JPH08184951A - Processing method and processing device for silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To enable processing of a photosensitive material having a transparent magnetic recording layer in an automatic developing machine without deteriorating S/N of the information magnetically recorded, by specifying the nip pressure of rollers when the material is processed in an automatic developing machine. CONSTITUTION: When a silver halide color photographic sensitive material each have at least one layer of red-sensitive layer, green-sensitive layer and blue-sensitive layer and a magnetic recording layer containing a ferromagnetic fine powder on a transparent base body is processed in an automatic developing machine having crossover rollers, the nip pressure of rollers is specified to 100 to 300g. The pressure is preferably 120 to 250g, and more preferably 140 to 200g. By this method, the photosensitive material can be smoothly carried without bending or meandering of the material. Further, the magnetic recording performance is improved and deterioration in the film property of the photosensitive layer and contamination by rollers during processing can be prevented.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and an apparatus for processing a silver halide color photographic light-sensitive material (hereinafter abbreviated as a light-sensitive material) having a magnetic layer, and more particularly to a processing method excellent in magnetic information reading performance and a processing method. It is to provide a processing device.

[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. However, recently, as disclosed in JP-A-4-68336, JP-A-4-73737, or JP-A-5-88283, a transparent magnetic recording layer is formed on the entire surface of a light-sensitive material, so Date / time, weather, reduction /
It is now possible to input shooting conditions such as enlargement ratio, number of reprints, areas to be zoomed, messages, development, print conditions, etc. into the sensitive material. Also, various information can be provided even when inputting to a video device such as a television / video, which is a promising method in the future.

Further, a beautiful image can be obtained by immersing such a light-sensitive material in various kinds of processing liquids for processing. However, since the labor cost is high, it is preferable to automatically perform these processes, and in this case, an automatic developing machine (also referred to as an automatic processor) is often used. In this case, an automatic processing machine that does not have a loss of magnetic reading is required. However, when a photosensitive material having a magnetic recording layer is processed by an automatic processor, dust in the processing liquid, tars produced by oxidation or eluate of a photosensitive material adheres to the magnetic recording layer during processing,
The magnetic recording layer is damaged by the transportation means such as rollers,
There were problems such as deterioration of magnetic properties.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to process a photosensitive material having a transparent magnetic recording layer by an automatic processor without degrading the S / N ratio of magnetically recorded information. It is an object of the present invention to provide a processing method and a processing apparatus for a silver halide photographic light-sensitive material. Another object is to provide a processing method or a processing apparatus for a silver halide photographic light-sensitive material which prevents generation of processing stains and maintains the beauty of a transmitted image.

[0005]

It has been found that the above problems can be solved by a processing method and a processing apparatus having the following configurations. (1) Crossover of 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 recording layer containing ferromagnetic fine powder. A method for processing a silver halide color photographic light-sensitive material, characterized in that a roller nip pressure when processed by an automatic processor having a roller is 100 to 300 g. (2) The automatic processor has a mechanism for reading information carried on an unprocessed silver halide light-sensitive material and determining processing conditions based on the read information. An apparatus for processing a silver halide color photographic light-sensitive material as described in (1) above. (3) The above-mentioned (1), wherein the transparent support is annealed polyethylene naphthalate.
5. A method for processing a silver halide color photographic light-sensitive material described in. (4) Crossover of 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 recording layer containing ferromagnetic fine powder. When processing with an automatic developing machine having a roller, the material of the roller is polybutylene terephthalate,
Ultra high density polyethylene resin, ultra high molecular weight polyethylene,
Polytetrafluoroethylene resin, polytetrafluoroethylene perfluoroalkoxyethylene resin, polyvinylidene fluoride resin, or other material coated with the above fluoropolymer material. An apparatus for processing a silver halide color photographic light-sensitive material, which is characterized in that (5) The roller nip pressure during processing by the automatic processor is 50 to 400 g, (4)
The processing device of the silver halide color photographic light-sensitive material described in. (6) The processing device for silver halide color photographic light-sensitive material as described in (4) above, wherein the silver halide color photographic light-sensitive material is coated with an emulsion for color negative or an emulsion for color reversal. . (7) The silver halide color photographic light-sensitive material processing apparatus as described in (4) above, wherein the magnetic recording layer has a blue filter concentration of 0.15 or less. (8) The automatic processor has a mechanism for reading information carried on an unprocessed silver halide light-sensitive material and determining processing conditions based on the read information. The processing device for silver halide color photographic light-sensitive material as described in (4) above. (9) The above-mentioned (4), wherein the transparent support is annealed polyethylene naphthalate.
The processing device of the silver halide color photographic light-sensitive material described in.

The details of the present invention will be described below. The roller according to the present invention is mainly not a submerged roller of an automatic development processor, but a crossover roller in a portion extending from one processing solution to the next processing solution. In the present invention, the crossover roller is important in terms of transporting the photosensitive material and preventing processing stains, and particularly in the photosensitive material having a magnetic recording layer, the nip pressure and material of the crossover roller are important. understood. Here, the roller nip pressure means a nip pressure for one pair of two rollers.

The roller-conveying type automatic developing machine conveys the photosensitive material by the nip pressure of the rollers. Therefore, a nip pressure above a certain level is required. On the other hand, the nip pressure should not be so strong as to destroy the emulsion surface of the light-sensitive material or the recording characteristics of the magnetic recording layer. Furthermore, it cannot be used without removing the dirt adhering to the photosensitive material. Therefore, as in the present invention, the roller nip pressure of the automatic developing machine is 100 g to 300 g, preferably 120 g to 250 g, and more preferably 140 to 2
When the amount is set to 00 g, the sensitive material can be quickly transported without being bent or meandering, the magnetic recording performance is good, the film quality of the photosensitive layer is not deteriorated, and the processing stain by the roller can be prevented. . In the present invention, as a method for setting the roller nip pressure to 100 to 300 g, the ring diameter of the ring-shaped spring may be changed, the elasticity of the spring may be changed, or an elastic plastic spring may be appropriately used instead of the metal spring. It can be set by deciding on.

On the other hand, even if the material of the roller of the automatic developing machine having the crossover roller is made to be a specific material, the sensitive material can be quickly conveyed without being bent or meandering, and the magnetic recording performance is further improved. The film quality is good, the film quality of the photosensitive layer is not deteriorated, and processing stains by the roller can be prevented. In this case, the roller nip pressure as described above is 50 to
It is preferably 400 g. As a result, the above effect can be made more remarkable.

