JPH0836248A - Processing method of silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To attain rapid desilverizing and to prevent react-out errors in magnetic recording. CONSTITUTION:This silver halide color photographic sensitive material has each at least one layer of red-sensitive, green-sensitive and blue-sensitive layers on the one surface of a transparent supporting body and a magnetic layer containing a ferromagnetic fine powder on the other surface of the supporting body. In the process of fixing and/or bleach-fixing of this photographic material after color developing, the fixing liquid and/or bleach-fixing liquid is processed by electrolysis to recover silver, while the current density for electrolysis is specified to 5-50mA/cm<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide color photographic light-sensitive material having a magnetic layer, and particularly to provide a processing method excellent in magnetic information reading performance.

[0002]

2. Description of the Related Art Conventionally, in a silver halide photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material), it is almost impossible to input or output various kinds of information at the time of photographing or printing, and it is slightly optical. It was only possible to input / output the shooting date and time. By the way, JP-A-4-68336 and JP-A-4-68336.
No. 73737, or as disclosed in Japanese Patent Laid-Open No. 5-88283, by providing a transparent magnetic recording layer on the entire surface of a light-sensitive material, shooting conditions such as date and time of shooting, weather, reduction / enlargement ratio, Number of reprints, areas you want to zoom,
It is possible to input the message, development, print conditions, etc. to the sensitive material. Also, various information can be provided even when inputting to video equipment such as TV / video.
This is a promising method for the future.

On the other hand, in such a method for processing a light-sensitive material, color development, desilvering, washing with water and stabilizing treatment are generally carried out. By the way, the desilvering process includes a fixing process and a bleach-fixing process, which has a function of removing silver from a light-sensitive material and accumulates as silver ions in the solution. As means for removing the accumulated silver ions and maintaining the performance, JP-A-48-18191, 50-98837 and 51-68 are known.
17, the method of using silver recovery by electrolysis described in JP-A-51-195358, JP-A-57-13900, etc. is used particularly in a major developing laboratory (large laboratory). In addition, the electrolytic silver recovery method described above has the advantage of facilitating low replenishment and regeneration of the processing solution, which is an important technology in addressing recent environmental problems.

[0004]

By the way, when a light-sensitive material having the above-mentioned transparent magnetic recording layer is processed by a fixing solution recovered by electrolytic silver or a bleach-fixing process, its magnetic recording performance is deteriorated. It became clear that the S / N ratio deteriorated and it was not possible to provide satisfactory information. Therefore, an object of the present invention is to provide a method for processing a silver halide color photographic light-sensitive material, which processes a light-sensitive material having a transparent magnetic recording layer without deteriorating the S / N ratio of magnetically recorded information. Furthermore, it is to provide a fixing and bleach-fixing process in which the amount of waste liquid is reduced and the desilvering performance and photographic performance are excellent by the electrolytic silver recovery method.

[0005]

It has been found that the above problems can be solved by the following processing method. That is, 1. At least one red-sensitive layer on each transparent support,
In a processing step of processing a silver halide color photographic light-sensitive material having a green-sensitive layer and a blue-sensitive layer and having a magnetic layer containing ferromagnetic fine powder in a processing solution having a fixing ability after color development, the fixing is performed. A processing method for a silver halide color photographic light-sensitive material, characterized in that the processing solution having the ability is processed while recovering electrolytic silver and the current density during electrolysis is 5 to 50 mA / cm ² . 2. The method for processing a silver halide color photographic light-sensitive material as described in the above item 1, wherein the processing solution having the fixing ability contains at least one of sulfinic acids represented by the following general formula (I). General formula (I)

[0006]

Embedded image

(In the formula, R represents a substituent on the benzene ring, and n represents an integer of 0 to 6. When n is 2 or more, R is
May be the same or different. M represents a hydrogen atom, alkali metal, alkaline earth, ammonium or amine. 3. The processing method for a silver halide color photographic light-sensitive material as described in the above item 1, wherein the processing solution is a bleach-fixing solution.

Here, as the processing liquid having fixing ability,
Examples thereof include a fixing solution and a bleach-fixing solution. The details of the present invention will be described below. The magnetic recording layer used in the present invention will be described in detail. The magnetic recording layer may be provided in the support or separately provided. If provided separately,
It may be on the emulsion layer side or on the opposite side. Although magnetic particles are used as a recording medium for the magnetic recording layer, the magnetic particles used in the present invention include ferromagnetic iron oxides such as γFe ₂ O ₃ (FeOx, 4/3 <x ≦ 3/2), Co Coated γFe ₂ O ₃ etc.
Adhering ferromagnetic iron oxide (FeOx, 4/3 <x ≦ 3/2), Co-depositing magnetite, other Co-containing ferromagnetic iron oxide, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy , And other ferrites such as hexagonal Ba
Ferrite, Sr ferrite, Pb ferrite, Ca ferrite, or their solid solutions or ion substitutes can be used, but Co-deposited γFe ₂ O ₃ and other Co-deposited ferromagnetic iron oxides with a Fe ²⁺ / Fe ³⁺ ratio Is preferably 0 to 10% from the viewpoint of transmission density. The manufacturing method of these ferromagnetic powders is known, and the ferromagnetic material used in the present invention can also be manufactured according to the known method. Shape of ferromagnetic material
Describe the size. The shape may be any of needle shape, rice grain shape, spherical shape, cubic shape, plate shape, etc., but needle shape is preferable in terms of electromagnetic conversion characteristics. When the particle size is needle-like, the major axis is preferably 0.01 to 0.8 μm, the major axis / minor axis ratio is preferably 2 to 100, and the major axis is 0.05 to 0.3 μm, the major axis / minor axis. The ratio is more preferably 4 to 15. 2 in specific surface area S _BET
It is preferably 0 m ² / g or more, particularly preferably 30 m ² / g or more.

The larger the saturation magnetization (σ s) of the ferromagnetic material is, the more preferable it is, but 50 emu / g or more, more preferably 70 em.
u / g or more, and practically 100 emu / g or less. The squareness ratio (σr / σs) of the ferromagnetic material is preferably 40% or more, more preferably 45% or more. If the coercive force (Hc) is too small, it will be easily erased, and if it is too large, it will not be possible to write depending on the system, so an appropriate value is preferable.
e or more and 3000 Oe or less, preferably 500 Oe or more 2
000 Oe or less, more preferably 650 Oe or more and 95
It is 0 Oe or less.

These ferromagnetic particles are disclosed in, for example, Japanese Patent Laid-Open No.
It may be surface-treated with silica and / or alumina, such as 9-23505 and those described in JP-A-4-096052. In addition, JP-A-4-195726 and 4-1.
92116, 4-259911, 5-081652.
A surface treatment with an inorganic and / or organic material as described may be applied. Furthermore, these ferromagnetic particles may be treated on their surface with a silane coupling agent or a titanium coupling agent. As the coupling agent, known materials such as those described in JP-B-1-261469 can be used, but the following compounds can also be used. Compound Example [1] -1. Vinyltrichlorosilane 〃 [1] -2. Vinyltriethoxysilane 〃 [1] -3. γ-methacryloxypropyltrimethoxysilane 〃 [1] -4. γ-glycidoxypropyltrimethoxysilane 〃 [1] -5. N-β (aminoethyl) γ-aminopropyl methyldimethoxysilane 〃 [1] -6. N-phenyl-γ-aminopropyl trimethoxysilane [1] -7. Vinyloctyltrimethoxysilane 〃 [1] -8. 10- (Vinyloxycarbonyl) nonyltrimethoxysilane 〃 [1] -9. p-Vinylphenyl triisopropylsilane 〃 [1] -10. 3- (Glycidyloxy) propyl triethoxysilane 〃 [1] -11. 3- (acryloyl) propyl trimethoxysilane 〃 [1] -12. 11- (methacryloyl) undecyl trimethoxysilane 〃 [1] -13. 3-Aminopropyl trimethoxysilane 〃 [1] -14. 3-Phenylaminopropyl trimethoxysilane 〃 [1] -15. 3-N, N-dibutylaminopropyl trimethoxysilane 〃 [1] -16. 3-Trimethylammoniopropyl trimethoxysilan iodide 〃 [1] -18. 3-Isocyanylpropyl methyldimethoxysilane 〃 [1] -19. 3- (Poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane 〃 [1] -20. 3-methoxy (poly (degree of polymerization 6) oxyethynyl) oxypropyl trimethoxysilane 〃 [1] -21. Decyltrimethoxysilane

Compound Example [2] -1. Isopropyltriisostearoyl titanate 〃 [2] -2. Isopropyl tridodecylbenzene sulfonyl titanate [2] -3. Isopropyl tris (dioctyl pyrophosphate) titanate 〃 [2] -4. Tetraisopropyl bis (dioctyl phosphite) titanate [2] -5. Tetraoctyl bis (ditridecyl phosphite) titanate 〃 [2] -6. Tetra (2,2'-diallyloxymethyl-1-butyl) bis (di-tridecyl) phosphite titanate 〃 [2] -7. Bis (dioctyl pyrophosphate oxyacetate titanate 〃 [2] -8. Bis (dioctyl pyrophosphate) ethylene titanate 〃 [2] -9. Isopropyltrioctanoyl titanate 〃 [2] -10. 〃 [2] -11. Isopropylisostearoyldiacrylic titanate 〃 [2] -12 Isopropyltri (dioctylphosphate) titanate 〃 [2] -13 Isopropyltricumylphenyl titanate 〃 [2] -14 isopropyltri (N-amidoethylaminoethyl) titanate 〃 [2] -15. Dicumylphenyloxyacetate titanate 〃 [2] -16. Diisostearoyl ethylene titanate

The addition amount of these silane coupling agent and titanium coupling agent to the magnetic particles is 1.0 to 2
00 wt% is preferable, and if it is less than this, the liquid stability is inferior, and if it is too much, the liquid stability is also poor. Preferably 1
˜75% by weight, more preferably 2 to 50% by weight. Further, the addition of these silane coupling agent and titanium coupling agent of the present invention is applied to the magnetic particles of the present invention by a generally known method to modify the surface of the magnetic particles and impart the coating solution stability of the magnetic material. be able to. That is, the coupling agent is processed by a direct processing method for magnetic particles and an integral blending method. The direct method is roughly classified into a dry method, a slurry method and a spray method.
The magnetic material obtained by the direct treatment method is excellent in that it can be added to the binder to surely modify the surface of the magnetic particles with the coupling agent. Among them, the dry method is generally performed by uniformly dispersing magnetic particles in an alcohol aqueous solution, an organic solvent or an aqueous solution of a silane coupling agent and then drying the magnetic particles. It is preferable to use a stirrer such as a Henschel mixer, a super mixer, a ready mixer, a V-type blender, and an open kneader. Among these stirrers, the open kneader is particularly preferable. It is preferable that magnetic particles and a small amount of water, or an organic solvent containing water and a coupling agent are mixed and stirred with an open kneader to remove water, and then finely dispersed. Further, the slurry method adds a coupling agent to the slurry when there is a step of making magnetic particles into a slurry in the production of a magnetic material, and has an advantage that it can be treated in the production step. The spray method adds a coupling agent to the magnetic particles in the drying step of the magnetic material, and has an advantage that it can be processed in the manufacturing step, but has a problem in uniformity of processing. The integral blending method is a method in which a coupling agent is added to magnetic particles and a binder, and it is necessary to knead well and is a simple method.

