2 - Processing method of silver halide color photographic light-sensitive material - Google Patents

Description

[0001]
[Industrial applications]
The present invention relates to a method for processing a silver halide color photographic light-sensitive material (hereinafter sometimes simply referred to as a light-sensitive material), and particularly to a processing method even when a long-term processing is performed using a bleaching agent having excellent biodegradability. The present invention relates to a processing method for improving the adhesiveness of a later photosensitive material, the wet heat discoloration of a yellow dye, and the magnetic output of a photosensitive material having a magnetic recording layer.
[0002]
[Prior art]
In general, the processing of a silver halide color photographic light-sensitive material is based on a color developing step and a desilvering step, and is performed using a processor called an automatic developing machine, including other auxiliary steps. In the desilvering step, silver produced in the color developing step is oxidized by the action of an oxidizing agent called a bleaching agent contained in the processing solution having the bleaching ability, and thereafter, the fixing contained in the processing solution having the fixing ability is performed. It is dissolved and removed from the photosensitive material by a silver ion solubilizing agent called an agent.
[0003]
On the other hand, from the standpoint of global environmental protection in recent years, ethylenediamine-N, N, N ', N'-tetraacetic acid and 1,3-propanediamine-N, N, N', which have been widely used as bleaching agents, have been used. It has been desired to use a material having excellent biodegradability with respect to a material such as N'-tetraacetic acid which is hardly biodegradable in nature. For example, a diamine type compound described in JP-A No. 4-313,752 may be used. Monoamine type compounds and the like described in JP-A-5-265159 and JP-A-6-161665 are described.
[0004]
[Problems to be solved by the invention]
In addition, since the nitrogen component in the treatment liquid is an environmental polluting component, from the standpoint of environmental protection, among these compounds having excellent biodegradability, a monoamine type compound having a small nitrogen component is preferable. However, among these monoamine type compounds having excellent biodegradability, if the processing of the photosensitive material is carried out for a long time using the compound, the processed photosensitive material becomes easily adherent. For example, a color negative film can be used as a negative sheet. It was confirmed that there was a problem that it became difficult to take out of the so-called bag, or that the yellow dye among the dyes forming an image tended to deteriorate in wet heat.
[0005]
Further, with respect to the photosensitive material having a magnetic recording layer described in International Publication WO 90/04205, a problem that the reading performance of magnetic recording was remarkably reduced was confirmed. The processing of a photosensitive material having a magnetic recording layer with a bleaching solution containing an iron (III) complex salt of an aminopolycarboxylic acid is described in JP-A-6-95318. It describes the effect of concentration change and liquid stability of the material on aging with heat and humidity, and no recognition of the effect on the reading of magnetic recording can be found.
Although the detailed reasons for these phenomena are not yet clear, it is presumed that some difference occurred in the adhesion of the processing solution components to the photosensitive material.
[0006]
Therefore, the first problem to be solved by the present invention is that even if the treatment is performed for a long time using a material having excellent biodegradability, the adhesiveness of the photosensitive material after the treatment and the wet heat discoloration of the yellow dye deteriorate. An object of the present invention is to provide a method of processing a silver halide color photographic light-sensitive material which is not to be performed. A second object of the present invention is to provide a processing method which does not lower magnetic recording reading performance even when processing a photosensitive material having a magnetic recording layer.
[0007]
[Means for Solving the Problems]
The above object has been achieved by the following method.Has a magnetic recording layerIn a method in which a silver halide color photographic light-sensitive material is subjected to desilvering processing after color development, followed by washing and / or stabilizing processing, a processing solution having the bleaching ability in the desilvering step is represented by the following general formula (1-a) A) a compound containing at least one iron (III) complex salt of a compound represented by the following general formula (A) to (I): At least one ofOrGentamicinofA method for processing a silver halide color photographic light-sensitive material, characterized by containing at least one kind.
General formula (1-a)
[0008]
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[0009]
(2) (where, L ₁ IsRepresents a alkylene group. M₁,Ma ₁ as well asMa _Two Represents a hydrogen atom or a cation, respectively. )
General formulas (A) to (I)
[0010]
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[0011]
(Where R₁, R₂, R₃, R₄, R₅, R₇And R₈Represents a hydrogen atom, an alkyl group or an aryl group, respectively. R₆Represents a hydrogen atom, an alkyl group, an aryl group, a nitro group, a carboxy group, a sulfo group, a sulfamoyl group, a hydroxy group, a halogen atom, an alkoxy group or a thiazolyl group. L₃And L₄Represents an alkylene group or an arylene group, respectively. R₉, R₁₀, And R₁₁Represents a halogen atom or an alkyl group, respectively. R₁₂And R_ThirteenRepresents a hydrogen atom, an alkyl group, an aryl group or a nitrogen-containing heterocyclic residue, respectively. R₁₄And R_FifteenRepresents a hydrogen atom, a halogen atom, an alkyl group or an aryl group, respectively. Note that R₁₄And R_FifteenMay combine with each other to form a benzene ring. R₁₆Represents a hydrogen atom or an alkyl group. R₁₇Represents an alkyl group or an aryl group. Y represents a halogen atom. Z₁Represents a group of nonmetallic atoms necessary for constituting a thiazolyl ring. Z₂Represents a nonmetallic atomic group necessary for forming a 6-membered hydrocarbon ring. n represents 0 or 1. m represents 1 or 2. k represents an integer of 3 to 20. )
[0012]
In the present invention, the light-sensitive material is processed with a color developing solution, desilvered, and then washed with water and / or processed with a stabilizing solution.
In the desilvering process, basically, after a bleaching process with a processing solution having a bleaching ability, a fixing process is performed with a processing solution having a fixing ability. As described above, the bleaching process and the fixing process may be performed separately, or may be performed simultaneously with a bleach-fixing solution having both bleaching ability and fixing ability (bleach-fixing process). Each of these bleaching, fixing and bleach-fixing processes may be performed in one tank or in two or more tanks.
[0013]
The processing solution having a bleaching ability in the present invention means a processing solution containing a bleaching agent among the processing solutions used in the desilvering step, and specifically refers to a bleaching solution and a bleach-fixing solution. Specific embodiments of the desilvering treatment in the present invention are described below, but are not limited thereto.
1. Bleaching-fixing
2. Bleaching and fixing
3. Bleaching-bleach fixing
4. Bleach-fix-bleach-fix
5. Bleaching-Bleaching-Fixing
6. Bleaching-bleach-fixing-bleach-fixing
7. Bleaching-fixing-fixing
8. Bleach-fix-bleach-fix
9. Bleaching-fixing
10. Bleaching-Bleaching
Note that a water washing step may be optionally provided between these treatments.
[0014]
First, the general formula of the present invention (1-aThe compound (1) will be described in detail. The number of carbon atoms described below is the number of carbon atoms excluding the substituent.
[0015]
L ₁ The alkylene group represented by, May have a substituent.
[0016]
Examples of the substituent include an aryl group (preferably having 6 to 12 carbon atoms, more preferably having 6 to 10 carbon atoms, particularly preferably having 6 to 8 carbon atoms, and examples thereof include phenyl and p-methylphenyl). An alkoxy group (preferably having 1 to 8 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, for example, methoxy, ethoxy, etc.), an aryloxy group (preferably having 1 to 8 carbon atoms) 6 to 12, more preferably 6 to 10 carbon atoms, particularly preferably 6 to 8 carbon atoms, such as phenyloxy and the like, and an acyl group (preferably 1 to 12 carbon atoms, more preferably carbon number). 2 to 10, particularly preferably 2 to 8 carbon atoms, for example, acetyl and the like.), Alkoxycarbonyl group (preferably 2 to 12 carbon atoms, more preferably Or 2 to 8 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, methoxycarbonyl and the like.), Acyloxy group (preferably 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, especially It preferably has 2 to 8 carbon atoms, for example, acetoxy and the like.), An acylamino group (preferably 1 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, Examples thereof include acetylamino and the like, and a sulfonylamino group (preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methanesulfonylamino. ), A sulfamoyl group (preferably having 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, particularly preferably 0 to 4 carbon atoms; Famoyl, methylsulfamoyl and the like.), Carbamoyl group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, such as carbamoyl and methylcarbamoyl) ), An alkylthio group (preferably having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably having 1 to 4 carbon atoms, such as methylthio and ethylthio), and a sulfonyl group. (Preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methanesulfonyl, etc.), a sulfinyl group (preferably 1 to 8 carbon atoms, More preferably, it has 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methanesulfinyl. Roxy group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxy group, nitro group, heterocyclic group (eg, imidazolyl, pyridyl) and the like. These substituents may be further substituted. When there are two or more substituents, they may be the same or different.
[0017]
L ₁ Alkylene represented byThe substituent of the group is preferably an alkoxy group, a carboxy group, a hydroxy group, or a sulfo group, and more preferably a carboxy group or a hydroxy group. The aliphatic hydrocarbon group represented by R is preferably an alkyl group, more preferably a chain alkyl group, and still more preferably methyl, ethyl, carboxymethyl, 1-carboxyethyl, 2-carboxyethyl, 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, 4-imidazolylmethyl And particularly preferably methyl, carboxymethyl, 1 Carboxyethyl, 2-carboxyethyl, 1,2-dicarboxyethyl, 1-carboxy-2-hydroxyethyl, 2-carboxy-2-hydroxyethyl, 2-hydroxyethyl, 1-carboxypropyl, 1-carboxybutyl, , 3-dicarboxypropyl, 1-carboxy-2-phenylethyl, 1-carboxy-3-methylthiopropyl.
[0023]
L ₁ soAlkylene group representedIs straightIt may be chain-like, branched or cyclic. Further, it may have a substituent, and as the substituent,the aboveReplacebaseOthers include an alkenyl group (preferably having 2 to 8 carbon atoms, more preferably having 2 to 6 carbon atoms, particularly preferably having 2 to 4 carbon atoms, and examples thereof include vinyl and allyl), and an alkynyl group (preferably having carbon atoms). 2 to 8, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as propargyl.).L ₁ soThe substituent of the alkylene group represented is preferably an aryl group, an alkoxy group, a hydroxy group, a carboxy group, or a sulfo group, and more preferably an aryl group, a carboxy group, or a hydroxy group.L ₁ soThe alkylene group represented by the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably substituted or unsubstituted methylene or ethylene.
[0024]
Preferred specific examples of the alkylene group include, for example, methylene, ethylene, trimethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1,2-cyclohexylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethyl Methylene, hydroxymethylmethylene, 2-hydroxyethylmethylene, carbamoylmethylmethylene, phenylmethylene, benzylmethylene, 4-imidazolylmethylmethylene, 2-methylthioethylmethylene, more preferably methylene, ethylene, methylmethylene, ethylmethylene, n -Propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, carboxyethylmethylene, hydroxymethylmethylene, benzylmethyl And methylene, ethylene, methylmethylene, ethylmethylene, n-propylmethylene, n-butylmethylene, 1-carboxymethylene, carboxymethylmethylene, and hydroxymethyl. Methylene and benzylmethylene.
[0025]
M₁,Ma ₁ as well asMa _Two Represents an organic or inorganic cation, for example, an alkali metal (Li⁺, Na⁺, K⁺, Cs⁺), Alkaline earth metals (Mg²⁺, Ca²⁺And the like, ammonium (ammonium, trimethylammonium, triethylammonium, tetramethylammonium, tetraethylammonium, tetrabutylammonium, 1,2-ethanediammonium and the like), pyridinium, imidazolium, phosphonium (tetrabutylphosphonium and the like) and the like. . M₁, M_TwoIs preferably an alkali metal or ammonium, more preferably Na⁺, K⁺, NH_Four ⁺It is.
[0026]
The general formula (1-aIn the case where the compound represented by the formula (1) has an asymmetric carbon in the molecule, it is preferable that at least one asymmetric carbon is an L-form from the viewpoint of biodegradability. Further, when the compound has two or more asymmetric carbons, the more the L-form structure of the asymmetric carbon part, the more preferable.