In the present invention, the roller nip pressure is 2
Fix both ends of the pair of rollers with a length of 0 to 30 cm with a coiled ring or elastic plastic ring, sandwich the sensitive material (length 30 cm, width 89 mm) 5 cm in the wet end for 1 minute, The tip of the light-sensitive material is pulled by a tension spring and is simply expressed in grams measured when the light-sensitive material starts to move.

As the roller material of the crossover roller of the automatic processor used in the present invention, as described above, polybutylene terephthalate (PBT), ultra high density polyethylene resin (HDPE), ultra high molecular weight polyethylene (UH) is used.
MPE), polytetrafluoroethylene resin (PTFE), polytetrafluoroethylene / perfluoroalkoxyethylene resin (PFA), polyvinylidene fluoride resin (PVD)
F) selected from the above or other materials coated with polytetrafluoroethylene perfluoroalkoxyethylene resin or polyvinylidene fluoride resin, which is the above-mentioned fluoropolymer material, are used. Although the details are not clear, it is considered that the material of these rollers is relatively slippery on the surface and has the property that liquid does not adhere to the surface, so that dust adhesion, tar adhesion, etc. are unlikely to occur.

For details of such resins, see
It is described in "Plastic Molding Material Commerce Handbook-Characteristics Database-1991 Edition" issued by Synthetic Resin Industry Newspaper. As the PBT, specifically, PBT manufactured by Toray or Dainippon Ink and Chemicals, “Barox” manufactured by Nippon GE Plastics, or the like can be used. PBT can be used as a glass fiber reinforced product or an unreinforced product depending on the site. It is preferable to use the glass-reinforced product and the unreinforced product in combination. As the HDPE, specifically, 0.
A polyethylene polymer having a density of 94 g / cm ³ or more, which is a compound containing an ethylene homopolymer and an ethylene-α-olefin copolymer, and is a Mitsui Petrochemical's Hi-Ze
x The compounds described in the technical data can be used. Others, Quantum Chemical, Sltex,
Companies such as Exxon, Dow, Mobil, etc. 30 a year
Manufactured 10,000 tons and easily available.

As UHMPE, unreinforced products are specifically suitable, for example, Mitsui Petrochemical's "Lubemer", "Hi-Zex Million", Sakushin Kogyo's "New Light", Asahi Kasei's "Sunfine", large. "Ultra High Molecular Weight Polyethylene UHMW" manufactured by Nippon Printing can be used.

PTFE is a polymer in which all the hydrogen atoms of polyethylene are replaced with fluorine. PTFE
Specifically, "Teflon" from Du Pont,
ICI "Fluon", Montecatini "Algoflon", Hoechst "Hos"
"taflon TF", "Tetra of Nitto Kagaku Kogyo Co., Ltd."
“Flo”, “Polyflon” manufactured by Osaka Metal Industry Co., Ltd. and the like can be used. Of these, when extrusion molding is carried out as it is to make a roller, Du Pont's Teflon TF1, TF5, TF6, TF7, and ICI's Fluo are used.
n CD1, G2, G1, Hoechst Host
aflon TF23, TF14, P of Osaka Metal Industry Co., Ltd.
olyflon PF600, PF500, PF700
Can be used. If this is applied to a roller made of another material, Du Pont's Teflon TF30, ICI
Fluon GP1 of the same company, Polyf of Osaka Metal Industry Co., Ltd.
The lon PF600 can be used.

As the PFA, specifically, Montec
"Algoflon" from atini Edison,
"Aclar" made by Allied Chemical,
"Rare Freon" made by Nippon Oil Seal Industry, "Rulon" made by Western Bear Lulon Industrial Co., Ltd., "Esflon" made by Sakagami Manufacturing Co., Ltd.
Etc. can be used.

Specific examples of PVDF include "Toataflon" manufactured by Toa Paint Co., Ltd., Tire & Rubber C
o. For example, “Exon” manufactured by Mitsui Chemicals, Inc. can be used.

As the other material for coating the above-mentioned fluoropolymer material on the surface, any plastic can be used, and examples thereof include polyvinyl chloride, polyethylene, polypropylene and polyvinylidene chloride.
As a coating method, it is preferable that the surface of each plastic is subjected to surface treatment such as electron beam or plasma treatment, and then the fluoropolymer material is coated to 0.5 to 40 μm. As the material of the roller other than the crossover roller of the automatic developing machine used in the present invention, the above-mentioned materials are preferably used, but materials other than those described above may be used. For example, polyvinyl chloride, polyvinylidene chloride, polyethylene, polypropylene, phenolic resin,
Examples include polyphenylene ether, polyester, and polyimide.

For example, as the roller material of the roller used in the liquid of the processing section of the automatic processor used in the present invention, P
VC (polyvinyl chloride resin), PP (polypropylene), PE (polyeletin), UHMPE (ultra high molecular weight polyeletin), PMP (polymethylpentene), PP
Thermoplastic resins such as S (polyphenylene sulfide), modified PPO (modified polyphenylene oxide), modified PPE (modified polyphenylene ether) are suitable.
Olefinic resins such as PP, PE and PMP can be injection-molded smoothly on the roller surface, and since the specific gravity is low, the rotational load can be reduced, so that the emulsion surface of the conveyed photosensitive material is not easily scratched and is suitable. These are often used for drum rollers in the turn section. UHMPE and PTFE
Materials such as (including PFA and PVDF) are suitable for the portion where the sensitive material is squeezed and the portion where the processing liquid requires water repellency. It has the effect of preventing the sensitive material from being scratched by the solidified substance of the deposit of the treatment liquid on the roller. A roller provided with these materials on the roller surface (including coating) is suitable for the roller located at the interface of the treatment liquid and the roller for the squeeze portion. PVC
Is suitable for being easily processed into a roller by extrusion molding. Further, it is preferable that the roller having a soft resin portion having a low hardness on the surface of the roller can be easily manufactured by the double extrusion molding, and the roller can be brought into soft contact with the photosensitive material. In addition to PVC, the modified P
PO, modified PPE, modified PPS, etc. are suitable because they have high rigidity and can withstand high rotational torque. It is preferable to use glass fiber-reinforced or mineral-added strengthening agents such as mica, talc and potassium titanate in order to further enhance rigidity. By adding the reinforcing material, the bending elastic modulus of the roller is improved, creep deformation due to aging can be prevented, and stable conveyance can be ensured without bending the roller after long-term use. Further, by adding an inorganic substance to the resin and molding, the surface can be roughened by the inorganic particles appearing on the roller surface to prevent it from slipping. The surface roughness of the roller can be controlled by adjusting the particle size and amount of the added inorganic material.