Next, the binder in which the magnetic particles of the present invention are preferably used will be described. The binder used in the present invention is a known thermoplastic resin conventionally used as a binder for magnetic recording media, a thermosetting resin, a radiation curable resin, a reactive resin, an acid, an alkali or a biodegradable polymer, Natural product polymer (cellulose derivative, sugar derivative, etc.)
And mixtures of these can be used. The Tg of the above resin is preferably -40 ° C to 300 ° C, and the weight average molecular weight is 20,000 to 1,000,000, preferably 50,000 to 300,000. Examples of the thermoplastic resin include vinyl chloride / vinyl acetate copolymers, vinyl chloride, copolymers of vinyl acetate and vinyl alcohol, maleic acid and / or acrylic acid, vinyl chloride / vinylidene chloride copolymers, vinyl chloride / vinyl chloride. Acrylonitrol copolymer, vinyl-based copolymers such as ethylene / vinyl acetate copolymer, nitrocellulose,
Cellulose diacetate, cellulose triacetate,
Cellulose acetate propionate, cellulose acetate butyrate, cellulose tripropionate, cellulose derivatives such as cellulose dodecanoate resin,
Acrylic resin, polyvinyl acetal resin, polyvinyl butyral resin, polyester polyurethane resin, polyether polyurethane resin, polycarbonate polyurethane resin, polyester resin, polyether resin, polyamide resin, amino resin, styrene butadiene resin, rubber resin such as butadiene acrylonitrile resin, Silicone resin and fluorine resin can be mentioned. The thermosetting resin or the reactive resin whose molecular weight becomes extremely large by heating, for example, phenol resin, phenoxy resin, epoxy resin, curable polyurethane resin, urea resin, melamine resin, alkyd resin, silicone resin, acrylic resin. System reaction resin, epoxy-polyamide resin, nitrocellulose melamine resin, a mixture of high molecular weight polyester resin and isocyanate prepolymer,
Included are urea formaldehyde resins, low molecular weight glycol / high molecular weight diol / polyisocyanate mixtures, polyamine resins, and mixtures thereof. As the radiation-curable resin, a resin obtained by bonding a group having a carbon-carbon unsaturated bond as a radiation-curable functional group to the thermoplastic resin is used. Preferred functional groups include an acryloyl group and a methacryloyl group. Of these binders, cellulose diacetate is preferred. In the binders listed above, polar groups (epoxy group, CO
₂ M, OH, NR ₂ , NR ₃ X, SO ₃ M, OSO
₃ M, PO ₃ M ₂ , OPO ₃ M ₂ , wherein M is hydrogen, an alkali metal or ammonium, and when there are plural M in one group, R may be different from each other, R is hydrogen or alkyl It is preferable to introduce (a base) from the viewpoint of dispersibility and durability of the magnetic material. The polar group content is in the range of preferably 10 ^-7 to 10 ^-3 equivalents, and more preferably 10 ^-6 to 10 ^-4 equivalents per gram of the polymer.

The binders listed above may be used singly or as a mixture of several kinds, and a known crosslinking agent of epoxy type, aziridine type, isocyanate type, and / or a radiation curable vinyl type monomer may be added for curing treatment. .. The isocyanate-based crosslinking agent is a polyisocyanate compound having two or more isocyanate groups, such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, naphthylene-1,5.
-Isocyanates such as diisocyanate, o-toluidine diisocyanate, isophorone diisocyanate, and triphenylmethane diisocyanate, and reaction products of these isocyanates and polyalcohols (for example, reaction product of 3 mol of tolylene diisocyanate and 1 mol of trimethylolpropane) , And polyisocyanates produced by condensation of these isocyanates. Radiation-curable vinyl monomers include
A compound that can be polymerized by irradiation with a carbon-
It is a compound having one or more carbon unsaturated bonds in the molecule, and is (meth) acrylic acid ester, (meth) acrylamide, allyl compound, vinyl ester, vinyl ester, vinyl heterocyclic compound, N-vinyl. Examples thereof include compounds, styrene, (meth) acrylic acid, crotonic acid, itaconic acid, olefinic acid and the like. Of these, preferred are (meth) acrylates of polyethylene glycol such as diethylene glycol di (meth) acrylate and triethylene glycol di (meth) acrylate having two or more (meth) acryloyl groups, trimethylolpropane tri (meth) acrylate, and the like. ) Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, a reaction product of a polyisocyanate and a hydroxy (meth) acrylate compound, and the like. These cross-linking agents are preferably 5 to 45 wt% with respect to the total binder containing the cross-linking agents.

A hydrophilic binder can also be used in the magnetic recording layer of the present invention. As the hydrophilic binder to be used, Research Disclosure No. 17643, 2
6 and pp. 651, No. 18716, water-soluble polymers, cellulose esters, latex polymers, water-soluble polyesters, etc. are exemplified. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. As the latex polymer, vinyl chloride-containing copolymer, vinylidene chloride-containing copolymer,
Examples thereof include acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers, butadiene-containing copolymers, and the like. The most preferred of these is gelatin. Gelatin is a so-called alkali-processed (lime-processed) gelatin that is immersed in an alkali bath before extraction of gelatin, an acid-processed gelatin that is immersed in an acid bath, and a double-immersed gelatin that has been subjected to both of these processes in the manufacturing process. Any of gelatin may be used. If necessary, a portion of colloidal albumin, casein,
Cellulose derivatives such as carboxymethyl cellulose and hydroxyethyl cellulose, agar, sodium alginate, starch derivatives, sugar derivatives such as dextran, synthetic hydrophilic colloids such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylic acid copolymer,
Polyacrylamide or derivatives thereof, partial hydrolysates, gelatin derivatives and the like may be used in combination with gelatin.

It is preferable to harden the magnetic recording material containing gelatin. As a hardener that can be used in the magnetic recording layer,
For example, aldehyde compounds such as formaldehyde and glutaraldehyde, ketone compounds such as diacetyl and cyclopentanedione, bis (2-chloroethylurea), 2-hydroxy-4,6-dichloro-1,3,3.
5-triazine and others U.S. Pat. No. 3,288,77
5, 2,732,303, British Patent 974,7
23, 1,167,207 and the like, compounds having a reactive halogen, divinyl sulfone, 5-acetyl-1,3-diacryloylhexahydro-1,3,5-triazine, and others. US Patent No. 3,
Compounds having a reactive olefin described in 635,718, 3,232,763, British Patent 994,869, etc., N-hydroxymethylphthalimide, and other U.S. Pat. No. 2,732,316. Issue 2
N-methylol compounds described in US Pat. No. 586,168, isocyanates described in US Pat. No. 3,103,437, and US Pat. No. 3,017,28.
0, 2,983,611 and the like, aziridine compounds, US Pat. Nos. 2,725,294 and 2,725,295 and the like, acid derivatives,
Examples thereof include epoxy compounds described in US Pat. No. 3,091,537 and halogen carboxaldehydes such as mucochloric acid. Alternatively, as an inorganic compound hardening agent, chrome alum, zirconium sulfate, JP-B-56-12853, JP-A-58-32699.
No., Belgian Patent No. 825,726, JP-A-60-22
5148, JP-A-51-126125, JP-B-58
Examples include carboxyl group-activating type hardeners described in JP-A-50699, JP-A-52-54427, US Pat. No. 3,321,313 and the like. The amount of the hardener used is usually 0.01 to 30% by weight based on dry gelatin,
It is preferably 0.05 to 20% by weight.

As the method of dispersing the above-mentioned magnetic material in the binder, various known means other than Japanese Patent Application No. 4-189652 can be used, but a kneader, a pin type mill, an annular type mill and the like are preferable. A combination of a kneader and a pin type mill or a kneader and an annular type mill is also preferable. As the kneader, there are open type, closed type, continuous type and the like, and kneaders such as a three-roll mill and Labo Plastomill are also used. Further, at the time of dispersion, the dispersant described in JP-A-5-088283 and other known dispersants can be used.

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

The magnetic recording layer of the present invention can be provided on the entire back surface of the photographic support by coating or printing, or in the form of stripes. It is also preferable to co-cast a solution of a binder in which magnetic particles are dispersed and a solution of a binder for preparing a support in the form of an entire surface or stripes to prepare a support having a magnetic recording layer. In this case, the compositions of the two kinds of polymers may be different, but it is preferable that they are the same. The method for applying this magnetic recording layer includes air doctor coat, blade coat, air knife coat, squeeze coat, impregnation coat, reverse roll coat, transfer roll coat, gravure coat, kiss coat, cast coat, spray coat, dip coat, bar coat. , Extrusion coat, etc. can be used, and other methods are also possible. For a detailed explanation of these, refer to "Coating Engineering", pages 253 to 277 (published by 46.3.20. Showa), published by Asakura Shoten. Has been described. By such a method, the magnetic recording layer coated on the support is subjected to a treatment for orienting the magnetic material in the layer while immediately drying, if necessary, and then the formed magnetic recording layer is dried. The transport speed of the support at this time is usually 2 m / min to 5
It is performed at 00 m / min and the drying speed is 20 ° C to 250 ° C.
Controlled by. There is a method of using a permanent magnet or a solenoid coil to orient the magnetic body. The strength of the permanent magnet is 2
000 Oe or more is preferable, and 3000 Oe or more is particularly preferable. In the case of a solenoid, it may be 500 Oe or more.
The timing of orientation during drying is described in Japanese Patent Application No. 5-0058.
As described in No. 22, the point where the residual solvent in the magnetic recording layer is 5% to 70% is desirable. If necessary, the surface is smoothed to produce the magnetic recording layer of the present invention. These are disclosed, for example, in JP-B-40-23625, JP-B-39-28368, and US Pat. No. 347.
No. 3960, etc. In addition, Japanese Patent Sho 41
The method disclosed in Japanese Patent No. 13181 is considered to be a basic and important technique in this field.

The magnetic recording layer has improved lubricity, curl adjustment,
Functions such as antistatic, adhesion prevention, and head polishing may be provided together, or another functional layer may be provided to impart these functions. If necessary, a protective layer adjacent to the magnetic recording layer may be provided to improve the scratch resistance. For example, inorganic or organic fine particles (eg, silica, SiO ₂ , SnO)
₂ , Al ₂ O ₃ , TiO ₂ , crosslinked polymethylmethacrylate, barium carbonate, fine silicone particles, etc.) are preferably added.

For example, by incorporating an additive in the magnetic recording layer,
By providing protrusions of 0.8μ or less on the back layer surface, magnetic output error due to dust at the time of magnetic input / output is prevented, S / N which is one of the magnetic characteristics is not deteriorated and photographic properties are affected. There is a way not to give. As a method of giving surface protrusions to the back surface, there are methods of adding particles to the back surface, causing brushing at the time of coating and drying, and intentionally generating Benard cells, but it means that the shape of the surface protrusions can be freely controlled. Therefore, it is preferable to add particles to the back surface.

The added particles are insoluble in the developing solution,
As the material, inorganic fine particles, polymer particles, crosslinked polymer particles and the like can be used. As an example of the particles of the present invention, as the inorganic particles, fine particles of inorganic substances such as barium sulfate, manganese colloid, titanium dioxide, strontium barium sulfate, and silicon dioxide, further synthetic silica obtained by, for example, a wet method or gelation of silicic acid. Examples include silicon dioxide such as titanium dioxide and titanium dioxide (rutile type or anatase type) produced by titanium slag and sulfuric acid. It can also be obtained by pulverizing from an inorganic material having a relatively large particle size, for example, 20 μm or more, and then classifying (vibrating filtration, air classification, etc.). Further, as the polymer compound, there are polytetrafluoroethylene, cellulose acetate, polystyrene, polymethyl methacrylate, polypropyl methacrylate, polymethyl acrylate, polyethylene carbonate, starch and the like, and pulverized and classified products thereof. In addition, acrylic acid ester, methacrylic acid ester, itaconic acid diester, crotonic acid ester, maleic acid diester, phthalic acid diester, styrene derivative, vinyl ester, acrylamides, vinyl ethers, allyl compounds, vinyl ketones, vinyl heterocyclic compounds , Allyl compound, acrylonitrile, methacrylonitrile, polyfunctional monomers, three-dimensional siloxane polymer, benzoguanamine / formaldehyde condensate, benzoguanamine / melamine / formaldehyde condensate, melamine / formaldehyde condensate, etc. The polymer compound which is a polymer of one kind or more may be formed into particles by various means, for example, a suspension polymerization method, a spray drying method, or a dispersion method. In order not to deteriorate the photographic property, the average particle size of the particles is preferably 0.1 μm to 1 μm, and the coating amount thereof is preferably 1 to 100 mg / m ² .

It is more preferable that at least one kind of the particles is a non-spherical inorganic particle having a Mohs hardness of 5 or more because it has an effect of cleaning the dirt attached to the magnetic head.
The composition of the non-spherical inorganic particles is aluminum oxide (α
-Alumina, γ-alumina, corundum, etc.), chromium oxide (Cr ₂ O ₃ ), iron oxide (α-Fe ₂ O ₃ ), silicon dioxide, titanium dioxide, oxides such as silicon carbide (SiC), silicon carbide Carbides such as titanium carbide and fine powders such as diamond are preferable, and aluminum oxide and chromium oxide (Cr ₂ O ₃ ) are more preferable. The non-spherical inorganic particles may be added to the magnet layer or may be overcoated on the magnet layer. As the binder used at this time, the binder described in the above-mentioned magnet layer binder can be used, and preferably the same binder as the binder for the magnet layer.