[0029]
More preferably, L in the general formula (1-a)₁Is a substituted or unsubstituted methylene or ethylene;₁, M_a1, M_a2Is a hydrogen atom, an alkali metal or ammonium, and more preferably L₁Is a substituted or unsubstituted methylene having a total carbon number of 1 to 10 including a substituent,₁, M_a1, M_a2Is a hydrogen atom, Na⁺, K⁺, NH₄ ⁺This is one of the cases.
[0030]
The general formula (1-a)), But the present invention is not limited thereto. In addition, compounds described as L in the compounds indicate that the asymmetric carbon portion of the described portion is L-form, and those without description indicate that the compound is a mixture of D and L.
[0031]
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[0032]
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[0035]
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[0036]
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[0038]
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[0039]
The above compound may be one in which the hydrogen atom of the carboxy group has become a cation. In this case, the cation is represented by the general formula (1-aM in)₁,Ma ₁ And Ma _Two Has the same meaning as defined for the cation represented by The general formula of the present invention (1-a) Are described, for example, in Journal of Inorganic and Nuclear Chemistry, Vol. 35, p. 523 (1973) (Journal of Inorganic and Nuclear Chemistry Vol. 35, 523 (1973)), Swiss Patent No. 561504 German Patent Nos. 39125551A1, 3939755A1 and 3939756A1, JP-A-5-265159 and JP-A-6-59422 (Exemplified compounds 1-42), 1Synthesis methods of -46, 1-52, and 1-53 are described in Synthesis Examples 1, 2, 3, 4, and 6. 6-95319 (the synthesis method of L-form of Exemplified Compounds 1-8, 1-11, 1-37, 1-38 and 1-40 is described in Synthesis Examples 2 to 6) and 6 Compounds can be synthesized according to the methods described in JP-A-161054 and JP-A-6-161665.
[0040]
In the present invention, the general formula (1-aAs the iron (III) complex salt of the compound represented by the formula (1), a compound previously extracted as an iron (III) complex salt may be added, or the compound represented by the general formula (1-a) And an iron (III) salt (for example, iron (III) nitrate, ferric chloride, etc.) may coexist to form a complex in the treatment solution. In addition, the general formula (1-a) May be used alone or in combination of two or more. In the present invention, the general formula (1-aIs more than the amount required for complex formation of iron (III) ions (for example, 0.5 mole, 1 mole, 2 moles, etc. with respect to iron (III) ion). It may be slightly excessive, and when it is excessive, it is usually preferable to make the excess in the range of 0.01 to 15 mol%.
[0041]
The organic acid iron (III) complex salt contained in the processing solution having the bleaching ability of the present invention may be used as an alkali metal salt or an ammonium salt. As the alkali metal salt, lithium salt, sodium salt, potassium salt and the like, and as the ammonium salt, ammonium salt, tetraethylammonium salt and the like can be mentioned.In the present invention, the ammonium ion concentration in the processing solution having bleaching ability is It is preferably from 0 to 0.4 mol / l, particularly preferably from 0 to 0.2 mol / l.
[0042]
In the present invention, the bleaching agent has a general formula (1-aIn addition to the iron (III) complex salt of the compound represented by the formula (1), for example, ethylenediamine-N, N, N ', N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediaminetetraacetic acid, glycol etherdiaminetetraacetic acid Iron (III) complex salts of known compounds such as acetic acid and 1,3-propanediamine-N, N, N ', N'-tetraacetic acid, and inorganic compounds such as red blood salts, persulfates, hydrogen peroxide and bromates The oxidizing agent of the formula (I) can be used in combination.1-a) Is preferably 70 to 100 mol%, more preferably 80 to 100 mol%, particularly preferably 100 mol%.
[0043]
In the present invention, the general formula (1-aThe compound represented by the formula (1) is suitably in the range of 0.003 to 3.00 mol / l, preferably in the range of 0.02 to 2.00 mol / l, and more preferably in the range of 0.05 to 1.00. Mol / l, and particularly preferably in the range of 0.08 to 0.5 mol / l. When the inorganic oxidizing agent as described above is used in combination, the total concentration of the iron (III) complex salt is 0. The range is preferably 0.005 to 0.030 mol / liter.
[0044]
In the present invention, at least one of the compounds represented by formulas (A) to (I) is added to the processing solution used in the desilvering step or subsequent steps.OrGentamicinofContains at least one.
[0045]
The compounds represented by formulas (A) to (I) will be described.
Among the compounds represented by formulas (A) to (I), preferred are compounds represented by formulas (B), (G) and (H), and more preferred are compounds represented by formulas (G) and (H). It is what is done.
R₁~ R₁₇The alkyl group in may be substituted, and is preferably a straight-chain, branched or cyclic one having 1 to 30 carbon atoms, and examples thereof include methyl, ethyl, octyl, dodecyl, tetradecyl, and octadecyl. .
R₁~ R₈The aryl group of may be substituted, may be monocyclic or condensed, and preferably has 6 to 20 carbon atoms, and examples thereof include phenyl and naphthyl.
R₆The sulfamoyl group in may be substituted and preferably has 0 to 30 carbon atoms, and examples thereof include sulfamoyl and N, N'-dimethylsulfamoyl. R₆The alkoxy group in may be substituted and preferably has 1 to 30 carbon atoms, for example, methoxy, ethoxy, octyloxy and the like. R₆May be substituted and may be bonded at the 2-, 4- or 5-position.
[0046]
L ₃ as well asL ₄ The alkylene group in may be substituted, and is preferably a straight-chain, branched or cyclic one having 1 to 10 carbon atoms, and examples thereof include methylene, ethylene and propylene.L ₃ as well asL ₄ The arylene group in may be substituted and preferably has 6 to 10 carbon atoms, and examples thereof include phenylene and naphthylene. R₆, R₉, R_Ten, R₁₁, R₁₄, R₁₅And the halogen atom for Y include a chlorine atom, a fluorine atom and a bromine atom. R₁₂And R₁₃Is preferably a 5- to 8-membered saturated or unsaturated one, and the hetero atom other than the nitrogen atom is preferably an oxygen atom or a sulfur atom. Examples of the nitrogen-containing heterocyclic residue include 2-oxazolyl, 3-isoxazolyl, 3-pyrrolyl, 2-imidazolyl, 5-pyrazolyl, 5-isothiazolyl, 2-1, 3,4-thiadiazolyl, 4-thiadiazolyl, -Pyridyl, 2-pyrimidyl and the like. Z₁Represents a group of nonmetallic atoms necessary for constituting a thiazolyl ring. The thiazolyl ring may be substituted and may be bonded at the 2-, 4- or 5-position. Z_TwoRepresents a group of nonmetallic atoms necessary for forming a 6-membered hydrocarbon ring, and may be saturated or unsaturated. Examples of the 6-membered hydrocarbon ring include a cyclohexane ring and a cyclohexene ring.
[0047]
Examples of the substituent in the above-mentioned optionally substituted group include an alkyl group (eg, methyl, ethyl), an aralkyl group (eg, phenylmethyl), an alkenyl group (eg, allyl), an alkynyl group, and an alkoxy group (eg, methoxy, ethoxy) ), An aryl group (eg, phenyl, p-methylphenyl), an amino group (eg, dimethylamino), an acylamino group (eg, acetylamino), a sulfonylamino group (eg, methanesulfonylamino), a ureido group, a urethane group, an aryloxy group ( For example, phenyloxy), sulfamoyl (eg, methylsulfamoyl), carbamoyl group (eg, carbamoyl, methylcarbamoyl), alkylthio group (eg, methylthio), arylthio group (eg, phenylthio), sulfonyl group (eg, methanes) Phonyl), sulfinyl group (eg, methanesulfinyl), hydroxy group, halogen atom (eg, chlorine atom, bromine atom, fluorine atom), cyano group, sulfo group, carboxy group, phosphono group, aryloxycarbonyl group (eg, phenyloxycarbonyl) , An acyl group (eg, acetyl, benzoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), an acyloxy group (eg, acetoxy), a carbonamido group, a sulfonamido group, and a nitro group.
[0048]
In the general formula (A), R₁, R₂, R₃And R₄Is preferably an alkyl group, and R₁, R₂, R₃And R₄Is more preferably an alkyl group having 5 to 20 carbon atoms. As Y, a chlorine atom is particularly preferred.
In the general formula (B), R₅And R₆Is preferably a hydrogen atom, n is preferably 0, and Z is₁Preferably represents a group of nonmetallic atoms necessary for forming an unsubstituted 4-thiazolyl ring.
In the general formula (C), R₇Is preferably a hydrogen atom, and R₈Is preferably an alkyl group, more preferably an alkyl group having 5 to 20 carbon atoms.
In the general formula (D), L₃Is preferably an alkylene group having 5 to 10 carbon atoms, and k is preferably 3 to 10.
In the general formula (E), R₉, R₁₀, And R₁₁Is preferably an alkyl group or a halogen atom each substituted with at least one halogen atom, and particularly preferably a halogen atom. Z₂Is preferably a group of nonmetallic atoms necessary for forming a cyclohexene ring.
In the general formula (F), R₁₂And R_ThirteenIs preferably a hydrogen atom, an alkyl group or a nitrogen-containing heterocyclic residue, respectively.₁₂Is more preferably a hydrogen atom, and R_ThirteenIs preferably a hydrogen atom or a 5- or 6-membered nitrogen-containing unsaturated heterocyclic residue.
In the general formula (G), R₁₄And R_FifteenIs preferably a hydrogen atom or bonded to each other to form a benzene ring, more preferably bonded to each other to form a benzene ring,₁₆Is preferably a hydrogen atom.
In the general formula (H), R₁₇Is preferably an unsubstituted alkyl group having 1 to 4 carbon atoms.
In the general formula (I), L₄Is preferably an unsubstituted alkylene group having 2 to 4 carbon atoms.
Specific examples of the compounds represented by formulas (A) to (I) used in the present invention are shown below, but the present invention is not limited thereto.
[0049]
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[0050]
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[0051]
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[0052]
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[0053]
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[0054]
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[0055]
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[0056]
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[0057]
The compounds represented by the general formulas (A) to (I) are described in JP-A-60-263938, JP-A-59-228247, JP-A-54-27424, JP-A-1-211751 and the like in addition to the above examples. And includes examples of such compounds.
[0058]
The above-mentioned used in the present inventionGentamicinTypes will be described. Of the present inventionGentamicinAre compounds known as antibiotics, RiceNational Patent Nos. 3,091,572 and 3,136,704No. etc.Can be referred to. GetRepresentative examples of ntamycins are listed below.
[0059]
Compound No. B-1 (gentamicin A₂)
B-2 (gentamicin A)
B-3 (gentamicin A₁)
B-4 (gentamicin B)
B-5 (gentamicin X₂)
B-6 (Antibiotic JI-20A)
B-7 (gentamicin B₁)
B-8 (Antibiotic G418)
B-9 (Antibiotic JI-20B)
B-10 (gentamicin C₁)
B-11 (gentamicin C_1a)
B-12 (gentamicin C₂)
B-13 (gentamicin C_2a)
B-14 (gentamicin C_2b)
[0060]
Used in the present inventionGentamicinThe methods for producing the same are described in the aforementioned patents, but commercially available ones can be used. Further, these properties and the like are described in MERCK & CO., INC., 11th edition (1989), THE MERCK INDEX AN ENCYCLOPEDIA OF CHEMICALS, DRUGS, AND BIOLOGICALS.
[0061]
In the present invention, the compounds represented by the general formulas (G) and (H) and gentamicins are preferred, and the compounds represented by the general formulas (G) and (H) are particularly preferred.
[0062]
The compounds represented by the general formulas (A) to (I) of the present invention,GentamicinAre used in the processing solution used in the desilvering step or the subsequent steps as described above, and the processing solution is preferably a processing solution having a bleaching ability (eg, a bleaching solution, a bleach-fixing solution), Washing water and a stabilizing solution are preferred, and washing water and a bleaching solution are more preferred. The addition amount of these compounds is preferably 1 mg to 1 g, more preferably 5 mg to 500 mg per liter of the processing solution used in the desilvering step or thereafter. In order to add these compounds to the processing solution, they may be directly added to the processing solution, added to a replenisher and / or a replenisher of the processing solution, or may be brought in from a pre-bath. These compounds may be added to the light-sensitive material. These compounds may be used alone or in combination of two or more.