A thermosetting resin is suitable for a conveying roller having a small diameter and a photosensitive material having a wide width and a long roller length. PF (phenolic resin), thermosetting urethane resin, and unsaturated polyester resin are preferable. Epoxy resins are also suitable for some processing solutions other than alkaline processing solutions. The PF is preferably a resol type, and Mitsui Toatsu Chemicals “OR-85” is particularly suitable. Graphite may be added for reinforcement. Since this roller can be made thin (for example, the outer diameter is 8 mm), the processing rack can be downsized.
As the thermosetting urethane resin, Nippon Unipolymer "Unilon", Dainippon Ink and Chemicals "Pandex", Takeda Chemical Industries "Takenate" and the like are suitable.

A roller coated with a fluorine-based resin is also preferable for preventing contamination with a developing solution. In particular,
The resin disclosed in JP-A-4-161955 can be used. An elastomer can be used for a soft roller such as a nip roller. For example, olefin elastomers, styrene elastomers, urethane elastomers, vinyl chloride elastomers and the like are preferable.

Next, the processing method of the present invention will be described in detail. The color developing solution (color developing solution) used for 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 a typical example thereof is 3-methyl-4-amino.
-N, N diethylaniline, 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-
Examples include N, 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-toluenesulfonates or sulfates 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 the 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, viscosity imparting agents, various chelating agents represented by aminopolycarboxylic acid, aminopolyphosphonic acid, alkylphosphonic acid, phosphonocarboxylic acid, 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-
Representative examples are N, N, N, N-tetramethylenephosphonic acid, ethylenediamine-di (o-hydroxyphenylacetic acid) and salts thereof.

Among the above, substituted hydroxylamine is most preferable as a 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 developer 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 is particularly preferable. The amount of the buffer added to the developer is
It is preferably 0.1 mol / liter or more, and particularly
It is particularly preferably from 0.1 mol / liter to 0.4 mol / liter. Further, a compound having biodegradability is preferable as the chelating agent. An example of this is Japanese Patent Laid-Open No. 63-
146998, JP-A-63-199295, JP-A-63-267750, JP-A-63-267751,
JP-A-2-229146, JP-A-3-186841
Examples thereof include chelating agents described in German Patent No. 3739610, European Patent No. 468325, and the like. 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 developer in the present invention is 3
The temperature is 0 to 55 ° C, preferably 35 to 55 ° C. The processing time is 20 seconds to 5 minutes, preferably 30 for the photographic light-sensitive material.
Second to 3 minutes and 20 seconds. The replenishment amount is 30 to 800 ml, preferably 50 to 500, per 1 square meter of the light-sensitive material.
It is about ml.

When the reversal process is performed, black and white development is usually performed 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. next,
The desilvering process of the present invention will be described in detail. The desilvering process generally has a bleaching process, a bleach-fixing process, and a fixing process, and there are various processes. Specific steps are shown below, but the invention is not limited thereto.

(Step 1) Bleach-fixing (step 2) Bleach-bleach-fixing (step 3) Bleach-bleach-fixing-fixing (step 4) Fixing-bleach-fixing (step 5) Bleach-fixing In the present invention, washing or stabilizing. Especially when the pre-bath of the bleaching step is the bleach-fixing step, a remarkable effect is exhibited.

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, as the compound forming the ferric complex salt in the liquid having a bleaching ability, 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.

The concentration of the ferric complex salt in the bleaching treatment solution of the present invention is appropriately in the range of 0.005 to 1.0 mol / liter, and 0.01 to 0.50 mol / liter.
It is preferably in the range of liter, more preferably 0.02.
The range is from 0.30 mol / liter. The concentration of the ferric complex salt in the replenisher for the processing solution having bleaching ability is
The amount is preferably 0.005 to 2 mol / liter, more preferably 0.01 to 1.0 mol / liter.

Various compounds can be used as a bleaching accelerator in a bath having a bleaching ability or a prebath thereof. For example, compounds having a mercapto group or a disulfide bond described in U.S. Pat. No. 3,893,858, German Patent 1,290,812, JP-A-53-95630 and Research Disclosure No. 17129 (July 1978). And Japanese Patent Publication No. 45-8506, Japanese Patent Laid-Open Nos. 52-20832, 53-3
2735, U.S. Pat. No. 3,706,561 and the like, and thiourea compounds or halides such as iodine and bromine ions are preferable because of their excellent bleaching power.

Other bleaching baths applicable to the present invention include bromide (eg, potassium bromide, sodium bromide, ammonium bromide) or chloride (eg, potassium chloride, sodium chloride, ammonium chloride). Alternatively, a rehalogenating agent such as iodide (eg, ammonium iodide) can be included. PH of borax, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate, tartaric acid, malonic acid, succinic acid, glutaric acid, etc. It is possible to add one or more kinds of inorganic acids and organic acids having a buffering capacity and their alkali metal or ammonium salts, or corrosion inhibitors such as ammonium nitrate and guanidine. Further, the bath having a bleaching ability may contain various other fluorescent whitening agents, antifoaming agents or surfactants, polyvinylpyrrolidone, organic solvents such as methanol.