Next, the transparent support of the present invention will be described in detail. As the transparent support of the present invention, triacetyl cellulose or polyethylene terephthalate which has been practically used for a color film can be used, but a polyethylene aromatic dicarboxylate polyester support is preferably used for magnetic recording property. Most desirable in terms of. The polyester of the present invention is formed by using a diol and an aromatic dicarboxylic acid as essential components, and examples of dibasic acids that can be often used as a mixture with other dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid and phthalic anhydride. acid,
Naphthalenedicarboxylic acid (2,6-, 1,5-, 1,4
-, 2,7-), diphenylene p, p'-dicarboxylic acid, tetrachlorophthalic anhydride, succinic acid, glutaric acid, adipic acid, sebacic acid, succinic anhydride, maleic acid, fumaric acid, maleic anhydride, itacone Acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1,1-di Carboxy-2-phenylethylene, 1,4-dicarboxymethylphenol, 1,3-dicarboxy-5phenylphenol, sodium 3-sulfoisophthalate

And the like. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus among the above-mentioned dicarboxylic acids. Next, as the diol, ethylene glycol, 1,3-propanediol, 1,2-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol are used. 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,
4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol,
Examples thereof include catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene and bisphenol A.

If desired, a monofunctional or trifunctional or higher polyfunctional hydroxyl group-containing compound or acid-containing compound may be copolymerized. The polyester of the present invention may be salicylic acid or the like, which may be copolymerized with a compound having a hydroxyl group and a carboxyl group (or its ester) at the same time in the molecule.

Among these diols and dicarboxylic acid monomers, preferred aromatic dicarboxylic acids are 2,6-naphthalenedicarboxylic acid (NDCA), terephthalic acid (TPA), isophthalic acid (IPA), orthophthalic acid (OPA), Paraphenylenedicarboxylic acid (PP
DC), as diol, (poly) ethylene glycol (PEG or EG)), cyclohexanedimethanol (CHDM), neopentyl glycol (NPG), bisphenol A (BPA), biphenol (BP), and hydroxycarboxylic acid as a copolymerization component. Examples of the acid include those obtained by copolymerizing para-hydroxybenzoic acid (PHBA) and 6-hydroxy-2-naphthalenecarboxylic acid (HNCA).

Of these, preferred polymers are polyethylene terephthalate, polyethylene naphthalate, homopolymers such as polycyclohexanedimethanol terephthalate (PCT), and terephthalic acid.
Copolymer of naphthalenedicarboxylic acid and ethylene glycol (mixing molar ratio of terephthalic acid and naphthalenedicarboxylic acid is preferably between 0.9: 0.1 and 0.1: 0.9, 0.8: 0.2-0.0.2). 2: 0.8 is more preferable), a copolymer of terephthalic acid, ethylene glycol and bisphenol A (mixing molar ratio of ethylene glycol and bisphenol A is preferably between 0.6: 0.4 and 0: 1.0, Further, 0.5: 0.5 to 0: 0.9 is preferable.), Isophthalic acid, para-phenylenedicarboxylic acid, a copolymer of terephthalic acid and ethylene glycol (isophthalic acid; para-phenylenedicarboxylic acid is used in a molar ratio of terephthalic acid). 1 is 0.1 to 0.
5, 0.1 to 0.5, and more preferably 0.2
.About.0.3, 0.2 to 0.3 are preferable), terephthalic acid, a copolymer of neopentyl glycol and ethylene glycol (the molar ratio of neopentyl glycol and ethylene glycol is 1: 0 to 0.7: 0.3). Preferably, 0.9: 0.1 to 0.6: 0.4) terephthalic acid, a copolymer of ethylene glycol and biphenol (the molar ratio of ethylene glycol and biphenol is 0:
1.0 to 0.8: 0.2 is preferable, and 0.1: 0.9 to 0.7: 0.3 is more preferable. ), Parahydroxybenzoic acid, a copolymer of ethylene glycol and terephthalic acid (the molar ratio of parahydroxybenzoic acid and ethylene glycol is preferably 1: 0 to 0.1: 0.9, more preferably 0.9: 0.1). .About.0.2: 0.8) and the like are preferable. Among these, polyesters containing 2,6-naphthalenedicarboxylic acid are particularly preferable. Specifically, it is a polyester containing 0.1-1.0 of 2,6-naphthalenedicarboxylic acid. Among them, polyethylene 2,6-naphthalate is particularly preferable.

These homopolymers and copolymers can be synthesized according to conventionally known methods for producing polyesters. For example, when the acid component is directly esterified with the glycol component, or when a dialkyl ester is used as the acid component, first, the transesterification reaction with the glycol component is performed, and this is heated under reduced pressure to remove the excess glycol component. By doing so, it can be synthesized. Alternatively, the acid component may be an acid halide and reacted with glycol. At this time, if necessary, a transesterification reaction catalyst, a polymerization reaction catalyst, or a heat resistance stabilizer may be added. Regarding these polyester synthesis methods, for example, Polymer Experimental Science Vol. 5, "Polycondensation and Polyaddition" (Kyoritsu Shuppan, 1980), pp. 103-136.
Page, "Synthetic Polymer V" (Asakura Shoten, 1971), 18th
It can be performed with reference to the descriptions on pages 7 to 286.

The preferred average molecular weight range for these polyesters is about 5,000 to 200,000. Further, in order to improve the adhesiveness with other polyesters, these polyesters may be partially blended with another polyester, or the monomers constituting the other polyester may be copolymerized, or these polyesters may be copolymerized. A monomer having an unsaturated bond can be copolymerized therein to radically crosslink. A polymer blend obtained by mixing two or more kinds of the obtained polymers is disclosed in JP-A-49
-5482, 64-4325 and JP-A-3-19271.
8. Research Disclosure 283,739-4
1, the same 284, 779-82, the same 294, 807-14
It can be easily formed according to the method described in 1.

The polyester of the present invention has a Tg of 50 ° C.
As described above, the conditions of use are not generally handled with sufficient care, and the temperature is often exposed to 40 ° C. especially in the midsummer outdoors. From this viewpoint, the Tg of the present invention is safe. The temperature is preferably 55 ° C or higher. More preferably, Tg is 60 ° C. or higher, and particularly preferably 70 ° C. or higher. Further, it is preferable that Tg is 90 ° C. or higher in order to complete the treatment. This is because the effect of improving the curling habit by this heat treatment disappears when exposed to a temperature exceeding the glass transition temperature, so that the temperature is a severe condition when used by general users, that is, the temperature in summer exceeds 40 ° C. Polyesters having a glass transition temperature above the temperature are preferred.

Next, examples of preferable specific compounds of the polyester used in the present invention are shown, but the present invention is not limited thereto. Polyester compound example P-0: [Terephthalic acid (TPA) / ethylene glycol (EG) (100/100)] (PET) Tg = 80 ° C. P-1: [2,6-naphthalenedicarboxylic acid (NDCA) / ethylene glycol (EG) (100/100)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)] Tg = 93 ° C. P-3: [TPA / Bisphenol A (BPA) (100/100)] Tg = 192 ° C

P-4: 2,6-NDCA / TPA / EG (50/50/100) Tg = 92 ° C. P-5: 2,6-NDCA / TPA / EG (75/25/100) Tg = 102 ° C P-6: 2,6-NDCA / TPA / EG / BPA (50/50/75/25) Tg = 112 ° C P-7: TPA / EG / BPA (100/50/50) Tg = 105 ° C P -8: TPA / EG / BPA (100/25/75) Tg = 135 ° C. P-9: TPA / EG / CHDM / BPA (100/25/25/50) Tg = 115 ° C.

P-10: IPA / PPDC / TPA / EG (20/50/30/100) Tg = 95 ° C. P-11: NDCA / NPG / EG (100/70/30) Tg = 105 ° C. P-12 : TPA / EG / BP (100/20/80) Tg = 115 ° C. P-13: PHBA / EG / TPA (200/100/100) Tg = 125 ° C. P-14: PEN / PET (60/40) Tg = 95 ° C. P-15: PEN / PET (80/20) Tg = 104 ° C. P-16: PAr / PEN (50/50) Tg = 142 ° C. P-17: PAr / PCT (50/50) Tg = 118 ° C P-18: PAr / PET (60/40) Tg = 101 ° C P-19: PEN / PET / PAr (50/25/25) Tg = 108 ° C P-20: TPA / 5-sulfoi Phthalic acid (SIP) / EG (95/5/100) Tg = 65 ℃ P-21: PEN / SIP / EG (99/1/100) Tg = 115 ℃

These supports of the present invention have a thickness of 50 μm or more and 300 μm or less. If it is less than 50 μm, it cannot withstand the shrinkage stress of the photosensitive layer generated during drying, while if it exceeds 300 μm, it is inconsistent with the purpose of reducing the thickness for compactness. More preferably from the strength of the waist, the thicker one is preferably 50 to 200 μm,
Furthermore, 80 to 115 μm is preferable, and 8 is particularly preferable.
It is 5 to 105 μm. All of the polyesters of the present invention as described above have a flexural modulus higher than that of TAC, and it was possible to realize the original thinning of the film. However, PE has strong bending elasticity among these.
T and PEN, with which TAC is 122 μm
The required film thickness can be reduced to 105 μm or less. Next, the polyester support of the present invention is characterized by being heat-treated, and in that case, it is necessary to perform the treatment at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours. This effect progresses faster as the heat treatment temperature increases. However, if the heat treatment temperature exceeds the glass transition temperature, the film tends to be curled. Therefore, this heat treatment needs to be performed at a temperature not higher than the glass transition temperature.

The heat treatment temperature is 40 ° C. or higher and lower than Tg, more preferably Tg −20 ° C. or higher and lower than Tg. Four
If the temperature is lower than 0 ° C., it takes a long time to obtain a sufficient curling effect, resulting in poor industrial productivity. The heat treatment may be performed at a constant temperature within this temperature range, or the heat treatment may be performed while cooling. The average cooling rate of cooling is −0.01 to −20 ° C./hour, more preferably −0.1 to −5 ° C./hour. This heat treatment time is 0.1 hours or more and 1500 hours or less, and more preferably 0.5 hours or more and 200 hours or less.
If the time is less than 0.1 hours, a sufficient effect cannot be obtained, and 1
When the time is 500 hours or more, the effect is saturated, but the support is likely to be colored or brittle.

In order to further increase the effect of eliminating the curling habit, after the heat treatment is performed at a temperature of Tg or higher and lower than the melting point (melting temperature determined by DSC) before this heat treatment, the heat history of the support is erased. The reheat treatment may be performed at a temperature of 40 ° C. or higher and lower than Tg. In the present invention, this heat treatment is referred to as "preheat treatment".
The heat treatment at 40 ° C. or higher and lower than Tg described in the preceding paragraph is called a “post heat treatment” to distinguish them. The pre-heat treatment temperature is Tg or higher and lower than the melting point, and more preferably Tg + 20 ° C. or higher and crystallization temperature (crystallization temperature determined by DSC) or lower.
When the pre-heat treatment is performed at a temperature equal to or higher than the melting point, the elasticity of the support is remarkably reduced, which causes problems in surface condition and transportability.
The pre-heat treatment may be carried out within this temperature range at a constant temperature (constant temperature pre-heat treatment), may be carried out while lowering the temperature (pre-heat treatment before cooling), or may be carried out while raising the temperature (rise of temperature). Pre-heat treatment). Pre-heat treatment time is 0.1 minutes or more 1500
The time is less than or equal to the hour, more preferably 1 minute or more and less than 1 hour. If it is less than 0.1 minutes, a sufficient effect cannot be obtained,
When it is 1500 hours or more, the effect is saturated, while the support is likely to be colored or brittle. After this pre-heat treatment, a post-heat treatment is carried out, but it may be rapidly cooled from the pre-heat treatment end temperature to the post-heat treatment start temperature, or may be gradually cooled to the post-heat treatment start temperature across Tg. Alternatively, the temperature may be once cooled to room temperature and then raised to the post-heat treatment temperature. Although there are several combinations of these pre-heat treatment and post-heat treatment methods, after the constant temperature pre-heat treatment at Tg + 20 ° C. or higher and the crystallization temperature or lower, a cooling rate of −0.1 to Tg−20 ° C. A post-heat treatment is preferably performed while cooling at -5 ° C / hour.