[0063]
When these compounds are difficult to dissolve, various auxiliary solvents can be added. Specific examples include methanol, ethanol, propanol, ethylene glycol, diethylene glycol, monoethanolamine, diethanolamine, triethanolamine, ethylenediamine, and the like.
[0064]
The processing solution having the bleaching ability of the present invention preferably contains a pH buffer, particularly preferably glycolic acid, succinic acid, maleic acid, malonic acid, glutaric acid, etc. Particularly, glycolic acid, malonic acid and succinic acid are preferred. The concentration of these buffers is preferably in the range of 0 to 3 mol / l, and particularly preferably in the range of 0.2 to 1.5 mol / l.
[0065]
In the present invention, the replenisher of the processing solution having the bleaching ability may be a liquid or a solid (powder, granules, tablets). In granules and tablets, it is also used as a binder. The use of a system surfactant is preferred.
To solidify the photographic processing agent, JP-A-4-29136, JP-A-4-85535, JP-A-4-85536, JP-A-4-88533, JP-A-4-85534, and JP-A-4-172341. As described in Japanese Patent Application Publication No. H07-27, a concentrated liquid or fine powder or a granular photographic processing agent and a water-soluble binder are kneaded and molded, or the water-soluble binder is sprayed on the surface of the temporarily formed photographic processing agent. Any means such as forming a coating layer can be adopted.
The method for producing the tablet processing agent can be produced by a general method described in, for example, JP-A-51-61837, JP-A-54-155038, JP-A-52-88025, and British Patent No. 1213808. Further, the granule treating agent can be produced by a general method described in, for example, JP-A Nos. 2-109042, 2-109043, 3-39735 and 3-39939. Further, the powder treating agent can be produced by a general method as described in, for example, JP-A-54-133332, British Patent Nos. 725892 and 729,862, and German Patent No. 3733861.
[0066]
When the replenisher of the processing solution having bleaching ability is composed of a liquid, it may be one liquid or a plurality of liquids composed of different components. Alternatively, two liquids are preferable, and one liquid is particularly preferable. At this time, the specific gravity of the replenisher is preferably 1.0 to 5 times, more preferably 1.5 to 3 times the specific gravity of the replenisher.
[0067]
The pH of the processing solution having the bleaching ability of the present invention is suitably from 3.0 to 7.0, and the pH of the bleaching solution is particularly preferably from 3.5 to 5.0. Is particularly preferably in the range of pH 4.0 to 6.5. In order to achieve such a pH, in the present invention, it is preferable to add the above-mentioned organic acid as a buffer agent. In addition, as an alkaline agent used for pH adjustment, ammonia water, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, and the like are preferable.
In order to adjust the pH of the processing solution having the bleaching ability of the present invention to the above-mentioned pH, the above-mentioned alkaline agent and a known acid (inorganic acid, organic acid) can be used.
[0068]
It is preferable that the treatment with the solution having the bleaching ability of the present invention is performed immediately after color development, but in the case of the reversal treatment, the treatment is performed via an adjustment bath (a bleach accelerating bath may be used). Is common. These adjustment baths may contain an image stabilizer described below.
In the present invention, in addition to the bleaching agent, the liquid having a bleaching ability includes a rehalogenating agent, a pH buffering agent and known additives described on page (12) of JP-A-3-144446, aminopolycarboxylic acids, and organic polycarboxylic acids. Phosphonic acids and the like can be used, and as the rehalogenating agent, sodium bromide, potassium bromide, ammonium bromide, potassium chloride, or the like is preferably used. 1 to 1.5 mol is preferable, 0.1 to 1.0 mol is more preferable, and 0.1 to 0.8 or less is particularly preferable.
[0069]
In the present invention, it is preferable to use a nitric acid compound, for example, ammonium nitrate, sodium nitrate or the like, for the liquid having bleaching ability. In the present invention, the concentration of the nitric acid compound in 1 liter of the liquid having bleaching ability is preferably 0 to 0.3 mol, more preferably 0 to 0.2 mol.
Normally, a nitric acid compound such as ammonium nitrate or sodium nitrate is added to prevent corrosion of stainless steel. In the present invention, even if the amount of the nitric acid compound is small, corrosion hardly occurs and desilvering is good.
[0070]
The replenishment amount of the solution having bleaching ability is 1 m²Per volume is preferably 30 to 600 ml, more preferably 50 to 400 ml.
The processing time when processing with the bleaching solution is preferably 7 minutes or less, particularly preferably 10 seconds to 5 minutes, and most preferably 15 seconds to 3 minutes.
The total time of the desilvering step is preferably shorter as long as the desilvering failure does not occur. The preferred time is 1 minute to 12 minutes, more preferably 1 minute to 8 minutes. The processing temperature is from 25 ° C to 50 ° C, preferably from 35 ° C to 45 ° C. In a preferable temperature range, the desilvering speed is improved, and generation of stain after processing is effectively prevented.
The processing solution having the bleaching ability of the present invention is particularly preferably subjected to aeration during processing, since the photographic performance is extremely stably maintained. Any means known in the art can be used for aeration, and air can be blown into a processing solution having bleaching ability, or air can be absorbed using an ejector.
When blowing air, it is preferable to discharge air into the liquid through an air diffuser having fine pores. Such a diffuser is widely used for an aeration tank in activated sludge treatment. Regarding aeration, items described in Z-121, Using Process C-41, Third Edition (1982), pages BL-1 to BL-2, published by Eastman Kodak Company, can be used. In the processing using the processing solution having the bleaching ability according to the present invention, it is preferable that the stirring is strengthened, and the processing is carried out as described in JP-A-3-33847, page 8, upper right column, line 6 The contents described in the second row from the lower left column can be used as they are.
[0071]
In the present invention, various bleaching accelerators can be added to the pre-bath of the processing solution having the bleaching ability. Such bleaching accelerators are described, for example, in U.S. Pat. No. 3,893,858, German Patent 1,290,821, British Patent 1,138,842, and No. 53-95630, Compounds having a mercapto group or disulfide group described in Research Disclosure No. 17129 (July, 1978), thiazolidine derivatives described in JP-A-50-140129, U.S. Pat. Nos. 706,561, thiourea derivatives, iodides described in JP-A-58-16235, polyethylene oxides described in German Patent 2,748,430, JP-B-45-8636. And the like. Further, the compounds described in U.S. Pat. No. 4,552,834 are also preferred. These bleaching accelerators may be added to the light-sensitive material.
[0072]
In the present invention, after the desilvering treatment, the substrate is treated with a processing solution such as washing water and / or a stabilizing solution.
In the present invention, the stabilizing solution is a conventional color negative film, a stabilizing solution used in the final processing step of the color reversal film, and used in the stabilizing step of the previous bath in the case of the final step or the rinsing step Some stabilizing solutions are included, but are preferably used as a final bath.
The stabilizing solution of the present invention is a compound which stabilizes a dye image (described later, for example, an aldehyde compound such as formalin) contained in the stabilizing solution. Prevents discoloration.
[0073]
A compound for stabilizing a dye image (hereinafter, referred to as an image stabilizer) can be added to the stabilizing solution. Examples of image stabilizers include benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adducts, hexamethylenetetramine and its derivatives, hexahydrotriazine and its derivatives, N-methylolurea and N-methylolpyrazole such as N-methylolpyrazole. -Methylol compounds, azolylmethylamines such as N, N'-bis (1,2,4-triazol-1-ylmethyl) piperazine and the like. These image stabilizers are described in JP-A-2-153348, JP-A-4-270344, JP-A-4-313375 (corresponding to European Patent Publication No. 504609A2) and 4-359249 (corresponding to European Patent Publication No. 519190A2). No. 5-34889, EP-A-521277 A1, and the like.
[0074]
In the present invention, when the concentration of free formaldehyde in the liquid is 0 to 0.01%, more preferably 0 to 0.005%, the effect is large and preferable.
Examples of image stabilizers for achieving such a free formaldehyde concentration include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, and N, N'-bis. Azolylmethylamines such as (1,2,4-triazol-1-ylmethyl) piperazine described in JP-A-4-331353 (corresponding to European Patent Publication 504609A2) are preferred. In particular, azoles such as 1,2,4-triazole and 1,4-bis (1,2,4-triazol-1-ylmethyl) described in JP-A-4-359249 (corresponding to EP-A-519190A2). Particularly preferred is the combination of azolylmethylamine and its derivatives such as piperazine.
Preferred image stabilizers are shown below, but are not limited thereto.
[0075]
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[0076]
Embedded image
[0077]
K-23 hexamethylenetetramine
K-24 N-methylol urea
In the present invention, the content of the image stabilizer is preferably from 0.001 to 0.1 mol, more preferably from 0.001 to 0.05 mol, per liter of the stabilizing solution.
[0078]
The stabilizing solution of the present invention may contain an organic acid such as acetic acid, citric acid, and sulfuric acid.In the present invention, the stabilizing solution has a hydroxy group in order to further exert the effect of the stabilizing solution. It is preferred to add a monobasic organic acid. The monobasic organic acid having a hydroxy group is composed of a linear or branched alkyl group having a hydroxy group site and an organic acid site. The compound preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. As the organic acid site, carboxylic acid, sulfonic acid, and phosphoric acid are preferable, and carboxylic acid is particularly preferable.
Specific examples of the monobasic organic acid having a hydroxy group include glycolic acid and butyric acid, and glycolic acid is particularly preferred.
The content of the organic acid in the stabilizing solution of the present invention is preferably 0.00001 to 0.5 mol, more preferably 0.0001 to 0.1 mol per liter of the stabilizing solution.
[0079]
The washing water and / or stabilizing solution of the present invention preferably contains various surfactants. In particular, when used in a processing solution (ie, a final bath) immediately before the drying step, there is an effect of preventing unevenness of water droplets during drying of the processed photosensitive material. The final bath may be either washing water or a stabilizing solution, but a stabilizing solution is preferred.
Examples of the surfactant include a polyalkylene glycol type nonionic surfactant, a polyhydric alcohol type nonionic surfactant, an alkylbenzene sulfonate type anionic surfactant, and a higher alcohol sulfate ester type anionic surfactant. , Alkyl naphthalene sulfonate type anionic surfactant, quaternary ammonium salt type cationic surfactant, amine salt type cationic surfactant, amino salt type amphoteric surfactant, betaine type amphoteric surfactant It is preferable to use a polyalkylene glycol-type nonionic surfactant, and particularly, a polyalkylene glycol-type nonionic surfactant of an alkylphenoxypolyethylene oxide or an alkylphenoxypolyhydroxypropylene oxide represented by the following general formula (W). Activators are preferred.
General formula (W)
[0080]
Embedded image
[0081]
(W is -CH₂CH₂O- or -CH₂CH (OH) CH₂O-₁₈And R₁₉Represents an alkyl group, and n represents 0 or 1. m is -CH₂CH₂O- or -CH₂CH (OH) CH₂Represents the number of moles of O- added. )
R₁₈And R₁₉The alkyl group of 3-20 carbon atoms, preferably 6-12 carbon atoms, particularly preferably octyl, nonyl and dodecyl, and m as the number of moles added is particularly preferably 6-14.
In the present invention, W is -CH₂CH (OH) CH₂A polyhydroxypropylene oxide type nonionic surfactant represented by O- is preferable because the effect of the present invention is remarkable.
It is also preferable to use a silicon surfactant having a high defoaming effect.
Examples of preferred surfactants are shown below, but the present invention is not limited thereto.
[0082]
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[0083]
The addition amount of the surfactant is 0.005 g to 3 g, preferably 0.02 to 0.3 g per liter of washing water and / or stabilizing solution.
If necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, alkanolamines described in U.S. Pat. It is also preferable to include the sulfinic acid compound described in JP 231051A.
[0084]
Further, in the present invention, the stabilizing solution may contain a water-soluble cellulose derivative. As the water-soluble cellulose derivative, hydroxycellulose and carboxymethylcellulose are preferable, and the content thereof is preferably 0.01 to 5.0 g, more preferably 0.05 to 1.0 g per liter of the stabilizing solution.
[0085]
It is preferable that the stabilizing solution of the present invention contains various chelating agents in order to improve the stability of the stabilizing solution and reduce the generation of dirt. Preferred chelating agents include organic carboxylic acid chelating agents, organic phosphoric acid chelating agents, inorganic phosphoric acid chelating agents, and polyhydroxy compounds. Particularly preferred chelating agents include aminodicarboxylic acids such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediamine-N, N′-disuccinic acid, iminodiacetic acid monopropionic acid, and 1-hydroxyethylidene-1,1-diphosphonic acid; Organic phosphonic acids such as N, N, N'-trimethylene phosphonic acid, diethylenetriamine-N, N, N ', N'-tetramethylene phosphonic acid, and maleic anhydride polymers described in EP 345,172 A1 Hydrolysates and the like can be given. The preferable addition amount of these chelating agents is 0.00001 to 0.01 mol per liter of the stabilizing solution.
[0086]
In the present invention, after the desilvering treatment, a treatment with a stabilizing solution may be performed after a washing treatment, or a treatment with a stabilizing solution may be directly performed without performing a washing treatment. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the material used such as a coupler), the use, the rinsing water temperature, the number of rinsing tanks (number of stages), the replenishment method such as countercurrent, forward flow, and other various conditions. Can be set in a wide range. Among them, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is described in Journal of the Society of Motion Picture and Television Engineers, Vol. 248-253 (May 1955). According to the multi-stage counter-current method described in the above document, the amount of washing water can be significantly reduced.
[0087]
The pH of the stabilizing solution and the washing water of the present invention is 4 to 9, preferably 5 to 8. The processing temperature and the processing time can be variously set depending on the characteristics of the photosensitive material, the use, and the like, but are generally from 15 to 45 ° C for 20 seconds to 10 minutes, preferably from 25 to 40 ° C for 30 seconds to 2 minutes. Further, in the treatment with the stabilizing solution of the present invention, when the treatment is directly performed with the stabilizing solution subsequent to the desilvering process without washing with water, the effect of preventing contamination is remarkably exhibited.
For the treatment with the stabilizing solution of the present invention, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.
The replenishment amount of each of the washing and stabilizing solutions of the present invention is 1 m²Per volume, it is preferably 50-3000 ml, more preferably 100-1200 ml, even more preferably 100-900 ml, and particularly preferably 200-600 ml. The total replenishment amount of the washing water and the stabilizing solution is 1 m for the photosensitive material.²50 to 3000 ml is preferable, 100 to 1500 ml is more preferable, 100 to 900 ml is more preferable, and 200 to 700 ml is particularly preferable.
The overflow solution accompanying the washing and / or replenishment of the stabilizing solution can be reused in another step such as a desilvering step.
In order to reduce the amount of washing water used, ion exchange or ultrafiltration is used, and it is particularly preferable to use ultrafiltration.
[0088]
In the water washing and stabilizing solution of the present invention, various ions such as calcium ions, magnesium ions, sodium ions, and potassium ions are used as eluted components from the solution water used for preparing the replenisher or from the light-sensitive material. Although a component is present, in the present invention, the concentration of sodium ion in the final treatment bath in the washing and stabilizing step is preferably in the range of 0 to 50 mg / liter, particularly preferably 0 to 20 mg / liter.
[0089]
In the present invention, when the processing solution having bleaching ability (eg, bleaching solution, bleach-fixing solution) contains the compound represented by the general formula (J), the wet heat fading of the yellow dye is further improved, When the photosensitive material has a magnetic recording layer, its magnetic recording reading performance is particularly excellent.
Next, the compound represented by formula (J) of the present invention will be described in detail.
[0090]
Embedded image
[0091]
(In the formula, Q represents a group of non-metallic atoms necessary to form a heterocyclic ring. P represents 0 or 1. Ma represents a hydrogen atom or a cation.)
The heterocyclic residue formed by Q is a 3- to 10-membered saturated or unsaturated heterocyclic residue containing at least one of N, O, or S atoms, and these may be monocyclic. Alternatively, a condensed ring may be formed with another ring.
[0092]
The heterocyclic residue is preferably a 5- or 6-membered aromatic heterocyclic residue, more preferably a 5- or 6-membered aromatic heterocyclic residue containing a nitrogen atom, and even more preferably a nitrogen-containing 1-membered aromatic heterocyclic residue. 5 to 6-membered aromatic heterocyclic residue containing 1 to 2 atoms.
[0093]
Specific examples of the heterocyclic residue include, for example, 2-pyrrolidinyl, 3-pyrrolidinyl, 2-piperidinyl, 3-piperidyl, 4-piperidyl, 2-piperazinyl, 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-pyridazinyl, -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-a Drill, 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-naphthyridinyl, 3-naphthyridinyl, 4-naphthyridinyl, 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-pteridinyl, 4-pteridinyl, 6-pteridinyl, 7-pteridinyl, 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-thiazolidyl, 4-thiazolidyl, 5-thiazolidinyl and the like Is mentioned.
[0094]
The heterocyclic residue is preferably 2-pyrrolyl, 2-imidazolyl, 4-imidazolyl, 3-pyrazolyl, 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-cinnoyl Nyl, 8-cinnolinyl, 2- (1,10-phenanthrolinyl), 5-tetrazolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl, and 4-oxazolyl, more preferably 2-imidazolyl, -Imidazolyl, 3-pyrazolyl, 2-pyridyl, 2-pyrazinyl, 2-indolyl, 3-indazolyl, 7-indazolyl, 2- (1,3,4-thiadiazolyl), 2- (1,3,4-oxadiazolyl) , 2-quinolyl, 8-quinolyl, 2-thiazolyl, 4-thiazolyl, 2-oxazolyl, and 4-oxazolyl, and more preferably 2-imidazolyl, 4-imidazolyl, 2-pyridyl, 2-quinolyl, and 8-quinolyl. And particularly preferably 2-imidazolyl, 4-imidazolyl, 2-pyridyl and 2-quinolyl. 2-pyridyl are most preferred.
[0095]
The heterocyclic residue is (CH₂)_PCO₂It may have a substituent in addition to Ma, and examples of the substituent include an alkyl group (preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms. And aralkyl groups (preferably having 7 to 20 carbon atoms, more preferably having 7 to 15 carbon atoms, particularly preferably having 7 to 11 carbon atoms), for example, phenyl. Methyl, phenylethyl and the like.), Alkenyl group (preferably an alkenyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, for example, allyl and the like) Alkynyl group (preferably an alkynyl group having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as propargyl and the like) And an aryl group (preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, particularly preferably 6 to 10 carbon atoms, such as phenyl and p-methylphenyl). ), An amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably 0 to 6 carbon atoms, such as amino, methylamino, dimethylamino, and diethylamino. ), An alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methoxy and ethoxy). An oxy group (preferably an aryloxy group having 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms; An acyl group (preferably an acyl group having 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as acetyl). An alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as methoxycarbonyl). It is preferably an acyloxy group having 1 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 8 carbon atoms, such as acetoxy, etc.), and an acylamino group (preferably 1 to 10 carbon atoms). And more preferably an acylamino group having 2 to 6 carbon atoms, particularly preferably 2 to 4 carbon atoms, such as acetylamino. It is. ), A sulfonylamino group (preferably a sulfonylamino group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, such as methanesulfonylamino). A sulfamoyl group (preferably a sulfamoyl group having 0 to 10 carbon atoms, more preferably 0 to 6 carbon atoms, and particularly preferably 0 to 4 carbon atoms, such as sulfamoyl and methylsulfamoyl); and a carbamoyl group. (Preferably a carbamoyl group having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as carbamoyl and methylcarbamoyl); and an alkylthio group (preferably carbon An alkylthio group having 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 4 carbon atoms; And arylthio groups (preferably having 6 to 20 carbon atoms, more preferably having 6 to 10 carbon atoms, particularly preferably having 6 to 8 carbon atoms, for example, phenylthio and the like). ), A sulfonyl group (preferably a sulfonyl group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms, such as methanesulfonyl and the like), and a sulfinyl group (preferably Is a sulfinyl group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 to 4 carbon atoms, such as methanesulfinyl and the like; a ureido group, a hydroxy group, a halogen atom (for example, Fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxyl, nitro, hydroxam Group, a mercapto group, a Hajime Tamaki (e.g. imidazolyl, pyridyl), and the like.
[0096]
These substituents may be further substituted. When there are two or more substituents, they may be the same or different. The substituent is preferably an alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, a nitro group, a mercapto group, and more preferably an alkyl group, an amino group, an alkoxy group, or a carboxyl group. , A hydroxy group, and a halogen atom, more preferably an amino group, a carboxyl group, and a hydroxy group, and particularly preferably a carboxyl group.
[0097]
p represents 0 or 1, and is preferably 0.
The cation represented by Ma 2 is an organic or inorganic cation, for example, an alkali metal ion (for example, Li⁺, Na⁺, K⁺, Cs⁺Etc.), alkaline earth metal ions (eg, Ca^{2 +}, Mg^{2 +}Etc.), ammonium (eg, ammonium, tetraethylammonium), pyridinium, phosphonium (eg, tetrabutylphosphonium, tetraphenylphosphonium, etc.).
[0098]
Among the compounds represented by the general formula (J), a compound represented by the following general formula (Ja) is preferable.
General formula (Ja)
[0099]
Embedded image
[0100]
(Where p and Ma have the same meanings as those of formula (J),¹Represents a group of non-metallic atoms necessary for forming a nitrogen-containing heterocyclic ring. )
[0101]
Q¹Is a 3- to 10-membered saturated or unsaturated heterocyclic residue containing at least one nitrogen atom, which may be monocyclic or May form a condensed ring with the ring of
[0102]
The nitrogen-containing heterocyclic residue is preferably a 5- or 6-membered nitrogen-containing aromatic heterocyclic residue, more preferably a 5- or 6-membered nitrogen-containing aromatic heterocyclic residue containing 1 or 2 nitrogen atoms. Group.
[0103]
Specific examples and preferred examples of the nitrogen-containing heterocyclic residue include the same as the heterocyclic residue in (J).
[0104]
The nitrogen-containing heterocyclic residue is (CH₂)_PCO₂It may have a substituent in addition to Ma, and as the substituent, those mentioned as the substituent of the heterocyclic group formed by Q in the general formula (J) can be applied. is there.
[0105]
p and Ma have the same meanings as those of formula (J), and their preferred ranges are also the same. Further, among the compounds represented by the general formula (Ja), a compound represented by the following general formula (Jb) is preferable.
General formula (Jb)
[0106]
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[0107]
(Wherein, Ma has the same meaning as that of formula (J). Q²Is a 5- or 6-membered nitrogen-containing heterocyclic group, which may be substituted with an alkyl group, amino group, alkoxy group, carboxyl group, hydroxy group, halogen atom, cyano group, nitro group, or mercapto group. )
[0108]
Among the compounds represented by the general formula (Jb), a compound represented by the following general formula (Jc) is more preferable.
General formula (Jc)
[0109]
Embedded image
[0110]
(Wherein, Ma has the same meaning as that of formula (J). Q³Represents a group of atoms necessary to form a pyridine ring or an imidazole ring, and is substituted with an alkyl group, an amino group, an alkoxy group, a carboxyl group, a hydroxy group, a halogen atom, a cyano group, a nitro group, or a mercapto group. Is also good. )
[0111]
Specific examples of the compound represented by formula (J) are shown below, but the invention is not limited thereto.
[0112]
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[0113]
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[0114]
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[0115]
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[0116]
Embedded image
[0117]
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[0118]
The above compounds may be used in the form of an ammonium salt, an alkali metal salt or the like.