The fixing agent component in the bleach-fixing solution and the fixing solution is
Known fixing agents, ie, thiosulfates such as sodium thiosulfate and ammonium thiosulfate; sodium thiocyanate,
Thiocyanates such as ammonium thiocyanate; ethylenebisthioglycolic acid, 3,6-dithia-1,8-
It is a water-soluble silver halide solubilizer such as thioether compounds such as octanediol, mesoionic compounds and thioureas, and these can be used alone or in admixture 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, it is preferable to use thiosulfates, particularly ammonium thiosulfate and sodium thiosulfate. The amount of fixer per liter is 0.3
Is preferably 2 to 2 mol, more preferably 0.5 to 1.0 mol. The bleach-fixing solution or fixing solution of the present invention preferably contains a sulfite (or bisulfite or metabisulfite) as a preservative, but is preferably 0.08-
0.4 mol / liter, more preferably 0.1 to 0.3
It is preferable that the content is mol / liter. By using this concentration range and further using the final bath of the present invention, not only the magnetic recording performance was remarkably improved, but also desirable results were shown in terms of image storability. The bleach-fixing solution or fixing solution of the present invention is a sulfite (for example, sodium sulfite, potassium sulfite, ammonium sulfite) or bisulfite (for example, ammonium bisulfite, sodium bisulfite, potassium bisulfite) described above as a preservative. In addition to containing sulfite ion-releasing compounds such as metabisulfite (eg, potassium metabisulfite, sodium metabisulfite, ammonium metabisulfite), aldehydes (benzaldexide, acetaldehyde, etc.), ketones (acetone, etc.) , Ascorbic acid, hydroxylamines and the like can be added as necessary.

Further, a bleaching solution, a bleach-fixing solution and a fixing solution may be added with a buffering agent, a fluorescent whitening agent, a chelating agent, a defoaming agent, an antifungal agent and the like, if necessary. In the bleaching solution and the bleach-fixing solution used in the present invention, the preferred pH range is 4.5.
It is -6.2 and more preferably 5-6. In some cases, the magnetic recording performance may not be sufficiently exhibited even if the pH is higher or lower than the normal pH. In the case of a fixer, pH 5
About 8 is desirable.

Bleaching solution, bleach-fixing solution, used in the present invention,
The replenishing amount of the fixing solution is 50 to 200 per 1 m ² of the light-sensitive material.
It is 0 ml. Particularly preferably 100 to 100
It is 0 ml. Further, after-wash water such as washing water or overflow solution of the stabilizing bath may be replenished if necessary.
The processing temperature of the bleaching solution, the bleach-fixing solution and the fixing solution is 20 to 50 ° C.
And preferably 30 to 45 ° C. Processing time is 1
It is 0 second to 3 minutes, preferably 20 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 light-sensitive material of the present invention is generally washed with water and / or stabilized after the desilvering process.

The rinsing water and / or the stabilizing solution may contain various surfactants in order to prevent unevenness of water droplets when the processed light-sensitive material is dried. 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 washing agents and / or stabilizing solutions may contain various chelating agents. 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-N,
Examples thereof include organic phosphonic acids such as N, N ′, N′-tetramethylenephosphonic acid, and hydrolyzates of maleic anhydride polymers described in European Patent 345,172A1.

The overflow solution accompanying the washing with water and / or the supplement 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 automatic processor which can be used in the present invention will be described in detail. The automatic developing machine having a crossover roller used for the photosensitive material in the present invention is preferably a roller-conveying type automatic developing machine, a conveying-type automatic developing machine with a timing belt and a leader, and a conveying-type automatic developing machine with a sprocket and a leader. It is preferable to have the photosensitive material conveying means described in JP-A-60-191257, JP-A-60-191258 and JP-A-60-191259. 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.

Among the functional items constituting the automatic processor, an important function for automatically supplying the processing liquid to the photosensitive material is:
They are agitation to physically diffuse the treatment chemicals and temperature control to accelerate the chemical reaction. For more information on these,
Photo Industry October issue (1974) page 82, July issue (19)
75) p. 41. In addition, as a function of the automatic processing machine before entering the processing tank, a sensitive material storage container (magazine,
Cassettes, cartridges, packaging materials, etc., photosensitive material joining means, cutting means (splicers, cutters, etc.), exposure devices, DX code and other information reading devices possessed by sensitive materials, and other detectors (eg, blind spot detection) And so on. In the present invention, a mechanism for reading the information carried on the magnetic recording layer of the sensitive material, changing various processing conditions of the sensitive material based on the information, and processing each sensitive material under desired conditions is provided. An automatic machine having one is preferable. This enables processing under suitable processing conditions for each photosensitive material to be processed. Specifically, even if the shooting conditions of color negatives, especially the aspect ratio and the printing conditions on photographic paper, etc. change, even if you are not a technical expert, you can always maintain a constant degree of fatigue of the processing liquid and a constant development finish quality. And you can always get a consistent print finish. In particular, in the present invention, since the information recorded in the magnetic recording layer of the sensitive material can be accurately read, the above effect becomes more effective when the automatic developing machine having this mechanism is used.
In the present invention, the processing conditions include development processing conditions (for example, replenishment amount of replenisher, amount of electricity to each processing tank, development processing time, etc.) and print processing conditions (for example, stretching magnification, exposure time, lens position change). Etc.).
Details regarding the reading of the information and the mechanism or method for determining the processing conditions based on the information include, specifically,
Mechanisms or methods described in JP-A-6-222514 and JP-A-6-222545 can be used.

Drying is also an essential function of the automatic developing machine after it leaves the processing tank. For this drying, Ryozo Kiryu's edition "Drying device" (published by Nikkan Kogyo Shimbun) and "Photo Industry" 7
For details, see page 41 of the monthly issue (1975). Further, as another aspect of the processing machine, the interface area (S) between the processing liquid and air is
Or opening ratio (degree) with respect to processing liquid volume (V) (K = S /
V). From these viewpoints, JP-A-53-578
There are applications such as No. 35 and No. 61-153645. Further, it is preferable that an automatic machine having a small liquid volume (V) in the processing machine has a relatively high liquid exchange rate, a small opening ratio (K) and a small tank liquid volume (V) in the case of a sparing process. From these viewpoints, JP-A-63-131138; 63-2160.
The method described in No. 50, etc. can be used.

In the example of the interaction between the processing machine parts and the liquid,
From the perspective of rust as an appropriate component, from the viewpoint of elution of photo-deteriorated components,
From the viewpoint of physical deterioration of parts. Regarding these viewpoints, JP-A-2-186342 and JP-A-2-18663 are available.
No. 44. Regarding the form of the processing tank for the processing material, it is described in the multi-chamber processing tanks filed in JP-A-1-267648; There are energization processing tanks and processing capsule processing of gaps (0.2 mm level) disclosed in EP0456210A2.
An example of an automatic processor suitable for the present invention will be described below. In the present invention, the shorter the air time when the photosensitive material moves between the processing solutions, that is, the shorter the crossover time, the better, and preferably 10 seconds or less, more preferably 7 seconds or less,
More preferably, it is 5 seconds or less.