The heat treatment of such a support may be carried out in a roll form, or may be carried out while being conveyed in a web form. When the heat treatment is carried out in the form of a roll, it may be carried out by any of a method in which the roll is heat-treated from room temperature in a constant temperature bath, and a method in which the roll is wound into a roll after being heated to a predetermined temperature during web conveyance. Although the method of (1) requires a long time for raising and lowering the temperature, it has an advantage of requiring less equipment investment. The method of (1) requires winding equipment at high temperature, but has an advantage that the heating time can be omitted. In the heat treatment in a roll, due to the heat shrinkage stress generated during the heat treatment, surface defects such as wrinkles due to winding tightness and cut-out of the core portion are likely to occur. For this reason, unevenness is given to the surface (for example, conductive inorganic fine particles such as SnO ₂ and Sb ₂ O ₅ are applied) to reduce creaking between the supports to prevent wrinkles due to winding tightening, and It is desirable to make a contrivance to prevent the cut edge of the winding core from appearing by giving a knurl to the end and slightly raising only the end. On the other hand, when the heat treatment is performed in the form of a web, a long post-heat treatment step is required, but a better surface condition of the support can be obtained as compared with the heat treatment in the form of a roll. Among these heat treatment methods, it is preferable that the pre-heat treatment is performed in a web shape and the post-heat treatment is performed in a roll shape. This is because when the pre-heat treatment is performed in the form of a web, planar defects are less likely to occur than in the case where the pre-heat treatment is performed in the form of a roll, and the post-heat treatment requires a relatively long time.

These heat treatments are carried out after film formation on the support, after glow discharge treatment, and after coating the back layer (antistatic agent, slip agent, etc.),
It may be carried out at any stage after the application of the undercoat. Preferred is after the antistatic agent is applied. As a result, it is possible to prevent the attachment of dust due to electrification, which causes a surface failure of the support during heat treatment. Furthermore, in the method for heat-treating the polyester of the present invention, in order to shorten the time, it is preferable to preliminarily heat to Tg or more for a short time (preferably, perform Tg treatment at 20 ° C. or higher and 100 ° C. or lower for 5 minutes to 3 hours). . Further, the roll core used in the heat treatment is preferably one having a built-in electric heater or a structure capable of flowing a high-temperature liquid so that it can be hollow or heated for efficient temperature propagation to the film. The material of the roll winding core is not particularly limited, but it is preferable that the material does not undergo strength reduction or deformation due to heat, and examples thereof include stainless steel and glass fiber-containing resin.

Next, in order to further enhance the function of the polyester of the present invention as a photographic support, it is preferable to coexist various additives. An ultraviolet absorber may be kneaded into these polyester films for the purpose of preventing fluorescence and imparting stability with time. It is desirable that the ultraviolet absorber has no absorption in the visible region, and the addition amount thereof is usually 0.01% by weight to 20% by weight, preferably 0.05% by weight based on the weight of the polyester film.
It is about 10% by weight to 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. 2,4-dihydroxybenzophenone as an ultraviolet absorber,
2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,
2 ', 4,4'-tetrahydroxybenzophenone,
Benzophenone-based compounds such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2
(2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2'-hydroxy-3'
Examples thereof include benzotriazole-based UV absorbers such as -di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

The refractive index of the preferred aromatic polyester of the present invention is as high as 1.6 to 1.7, whereas the refractive index of gelatin which is the main component of the photosensitive layer coated thereon is 1. The value is 50 to 1.55, which is smaller than this value. Therefore, when light enters from the film edge, it is easily reflected at the interface between the base and the emulsion layer. Therefore, the polyester film causes a so-called light piping phenomenon (fogging). As a method of avoiding such a light piping phenomenon, a method of incorporating inert inorganic particles and the like into a support, a method of adding a dye, and the like are known. A preferred method for preventing light piping in the present invention is a method by adding a dye that does not significantly increase film haze. At this time, the dye used for film dyeing is not particularly limited, but the color tone is preferably gray dyeing due to the general property of the light-sensitive material, and the dye is excellent in heat resistance in the film forming temperature range of the polyester film. Further, those having excellent compatibility with polyester are preferable. From the above viewpoints, as the dye, it is possible to achieve the object by mixing commercially available dyes for polyester such as Diaresin manufactured by Mitsubishi Kasei and Kayaset manufactured by Nippon Kayaku. Regarding the dyeing density, the color density in the visible light region was measured with a color densitometer manufactured by Macbeth Co., and at least 0.
It must be 01 or more. More preferably 0.
It is 03 or more.

The polyester film according to the present invention can be imparted with slipperiness according to the intended use, and the slipperiness imparting means is not particularly limited.
A general method is kneading an inactive inorganic compound or coating a surfactant. Such inert inorganic particles include SiO ₂ , TiO ₂ , BaSO ₄ , CaC.
Examples are O ₃ , talc, kaolin and the like. Further, in addition to the slipperiness imparted by an external particle system in which inert particles are added to the polyester synthesis reaction system described above, a slipperiness imparting method by an internal particle system in which a catalyst or the like added during the polyester polymerization reaction is precipitated can also be adopted. Is. These slipperiness imparting means are not particularly limited, but transparency is an important requirement for the support for photographic light-sensitive materials. It is desirable to select SiO ₂ having a refractive index relatively close to that, or an internal particle system capable of relatively reducing the precipitated particle size. Further, in the case of imparting slipperiness by kneading, a method of laminating a layer imparted with a function in order to obtain more transparency of the film is also preferable. Specific examples of this means include a co-extrusion method using a plurality of extruders and feed blocks, or a multi-manifold die.

When any of these polyester films is used as a support, since each of these polyester supports has a hydrophobic surface, a photographic layer (for example, a photosensitive halogen) containing a protective colloid mainly containing gelatin is provided on the support. It is very difficult to firmly bond the silver halide emulsion layer, the intermediate layer, the filter layer, etc.). The conventional techniques used to overcome such difficulties include (1) chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment,
After surface activation treatment such as laser treatment, mixed acid treatment, ozone oxidation treatment, etc., a method of directly applying a photographic emulsion to obtain adhesive strength, and (2) after performing these surface treatments once,
Alternatively, there are two methods: a method of providing an undercoat layer without surface treatment and coating a photographic emulsion layer on the undercoat layer. (For example, U.S. Pat. Nos. 2,698,241, 2,764,520, 2,864,755, 3,462,335, 3,475,193, 3,143,421. No. 3,501,301, No. 3,460,944, No. 3,674,531, British Patent No. 788,365,
No. 804,005, No. 891,469, Japanese Patent Publication No. 48
-43122, 51-446, etc.).

In all of these surface treatments, some co-polar groups are formed on the surface of the support, which was originally hydrophobic,
This is probably due to an increase in the cross-linking density of the surface.As a result, it is thought that the affinity of the components contained in the undercoating liquid with polar groups increases, or that the fastness of the adhesive surface increases. To be Furthermore, an adhesion mechanism due to generation of radicals is also considered. In addition, various ideas have been made for the constitution of the undercoat layer, and a layer that adheres well to the support (hereinafter referred to as the undercoat first layer) is provided as the first layer.
A resin containing both a hydrophobic group and a hydrophilic group, which is a so-called multi-layer method in which a hydrophilic resin layer that adheres well to the photographic layer as a second layer (hereinafter referred to as the second undercoat layer) is applied thereon. There is a single layer method in which only one layer is applied.

Among the surface treatments, ultraviolet irradiation treatment, flame treatment, corona treatment and glow treatment are preferable. First, the ultraviolet irradiation treatment will be described below. These are Japanese Examined Patent Publication Nos. 43-2603, 43-2604, and 4
It is preferably carried out by the treatment method described in No. 5-3828. The mercury lamp is a high-pressure mercury lamp composed of a quartz tube, and it is preferable that the wavelength of ultraviolet rays is between 180 and 320 nm. The UV irradiation may be performed in the stretching step of the support, at the time of heat setting, or after the heat setting. Regarding the method of ultraviolet irradiation, a high-pressure mercury lamp having a main wavelength of 365 nm can be used as the light source if there is no problem in the performance of the support that the surface temperature of the support rises to around 150 ° C. When low temperature treatment is required, a low pressure mercury lamp having a dominant wavelength of 254 nm is preferable. It is also possible to use an ozone-less type high pressure mercury lamp and a low pressure mercury lamp. Regarding the amount of treated light, as the amount of treated light increases, the adhesive force between the support and the layer to be adhered improves, but as the amount of light increases, the support becomes colored,
In addition, the problem that the support becomes brittle occurs. Therefore,
For ordinary plastic films such as polyester and polyolefin, a high-pressure mercury lamp having a main wavelength of 365 nm is used, and the irradiation light amount is preferably ^{20 to} 10000 (mJ / cm ² ), more preferably 50 to 2000 (mJ / cm ² ). is there. 254nm
In the case of a low-pressure mercury lamp whose main wavelength is
00 to 10,000 (mJ / cm ² ) is preferable, and more preferably 3
It is from 00 to 1500 (mJ / cm ² ). Next, the corona discharge treatment will be described in any conventionally known method, for example, JP-B-48-5043, JP-A-47-51905, and JP-A-4-.
7-28067, 49-83767, 51-4
It can be achieved by the method disclosed in No. 1770, No. 51-131576 or the like. Discharge frequency is 50Hz
~ 5000 KHz, preferably 5 KHz ~ several 100 KH
z is suitable and particularly preferably 10 Hz to 30 KHz. If the discharge frequency is too low, stable discharge cannot be obtained and pinholes are generated in the object to be treated, which is not preferable. On the other hand, if the frequency is too high, a special device for impedance matching is required, which increases the cost of the device, which is not preferable. Regarding the treatment strength of the object to be treated, it is usually 0.001 KV · A · min / m ^{2 to 5} KV · A · min / m ² , preferably 0.01 KV · A · min / m ^{2 to 1} KV · A · min /
m ² is suitable. The gap clearance between the electrode and the dielectric roll is 0.5 to 2.5 mm, preferably 1.0 to 2.0.
mm is appropriate. As the corona discharge treatment machine, a solid state corona treatment machine 6KVA model manufactured by Pillar can be used. Further, as the flame treatment, natural gas, liquefied propane gas, etc. can be used, and the mixing ratio with air is important. A preferable gas / air mixing ratio is a volume ratio of 1/14 to 1/22 for propane, more preferably 1/16 to 1
/ 19. For natural gas, it is 1/6 to 1/10, and more preferably 1/7 to 1/9. Flame treatment amount is 1 to 5
It is 0 Kcal / m ² , more preferably 3 to 20 Kcal / m ² .
Further, it is more effective that the distance between the tip of the internal flame of the burner and the support is less than 4 cm. As the processing device, a frame processing machine manufactured by Kasuga Electric Co., Ltd. can be used. The backup roller that supports the support at the time of processing is preferably a hollow roll, and it is preferable that a cooling liquid is passed through the backup roller to maintain a constant temperature.

The glow discharge treatment, which is an effective surface treatment, can be performed by any conventionally known method, for example, Japanese Patent Publication No.
5-7578, 36-10336, 45-22
No. 004, No. 45-22005, No. 45-24040.
No. 46-43480, U.S. Pat. No. 3,057,79.
No. 2, No. 3,057,795, No. 3,179,482
Issue 3, Issue 3,288,638, Issue 3,309,299
Issue No. 3,424,735 Issue No. 3,462,335
Issue 3, Issue 3,475,307, Issue 3,761,299
No., British Patent No. 997,093, JP-A-53-1292.
No. 62 or the like can be used. In particular, it was found that the glow treatment is particularly effective as a surface treatment that simultaneously satisfies the required adhesion, yellowing suppression and blocking prevention for a polyester support having a Tg of 90 ° C. or higher and 200 ° C. or lower, which is preferable in the present invention. . There is a method of introducing various gases such as oxygen, nitrogen, helium or argon into the atmosphere of glow discharge treatment, but in the case of the polyester support of the present invention, even if a special gas is introduced, the effect of significantly adhering is achieved. Is not found, the price of gas is expensive, and it is not industrially suitable. On the other hand, when water vapor is introduced, it has an adhesion effect equal to or higher than that of the case of introducing a special gas, and the price is significantly low, which is an industrially excellent method.

The steam partial pressure of the present invention for carrying out glow discharge treatment in the presence of steam is preferably 10% or more and 100% or less, more preferably 40% or more and 90% or less.
If it is less than 10%, it becomes difficult to obtain sufficient adhesiveness.
The gas other than water vapor is air composed of oxygen, nitrogen and the like.
The method of quantitatively introducing water vapor into the glow discharge treatment atmosphere is as follows. Can be achieved by quantifying. Further, when the film to be surface-treated is subjected to vacuum glow discharge treatment in a preheated state, the adhesiveness is improved in a shorter time than that at room temperature,
It has been found that yellowing can be significantly reduced. The preheating described here is different from the heat treatment for improving the rolling behavior described later. The preheating temperature is preferably 50 ° C. or higher and Tg or lower, more preferably 70 ° C. or higher and Tg or lower, and further preferably 90 ° C. or higher and Tg or lower. If it is preheated at a temperature of Tg or higher, the adhesion will be slightly deteriorated. Specific methods for raising the polymer surface temperature in vacuum include heating with an infrared heater and heating with contact with a hot roll.
For example, if you want to preheat the film surface to 115 ℃, 115
It is sufficient to contact the film with a hot roll at 0 ° C. for at most 1 second. The heating method is not limited to the above-mentioned method, and widely known heating methods can be used.