The compound represented by the above general formula (J) can be synthesized according to the method described in Organic Synthesis Collective Volume 3, page 740, or a commercially available product can be used.
Preferred among the above exemplified compounds are (J-6), (J-7), (J-8), (J-13), (J-14), (J-20), and (J-22). ), (J-29) and (J-49), with (J-7) being particularly preferred.
[0119]
The compound represented by formula (J) of the present invention is preferably contained in an amount of 0.001 to 0.3 mol, more preferably 0.005 to 0.2 mol, per liter of the processing solution having bleaching ability. , 0.01 to 0.10 mol is particularly preferred. At this time, you may make it exist by bringing in from a previous bath. These compounds may be used alone or in combination of two or more.
[0120]
Processing solutions having a fixing ability include sulfites (eg, sodium sulfite, potassium sulfite, ammonium sulfite), hydroxylamines, hydrazines, and bisulfite adducts of aldehyde compounds (eg, sodium acetaldehyde bisulfite, Preferably, a compound described in JP-A-3-158848) or a sulfinic acid compound described in JP-A-1-231051 can be contained. Further, various fluorescent whitening agents, defoaming agents, surfactants, and organic solvents such as polyvinylpyrrolidone and methanol can be contained.
Further, it is preferable to add a chelating agent such as various aminopolycarboxylic acids or organic phosphonic acids to the processing solution having a fixing ability for the purpose of stabilizing the processing solution. Preferred chelating agents include 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediamine-N, N, N ', N'-tetrakis (methylenephosphonic acid), nitrilotrimethylenephosphonic acid, and ethylenediamine-N, N, N'. , N'-tetraacetic acid, diethylenetriaminepentaacetic acid, trans-1,2-cyclohexanediamine-N, N, N ', N'-tetraacetic acid, and 1,2-propylenediaminetetraacetic acid.
[0121]
It is also preferable to add a buffer to the bleach-fix solution or the fix solution in order to keep the pH of the solution constant. For example, phosphates, imidazoles such as imidazole, 1-methyl-imidazole, 2-methyl-imidazole and 1-ethyl-imidazole, triethanolamine, N-allylmorpholine, N-benzoylpiperazine and the like can be mentioned.
[0122]
In the desilvering step, it is preferable that the stirring is strengthened as much as possible. As a specific method of strengthening the stirring, the emulsion surface of the light-sensitive material described on page 8, right upper column, line 6 to lower left column, second line of JP-A-62-183460 and JP-A-3-33847 can be used. A method of colliding a jet of a processing solution, a method of increasing a stirring effect by using a rotating means disclosed in Japanese Patent Application Laid-Open No. 62-183461, and a method of moving a photosensitive material while contacting a wiper blade provided in the solution with an emulsion surface. And a method of increasing the stirring effect by making the emulsion surface turbulent, and a method of increasing the circulating flow rate of the entire processing solution. Such a stirring improving means is effective in any of a bleaching solution, a bleach-fixing solution and a fixing solution. It is considered that improving the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently increases the desilvering speed. The means for improving the stirring is more effective when a bleaching accelerator is used, and can remarkably increase the accelerating effect or eliminate the fixing inhibition effect of the bleaching accelerator.
[0123]
The automatic developing machine used for the light-sensitive material of the present invention preferably has a light-sensitive material conveying means described in JP-A-60-191257, JP-A-60-191258, and JP-A-60-191259. As described in Japanese Patent Application Laid-Open No. 60-191257, such a transport means can significantly reduce the carry-in of the processing solution from the pre-bath to the post-bath, and is highly effective in preventing performance deterioration of the processing solution. Such an effect is particularly effective in shortening the processing time in each step and reducing the replenishing amount of the processing solution.
The solution having the bleaching ability of the present invention can be reused after collecting the overflow solution after use in the treatment, correcting the composition by adding components, and so on. Such a method of use is usually called reproduction, but the present invention can also preferably perform such reproduction. Regarding the details of the reproduction, the matters described in pages 39 to 40 of Fujifilm Processing Manual, Fujicolor Negative Film, CN-16 processing (revised in August 1990) issued by Fuji Photo Film Co., Ltd. can be applied.
[0124]
Regarding the regeneration of the liquid having the bleaching ability, a method described in "Basics of photographic engineering-silver halide photography-" (edited by The Photographic Society of Japan, published by Corona Co., Ltd., 1979) and the like can be used in addition to the aeration described above. Specifically, in addition to electrolytic regeneration, a method of regenerating a bleaching solution with bromic acid, zinc acid, bromine, bromine precursor, persulfate, hydrogen peroxide, hydrogen peroxide using a catalyst, bromite, ozone, etc. No.
In the regeneration by electrolysis, the cathode and the anode are placed in the same bleaching bath, or the anode and the cathode are separated from each other by using a diaphragm to regenerate. And / or regenerating the fixing solution at the same time. The regeneration of the fixing solution and the bleach-fixing solution is carried out by electrolytic reduction of accumulated silver ions. In addition, it is also preferable to remove accumulated halogen ions with an anion exchange resin in order to maintain fixing performance.
The solution having bleaching ability of the present invention has an oxygen permeation rate of 1 cc / m during storage.². day. It is preferable to put in a closed container of atm or more.
[0125]
The replenisher of the solution having bleaching ability basically contains the concentration of each component calculated by the following formula. Thereby, the concentration in the mother liquor can be kept constant.
C_R= C_T× (V₁+ V₂) / V₁+ C_P
C_R: Concentration of components in replenisher
C_T: Concentration of components in mother liquor (treatment tank liquid)
C_P: Concentration of components consumed during processing
V₁: 1m²Of replenisher with bleaching ability for different photosensitive materials (ml)
V₂: 1m²Amount brought in from the previous bath by the photosensitive material (ml)
[0126]
Next, the color developing solution will be described.
As the color developing solution, compounds described in JP-A-4-121739, page 9, upper right column, line 1 to page 11, lower left column, line 4 can be used. Particularly, color developing agents for rapid processing include 2-methyl-4- [N-ethyl-N- (2-hydroxyethyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (3-Hydroxypropyl) amino] aniline and 2-methyl-4- [N-ethyl-N- (4-hydroxybutyl) amino] aniline are preferred.
The color developing solution preferably contains a color developing agent in an amount of 0.01 to 0.08 mol / l, particularly preferably 0.015 to 0.06 mol / l, and more preferably 0.02 to 0. It is preferably contained at a rate of 05 mol / l. It is preferable that the replenisher of the color developing solution contains 1.1 to 3 times this value.
[0127]
The color developing solution may be a pH buffer such as an alkali metal carbonate, borate or phosphate, a chloride salt, a bromide salt, an iodide salt, a benzimidazole, a benzothiazole or a mercapto compound. It generally contains an inhibitor or an antifoggant. Also, if necessary, besides hydroxylamine and diethylhydroxylamine, N, N-bis (2-sulfonatoethyl) hydroxylamine and other hydroxylamines represented by the general formula (I) in JP-A-3-144446. Amines, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, various preservatives such as triethanolamine, catecholsulfonic acids, organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, Development accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity-imparting agents, aminopolycarboxylic acids, aminopolyphosphones Acid, alkyl pho Various chelating agents represented by fonic acid and phosphonocarboxylic acid, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethylidene-1,1 Representative examples include diphosphonic acid, nitrilo-N, N, N-trimethylenephosphonic acid, ethylenediamine-N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof. Can be mentioned.
[0128]
The processing temperature of the color developer is 20 to 55 ° C, preferably 30 to 55 ° C. The processing time is 20 seconds to 10 minutes, preferably 30 seconds to 8 minutes for the photographic material. The time is more preferably 1 minute to 6 minutes, and particularly preferably 1 minute 10 seconds to 3 minutes 30 seconds. In the case of a printing material, it is 10 seconds to 1 minute and 20 seconds, preferably 10 seconds to 60 seconds, and more preferably 10 seconds to 40 seconds.
[0129]
When the reversal process is performed, color development is usually performed after black and white development. The black-and-white developer includes dihydroxybenzenes such as hydroquinone and hydroquinone monosulfonate; 3-pyrazolidones such as 1-phenyl-3-pyrazolidone and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone; Known black and white developing agents such as aminophenols such as -methyl-p-aminophenol can be used alone or in combination. The above-mentioned black-and-white developer is also used in the processing of black-and-white photosensitive materials.
The color developing solution and the black-and-white developing solution generally have a pH of 9 to 12. The replenishment amount of these developing solutions depends on the color photographic light-sensitive material to be processed, but is generally 3 liters or less per square meter of the photographic material, and can be reduced to 500 ml or less by reducing the bromide ion concentration in the replenishing solution. You can also. When the replenishment amount is reduced, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the contact area of the processing tank with air.
[0130]
The contact area between the photographic processing solution and air in the processing tank can be represented by the aperture ratio defined below. That is,
Aperture ratio = [contact area between processing solution and air (cm²)] ÷ [Capacity of processing solution (cm³)]
The above aperture ratio is preferably 0.1 or less, more preferably 0.001 to 0.05. As a method of reducing the aperture ratio in this way, in addition to providing a shield such as a floating lid on the photographic processing liquid surface of the processing tank, a method using a movable lid described in JP-A-1-82033, 63-216050 can be mentioned. Further, a method of contacting a liquid covering the processing liquid surface, such as liquid paraffin, or a low-oxidizing and / or non-oxidizing gas with the processing liquid surface may also be used. The reduction of the aperture ratio is preferably applied not only to both the color development and black-and-white development steps but also to the following various steps, for example, all the steps such as bleaching, bleach-fixing, fixing, washing and stabilization. The amount of replenishment can also be reduced by using means for suppressing the accumulation of bromide ions in the developer.
[0131]
In addition, when the replenishment rate is reduced or when a high bromide ion concentration is set, as a method for increasing the sensitivity, 1-phenyl-3-pyrazolidone or 1-phenyl-2-methyl-2-hydroxymethyl-3-pyrazolidone is used. It is also preferable to use thioether compounds represented by pyrazolidones and 3,6-dithia-1,8-octanediol, sodium thiosulfate and potassium thiosulfate as development accelerators.
These development accelerators can be preferably used in the color developing solution.
[0132]
The shape and structure of the container for accommodating the color developer constituting the color developer can be arbitrarily designed according to the purpose. For example, JP-A-58-97046, JP-A-63-50839, and JP-A-1-235950. And those having a flexible structure such as bellows described in JP-A-63-45555 and JP-A-58-52065, JP-A-62-246061, and JP-A-62-134646. It is preferable to use a container having a plurality of containers each having a variable inner volume described in JP-A-2-264950.
In order to supply the color developing agent from these containers to the processing liquid tank of the developing machine, the developer may be once put into a replenishing solution tank and mixed or diluted with water automatically or manually. And water may be separately sent directly to the treatment liquid tank.
At the time of such an operation, it is preferable that the lid of the container is constructed so as to be opened with a single touch. Examples of such an operation are described in Japanese Utility Model Application Laid-Open No. 61-128646, Japanese Patent Application Laid-Open Nos. ing.
[0133]
The color developer has a carbon dioxide permeation rate of 25 ml / m.²  It is preferable to fill a container made of a material of 24 hrs.atm or less so that the porosity is 0.15 to 0.05.
Preferred materials having such a carbon dioxide permeation rate include polyethylene terephthalate, polyvinyl chloride, polyvinylidene chloride, laminated materials of polyethylene or polypropylene and nylon, laminated materials of polyethylene or polypropylene and aluminum, glass and the like. Those having a thickness of 300 to 2000 microns are preferable. In particular, polyethylene terephthalate or a laminated material of polyethylene and nylon having a thickness of 500 to 1000 microns is suitable for carbon dioxide permeability and mechanical properties. The balance of strength and weight is the most preferable. The material of the container used in the present invention has an oxygen permeation rate of 20 ml / m2.²It is preferably at most 24 hrs · atm.