In order to achieve the above short-time crossover, the present invention preferably uses a roller-conveying type automatic developing machine or a leader-conveying type cine-type automatic developing machine. The roller transport type automatic processor is the June issue of Photographic Engineering (19
75) Those described on page 14 are preferable. The cine-type automatic processor of the leader transport system is the March issue of Photographic Engineering (1975) 7.
Those described on page 0 are preferable. In the former, such a method is used for Hope RA2016V, RA2616V, etc. and RP2.
010V, 208RP, P3X2007V and RF0
506V, RF1105V, RF2409V, etc. and C0
509V, C1106V, etc. can be used. Other companies such as those manufactured by Colenta, Cleonite, San Marco and Noritz can also be used. In the latter, an automatic processor FP-550B manufactured by Fuji Photo Film Co., Ltd. is used. Other companies such as those manufactured by Noritsu and Agfa can be used. In either case, it is preferable that the linear velocity of conveyance is high, but in the above-mentioned leader system, it is 30 per minute.
cm-2 m is general, and preferably 50 cm-1.
It is 5m. Further, in order to shorten the crossover time and prevent the processing liquid from being mixed, the structure of the crossover rack preferably has the mixing prevention plate described in JP-A-3-126943.

In the present invention, it is preferable that the stirring of each processing solution is strengthened as much as possible so that the effects of the present invention can be more effectively exhibited. As a concrete method of strengthening stirring,
JP-A-62-183460, JP-A-62-18346
No. 1, that is, a color negative film processor FP-230 manufactured by Fuji Photo Film Co., Ltd.
A method in which a jet of a processing solution is made to collide with an emulsion surface of a light-sensitive material as used in B, a method of providing a stirring effect by using a rotating means of JP-A-62-183461, and further provided in the solution. Examples thereof include a method of moving a light-sensitive material (film) while bringing the wiper blade into contact with the emulsion surface to make the emulsion surface turbulent, thereby improving the stirring effect, and a method of increasing the circulation flow rate of the entire processing solution. Of these, the method of colliding the jet stream of the processing liquid is the most preferable, and it is preferable to adopt this method for all the processing tanks.

In particular, in processing with a processing solution having a fixing ability, after the photosensitive material comes into contact with the processing solution having a fixing ability, 1
By colliding the jets within 5 seconds, the effect of the present invention is significantly improved. It is more preferably 10 seconds or less, still more preferably 5 seconds or less. The reason why such an effect is obtained is not yet known, but if stirring is weak immediately after the light-sensitive material comes into contact with a liquid having fixing ability, a factor causing residual color may occur, causing a strong jet collision. Therefore, it is considered that this factor can be removed.

The method of jet impingement in each treatment liquid is described more specifically in JP-A-62-183460, page 3, lower right column to page 4, lower right column, Examples of the invention. A method in which the liquid pumped by a pump is discharged from a nozzle provided facing the emulsion surface is preferable. As a pump, Iwaki magnet pumps MD-10, MD-15, M
D-20 etc. can be used. The hole diameter of the nozzle is 0.5 to 2 mm, preferably 0.8 to 1.5 mm. Further, it is preferable that the nozzle is opened in a circular shape as perpendicular as possible to the chamber plate surface and the film surface, and the angle is 60 degrees to 12 degrees from the transport direction side.
At 0 degrees, the shape may be rectangular or slit. The number of nozzles is 1 to 50, preferably 10 to 30 per liter of tank capacity. Further, if the jet flow hits a part of the film in a biased manner, uneven development and residual color unevenness occur. Therefore, it is preferable to sequentially shift the positions of the nozzles so that they do not hit the same place. A preferable arrangement of the nozzles is, for example, as shown in FIG. 3, a row of about 4 to 8 holes which are perpendicular to the carrying direction and whose positions are gradually changed at appropriate intervals. If the distance from the nozzle to the film is too short, the above-mentioned unevenness is likely to occur, and if it is too far, the stirring effect is weakened. Therefore, the distance is preferably 1 to 12 mm, more preferably 3 to 9 mm.

The flow velocity of the liquid discharged from each nozzle also has an optimum range, and is preferably 0.5 to 5 m / sec, particularly preferably 1 to 3 m / sec. The circulation of the whole processing solution is
A circulation system may be provided only through the nozzle or separately. The total circulation flow rate is 0.2 to 5 liters per minute, preferably 0.5 to 5 liters per 1 liter of tank volume for each treatment tank.
Although it is 4 liters, it is preferable that the circulation flow rate is relatively high in each of the desilvering steps of bleaching, bleach-fixing and fixing, and the preferable range is 1.5 to 4 liters. The automatic processor used in the processing of the present invention preferably has a device for aerating the bleaching solution. Aeration can prevent a decrease in the bleaching rate due to the formation of a divalent iron complex during continuous processing and the formation of a cyan leuco dye called defective color restoration.

Aeration is disclosed in Japanese Unexamined Patent Publication No. 26-17674.
As described in No. 6 and No. 2-176747, it is preferable to supply a flow rate of 0.01 liter or more per liter of the treatment tank using a porous nozzle having a pore size of 300 μm or less. The process of continuously or intermittently processing the light-sensitive material while replenishing the replenisher is called the running process. It will be easier. Therefore, when aeration is performed, a large amount of bubbles are generated and may overflow from the processing tank. In order to prevent this, it is preferable to provide a defoaming means, and specifically, JP-A-4-3057, JP-A-4-56853, and JP-A-4-56853.
The method described in Japanese Patent No. 56854 is effective.

In the treatment of the present invention, it is preferable to correct the evaporative concentration of the treatment liquid during the running treatment.
The most preferable evaporation correction method is to add water corresponding to the amount of evaporation in anticipation, and as described in JP-A-4-1756, the information on the operating time, stop time, and temperature control time of the automatic processor is used. The amount of water added is calculated based on the coefficient determined in advance. In addition to this, JP-A-3
-248155, 3-249644, 3-24
No. 9645, No. 3-249646, No. 4-14042
An evaporation correction method using a liquid level sensor, such as that described in No. 3, is also preferable.

It is also necessary to devise a method of reducing the amount of evaporation, which can be achieved by reducing the opening area or adjusting the air volume of the exhaust fan. For example, the preferable opening ratio of the color developing solution is as described above, but it is preferable to reduce the opening area of other processing solutions as well.
The exhaust fan is attached to prevent dew condensation during temperature control, but the preferable exhaust volume is 0.1 m ² -1 per minute.
m ² . A particularly preferable displacement is 0.2 m ²
~ 0.4 m ² .