The thus preheated support is subjected to glow discharge treatment. Important processing conditions other than the steam partial pressure, the preheating temperature of the support, etc. are vacuum degree, inter-electrode voltage, discharge frequency, etc. Can be mentioned. By controlling these treatment conditions, it becomes possible to carry out glow discharge treatment that achieves both adhesion and suppression of yellowing. The pressure during glow discharge treatment is preferably 0.005 to 20 Torr.
It is more preferably 0.02 to 2 Torr. If the pressure is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained. On the other hand, if the pressure is too high, stable discharge will not occur. The voltage is 500 to 500.
It is preferably between 0V. More preferably 500 to 3000
V. If the voltage is too low, the surface of the support cannot be sufficiently modified and sufficient adhesiveness cannot be obtained.
On the other hand, if the voltage is too high, the surface will be deteriorated, and conversely the adhesiveness will decrease. The discharge frequency used is, as seen in the prior art, from direct current to several 1000 MHz, preferably 50 Hz to 20 MHz, and more preferably 1 KHz.
~ 1 MHz. Discharge treatment intensity is 0.01 KV · A
· Min / m ² ～5KV · A · min / m ^2, more preferably a desired adhesive performance at 0.15KV-A · min / m ² ～1KV · A · min / m ^2.

It is preferable that the temperature of the support thus subjected to the glow discharge treatment is immediately lowered by using a cooling roll. The support is likely to be plastically deformed by an external force as the temperature rises, and the flatness of the support is impaired. Further, low-molecular weight substances (monomers, oligomers, etc.) may be deposited on the surface of the support, which may deteriorate transparency and blocking resistance. Next, regarding the undercoating method (2), all of these methods have been well researched. For example, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid are used for the first undercoating layer in the multilayer method. , A lot of polymers such as polyethyleneimine, epoxy resin, grafted gelatin and nitrocellulose, including copolymers starting from monomers selected from maleic anhydride, etc. Its properties have been investigated mainly for gelatin. In the single layer method, good adhesion is often achieved by swelling many supports and interfacially mixing with the hydrophilic undercoat polymer. Examples of the hydrophilic undercoating polymer used in the present invention include water-soluble polymers, cellulose esters, latex polymers and water-soluble polyesters. Water-soluble polymers include gelatin, gelatin derivatives, casein, agar, sodium alginate, starch, polyvinyl alcohol, polyacrylic acid copolymers, maleic anhydride copolymers, etc., and carboxymethyl cellulose, hydroxyethyl cellulose as cellulose ester. And so on. Examples of the latex polymer include vinyl chloride-containing copolymers, vinylidene chloride-containing copolymers, acrylic acid ester-containing copolymers, vinyl acetate-containing copolymers and butadiene-containing copolymers. Of these, gelatin is the most preferable.

As the compound for swelling the support used in the present invention, resorcin, chlorresorcin, methylresorcin, o-cresol, m-cresol, p-cresol, phenol, o-chlorophenol, p-chlorophenol, di-dichloromethane. Examples include chlorophenol, trichlorophenol, monochloroacetic acid, dichloroacetic acid, trifluoroacetic acid, and chloral hydrate. Of these, resorcin and p-chlorophenol are preferred. Various gelatin hardeners can be used in the subbing layer of the present invention. As gelatin hardening agents, chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glutaraldehyde, etc.), isocyanates, active halogen compounds (2,4-dichloro-6-hydroxy-S-triazine, etc.), epichlorohydrin resin And so on.

The subbing layer of the present invention includes SiO ₂ , Ti.
O ₂ and inorganic fine particles such as a matting agent or polymethylmethacrylate copolymer fine particles (1 to 10 μm) can be contained as a matting agent. In addition to this, the undercoat liquid may contain various additives as required. For example, surfactants, antistatic agents, antihalation agents, coloring dyes, pigments, coating aids, antifoggants and the like. In the present invention, when the undercoat liquid for the first undercoat layer is used, it is not necessary to include an etching agent such as resorcin, chloral hydrate, chlorophenol, etc. in the undercoat liquid. However, if desired, an etching agent as described above may be contained in the base coat. The undercoat liquid according to the present invention is a generally well-known coating method, for example, a dip coating method, an air knife coating method, a curtain coating method, a roller coating method, a wire bar coating method,
Gravure coating method or US Pat. No. 2,681,29
It can be applied by the extrusion coating method using the hopper described in No. 4 specification. If desired, US Pat. Nos. 2,761,791 and 3,508,
947, 2,941,898, and 3,52
No. 6,528, Yuji Harazaki, “Coating Engineering”, page 253 (1973, published by Asakura Shoten), etc., can be used to simultaneously coat two or more layers. In the present invention, the support is preferably polyethylene-2,6-naphthalenedicarboxylate at 100 ° C to
Heat treated for 24 hours between 115 ° C and the thickness of the support
85 μm to 105 μm, the surface of which is subjected to ultraviolet irradiation treatment or glow discharge treatment, and the non-photosensitive hydrophilic layer on the back side is a gelatin layer of 1 to 7 μm and the non-photosensitive hydrophilic layer. Is a cellulose binder of 0.5 to 5 μm. At this time, the weight ratio of the gelatin amount of the non-photosensitive hydrophilic layer of the back layer to the gelatin layer of the emulsion layer on the opposite side is preferably 0.1 to 0.5.

Next, the processing method of the present invention will be described in detail. The fixing solution and the bleach-fixing solution of the present invention are electrolytic silver recovered. That is, a processing method in which the photosensitive material is continuously processed while the silver is continuously collected in-line, or a part or all of the fixing solution or the bleach-fixing solution is a tank solution after the overflow solution is silver-collected in a batch manner. The present invention corresponds to a so-called regeneration type processing method that is reused as a replenisher or a replenisher. That is,
In the present invention, when the light-sensitive material having the above-mentioned transparent magnetic recording layer is treated with a fixing solution or a bleach-fixing solution which has been subjected to electrolytic silver recovery treatment, an oxide (fine silver sulfide or sulfur component) of the processing solution is treated. ) Adheres to the magnetic recording layer, deteriorates the S / N ratio, and hinders reading and writing of information. The electrolytic silver recovery method of the present invention may be any method as long as a current is applied between the cathode and the anode and brought into contact with the treatment liquid to deposit metallic silver on the cathode, for example, JP-A-48-181.
No. 91, No. 50-98837, No. 51-6817,
The methods described in JP-A Nos. 54-11020 and 60-177193 can be used. Titanium, carbon, stainless steel, and nickel can be preferably used as the material of the anode and the cathode. In the present invention, the method of rotating the cathode is preferable because of the improvement of the S / N ratio,
The preferred rotation speed is 10 to 1000 rpm, most preferably 20 to 500 rpm. The current density of the electrode is 5 to 50 mA / cm ² , and preferably 10 to 40 m.
A / cm ² . If the current density is lower than this, the silver recovery efficiency will be insufficient, resulting in poor desilvering.
The ratio is not good either. Further, if it is high, the S / N ratio of magnetic recording is deteriorated, which is not desirable. The method of the present invention can remarkably obtain the effects of the present invention particularly when it is introduced into a bleach-fixing solution.

Next, the desilvering process in the present invention will be described in detail. In the desilvering step, bleaching and fixing may be performed in separate steps, may be simultaneously performed in the form of a bleaching step, and a plurality of these steps may be combined. Specific steps are shown below, but the invention is not limited thereto.

(Step 1) Bleach-fixing (step 2) Bleach-fixing (step 3) Bleach-bleach-fixing (step 4) Bleach-bleach-fixing-fixing (step 5) Fixing-bleach-fixing These bleaching and bleach-fixing The individual steps of the fixing step may be divided into a plurality of baths if necessary, and a cascade method may be adopted. In the present invention, the processing solution having a bleaching ability is a bleach-fixing solution, and the desilvering step is the step 2 described above.
In this case, it is preferable that the effect is remarkable and the process can be simplified. Further, the electrolytic silver recovery method of the present invention is introduced into a fixing solution or a bleach-fixing solution, and when there are a plurality of baths, the silver recovery may be performed in at least one bath.

As the bleaching agent used in the processing solution having bleaching ability, aminopolycarboxylic acid iron (III) complex, persulfate, bromate, hydrogen peroxide, red blood salt and the like can be used. The polycarboxylic acid (III) complex can be most preferably used. The ferric iron complex salt used in the present invention may be added and dissolved as a complexed iron complex salt in advance, and the complex forming compound and the ferric iron salt (for example, ferric sulfate, ferric chloride) may be added. Iron, ferric bromide, iron (III) nitrate, iron (III) ammonium sulfate, etc.) may coexist to form a complex salt in a liquid having a bleaching ability. The complex-forming compound may be slightly in excess of the amount required for complex formation with ferric ion, and when it is added in an excess amount, it is usually 0.01 to 1
It is preferable to make it excessive in the range of 0%.

In the present invention, the compounds forming a ferric complex salt in a liquid having a bleaching ability include ethylenediaminetetraacetic acid (EDTA), 1,3-propanediaminetetraacetic acid (1,3-PDTA), Diethylenetriaminepentaacetic acid, 1,2-cyclohexanediaminetetraacetic acid, iminodiacetic acid, methyliminodiacetic acid, N- (2-acetamido) iminodiacetic acid, nitrilotriacetic acid, N- (2-carboxyethyl) iminodiacetic acid, N- (2-Carboxymethyl) iminodipropionic acid, β-alanine diacetic acid, 1,
4-diaminobutane tetraacetic acid, glycol ether diamine tetraacetic acid, N- (2-carboxyphenyl) iminodiacetic acid, ethylenediamine-N- (2-carboxyphenyl) -N, N ', N'-triacetic acid, ethylenediamine-
N, N'-disuccinic acid, 1,3-diaminopropane-
N, N'-disuccinic acid, ethylenediamine-N, N'-
Examples thereof include dimaleonic acid and 1,3-diaminopropane-N, N′-dimalonic acid, but are not particularly limited thereto.

In the present invention, as a bleaching agent for a liquid having a bleaching ability, an inorganic oxidizing agent may be used as a bleaching agent in addition to the above-mentioned ferric iron complex salt as long as the effect of the present invention is not impaired. Examples of such an inorganic oxidizing agent include hydrogen peroxide, persulfate, and bromate, but are not particularly limited thereto. The concentration of the ferric complex salt in the bleaching treatment solution of the present invention is 0.00
A range of 5 to 1.0 mol / liter is suitable, and 0.0
The range is preferably 1 to 0.50 mol / liter, and more preferably 0.02 to 0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is preferably 0.005 to 2 mol /
It is liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in the bleaching solution, the bleach-fixing solution and / or their pre-bath. For example, U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630, Research Disclosure No. 17129 (July 1978).
Compounds having a mercapto group or a disulfide bond described in JP-B-45-8506 and JP-A-52-20832.
No. 53-32735, U.S. Pat. No. 3,706,561 and the like, and halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

In addition, the bleaching solution or bleach-fixing solution applicable to the present invention includes bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). ) Or iodide (eg, ammonium iodide) or the like. If necessary, borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate,
One or more inorganic acids with pH buffering ability such as citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, organic acids and their alkali metal or ammonium salts, or ammonium nitrate, guanidine, etc. Agents and the like can be added. Further, the bleaching solution and the bleach-fixing solution may contain various other fluorescent whitening agents, antifoaming agents, surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The bleach-fixing solution or the fixing agent used in the fixing solution is a known fixing agent, that is, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; thiocyanates such as sodium thiocyanate and ammonium thiocyanate;
Ethylenebisthioglycolic acid, 3,6-dithia-1,
It is a water-soluble silver halide solubilizer such as thioether compounds such as 8-octanediol, mesoionic compounds and thioureas, and these can be used alone or in combination of two or more. Further, a special bleach-fixing solution containing a combination of a fixing agent described in JP-A-55-155354 and a large amount of a halide such as potassium iodide can be used. In the present invention, thiosulfate,
It is particularly preferable to use ammonium thiosulfate and sodium thiosulfate. The amount of fixing agent per liter is
The amount is preferably 0.3 to 2 mol, more preferably 0.5 to 1.0 mol.