[0134]
Here, the porosity is a value obtained by subtracting the filling amount (ml) of the color developer from the volume (ml) of the container containing the color developer and dividing the value by the volume (ml) of the container. The liquid color developer of the present invention is preferably filled in the above-mentioned container so as to have a porosity of 0.15 to 0.05.
[0135]
The color developing agent can be used as it is as a color developing solution or a replenishing solution. However, it is preferably mixed and diluted with water to be used as a color developing solution or a replenishing solution. When used as a color developing solution, it is preferable to add a starter containing a pH adjuster, bromide, etc., in addition to water.
When used as a replenisher, it may be mixed and diluted with water in advance and stocked in a replenisher tank, and then used to replenish the processing solution tank with a fixed amount from here. It may be used such that it is directly replenished in a fixed amount and mixed and diluted in the processing solution tank. Further, as an intermediate method, a method of feeding the solution to the treatment liquid tank while continuously mixing and diluting with water may be used. In this case, a known method such as providing a mixing tank in the middle can be applied.
[0136]
Compounds and processing conditions described in JP-A-4-125558, page 7, lower left column, line 10 to page 8, lower right column, line 19 can be applied to the processing solution having a fixing ability.
Particularly, in order to improve the fixing speed and the preservability, the compounds represented by the general formulas (I) and (II) of JP-A-6-301169 are used alone or in combination in a processing solution having a fixing ability. Preferably. It is also preferable to use sulfinic acid described in JP-A 1-2224762, in addition to p-toluenesulfinate, from the viewpoint of improving the preservation. It is preferable to use ammonium as a cation in the solution having the bleaching ability or the solution having the fixing ability from the viewpoint of improving the desilvering property, but it is more preferable to reduce or eliminate ammonium for the purpose of reducing environmental pollution. .
In the bleaching, bleach-fixing, and fixing steps, it is particularly preferable to perform jet stirring described in JP-A-1-309059.
The replenishment rate of the replenisher in the bleach-fixing or fixing step is 1 m²Per 100 to 1000 ml, preferably 150 to 700 ml, particularly preferably 200 to 600 ml.
[0137]
In the bleach-fixing and fixing steps, it is preferable to install various silver recovery devices in-line or off-line to recover silver. By installing in-line, the processing can be performed with a reduced silver concentration in the solution, and as a result, the amount of replenishment can be reduced. It is also preferable to recover silver off-line and reuse the remaining solution as a replenisher.
The bleach-fixing step and the fixing step can be composed of a plurality of processing tanks, and each tank is preferably a cascade pipe to use a multistage countercurrent system. In general, a two-tank cascade configuration is efficient in view of the balance with the size of the developing machine, and the ratio of the processing time in the former tank to the latter tank is in the range of 0.5: 1 to 1: 0.5. It is particularly preferable that the ratio be in the range of 0.8: 1 to 1: 0.8.
It is preferable that a free chelating agent not forming a metal complex is present in the bleach-fixing solution or the fixing solution from the viewpoint of improving the preservability. These chelating agents are preferably represented by the general formula (1) of the present invention. It is particularly preferred to use at least one of the compounds obtained.
[0138]
In the process of the present invention, it is particularly preferable to carry out the correction of the evaporation of the processing liquid disclosed in Hatsumei Kyokai Technical Report No. 94-4992. In particular, a method of performing correction using temperature and humidity information of a developing machine installation environment based on (Equation 1) on page 2 is preferable. The water used for the evaporation correction is preferably collected from a washing replenishing tank, and in that case, it is preferable to use deionized water as the washing replenishing water.
[0139]
The processing of the present invention can be performed using various developing processing apparatuses. Preferred development processing apparatuses include cine-type development processing apparatuses such as Fuji Photo Film Co., Ltd.'s automatic developing machines FNCP-300II, FNCP-600II and FNCP-900II, and Fuji Photo Film Co., Ltd.'s automatic developing machine FP-300. 560B, FP-350, etc., a cine-type development processing apparatus of a leader transport system called a minilab, an automatic developing machine HM-55S, H8-440W-4, HM-60R, HR-6-8360 manufactured by Noritz Koki Co., Ltd. And a roller transport type developing apparatus such as HOPE 138 and HOPE 2409V manufactured by HOPE Corporation of the United States. As for the stirring method, material, and the like of the development processing apparatus, those described in JP-A-4-130432 are preferable.
[0140]
Next, the preferred silver halide color photographic light-sensitive material of the present invention will be described. The silver halide color photographic light-sensitive material to which the present invention can be preferably applied includes a color negative film and a color reversal film coated with a silver iodobromide emulsion, and in particular, a color negative film.Is goodGood.
[0141]
Next, the present inventionPertain toA photosensitive material having a magnetic recording layer will be described. The magnetic recording layer is formed by coating an aqueous or organic solvent-based coating solution in which magnetic particles are dispersed in a binder on a support._TwoO_ThreeFerromagnetic iron oxide, Co-coated γFe_TwoO_Three, Co-coated magnetite, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite, and the like. Among them, Co-coated γFe_TwoO_ThreeCo-coated ferromagnetic iron oxide such as The shape may be any of a needle shape, a rice grain shape, a spherical shape, a cubic shape, a plate shape, and the like. S for specific surface area_BETAt 20m^Two/ g or more is preferable, and 30 m^Two/ g or more is particularly preferred. The saturation magnetization (σs) of the ferromagnetic material is preferably 3.0 × 10^Four~ 3.0 × 10^FiveA / m, particularly preferably 4.0 × 10^Four~ 2.5 × 10^FiveA / m. The ferromagnetic particles may be subjected to a surface treatment with silica and / or alumina or an organic material. Further, the surface of the magnetic particles may be treated with a silane coupling agent or a titanium coupling agent as described in JP-A-6-161032. Also, magnetic particles having a surface coated with an inorganic or organic substance described in JP-A-4-259911 and JP-A-5-81652 can be used.
[0142]
Next, as the binder used for the magnetic particles, thermoplastic resins, thermosetting resins, radiation-curable resins, reactive resins, acids, alkalis or biodegradable polymers, natural polymers described in JP-A-4-219569 (Cellulose derivatives, sugar derivatives, etc.) and mixtures thereof can be used. The glass transition temperature Tg of the resin is −40 ° C. to 300 ° C., and the weight average molecular weight is 2,000 to 1,000,000. Examples thereof include vinyl copolymers, cellulose diacetate, cellulose triacetate, cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, tolylene diisocyanate). Reaction products of 3 mol of isocyanate and 1 mol of trimethylolpropane), and polyisocyanates formed by condensation of these isocyanates, and the like, which are described in, for example, JP-A-6-59357.
[0143]
As a method for dispersing the above-mentioned magnetic substance in the binder, a kneader, a pin-type mill, an annular-type mill, etc. are preferably used, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used.
The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 100, and more preferably 1: 100 to 30: 100. The coating amount of the magnetic particles is 0.005 to 3 g / m.², Preferably 0.01 to 2 g / m², More preferably 0.02 to 0.5 g / m²It is.
The magnetic recording layer used in the present invention can be provided on the entire back surface or in a stripe shape by coating or printing on the back surface of the photographic support. As a method of applying the magnetic recording layer, an air doctor, a blade, an air knife, a squeeze, an impregnation, a reverse roll, a transfer roll, a gravure, a kiss, a cast, a spray, a dip, a bar, an extrusion, and the like can be used. The coating solution described in 341436 or the like is preferable.
[0144]
The magnetic recording layer may have functions such as lubricity improvement, curl control, antistatic, anti-adhesion, head polishing, or another functional layer may be provided to impart these functions. Of these, abrasives of non-spherical inorganic particles in which at least one or more of the particles has a Mohs hardness of 5 or more are preferred. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and the same binder as the binder for the magnetic recording layer is preferable. As for the photosensitive material having a magnetic recording layer, US Pat. No. 5,336,589, US Pat.
5,229,259, 5,215,874 and EP 466,130.
[0145]
The light-sensitive material of the present invention is preferably a photographic light-sensitive material, and the support is preferably polyester. For details, refer to Published Technical Report, Official Technique No. 94-6023 (Invention Association; 1994.3). .15.).
The polyester used in the present invention is formed by using diol and aromatic dicarboxylic acid as essential components. As aromatic dicarboxylic acids, 2,6-, 1,5-, 1,4- and 2,7-naphthalenedicarboxylic acid, terephthalic acid Examples of the acid, isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexanedimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred are polyesters containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferred. The average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, and preferably 90 ° C. or higher.
[0146]
Next, the polyester support is subjected to a heat treatment at 40 ° C. or more and less than Tg, more preferably at Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in a roll shape or may be performed while transporting the support in a web shape. The surface is provided with irregularities (for example, SnO₂And Sb₂O₅Or other conductive inorganic fine particles) to improve the surface state. It is also desirable to take measures such as applying knurls to the ends and raising the ends only slightly so as to prevent the cut end of the winding core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), or after the application of the undercoat. Preferably after application of the antistatic agent.
An ultraviolet absorber may be incorporated into this polyester. To prevent light piping, the purpose can be achieved by kneading dyes or pigments commercially available for polyesters such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku.
[0147]
Next, the photosensitive material used in the present invention is preferably subjected to a surface treatment in order to adhere the support and the photosensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high-frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, and ozone oxidation treatment. Among the surface treatments, preferred are an ultraviolet irradiation treatment, a flame treatment, a corona treatment, and a glow treatment.
Next, the undercoating method will be described. It may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including a copolymer starting from a monomer selected from among maleic anhydride, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin. Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, gelatin hardeners such as chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, and active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine) And the like, epichlorohydrin resin, active vinyl sulfone compound and the like. SiO₂, TiO₂And inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm) as a matting agent.
[0148]
In the photosensitive material used in the present invention, an antistatic agent is preferably used. Examples of such antistatic agents include polymers containing carboxylic acid and carboxylate and sulfonate, cationic polymers, and ionic surfactant compounds.
The most preferred antistatic agents are ZnO, TiO₂, SnO₂, Al₂O₃, In₂O₃, SiO₂, MgO, BaO, MoO₃, V₂O₅At least one type of volume resistivity selected from the group consisting of 10⁷Ω · cm or less, more preferably 10⁵Particle size of less than Ω · cm 0.001 to 1.0 μm Crystalline metal oxide or fine particles of these composite oxides (Sb, P, B, In, S, Si, C, etc.) Or fine particles of these composite oxides. The content in the photosensitive material is 5 to 500 mg / m²And particularly preferably 10 to 350 mg / m.²It is. The ratio of the amount of the conductive crystalline oxide or its composite oxide to the binder is preferably from 1/300 to 100/1, and more preferably from 1/100 to 100/5.
[0149]
Further, it is preferable that the photosensitive material has a slip property. The slip agent-containing layer is preferably used on both the photosensitive layer surface and the back surface. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when the stainless steel ball having a diameter of 5 mm was conveyed at 60 cm / min (25 ° C., 60% RH). In this evaluation, even if the surface of the photosensitive layer is replaced as the partner material, the values are almost the same level.
Usable slip agents include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes include polydimethylsiloxane, polydiethylsiloxane, polystyrylmethylsiloxane. And polymethylphenylsiloxane. The additional layer is preferably the outermost layer of the emulsion layer or the back layer. Particularly, polydimethylsiloxane and an ester having a long-chain alkyl group are preferable.
[0150]
Further, it is preferable that the photosensitive material has a matting agent. The matting agent may be on either the emulsion side or the back side, but is preferably added to the outermost layer on the emulsion side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. The particle size is preferably 0.8 to 10 μm, and the particle size distribution is also preferably narrow. It is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. .
It is also preferable to simultaneously add fine particles having a size of 0.8 μm or less in order to enhance the matt property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0. 3 μm)), polystyrene particles (0.25 μm), and colloidal silica (0.03 μm).