The drying conditions of the photosensitive material also affect the evaporation of the processing liquid. As drying method, it is preferable to use a ceramic hot air heater is preferably min 4m ² liters to 20 m ² as a supply air volume, particularly 6 m ² through 10m ² preferable. Ceramic hot air and heater heating prevention thermostat are preferably operated by heat transfer,
The attachment position is preferably on the leeward or upwind side through a heat radiation fin or a heat transfer section. The drying temperature is preferably adjusted according to the water content of the light-sensitive material to be processed.
The optimum temperature is 45 to 55 ° C. for the 5 mm width film and 55 to 65 ° C. for the Brownie film. A replenishing pump is used for replenishing the processing liquid, and a bellows type replenishing pump is preferable. Also, as a method of improving replenishment accuracy,
In order to prevent backflow when the pump is stopped, it is effective to reduce the diameter of the liquid feeding tube to the refill nozzle. The preferred inner diameter is 1 to 8 mm, and the particularly preferred inner diameter is 2
To 5 mm.

Although various component materials are used in the automatic processor, the preferred materials are described below. A modified PPO (modified polyphenylene oxide) resin and a modified PPE (modified polyphenylene ether) resin are preferable as a tank material such as a processing tank and a temperature control tank, and as a material for guides of the processing rack and the liquid contact part. Examples of the modified PPO include "Noryl" manufactured by GE Plastics Co., Ltd., and modified PPE include "Zylon" manufactured by Asahi Kasei Kogyo Co., Ltd. and "Yupiace" manufactured by Mitsubishi Gas Chemical Company.
These materials have excellent chemical resistance to a developing solution, a fixing solution, a bleach-fixing solution and the like. These materials are suitable for injection molding and have an advantage that various hollow molding such as low foam molding, sympress molding, and gas counter pressure molding can be performed. By using these molding methods, it has become possible to integrally mold the processing tank and temperature control tank, as well as the guides and racks having a complicated structure. Furthermore, it became possible to make thick members such as thick molded bodies and blocks. It can also be used for large housing members such as covers for automatic processors by engineering blow molding. Since these materials have a higher heat resistance temperature than general ABS, they can be used as a material for drying members of an automatic processor. When heat resistance and rigidity are required, glass fiber reinforced or filler-added grade can be used.

ABS (acrylonitrile-butadiene-styrene resin) has a chemical resistance to a processing solution (for example, a color developing solution, a bleaching solution, a fixing solution, a bleach-fixing solution). It can be used for racks and racks. ABS resin from each company such as "Denka" manufactured by Denki Kagaku Kogyo, "Psycholac" manufactured by Ube Industries, Mitsubishi Monsanto Kasei, and Japan Synthetic Rubber can be used. ABS is 80 ℃
It is preferably used in the following environment. Further, ABS is a material suitable for the housing of an automatic processor because it has good moldability by injection molding, has few sink marks during molding, and can be molded with good flatness. This material is also suitable for the processor supply section and cassettes.

The olefinic resins PE (polyethylene) and PP (polypropylene) have high chemical resistance to processing solutions in general (eg, color developing solution, bleaching solution, fixing solution, stabilizing solution). There is. PE has many products such as Showa Denko and Ube Industries. PP is Ube Industries, Chisso,
There are many products such as Mitsui Toatsu Chemical and Asahi Kasei. It is used as a material for replenishment tanks and waste liquid tanks in automatic processors. Since the material is inexpensive and the large-sized tank can be easily manufactured by hollow molding, it can be preferably used in a portion that does not require high dimensional accuracy.

PVC (polyvinyl chloride resin) is
It has excellent chemical resistance, is inexpensive and can be easily welded, and has excellent workability. Many types of PVC are produced by many companies, such as various chemical manufacturers such as the electrochemical industry and Riken Vinyl Industry. Sheet materials extruded from Takiron Industrial "Taquilon Plate" and Mitsubishi Plastics "Hishi Plate" are commercially available, and various modified PVCs are also commercially available and can be easily used.
Acrylic-modified PVC is commercially available from in-cylinder plastic “Kyduck” and Sunarrow Chemical. Acrylic modified PVC has a smooth surface and good water repellency, and when used in a tank, it is a suitable material that does not easily cause precipitation of a processing solution (eg, precipitation of a main agent from a color developing solution). As a device for extruding PVC or smoothing the surface of an injection-molded article, it is highly effective to add soybean oil or the like in addition to modified PVC to improve the fluidity during molding. The addition of soybean oil (preferably modified soybean oil) not only smoothes the resin surface and does not impair the quality of the photosensitive material due to scratches, but also has the effect of improving the fluidity during molding.

As a material for the guide of the processing tank or the processing section in order to prevent the deposition of the color developing agent or the like and to improve the transportability of the light-sensitive material,
Crystalline polymers can be used. PBT (polybutylene terephthalate), HDPE (ultra high density polyethylene resin), PTFE (polytetrafluoroethylene resin),
PFA (ethylene tetrafluoride / perfluoroalkoxy ethylene resin), PVDF (polyvinylidene fluoride resin)
And the like are suitable for a guide in contact with a photosensitive material and a liquid interface portion where a processing liquid (for example, a color developing solution) is likely to be deposited. The above-mentioned fluoride is effective even if it is coated on another material such as PPE. Gears and sprockets in the processing section include PA (polyamide), PBT (polybutylene terephthalate), UHMPE (ultra high molecular weight polyethylene), PPS (polyphenylene sulfide), LCP.
(Whole aromatic polyester resin, liquid crystal polymer), PEE
Thermoplastic crystalline resins such as K (polyether ether ketone) are suitable. Examples of PA include polyamide resins such as 66 nylon, 6 nylon, and 12 nylon, as well as aromatic polyamides having an aromatic ring in the molecular chain and modified polyamides. Toray and DuPont “Zytel” are suitable as 66 nylon and 6 nylon, and Toray “Rilsan” and Daicel Hüls “Daiamide” are suitable as 12 nylon. Suitable aromatic polyamides include Mitsubishi Gas Chemical's "Renny" polyamide MXD6, and modified polyamides such as Mitsui Petrochemical's "Alen" modified polyamide 6T. PA is preferably a glass fiber reinforced or carbon fiber reinforced grade because it has a high water absorption rate and easily swells in the treatment liquid. Aromatic polyamides have a relatively low water absorption rate and thus are less likely to swell, and high dimensional accuracy can be obtained.
In addition, high molecular weight products such as MC nylon obtained by compression molding can obtain sufficient performance without fiber reinforcement. In addition, oil-impregnated nylon resin such as "Polyslider" is also used. PBT is P
Contrary to A, it has a very low water absorption rate and therefore has high chemical resistance to the treatment liquid. Toray and Dainippon Ink and Chemicals PBT and Nippon GE Plastics "Barox"
Is used. PBT is used depending on the site, whether it is a glass fiber reinforced product or an unreinforced product. In order to improve the meshing of gears, it is preferable to use a glass reinforced product and an unreinforced product in combination. As UHMPE, non-reinforced products are suitable, and Mitsui Petrochemical's “LUMBMER”, “HIZEX Million”, Sakushin Kogyo “New Light”, Asahi Kasei “Sunfine”, Dai Nippon Printing “Ultra High Molecular Weight Polyethylene UHMW” are suitable. ing. As the PPS, those reinforced with glass fiber or carbon fiber are preferable. For LCP, I
CI Japan “Victrex”, Sumitomo Chemical “Econol”, Nippon Oil “Zyder”, Polyplastics “Vectra” and the like can be used. PEEK is a suitable material that has extremely good chemical resistance and durability against any processing liquid of the developing machine and is an unreinforced product and exhibits sufficient performance.