The bleach-fixing solution and the fixing solution are represented by the general formula (I) above.
It is preferable to contain the compound (1) in the sense that the S / N ratio of magnetic recording is improved. General formula (I)

[0062]

Embedded image

In the formula, R represents a substituent of the benzene ring, and n represents an integer of 0-6. When n is 2 or more, R
May be the same or different. Preferred substituents include
It represents an alkyl group having 1 to 3 carbon atoms, a substituted alkyl group, an alkoxy group, a hydroxyl group, an amino group, a nitro group, a carboxylic acid, a sulfonic acid, a halogen atom, a phosphonic acid, or the like.
As the substituent of the alkyl group, a hydroxy group, carboxylic acid, sulfonic acid and the like are preferable. M represents a hydrogen atom, an alkali metal, an alkaline earth, ammonium, or an amine.
Specific examples of preferable compounds are shown below, but the invention is not limited thereto.

[0064]

[Chemical 4]

[0065]

Embedded image

[0066]

[Chemical 6]

[0067]

[Chemical 7]

The amount of these compounds added is 0.01 to 2 mol, preferably 0.05 to 1 mol, per liter of the treatment liquid. The bleach-fixing solution and the fixing solution of the present invention further include, as a preservative, sulfite (eg, sodium sulfite, potassium sulfite, ammonium sulfite), bisulfite (eg, ammonium bisulfite, sodium bisulfite, potassium bisulfite). It is preferable to contain a sulfite ion-releasing compound such as metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite). These compounds are preferably contained in an amount of about 0.02 to 0.05 mol / liter in terms of sulfite ion, and more preferably 0.04 to 0.40 mol / liter.

As a preservative for the bleach-fixing solution and the fixing solution,
A sulfite is generally added, but ascorbic acid, a carbonyl bisulfite adduct, a carbonyl compound, or the like may be added. Further, a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like may be added to the bleach-fixing solution and the fixing solution, if necessary.

Bleaching solution, bleach-fixing solution, used in the present invention,
In the fixer, the pH range is preferably 3 to 10, and more preferably 4 to 9. Among them, in the bleaching solution and the bleach-fixing solution, the pH range of 4 to 5.8 is particularly preferable. The bleaching solution, the bleach-fixing bath and the replenishing amount to the fixing bath used in the present invention are ²⁰ to 800 ml per 1 m ² of the light-sensitive material. It is particularly preferably 25 to 500 ml, and further preferably 30 to 300 ml.
Particularly, in the fixing solution and the bleach-fixing solution for recovering electrolytic silver, the replenishing amount can be reduced, and the replenishing amount of 30 to 300 ml is most preferable from the viewpoint of exerting the effect of the present invention. The processing temperature of the bleaching solution, the bleach-fixing solution, and the fixing solution applicable to the present invention is 20 to 50 ° C.,
It is preferably 30 to 40 ° C. Processing time is 1 each
It is 0 second to 3 minutes, preferably 10 seconds to 2 minutes.

The processing solution having a bleaching ability of the present invention is particularly preferably subjected to aeration during processing because the photographic performance is kept extremely stable. Means known in the art can be used for the aeration, and blowing of air into the processing liquid having a bleaching ability or absorption of air using an ejector can be performed. At the time of blowing air, it is preferable to discharge the air into the liquid through an air diffusing tube having fine pores. Such an air diffuser is widely used as an aeration tank in activated sludge treatment. Regarding aeration, Z-121, Eusing Process C-41, No. 3, issued by Eastman Kodak Company.
The matters described in the edition (1982), pages BL-1 to BL-2 can be used. In the processing using the processing solution having the bleaching ability of the present invention, it is preferable that the stirring is strengthened, and the implementation thereof is described in JP-A-3-33847, No. 8
The contents of the page, upper right column, line 6 to lower left column, line 2
It can be used as is.

In the desilvering process, it is preferable that the stirring is strengthened as much as possible. Specific examples of the method for strengthening stirring include a method in which a jet of a processing solution is made to collide with the emulsion surface of a light-sensitive material described in JP-A-62-183460, and JP-A-62-1834.
A method of increasing the stirring effect using the rotating means of No. 61, and further moving the light-sensitive material while bringing the emulsion surface into contact with the wiper blade provided in the liquid to make the emulsion surface turbulent, thereby further improving the stirring effect. Examples thereof include a method for improving the method and a method for increasing the circulation flow rate of the entire processing solution. Such a stirring improving means is effective for any of the bleaching solution, the bleach-fixing solution and the fixing solution. It is considered that the improvement of the stirring speeds up the supply of the bleaching agent and the fixing agent into the emulsion film, and consequently the desilvering rate. Further, the above-mentioned means for improving the stirring is more effective when a bleaching accelerator is used, and can significantly increase the accelerating effect or eliminate the fixing inhibiting effect of the bleaching accelerator.

The automatic developing machine used for the light-sensitive material of the present invention is disclosed in JP-A-60-191257, JP-A-60-191258 and JP-A-60-1912.
It is preferable to have a photosensitive material conveying means described in No. 59. As described in the above-mentioned JP-A-60-191257, such a conveying means can remarkably reduce the carry-in of the treatment liquid from the front bath to the rear bath, and is highly effective in preventing the performance deterioration of the treatment liquid. Such an effect is particularly effective for reducing the processing time in each step and reducing the replenishing amount of the processing solution.

The color developing solution used in the development processing of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine type color developing agent as a main component. As the color developing agent, aminophenol compounds are also useful, but p-phenylenediamine compounds are preferably used, and typical examples thereof include 3-methyl-4-amino-N, N diethylaniline and 3-methyl. -4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl -β-methoxyethylaniline, 4-amino-3-methyl-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N-
(3-Hydroxypropyl) aniline, 4-amino-3-methyl-N-ethyl-N- (2-hydroxypropyl) aniline, 4-
Amino-3-ethyl-N-ethyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-propyl-N- (3-
Hydroxypropyl) aniline, 4-amino-3-propyl
-N-methyl-N- (3-hydroxypropyl) aniline, 4-amino-3-methyl-N-methyl-N- (4-hydroxybutyl) aniline, 4-amino-3-methyl-N-ethyl-N -(4-hydroxybutyl) aniline, 4-amino-3-methyl-N-propyl
-N- (4-hydroxybutyl) aniline, 4-amino-3-ethyl-N-ethyl-N- (3-hydroxy-2-methylpropyl) aniline, 4-amino-3-methyl-N, N-bis (4-hydroxybutyl) aniline, 4-amino-3-methyl-N, N-bis (5-
Hydroxypentyl) aniline, 4-amino-3-methyl-N
-(5-hydroxypentyl) -N- (4-hydroxybutyl) aniline, 4-amino-3-methoxy-N-ethyl-N- (4-hydroxybutyl) aniline, 4-amino-3-ethoxy-N, Examples thereof include N-bis (5-hydroxypentyl) aniline, 4-amino-3-propyl-N- (4-hydroxybutyl) aniline, and their sulfates, hydrochlorides or p-toluenesulfonates. Among these, especially 3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 4-amino-3-methyl-N-ethyl-N- (3-hydroxypropyl)
Aniline, 4-amino-3-methyl-N-ethyl-N- (4-hydroxybutyl) aniline and their hydrochlorides, p-toluenesulphonates or sulphates are preferred. Two or more of these compounds can be used in combination depending on the purpose.

The amount of the aromatic primary amine developing agent used is preferably 0.0002 mol to 0.2 mol, and more preferably 0.001 mol to 1 mol, per liter of color developing solution.
It is 0.1 mol. Color developing solutions include hydroxylamine and diethylhydroxylamine, as well as JP-A-3-144.
Hydroxylamines represented by the general formula (I) of No. 446, sulfites, hydrazines such as N, N-biscarboxymethylhydrazine, phenylsemicarbazides, triethanolamine, various preservatives such as catecholsulfonic acid, Organic solvents such as ethylene glycol and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts, development accelerators such as amines, dye-forming couplers, competitive couplers, 1-phenyl-3
-Auxiliary developing agents such as pyrazolidone, tackifiers, various chelating agents represented by aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, phosphonocarboxylic acids, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid , Diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid,
1-hydroxyethylidene-1,1-diphosphonic acid, nitrilo
-N, N, N-trimethylenephosphonic acid, ethylenediamine-N,
N, N, N- tetramethylenephosphonic acid, ethylenediamine-
Di (o-hydroxyphenylacetic acid) and salts thereof can be mentioned as representative examples.

Of the above, substituted hydroxylamine is most preferable as the preservative, and among them, diethylhydroxylamine, monomethylhydroxylamine or an alkyl group substituted with a water-soluble group such as a sulfo group, a carboxy group or a hydroxyl group is used as a substituent. Those having are preferred. The most preferable example is N, N-bis (2-sulfoethyl).
Hydroxylamine, monomethylhydroxylamine,
Examples include diethylhydroxylamine.

Any antifoggant can be added to the color developing solution used in the present invention, if necessary. As the antifoggant, alkali metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifoggants can be used. Examples of the organic antifoggants include benzotriazole, 6-nitrobenzimidazole,
5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chloro-
Representative examples thereof include nitrogen-containing heterocyclic compounds such as benzotriazole, 2-thiazolyl-benzimidazole, 2-thiazolylmethyl-benzimidazole, indazole, hydroxyazaindolizine and adenine.

The color developing solution used in the present invention preferably has a pH range of about 9.5 to 10.5. If the developing activity can be maintained, it is preferable that the pH of the developing tank liquid is low also in the sense of preventing the generation of ammonia gas from the waste liquid. The most preferable pH of the tank liquid is 9.9 to 1
It is about 0.4. In order to maintain the above pH, it is preferable to use various buffers. As the buffer, carbonate,
Phosphate, borate, tetraborate, hydroxybenzoate, glycyl salt, N, N-dimethylglycine salt, leucine salt, norleucine salt, guanine salt, 3,4-dihydroxyphenylalanine salt, alanine salt, amino Butyrate,
2-amino-2-methyl-1,3-propanediol salt, valine salt, proline salt, trishydroxyaminomethane salt, lysine salt and the like can be used. The use of carbonate or phosphate is particularly preferable. The amount of the buffer added to the developer is preferably 0.1 mol / liter or more, and particularly preferably 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. Examples of this are JP-A-63-146998 and JP-A-63-199295.
JP-A-63-267750, JP-A-63-267
751, JP-A-2-229146, and JP-A-3-18.
6841, German Patent 3739610, European Patent 468.
The chelating agent described in No. 325 and the like can be mentioned.
It is preferable that the processing solution in the color developing solution replenishing tank or the processing tank is shielded with a liquid agent such as a high-boiling point organic solvent to reduce the contact area with air. Liquid paraffin is most preferable as the liquid shield agent. It is particularly preferable to use it as a replenisher. The processing temperature of the color developing solution in the present invention is 30 to 55 ° C, preferably 35 to 55 ° C.
The processing time is 20 seconds to 5 minutes, preferably 30 seconds to 3 minutes and 20 seconds in the light-sensitive material for photography. In addition, the replenishment amount is 1
30-800 ml per square meter, preferably 50-
It is about 500 ml.

When reversal processing is carried out, black and white development is usually carried out before color development. In this black-and-white developer, known black-and-white developing agents such as dihydroxybenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol are used alone. Alternatively, they can be used in combination. Any development accelerator can be added to the developer used in the present invention, if necessary. As a development accelerator, Japanese Patent Publication No. 37-16088, No. 37-5987, No. 38-7826
No. 44-12380, No. 45-9019 and U.S. Pat.
Thioether compounds represented by JP-A No. 247, etc.
-49829 and 50-15554, p-phenylenediamine compounds, JP-A-50-137726, JP-B-44-300
74, quaternary ammonium salts represented by JP-A-56-156826 and JP-A-52-43429, U.S. Pat. No. 2,494,903,
No. 3,128,182, No. 4,230,796, No. 3,253,919, Japanese Patent Publication No. 41-11431, U.S. Patent No. 2,482,546, No. 2,596,92
6 and 3,582,346, etc., amine compounds, JP-B-37-16088, JP-B-42-25201, U.S. Pat.
No. 4, Japanese Patent Publication Nos. 41-11431 and 42-23883, and U.S. Pat.
Polyalkylene oxides represented by 532,501 and the like,
In addition, 1-phenyl-3-pyrazolidones, imidazoles, etc. can be added as necessary.