[0151]
The photosensitive material used in the present invention is preferably described in JP-A-4-125558, page 14, upper left column, line 1 to page 18, lower left column, line 11. In particular, as the silver halide emulsion, a silver iodobromide emulsion having an average silver iodide content of 3 to 20 mol% is preferable. It is preferably a heavy-structured particle. Further, the inside and outside may have a clear layered structure. The aspect ratio is particularly preferably 5 to 20, and more preferably 6 to 12.
Further, monodisperse emulsions described in U.S. Pat. Nos. 3,574,628 and 3,655,394 are also preferable.
The light-sensitive material used in the present invention preferably has a layer containing a non-light-sensitive fine grain silver halide having an average particle size of 0.02 to 0.2 μm. The fine grain silver halide is preferably silver bromide containing 0.5 to 10 mol% of silver iodide.
[0152]
Additives used in the light-sensitive material used in the present invention are described below.
[0153]
Although various dye-forming couplers can be used in the light-sensitive material of the present invention, the following couplers are particularly preferred.
Yellow coupler: a coupler represented by the formula (I) or (II) of EP 502,424A; a coupler represented by the formula (1) or (2) of EP 513,496A (particularly, Y-28 on page 18); EP 568 , 037A, a coupler represented by the formula (I) of claim 1; US 5,066,576, a coupler represented by the general formula (I), column 45, line 45-55; General description of paragraph 0008 of JP-A-4-274425. Couplers described in claim 1 on page 40 of EP 498,381 A1 (especially D-35 on page 18); couplers represented by formula (Y) on page 4 of EP 447,969 A1 ( In particular, Y-1 (page 17), Y-54 (page 41)); US Pat. No. 4,476,219, columns 7 to 36 to 58, formulas (II) to (II). Couplers represented by V) (in particular II-17, 19 (column 17), II-24 (column 19)).
Magenta couplers: JP-A-3-39737 (L-57 (lower right of page 11), L-68 (lower right of page 12), L-77 (lower right of page 13); EP 456,257 [A-4]- 63 (page 134), [A-4] -73, -75 (page 139); M-4, -6 (page 26) and M-7 (page 27) of EP 486,965; EP 571, 959A M-45 (page 19); JP-A-5-204106 (M-1) (page 6); JP-A-4-362263, paragraph 0237 M-22.
Cyan coupler: CX-1,3,4,5,11,12,14,15 of JP-A-4-204843 (pages 14 to 16); C-7,10 (page 35), 34 of JP-A-4-43345 , 35 (page 37), (I-1), (I-17) (pages 42 to 43); a coupler represented by the general formula (Ia) or (Ib) according to claim 1 of JP-A-6-67385.
Polymer couplers: P-1, P-5 in JP-A-2-44345 (page 11).
[0154]
As the coupler in which the coloring dye has an appropriate diffusibility, those described in US Pat. No. 4,366,237, GB 2,125,570, EP 96,873B, and DE 3,234,533 are preferable.
Couplers for correcting unnecessary absorption of color-forming dyes are yellow colored cyan couplers represented by the formulas (CI), (CII), (CIII) and (CIV) described on page 5 of EP 456,257A1 (especially page 84). YC-86), the yellow colored magenta coupler ExM-7 (page 202), EX-1 (page 249), EX-7 (page 251) described in the EP, and the magenta colored pigment described in US 4,833,069. Colorless masking represented by formula (A) in cyan coupler CC-9 (column 8), CC-13 (column 10), US Pat. No. 4,837,136 (2) (column 8), claim 1 of WO 92/11575. Couplers (especially the exemplified compounds on pages 36 to 45) are preferred.
[0155]
Next, a container (patrone) for the photosensitive material to be processed by the method of the present invention will be described. The main material of the patrone used may be a metal or a synthetic plastic, but is preferably a plastic material such as polystyrene, polyethylene, polypropylene, and polyphenyl ether.
The patrone of the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonions, anions, cations, betaine-based surfactants and polymers can be preferably used. These antistatic patrones are described in JP-A Nos. 1-312537 and 1-312538. In particular, the resistance at 25 ° C. and 25% RH is 10¹²Ω or less is preferable. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded in order to impart light-shielding properties. The size of the patrone may be the same as the current 135 size, and it is effective to reduce the diameter of the current 135 size 25 mm cartridge to 22 mm or less in order to reduce the size of the camera. The volume of the patrone case is 30cm³Less than 25cm³It is preferable to set the following. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.
[0156]
In addition, the patrone may be a type in which the film is sent out by rotating the spool, or the film tip is housed in the patrone body, and the film tip is sent out from the patrone port by rotating the spool shaft in the film sending direction. May be. These are disclosed in US Pat. Nos. 4,834,306 and 5,226,613. The developed light-sensitive material can be stored again in the patrone. In this case, the patrone used may be the same as the photosensitive material before processing or may be different.
[0157]
【Example】
Examples belowAnd reference examplesThe present invention will be described in more detail below, but the present invention is not limited to these.
(Reference example)
On a cellulose triacetate film support provided with an undercoat layer, each layer having the following composition was applied in multiple layers to prepare a color negative film.
[0158]
(Photosensitive layer composition)
The main materials used for each layer are classified as follows:
ExC: Cyan coupler UV: UV absorber
ExM: Magenta coupler HBS: High boiling organic solvent
ExY: Yellow coupler H: Gelatin hardener
ExS: sensitizing dye
The number corresponding to each component is g / m²The coating amount is expressed in units. For silver halide, the coating amount is expressed in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units per mol of silver halide in the same layer.
[0159]
First layer (anti-halation layer)
Black colloidal silver Silver 0.09
Gelatin 1.60
ExM-1 0.12
ExF-1 2.0 × 10^-3
Solid disperse dye ExF-2 0.030
Solid disperse dye ExF-3 0.040
HBS-1 0.15
HBS-2 0.02
[0160]
Second layer (middle layer)
Silver iodobromide emulsion M silver 0.065
ExC-2 0.04
Polyethyl acrylate latex 0.20
Gelatin 1.04
[0161]
Third layer (low-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion A silver 0.25
Silver iodobromide emulsion B silver 0.25
ExS-1 6.9 × 10^-5
ExS-2 1.8 × 10^-5
ExS-3 3.1 × 10^-4
ExC-1 0.17
ExC-3 0.030
ExC-4 0.10
ExC-5 0.020
ExC-6 0.010
Cpd-2 0.025
HBS-1 0.10
Gelatin 0.87
[0162]
4th layer (medium speed red-sensitive emulsion layer)
Silver iodobromide emulsion C silver 0.70
ExS-1 3.5 × 10^-4
ExS-2 1.6 × 10^-5
ExS-3 5.1 × 10^-4
ExC-1 0.13
ExC-2 0.060
ExC-3 0.0070
ExC-4 0.090
ExC-5 0.015
ExC-6 0.0070
Cpd-2 0.023
HBS-1 0.10
Gelatin 0.75
[0163]
Fifth layer (high-sensitivity red-sensitive emulsion layer)
Silver iodobromide emulsion D silver 1.40
ExS-1 2.4 × 10^-4
ExS-2 1.0 × 10^-4
ExS-3 3.4 × 10^-4
ExC-1 0.10
ExC-3 0.045
ExC-6 0.020
ExC-7 0.010
Cpd-2 0.050
HBS-1 0.22
HBS-2 0.050
Gelatin 1.10
[0164]
6th layer (middle layer)
Cpd-1 0.090
Solid disperse dye ExF-4 0.030
HBS-1 0.050
Polyethyl acrylate latex 0.15
Gelatin 1.10
[0165]
7th layer (low sensitivity green emulsion layer)
Silver iodobromide emulsion E silver 0.15
Silver iodobromide emulsion F silver 0.10
Silver iodobromide emulsion G silver 0.10
ExS-4 3.0 × 10^-5
ExS-5 2.1 × 10^-4
ExS-6 8.0 × 10^-4
ExM-2 0.33
ExM-3 0.086
ExY-1 0.015
HBS-1 0.30
HBS-3 0.010
Gelatin 0.73
[0166]
8th layer (medium speed green-sensitive emulsion layer)
Silver iodobromide emulsion H silver 0.80
ExS-4 3.2 × 10^-5
ExS-5 2.2 × 10^-4
ExS-6 8.4 × 10^-4
ExC-8 0.010
ExM-2 0.10
ExM-3 0.025
ExY-1 0.018
ExY-4 0.010
ExY-5 0.040
HBS-1 0.13
HBS-3 4.0 × 10^-3
Gelatin 0.80
[0167]
9th layer (high sensitivity green-sensitive emulsion layer)
Silver iodobromide emulsion I silver 1.25
ExS-4 3.7 × 10^-5
ExS-5 8.1 × 10^-5
ExS-6 3.2 × 10^-4
ExC-1 0.010
ExM-1 0.020
ExM-4 0.025
ExM-5 0.040
Cpd-3 0.040
HBS-1 0.25
Polyethyl acrylate latex 0.15
Gelatin 1.33
[0168]
10th layer (yellow filter layer)
Yellow colloidal silver silver 0.015
Cpd-1 0.16
Solid disperse dye ExF-5 0.060
Solid disperse dye ExF-6 0.060
Oil-soluble dye ExF-7 0.010
HBS-1 0.60
Gelatin 0.60
[0169]
11th layer (low-sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion J silver 0.09
Silver iodobromide emulsion K silver 0.09
ExS-7 8.6 × 10^-4
ExC-8 7.0 × 10^-3
ExY-1 0.050
ExY-2 0.22
ExY-3 0.50
ExY-4 0.020
Cpd-2 0.10
Cpd-3 4.0 × 10^-3
HBS-1 0.28
Gelatin 1.20
[0170]
12th layer (high-sensitivity blue-sensitive emulsion layer)
Silver iodobromide emulsion L Silver 1.00
ExS-7 4.0 × 10^-4
ExY-2 0.10
ExY-3 0.10
ExY-4 0.010
Cpd-2 0.10
Cpd-3 1.0 × 10^-3
HBS-1 0.070
Gelatin 0.70
[0171]
13th layer (first protective layer)
UV-1 0.19
UV-2 0.075
UV-3 0.065
HBS-1 5.0 × 10^-2
HBS-4 5.0 × 10^-2
Gelatin 1.8
[0172]
Fourteenth layer (second protective layer)
Silver iodobromide emulsion M silver 0.10
H-1 0.40
B-1 (1.7 μm in diameter) 5.0 × 10^-2
B-2 (diameter 1.7 μm) 0.15
B-3 0.05
S-1 0.20
Gelatin 70
[0173]
Further, in order to improve the preservability, processability, pressure resistance, fungicide / antibacterial property, antistatic property and coatability of each layer, W-1 to W-3, B-4 to B-6, F -1 to F-17 and iron, lead, gold, platinum, palladium, iridium, and rhodium salts.
[0174]
[Table 1]
[0175]
In Table 1,
(1) Emulsions J to L were subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.
(2) Emulsions A to I were subjected to gold sensitization, sulfur sensitization and selenium sensitization in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer according to the examples of JP-A-3-237450. ing.
(3) For preparing tabular grains, low molecular weight gelatin is used according to the examples of JP-A-1-158426.
(4) Dislocation lines described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.
(5) Emulsion L is a double-structured grain containing an internal high iodine core described in JP-A-60-143331.
[0176]
Preparation of dispersion of organic solid disperse dye
ExF-2 below was dispersed by the following method. That is, 21.7 ml of water, 3 ml of a 5% aqueous solution of sodium p-octylphenoxyethoxyethoxyethanesulfonate and 0.5 g of a 5% aqueous solution of 0.5 g of p-octylphenoxypolyoxyethylene ether (polymerization degree 10) were mixed in a 700 ml pot mill. And 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added thereto, and the contents were dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the fine dye particles was 0.44 μm.
[0177]
Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively. ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of EP549,489A. The average particle size was 0.06 μm.
[0178]
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[0179]
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[0180]
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[0181]
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[0182]
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[0183]
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[0184]
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[0185]
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[0186]
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[0187]
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[0188]
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[0189]
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[0190]
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[0191]
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[0192]
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[0193]
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[0194]
The above sample 101 was cut into a 135-type film size (corresponding international standard ISO 1007) and subjected to wedge exposure.²Was processed under the following conditions for two months. The processor used was an automatic developing machine FNCP-300II manufactured by Fuji Photo Film Co., Ltd., and the temperature of the processing solution was set to the processing temperature continuously during the test period.