Ultrahigh molecular weight polyethylene is preferable as the material for the bearing and the like. Normally, stainless steel (SU) is used as springs and springs used in processing solutions of automatic processors.
S316), titanium or the like is used. Plastic springs can be used if the spring or spring cannot be made properly with titanium. Little deformation when a load is applied (Hook's critical strain is 1.6%
Below) PBT (eg Japan GE Plastics “Barox 310” etc.), PP (eg Asahi Kasei “M-1500” etc.), Modified PPO (eg Japan GE Plastics “Nonil 731J” etc.), Modified P
Used in PE (eg Asahi Kasei “Zylon 220V” etc.). When the spring force is weak, it is also effective to use a glass fiber reinforced material. In order for the spring to obtain a stable nip force for a long period of time, PSF
(Polysulfone), PAR (Polyarylate), PES
(Polyethersulfone), PEI (polyetherimide), PAI (polyamideimide) are suitable. Especially, the amorphous resin of Super Embra is excellent and PSF,
PES and PEI are particularly preferable. PSF is Amoco "Udel P1700", PES is ICI "VICTR
EX 4800G "and PEI can be used from Japan GE Plastics" Ultem ". PEEK, PPS, LCP for springs that are used for a long time under heavy load
A crystalline resin such as is used. Amorphous resin has less creep and has very good dimensional accuracy during molding, so it is extremely suitable for low-load springs. Crystalline resin is suitable for parts that require high fatigue limit stress, and PEEK is
ICI "VICTREX 450G", PPS "Ryton", LCPI type Sumitomo Chemical "Econor E200
0 ", LCP type II plastic" Bectra A95 "
"0" is a typical grade.

As a soft material such as a squeeze roller,
Foam, vinyl chloride resin, silicon foam resin, and urethane foam resin are suitable. Examples of the urethane foam resin include "Rubicel" manufactured by Toyo Polymer Co., Ltd. EPD for rubber and elastomers such as pipes, pipe joints, agitation jet pipe joints, and sealing materials
M rubber, silicone rubber, viton rubber, olefin elastomer, styrene elastomer, urethane elastomer, vinyl chloride elastomer and the like are preferable. As specific examples, "Sumiflex" manufactured by Sumitomo Bakelite Co., Ltd., "Milastomer" (olefin-based elastomer) manufactured by Mitsui Petrochemical Co., Ltd., "Thermoran" (olefin-based elastomer containing rubber) manufactured by Mitsubishi Petrochemical Co., Ltd., The same "Lavalon", Japan Monsanto Kasei Co., Ltd. or AES
Examples include "Santoprene" manufactured by Japan Co., Ltd., "Sunplane" manufactured by Mitsubishi Kasei Vinyl Co., Ltd. (high-elasticity vinyl chloride elastomer), and silicone rubber and binder rubber described in JP-A-3-198052.

As a core material of a belt such as a conveyor belt,
Ultra high strength polyethylene resin fiber (for example, Japanese Patent Laid-Open No. 4-6
No. 554), polyvinylidene fluoride resin fibers (for example, described in JP-A-4-16941), aramid fibers (for example, “Kepra” manufactured by Toray DuPont Co., Ltd.) and the like can be used. Regarding the materials such as plastics used in each part including the processing tank of the processing equipment described above, "Plastic Molding Material Commerce Handbook-Characteristic Database- 1991 Edition" published by Synthetic Resin Industry Newspaper Co., Ltd. It can be easily selected and obtained based on the above.

The replenishing cartridge used in the present invention may be made of any material such as paper, plastic, metal, etc., but a plastic material having an oxygen permeability coefficient of 50 ml / m ² · atm · day or less is particularly preferable. . The oxygen permeability coefficient is "O ₂ permeatio
no of plastic container. Mo
dern Packing; N. J. Calyan. 1
968) December issue, pages 143-145. Specific examples of preferable plastic materials include vinylidene chloride (PVDC), nylon (NY), polyethylene (PE), polypropylene (PP), polyester (PES), ethylene-vinyl acetate copolymer (EVA), ethylene-vinyl. Alcohol copolymer (EVAL), polyacrylonitrile (PA
N), polyvinyl alcohol (PVA), polyethylene terephthalate (PET), and the like. For the purpose of reducing oxygen permeability, PVDC, NY, PE,
The use of EVA, EVAL and PET is preferred.

These materials may be used alone and may be molded and used, or a method of forming a film and laminating a plurality of kinds (so-called composite film) may be used.
Further, as the shape of the container, various types such as bottle type, cubic type, billow type and the like can be used, but the present invention is a cubic type and a flexible type which is easy to handle and can be reduced in volume after use. Structures similar to are particularly preferred. When used as a composite film, the structures shown below are particularly preferable, but not limited thereto.