The light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process. The amount of rinsing water in the rinsing step depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), application, and further, the rinsing water temperature, the number of rinsing tanks (number of stages), replenishment method such as countercurrent, forward flow, and various other conditions It can be set in a wide range. Of these, the relationship between the number of washing tanks and the water volume in the multi-stage countercurrent system is described in the Journal of the
Society of Motion Picture and Television Engineer
s Volume 64, pages 248 to 253 (May 1955 issue). According to the multi-stage countercurrent method described in the above-mentioned document, the amount of washing water can be greatly reduced, but due to the increase in the residence time of water in the tank, bacteria propagate, and the suspended matter produced adheres to the photosensitive material, etc. Problem arises. In the processing of the color light-sensitive material of the present invention, the method of reducing calcium ion and magnesium ion described in JP-A-62-288838 can be used very effectively as a solution to such a problem. In addition, JP-A-57
-8,542 isothiazolone compounds, siabendazoles, chlorinated fungicides such as chlorinated sodium isocyanurate, and other benzotriazoles, etc. Hiroshi Horiguchi "Chemistry of Antibacterial and Antifungal Agents" (1986) Sankyo Publishing "Sterilization, sterilization and antifungal technology of microorganisms" edited by the Society for Hygiene Technology (1982) Industrial Technology Association, "Antibacterial and Antifungal Encyclopedia" edited by Japan Society for Antibacterial and Antifungal (1986)
It is also possible to use the bactericide described in.

Rinsing water in processing the light-sensitive material of the present invention
The pH is 4-9, preferably 5-8. The washing water temperature and the washing time can be variously set depending on the characteristics of the light-sensitive material, the use, etc., but in general, it is 20 seconds to 10 minutes at 15 to 45 ° C., preferably
A range of 30 seconds to 5 minutes at 25-40 ° C is selected. Further, the light-sensitive material of the present invention can be directly processed with a stabilizing solution instead of the above washing with water. In such stabilization treatment, all known methods described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345 can be used.

In the stabilizing solution, a compound for stabilizing the dye image, for example, benzaldehydes such as formalin and m-hydroxybenzaldehyde, formaldehyde bisulfite adduct, hexamethylenetetramine and its derivative, hexahydrotriazine and its derivative, Examples include N-methylol compounds such as dimethylol urea and N-methylol pyrazole, organic acids and pH buffering agents. The addition amount of these compounds is preferably 0.001 to 0.02 mol per liter of the stabilizing solution, but the lower the free formaldehyde concentration in the stabilizing solution is, the less the formaldehyde gas is scattered, which is preferable. From this point of view, examples of the dye image stabilizer include m-hydroxybenzaldehyde, hexamethylenetetramine, N-methylolpyrazole, N-methylolazoles described in JP-A-4-270344, N, N'-bis (1 , 2,4-Triazol-1-ylmethyl) piperazine etc.
Azolylmethylamines described in 13753 are preferred. Particularly, azoles such as 1,2,4-triazole described in JP-A-4-359249 (corresponding to European Patent Publication No. 519190A2) and 1,4-bis (1,2,4)
The combined use of azolylmethylamine and its derivatives such as -triazol-1-ylmethyl) piperazine is preferable because of high image stability and low formaldehyde vapor pressure. In addition, if necessary, ammonium compounds such as ammonium chloride and ammonium sulfite, metal compounds such as Bi and Al, optical brighteners, hardeners, US Pat.
It is also preferable to contain an alkanolamine described in JP-A-86,583 or a preservative that can be contained in the fixing solution or the bleach-fixing solution, for example, a sulfinic acid compound described in JP-A-1-231510. .

The washing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets during drying of the processed light-sensitive material. Among these, it is preferable to use a nonionic surfactant, and an alkylphenol ethylene oxide adduct is particularly preferable. Octyl, nonyl, dodecyl and dinonylphenol are particularly preferable as the alkylphenol, and 8 to 14 are particularly preferable as the number of moles of ethylene oxide added. Further, it is also preferable to use a silicon-based surfactant having a high defoaming effect.

Various chelating agents are preferably contained in the washing water and / or the stabilizing solution. Preferred chelating agents include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, N, N, N '.
-Trimethylenephosphonic acid, diethylenetriamine-
Organic phosphonic acids such as N, N, N ', N'-tetramethylenephosphonic acid, or European Patent 345,172A
Examples thereof include the hydrolyzate of the maleic anhydride polymer described in No. 1 and the like.

The overflow solution accompanying the above washing with water and / or supplementation of the stabilizing solution can be reused in other steps such as the desilvering step. In the processing using an automatic processor, etc., when the above processing solutions are concentrated by evaporation,
In order to correct the concentration by evaporation, it is preferable to replenish an appropriate amount of water or a correction solution or a processing replenishing solution. The specific method for replenishing water is not particularly limited, but among them, a monitor water tank different from the bleaching tank described in JP-A-1-254959 and 1-254960 is installed, and water in the monitor water tank is installed. The amount of water vaporized in the bleaching tank is calculated from the amount of water vaporized in the bleaching tank, and the bleaching tank is replenished with water in proportion to the amount of water vaporized.
Nos. 3,249,644, 3,249,645, and 3,249,646, the evaporation correction method using a liquid level sensor and an overflow sensor are preferable.
As the water for correcting the evaporation of each treatment liquid, tap water may be used, but deionized water or sterilized water which is preferably used in the above washing step is preferably used.

Next, the light-sensitive material of the present invention will be described.
The present invention can be applied to any light-sensitive material having the above-mentioned transmission support, but is preferably applied to a color negative film and a color reversal film. The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangement, etc.) applied in the present invention, and the processing method and processing additive applied for processing the light-sensitive material are , The following patent publications, especially European patents EP 0,3
Those described in No. 55,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0087]

[Table 1]

[0088]

[Table 2]

[0089]

[Table 3]

[0090]

[Table 4]

[0091]

[Table 5]

The silver halide emulsion used in the present invention is
Silver iodobromide, silver iodochloride, silver iodochlorobromide, silver chlorobromide, silver bromide,
Emulsions of various halogen compositions such as silver chloride can be used. In particular, the present invention preferably has a layer containing a silver iodobromide emulsion and has an iodine content of 0.1 to 10
It is preferable to use an emulsion containing about mol%. As the coating amount of silver is not particularly limited, 2g~10g / m ² approximately, and more preferably may contain about 3 to 8 g / m ^2. The light-sensitive material used in the present invention may contain various couplers, but the details are as shown in Table 2. Further, as a cyan coupler, Japanese Patent Application Laid-Open No. 2-3314
In addition to the diphenylimidazole type cyan couplers described in No. 4, 3-hydroxypyridine type cyan couplers described in European Patent EP0,333,185A2 (among others, the 4-equivalent coupler of the coupler (42) listed as a specific example is chlorine). Those having a leaving group and made into two equivalents, couplers (6) and (9) are particularly preferable), and cyclic active methylene cyan couplers described in JP-A-64-32260 (among others, listed as specific examples). (Coupler Examples 3, 8, 34 are especially preferred).

Further, in the light-sensitive material according to the present invention, a hydrophilic colloid layer can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76 for the purpose of improving image sharpness and the like. Such dyes (among others, oxonol dyes) can be added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more. In the color photographic light-sensitive material according to the present invention, it is preferable to use a color image storability-improving compound as described in European Patent EP 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) and / or the compound (F) which chemically bonds with the aromatic amine developing agent remaining after the color development processing to form a chemically inactive and substantially colorless compound.
Alternatively, the compound (G) which chemically bonds with an oxidized product of an aromatic amine color developing agent remaining after the color developing treatment to form a chemically inactive and substantially colorless compound is used simultaneously or alone. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing. Further, to the light-sensitive material according to the present invention, a fungicide such as that described in JP-A-63-271247 is added in order to prevent various molds and bacteria that propagate in the hydrophilic colloid layer and deteriorate the image. Preferably. In the present invention, it is preferable that the dry film thickness of the silver halide color photographic light-sensitive material excluding the support is 25 μm or less in order to reduce the carryover amount and increase the silver recovery rate. Particularly, it is preferably about 13 to 23 μm, more preferably about 9 to 19 μm. These film thicknesses can be reduced by reducing the gelatin amount, silver amount, oil amount, coupler amount, etc., but it is most preferable to reduce the gelatin amount. Here, the film thickness is 25 ° C. for the sample,
After being left at 60 RH% for 2 weeks, it can be measured by a conventional method.

In the silver halide color photographic light-sensitive material used in the present invention, the film swelling degree of the photographic layer is 1.5 to.
A value of 4.0 is preferable from the viewpoint of improving stain and improving image storability. Particularly, in the range of 1.5 to 3.0, a further effect can be obtained. The swelling degree of the present invention means a value obtained by dividing the film thickness of the photographic layer after dipping the color light-sensitive material in distilled water at 33 ° C. for 2 minutes by the film thickness of the dried photographic layer.

The photographic layer means a hydrophilic colloid group layer including at least one photosensitive silver halide emulsion layer and having a water-permeable relationship with this layer. The back layer provided on the opposite side of the support from the photographic photosensitive layer is not included. The photographic layer is usually formed of a plurality of layers involved in photographic image formation, and in addition to the silver halide emulsion layer, an intermediate layer, a filter layer, an antihalation layer, a protective layer and the like are included.

Any method may be used to adjust the degree of swelling described above. For example, the amount and type of gelatin used in the photographic film, the amount and type of hardener, or the drying conditions after coating the photographic layer. And can be adjusted by changing the aging condition. It is advantageous to use gelatin for the photographic layer, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. Use of various synthetic hydrophilic polymer substances such as single or copolymers of polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole. You can As the gelatin, acid-treated gelatin may be used in addition to lime-treated gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. Examples of the gelatin derivative include gelatin such as acid halide,
Those obtained by reacting various compounds such as acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds are used.

As the gelatin-graft polymer, a homopolymer or a copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene are grafted onto gelatin. What was made to use can be used. In particular, a graft polymer with a polymer having a certain degree of compatibility with gelatin, for example, a polymer such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, or hydroxyacyl methacrylate is preferable.
Examples of these are U.S. Pat. Nos. 2,763,625 and 2,8.
31, 767, 2,956, 884 and the like. Typical synthetic hydrophilic polymer substances are, for example, West German patent application (OLS) 2,312,708, US Pat.
No. 620,751, No. 3,879,205, Japanese Patent Publication No. 4
No. 3-7561.

Examples of hardening agents include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glital aldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane. Derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinyl Sulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid etc.), isoxazoles, dialdehyde starch, 2-black And 6-hydroxy-triazinyl gelatin can be used alone or in combination. Particularly preferred hardeners are aldehydes,
They are active vinyl compounds and active halogen compounds.

The light-sensitive material according to the present invention may be exposed to visible light or infrared light. The exposure method may be low-illuminance exposure or high-illuminance short-time exposure, and in the latter case, a laser scanning exposure method in which the exposure time per pixel is shorter than 10 ⁻⁴ seconds is preferable. Further, it is preferable to use the band stop filter described in U.S. Pat. No. 4,880,726 upon exposure. As a result, light color mixture is removed, and color reproducibility is significantly improved.

The processing method of the present invention can be applied to various photosensitive materials. In particular, a color negative film, a color reversal film, a motion picture negative film, a motion picture positive film, and the like can be mentioned, but application to a color negative film is particularly preferable.

[0102]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited thereto. Example 1 (1) Material of Support, etc. Each support used in this example was prepared by the following method. PEN: 100 parts by weight of a commercially available poly (ethylene-2,6-naphthalate) polymer corresponding to P-1 in the text and 2 parts by weight of Tinuvin P.326 (manufactured by Geigy) as an ultraviolet absorber and a conventional method. After being dried at 300 ° C, it is melted at 300 ° C, extruded from a T-die for longitudinal stretching of 140 ° C 3.3 times, and then transversely stretched at 130 ° C 3.3 times, and further at 250 ° C for 6 seconds. Heat fixed. The glass transition temperature was 120 ° C.・ TAC: Methylene chloride / methanol = 82/8 wt by a normal solution casting method of triacetyl cellulose
Ratio, TAC concentration 13%, plasticizer TPP / BDP = 2/1
(Here TPP; triphenyl phosphate, BD
15% by weight of P; biphenyl diphenyl phosphate)
The band method was used.

(2) Coating of Undercoat Layer Each of the above supports is subjected to corona discharge treatment on both sides thereof, and then the undercoat liquid having the following composition is applied to provide the undercoat layer on the high temperature surface side during stretching. It was For the corona discharge treatment, a solid state corona treatment machine 6KVA model manufactured by Pillar Co. is used, and a 30 cm width support is treated at 20 m / min. At this time, the object to be treated was treated at 0.375 KV · A · min / m ^{2 based on} the current / voltage readings. The discharge frequency during processing is 9.6KHz,
The gap clearance between the electrode and the dielectric roll is 1.6.
It was mm.