[0195]
[0196]
The composition of the treatment liquid is shown below.
[0197]
[0198]
[0199]
[0200]
The adhesiveness of the photosensitive material treated with the above method was evaluated by the following method. In addition, light fading was also evaluated.
Adhesion: The sample at the end of the treatment was cut into a length of 23 cm and placed in a Fujicolor negative sheet <SP roll plain fabric / Fujicolor Sales Co., Ltd.>. Thereafter, a paper-based mount is applied to both sides of the negative sheet, and 1 kg / 25 cm under the condition of wet heat (60 ° C./60%).²Weighted. After a lapse of 4 weeks in this state, the adhesion between the sample and the negative sheet was evaluated.
：: A level at which the sample can be quickly taken out of the negative sheet and the sample is not damaged.
Δ: The adhesiveness between the sample and the negative sheet was slightly felt, but it was at a level at which it could be taken out.
X: A level at which the adhesion between the sample and the negative sheet is strong, and a trace of adhesion remains on the sample taken out.
[0201]
Wet heat: The density of the sample after the treatment was measured, and Dmax measured by blue light (B light) fading was read from the characteristic curve. Next, the photosensitive material after measurement was stored under the following conditions, and Dmax after aging was measured in the same manner. Then, the change over time in Dmax of the yellow dye was determined as follows.
Storage conditions: temperature: 60 ° C, relative humidity: 80%, 2 weeks
Change with time of Dmax (ΔDmax (B))
= (Dmax before storage)-(Dmax after storage)
Table 2 shows the results.
[0202]
[Table 2]
[0203]
Table 2 shows that, in the present invention, the adhesiveness after the treatment is low, and the wet heat fading is good.
[0204]
(Example1)
To the support and back layer of the photosensitive material prepared as follows,Reference exampleWas coated to obtain a photosensitive material sample 102.
[0205]
1) Support
The support used in this example was prepared by the following method.
100 parts by weight of a polyethylene-2,6-naphthalate polymer and Tinuvin P. as an ultraviolet absorber. After drying 2 parts by weight of 326 (manufactured by Ciba-Geigy), the mixture was melted at 300 ° C., extruded from a T-die, and then longitudinally stretched 3.3 times at 140 ° C., followed by 130 ° C. And then heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26, and I-26 described in Japanese Patent Publication No. 94-6023). 27, II-5) was added in an appropriate amount. Further, the support was wound around a stainless steel winding core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support with which a winding habit was not easily formed.
[0206]
2) Application of undercoat layer
The support was subjected to a corona discharge treatment, a UV discharge treatment, and a glow discharge treatment on both surfaces, and then gelatin was applied to each surface at 0.1 g / m 2.², Sodium α-sulfodi-2-ethylhexyl succinate 0.01 g / m 2², Salicylic acid 0.04 g / m², P-chlorophenol 0.2 g / m², (CH₂= CHSO₂CH₂CH₂NHCO)₂CH₂0.012 g / m², Polyamide-epichlorohydrin polycondensate 0.02 g / m²(10cc / m², Using a bar coater), and an undercoat layer was provided on the high temperature side during stretching. Drying was carried out at 115 ° C. for 6 minutes (all rollers and conveying devices in the drying zone were at 115 ° C.).
3) Coating of back layer
An antistatic layer, a magnetic recording layer, and a sliding layer having the following composition were provided as a back layer on one surface of the support after the undercoating.
[0207]
3-1) Coating of antistatic layer
The specific resistance of the tin oxide-antimony oxide composite having an average particle diameter of 0.005 μm is 0.2 g / m of a dispersion of fine particle powder (secondary aggregate particle diameter of about 0.08 μm) having a resistivity of 5 Ω · cm.², Gelatin 0.05g / m², (CH₂  = CHSO₂CH₂CH₂NHCO)₂CH₂  0.02 g / m², Poly (degree of polymerization 10) oxyethylene-p-nonylphenol 0.005 g / m²And resorcinol.
3-2) Coating of magnetic recording layer
3-poly (degree of polymerization 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area 43 m²/ G, major axis 0.14 μm, single axis 0.03 μm, saturation magnetization 89 emu / g, Fe⁺²/ Fe⁺³= 6/94, surface treated with aluminum oxide silicon oxide with 2% by weight of iron oxide) 0.06 g / m²To 1.2 g / m of diacetyl cellulose²(The dispersion of iron oxide was carried out with an open kneader and a sand mill.)₂H₅C (CH₂OCONH-C₆H₃(CH₃) NCO)₃  0.3g / m²Was coated with a bar coater using acetone, methyl ethyl ketone, and cyclohexanone as a solvent to obtain a 1.2 μm-thick magnetic recording layer. 10 mg each of abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as a matting agent / M²Was added so that Drying was performed at 115 ° C for 6 minutes (all rollers and transporting devices in the drying zone were at 115 ° C). D of magnetic recording layer with X-light (blue filter)^BIs about 0.1, the saturation magnetization moment of the magnetic recording layer is 4.2 emu / g, and the coercive force is 7.3 × 10⁴A / m and the squareness ratio were 65%.
[0208]
3-3) Preparation of sliding layer
Diacetyl cellulose (25 mg / m²), C₆H_ThirteenCH (OH) C₁₀H₂₀COOC₄₀H₈₁  (Compound a, 6 mg / m²) / C₅₀H₁₀₁O (CH₂CH₂O)₁₆H (compound b, 9 mg / m²) The mixture was applied. This mixture was melted at 105 ° C. in xylene / propylene monomethyl ether (1/1), poured and dispersed in propylene monomethyl ether (10-fold amount) at room temperature, and then dispersed in acetone ( The average particle diameter was adjusted to 0.01 μm) before the addition. 15 mg / m 2 of silica particles (0.3 μm) as a matting agent and aluminum oxide (0.15 μm) coated with 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as an abrasive²Was added so that Drying was performed at 115 ° C for 6 minutes (all rollers and transporting devices in the drying zone were 115 ° C). The sliding layer has a dynamic friction coefficient of 0.06 (stainless hard ball of 5 mmφ, load of 100 g, speed of 6 cm / min), a static friction coefficient of 0.07 (clip method), and a kinetic friction coefficient of an emulsion surface and a sliding layer described later of 0.12. Excellent characteristics.
[0209]
The sample 102 prepared as described above is cut into a width of 24 mm and a size of 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at 0.7 mm from the width direction of one side of the length of the photosensitive material. A set of these two sets provided at intervals of 32 mm was prepared, and FIG. 1 to FIG. 7 was housed in a plastic film cartridge.
[0210]
The sample 102 was subjected to wedge exposure, and then loaded into a camera having a magnetic recording device made of a permalloy material with a head gap of 5 μm, a number of turns of 50, and digital saturation recording at a recording wavelength of 50 μm. The sample 102 on which the magnetic information is written in this way isReference exampleExcept for changing the developing solution, bleaching solution and stabilizing solution to the following along with the sample 101 cut, processed and exposed in the same manner asReference exampleThe treatment was performed by the method described in (1). At this time, the ratio of the processing amounts of the sample 101 and the sample 102 was 5: 1.
[0211]
[0212]
[0213]
[0214]
After processing under each condition,Reference exampleIn the same manner as in the above, the adhesion and wet heat fading of the sample 101 were examined. Further, the output signal level of the isolated frequency was measured using a magnetic reproducing head made of a sendust material for the sample 102 of 150 m retroactively from the end of the processing, with a head gap of 2.5 μm, a number of turns of 2,000, and a sendust material. Table 3 shows the results. In addition, as for the result of the magnetic output, the average of the output from the start of measurement to 1 m was set to 100, and the average output for the final 1 m was expressed by%.
[0215]
[Table 3]
[0216]
As shown in Table 3, in the present invention, its effectiveness was also obtained for magnetic output.
[0217]
(Example2)
Example 1 except that the bleaching solution and the stabilizing solution were replaced with the following:1Evaluation was performed in the same manner as described above.
[0218]
[0219]
[0220]
After processing under each condition,1As a result, excellent effects were confirmed.
[0221]
(Example3)
Example1The sample 102 described in the above is similarly cut, processed, exposed and written with magnetic information.Reference example6m per day by mixing with sample 101^TwoEach of the photographic materials was processed for three months under the following conditions. At this time, the ratio of the processing amounts of the samples 101 and 102 was 5: 2. The processor used was an automatic processor FP-560B manufactured by Fuji Photo Film Co., Ltd. In addition, the remodeling was performed so that the overflow solution of the bleaching bath was not discharged into the post-bath but was entirely discharged to the waste liquid tank. Further, this FP-560B is equipped with an evaporation correction means described in Japanese Patent Application Laid-Open No. 94-4992 (Invention Association). The processing steps and the composition of the processing solution are shown below.
[0222]
The stabilizing solution and the fixing solution were of the countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the color developing solution brought into the bleaching step, the amount of the bleaching solution brought into the fixing step, and the amount of the fixing solution brought into the washing step were 35 mm in width of the photosensitive material and 1 m in width.²They were 65 ml, 50 ml, 50 ml and 50 ml, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous process.
The opening area of the above processor is 100 cm with the color developer.²120cm with bleach², Other processing liquid is about 100cm²Met.
[0223]
The composition of the treatment liquid is shown below.
[0224]
[0225]
[0226]
(Wash water) Common to tank liquid and replenisher
Tap water is passed through a mixed-bed column filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type strongly basic anion exchange resin (Amberlite IRA-400). Then, the concentration of calcium and magnesium ions was reduced to 3 mg / l or less, followed by pretreatment by adding 20 mg / l of sodium diisocyanurate and 150 mg / l of sodium sulfate. The pH of this solution was in the range of 6.5 to 7.5.
[0227]
[0228]
Example of processing results1In the same manner as in the above, excellent results were obtained with respect to the adhesion, wet heat fading, and magnetic output of the photographic material after processing.
[0229]
According to the present invention,Has a magnetic recording layerOf photosensitive materialAfter processingAdhesiveness, wet heat discoloration, andIs magneticAn excellent processing method can be provided for output performance.

Claims (2)

In a method of subjecting a silver halide color photographic light-sensitive material having a magnetic recording layer to color development, desilvering, and then washing with water and / or stabilizing, the following processing solution having bleaching ability in the desilvering step is used. The processing solutions containing at least one iron (III) complex salt of the compound represented by the formula (1-a) and used in the desilvering step or the subsequent steps are represented by the following general formulas (A) to (I) the method for processing a silver halide color photographic light-sensitive material characterized by containing at least one of the at least one or gentamycin such compound represented by.
General formula (1-a)
(In the formula, L ₁ represents an alkylene group. M ₁ , 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 represent a hydrogen atom, an alkyl group or an aryl group. R ₆ represents a hydrogen atom, an alkyl group or an aryl group. , A nitro group, a carboxy group, a sulfo group, a sulfamoyl group, a hydroxy 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 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 residue, and R ₁₄ and R ₁₅ represent a hydrogen atom and a halogen, respectively. R ₁₄ and R ₁₅ may combine with each other to form a benzene ring, R ₁₆ represents a hydrogen atom or an alkyl group, and R ₁₇ represents an alkyl group or an aryl group. Represents a kill group or an aryl group, Y represents a halogen atom, Z ₁ represents a group of nonmetallic atoms necessary for forming a thiazolyl ring, and Z ₂ represents a group necessary for forming a 6-membered hydrocarbon ring. N represents 0 or 1. m represents 1 or 2. k represents an integer of 3 to 20. 2. The silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution having bleaching ability contains at least one compound represented by the following general formula (J). Processing method.
General formula (J)
(In the formula, Q represents a group of nonmetallic atoms necessary to form a heterocyclic ring. P represents 0 or 1. Ma represents a hydrogen atom or a cation.)