Gelatin 3 g Distilled water 250 ml Sodium-α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Further, an undercoat layer having the following composition was provided on the support TAC. Gelatin 0.2g Salicylic acid 0.1g Methanol 15ml Acetone 85ml Formaldehyde 0.01g

(3) Coating of Back Layer The following back layers 1 to 3 were coated on one side of the undercoated support prepared in (2). A) Back first layer Co-containing acicular γ-iron oxide fine powder (contained as a gelatin dispersion, average particle size 0.08 μm) 0.2 g / m ² gelatin 3 g / m ² described in the following chemical formula 8. 0.1 g / m ² Compound described in Chemical formula 9 below 0.02 g / m ² Poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

[0106]

Embedded image

[0107]

[Chemical 9]

(B) Second layer of back gelatin 0.05 g / m ² conductive material [S _n O ₂ / Sb ₂ O ₃ (9: 1), particle size 0.15 μm] 0.16 mg / m ² dodecylbenzenesulfone Acid soda 0.05g / m ²

C) Third layer of back gelatin 0.5 g / m ² polymethylmethacrylate (average particle size 1.5 μm) 0.02 g / m ² cetyl stearate (sodium dodecylbenzenesulfonate dispersion) 0.01 g / m ² Sodium di (2-ethylhexyl) sulfosuccinate 0.01 g / m ² Compound represented by the following chemical formula 10 0.01 g / m ²

[0110]

[Chemical 10]

The coercive force of the obtained back layer is 960 Oe.
Met.

(4) Heat Treatment of Support After the undercoat layer and the back layer were coated and dried and wound by the above method, heat treatment was conducted at 110 ° C. for 48 hours. The photosensitive layer shown in (5) was coated on the two types of supports prepared by the above method to prepare a photosensitive material. The PEN support was used as sample 101, and the TAC support was used as sample 102. A sample 103 was the PEN support that had not been subjected to the heat treatment (4).

(5) Preparation of Photosensitive Layer Next, on the side opposite to the back layer obtained as described above, from page 20, left column, line 20 to page 114 of JIII Journal of Technical Disclosure No. 94-6023 (1994). The photosensitive layer described on page was applied.

The light-sensitive material prepared as described above is set to 24 mm.
The width is cut into 160 cm, and two 2 mm square perforations are provided at a distance of 5.8 mm at a position 0.7 mm from one side in the length direction of the photosensitive material. The two sets were provided at intervals of 32 mm to produce US Pat.
6,887, FIG. 1-FIG. It was housed in the plastic film cartridge described in 7.
The head gap 5 was applied to this sample from the coated surface side of the magnetic recording layer.
100mm between the above perforations of the light-sensitive material, using a head capable of inputting and outputting of μm and 2000 turns.
The FM signal was recorded at a feed rate of / s. After the FM signal was recorded, the emulsion surface was subjected to uniform exposure for 1000 cms, and each processing was carried out by the methods described below. Then, the emulsion film was stored again in the original plastic film cartridge. Next, the stored film was pulled out, and the signal was read at the same speed as when the signal was recorded by the above head, and it was examined whether or not the signal was correctly output. Table 6 shows the ratio of the number of error bits to the number of input bits. If this error rate is 0.01% or less, there is no practical problem, but
1% or more is NG. The residual silver amount of the processed light-sensitive material was measured by the following method. Similarly, the degree is shown in Table 6.

Method of measuring the amount of residual silver: The amount of silver remaining in the light-sensitive material exposed to 1000 cms of gray was measured by fluorescent X-ray analysis. Next, the details of the performed processing will be described. The samples described above are
A gray exposure of 1000 cms was given at a color temperature of 4800 K, and processing was carried out by a cine type automatic developing machine with the following processing steps and processing solutions. The bleach-fix solution is as shown in Table 6,
The electrolytic silver recovery method was changed, and each of them was sequentially processed.

(Processing step) Processing step Temperature Time Replenishment amount * Color development 45 ° C 60 seconds 10 Bleach fixing 40 ° C 60 seconds 20 Stability (1) 40 ° C 15 seconds-Stability (2) 40 ° C 15 seconds-Stability (3) 40 ℃ 15 seconds 20 Dry 75 ℃ 30 seconds- (Stability was set to 3 tank counter-current method from (3) to (1).) * Per 24 shots (about 1105mm)

The composition of each processing liquid is as follows. (Color developer) (Unit: g) Tank solution Replenisher Diethylenetriaminepentaacetic acid 4.0 4.0 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 0.5 Sodium sulfite 4.0 8.0 Potassium carbonate 38.0 38.0 Potassium bromide 4.0-iodo Potassium iodide 1.3 mg-hydroxylamine sulfate 4.8 8.0 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 18.5 28.0 Water was added to 1.0 liter 1.0 liter pH (potassium hydroxide And adjusted with sulfuric acid) 10.05 10.40

(Bleaching Fixing Solution) (Unit: g) Tank Solution Replenishing Solution Ethylenediamine- (2-carboxyphenyl) -N, N ′, N′-triacetic acid 0.18 mol 0.20 mol Ferric chloride 0.16 mol 0.18 mol Ammonium thiosulfate aqueous solution (700 g / liter) 300 ml 330 ml Ammonium iodide 1.0-Ammonium sulfite 20.0 40 p-Toluenesulfinate sodium 20.0 25 Succinic acid 12.0 12.0 Water is added 1.0 liter 1.0 liter pH (adjusted with nitric acid and aqueous ammonia) 6.0 5.5

(Stabilizing Solution) The tank solution and the replenishing solution have the same formulation (unit: g) sodium p-toluenesulfinate 0.03 polyoxyethylene-p-monononylphenyl ether (average degree of polymerization: 10) 0.2 chlorinated sodium isocyanurate O .02 Deionized water (conductivity 5μs / cm or less) 1000ml pH 6.5 Bleach-fixer
A so-called in-line silver recovery system was adopted, which directly recovers silver from the tank liquid and processes it. The sixth condition for electrolytic silver recovery
As shown in the table, until the current density and the number of rotations of the cathode are changed and the tank liquid amount is replenished three times under each condition,
After continuous processing, the error rate of magnetic recording and the amount of residual silver of the photosensitive material after processing were determined. In each running process, the change in density of yellow stain (increase in stain) at the start and at the end was measured. The silver recovery device used was a modified Mazda Sangyo (BF12). The above results are shown in Table 6.

[0120]

[Table 6]

As is clear from the results shown in Table 6, by applying the electrolytic silver recovery method of the present invention, sufficient bleaching performance can be obtained in rapid processing and the increase in stain is small. In addition, it can be seen that the signal recorded on the magnetic recording layer can be processed without being damaged. It was also found that when PEN (Sample 101) having a heat-treated support was selected, the read error of magnetic recording information was further reduced.

Example 2 Sample 101 described in Example 1 of the present application was subjected to continuous tone wedge exposure at a color temperature of 4800K, and a running process (processing liquid accumulation) was carried out by a cine type automatic developing machine with the following processing steps and processing solutions. Until the replenishment amount is three times the tank capacity). In addition, as shown in Table 7, the fixing solution was changed in additives, and each of them was sequentially exchanged and a running process was performed. In the same manner as in Example 1, the fixing solution (1) was subjected to in-line electrolytic silver recovery. It was After the running process was completed, in the same manner as in Example 1, samples 101 to 103 were subjected to FM signals and exposure, and as shown in Table 7, processing was performed in combination with individual fixing solution compositions, and the magnetic recording information read accuracy and The amount of residual silver was evaluated. The treatment process and the treatment liquid composition are shown below.

(Processing step) Processing time Processing temperature Replenishment amount * Tank capacity Color development 1 minute 00 seconds 45.0 ° C 260 ml 5 liters Bleach 30 seconds 40.0 ° C 130 ml 3 liters Fixed (1) 30 seconds 40.0 ° C-3 Liter settling (2) 30 seconds 40.0 ℃ 100 ml 3 liter water wash 20 s 40.0 ℃ 800 ml 1.5 liter stability (1) 20 s 40.0 ℃ −2 liter stability (2) 20 s 40.0 ℃ 130 ml 2 liter dry Drying 30 seconds 65 ° C * Replenishment amount per 1 m ² of the light-sensitive material is the countercurrent system of the fixing solution and stabilizing solution from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath. The amount of developing solution brought into the bleaching process, the amount of bleaching solution brought into the fixing process, the amount of fixing solution brought into the washing process and the amount of washing solution brought into the stabilizing process are 1 m ² of the light-sensitive material.
40 ml, 35 ml,
It was 35 ml and 35 ml. Also,
The crossover time was 4 seconds in each case, and this time is included in the processing time of the previous step.

The composition of the processing liquid is shown below. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 4.0 4.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 3.0 Sodium sulfite 4.0 6.7 Potassium carbonate 40.0 40.0 Potassium bromide 2.0-Potassium iodide 1.3 mg-hydroxylamine sulfate 4.8 6.8 disodium-N, N-bis (sulfonate ethyl) hydroxylamine 6.0 2.9 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino] aniline sulfate 11.0 14.3 Add water 1.0 liter 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.55

(Bleaching solution) Tank solution (g) Replenishing solution (g) 1,3-Propanediaminetetraacetic acid 0.33 mol 0.44 mol Iron (III) ammonium ammonium bromide 70.0 91.0 Ammonium nitrate 14.0 18.2 Succinic acid 60.0 78.0 Glutaric acid 20.0 26.0 Adipic acid 10.0 13.0 Maleic acid 20.0 26.0 Add water 1.0 liter 1.0 liter pH (adjusted with ammonia water) 4.4 4.0

(Fixer) Tank solution (g) Replenisher (g) Ammonium sulfite 19 57 Ammonium thiosulfate aqueous solution (700 g / liter) 280 ml 840 ml Additive (general formula (I), see Table 7) 0.15 mol 0.20 Mol imidazole 15 45 Ethylenediaminetetraacetic acid 15 45 Add water 1.0 liter 1.0 liter pH (prepared with aqueous ammonia and acetic acid) 7.4 7.4

(Washing water) Tap water was used as an H-type strongly acidic cation exchange resin (Amberlite IR-produced by Rohm and Haas).
120B) and OH-type strongly basic anion exchange resin (Amberlite IR-400) were passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 mg.
/ Liter or less, followed by sodium diisocyanurate dichloride 20 mg / liter and sodium sulfate 150
mg / l was added. The pH of this liquid is 6.5 to 7.
It was in the range of 5.

(Stabilizer) Common to tank liquid and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization: 10) 0.2 Ethylenediaminetetraacetic acid disodium salt 0.05 1, 2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 Water was added and 1.0 liter pH 8.5 The results are shown in Table 7.

[0129]

[Table 7]

The results of Table 7 are similar to those of Table 6 of Example 1, and good results can be obtained in the present invention even if the processing steps are changed.

[0131]

According to the constitution of the present invention, a rapid desilvering process can be achieved by using a light-sensitive material having a magnetic recording layer on the back surface opposite to the emulsion layer, and the magnetic recording can be read. I was able to prevent the error.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] November 7, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0116

[Correction method] Change

[Correction content]

(Processing step) Processing step Temperature Time Replenishment amount * Color development 45 ° C 60 seconds 10 Bleach fixing 40 ° C 60 seconds 20 Stability (1) 40 ° C 15 seconds-Stability (2) 40 ° C 15 seconds-Stability (3) 40 ℃ 15 seconds 20 Dry 75 ℃ 30 seconds- (Stability was set to 3 tank counter-current method from (3) to (1).) * 24mm width x 1600mm per

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display location G03C 5/00 A 7/00 510 7/44

Claims (3)

[Claims] 1. A silver halide color photographic light-sensitive material having at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer on a transparent support, and a magnetic layer containing ferromagnetic fine powder. In the processing step of processing with a processing solution having a fixing ability after color development, the processing solution having a fixing ability is processed while collecting electrolytic silver and the current density during electrolysis is 5 to 50 m.
A / cm ² is a method for processing a silver halide color photographic light-sensitive material. 2. The processing of a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution having the fixing ability contains at least one sulfinic acid represented by the following general formula (I). Method. General formula (I) (In the formula, R represents a substituent of a benzene ring, and n is 0 to 6
Represents the integer. When n is 2 or more, R may be the same or different. M represents a hydrogen atom, alkali metal, alkaline earth, ammonium or amine. 3. The method for processing a silver halide color photographic light-sensitive material according to claim 1, wherein the processing solution is a bleach-fixing solution.