PE / EVAL / PE PE / aluminum foil / PE NY / PE / NY NY / PE / EVAL PE / NY / PE / EVAL / PE PE / NY / PE / PE / PE / NY / PE ・ PE / SiO ₂ film / PE ・ PE / PVDC / PE ・ PE / NY / aluminum foil / PE ・ PE / PP / aluminum foil / PE ・ NY / PE / PVDC / NY ・ NY / EVAL / PE / EVAL / NY ・ NY / PE / EVAL / NY ・ NY / PE / PVDC / NY / EVAL / PE ・ PP / EVAL / PE ・ PP / EVAL / PP ・ NY / EVAL / PE ・ NY / Aluminum foil / PE ・ Paper / Aluminum foil / PE ・ Paper / PE / Aluminum foil / PE ・ PE / PVDC / NY / PE ・ NY / PE / Aluminum foil / PE ・ PET EVAL / PE · PET / aluminum foil / PE · PET / aluminum foil / PET / PE

The thickness of the composite film is about 5 to 1500 microns, preferably about 10 to 1000 microns. The content of the finished container is 100 ml to 20 liter, preferably 500 ml to
It is about 10 liters. The above container (cartridge)
May have a cardboard or plastic outer box,
It may be formed integrally with the outer box. Various processing liquids can be filled in the cartridge of the present invention. For example, a color developing solution, a black and white developing solution, a bleaching solution, an adjusting solution, an inversion solution, a fixing solution, a bleach-fixing solution, a stabilizing solution and the like can be mentioned. It is preferred to use developers, fixers and bleach-fixers.

The magnetic recording layer used in the present invention will be described in detail. The magnetic recording layer may be adjacent to the support or may be present via another photographic constituent layer. 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 Co-deposited ferromagnetic iron oxide (FeO) such as γFe ₂ O ₃
x, 4/3 <x ≦ 3/2), Co-deposited magnetite, other Co-containing ferromagnetic iron oxide, Co-containing magnetite, ferromagnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, and other ferrites, for example, Hexagonal Ba ferrite, S
r-ferrite, Pb-ferrite, Ca-ferrite or their solid solutions or ion-substitutes can be used, but Co-coated ferromagnetic iron oxides such as γFe ₂ O ₃ with a Fe ²⁺ / Fe ³⁺ ratio of 0. From 10% is preferable 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, 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 can be prepared, for example, in Japanese Patent Laid-Open No.
It may be surface-treated with silica and / or alumina such as those described in JP-A-9-23505 and JP-A-4-096052. Further, JP-A-4-195726, JP-A-4-192116, JP-A-4-259911, and JP-A-5-0.
Surface treatment with an inorganic and / or organic material as described in No. 81652 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 Japanese Patent Publication No. 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. Among 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 alone or as a mixture of several kinds, and a known epoxy-based, aziridine-based or isocyanate-based crosslinking agent and / or a radiation-curable vinyl-based 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 a 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 a method for dispersing the above-mentioned magnetic material in the binder, various known means other than, for example, Japanese Patent Application No. 4-189652 can be used. A combined use 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 back surface of a photographic support by coating or printing and provided in the entire surface 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, an additive is incorporated 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 particles added 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. Further, acrylic acid esters, methacrylic acid esters, itaconic acid diesters, crotonic acid esters, maleic acid diesters, phthalic acid diesters, styrene derivatives, vinyl esters, 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),
Carbides such as silicon carbide and titanium carbide, fine powders such as diamond are preferable, and more preferably aluminum oxide,
Chromium oxide (Cr ₂ O ₃ ) is good. 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. In the present invention, the magnetic recording layer as described above preferably has a blue filter concentration of 0.15 or less. If it is higher than this, the graininess in the image is deteriorated and the printing conditions of the printer are deviated when the photographic material is printed on the print material after processing, and the color tone is not good and the finish is difficult.

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. Such a polyester is formed by using a diol and an aromatic dicarboxylic acid as essential components, but as a dibasic acid that can be often used as a mixture with other dicarboxylic acids,
Terephthalic acid, isophthalic acid, phthalic acid, phthalic anhydride, 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 Acid, itaconic acid, citraconic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, 1,4-cyclohexanedicarboxylic acid, halogenated terephthalic acid, bis (p-carboxyphenol) ether, 1 , 1-
Dicarboxy-2-phenyl ethylene, 1,4-dicarboxymethylphenol, 1,3-dicarboxy-5
Examples thereof include phenylphenol and sodium 3-sulfoisophthalate. The essential aromatic dicarboxylic acid is one having at least one benzene nucleus among the above-mentioned dicarboxylic acids. Next, as diols, ethylene glycol, 1,3-propanediol, 1,2
-Propanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 1,
7-heptanediol, 1,8-octanediol,
1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanediol, 1,1-cyclohexanedimethanol, catechol, resorcin, hydroquinone, 1,4-benzenedimethanol, dimethylolnaphthalene, p-hydroxyethyloxybenzene, bisphenol A, etc. can be mentioned.

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

As the monomers of these diols and dicarboxylic acids, first, preferable 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.

Of the above, polyesters containing naphthalenedicarboxylic acid are particularly preferable. Specifically, it is a polyester containing 0.1 to 1.0 of naphthalene dicarboxylic acid. Particularly preferred is polyethylene naphthalate, and most preferred is polyethylene-2,6-.
It is naphthalate.

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 (NDC
A) / Ethylene glycol (EG) (100/10
0)] (PEN) Tg = 119 ° C. P-2: [terephthalic acid (TPA) / cyclohexanedimethanol (CHDM) (100/100)]
Tg = 93 ° C. P-3: [TPA / bisphenol A (BPA) (1
00/100)] Tg = 192 ° C

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

P-10: IPA / PPDC / TPA / E
G (20/50/30/100) Tg = 95 ° C. P-11: NDCA / NPG / EG (100/70/3)
0) 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 (50/25/2
5) Tg = 108 ° C. P-20: TPA / 5-sulfoisophthalic acid (SI
P) / EG (95/5/100)
Tg = 65 ° C. P-21: PEN / SIP / EG (99/1/100)
Tg = 115 ° C

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, and more preferably PEN, and when used, the film thickness required to be 122 μm in TAC is 105
It is possible to reduce the thickness to μm or less. Next, the polyester support of the present invention is preferably subjected to annealing (heat treatment). The heat treatment is performed at a temperature of 40 ° C. or higher and a glass transition temperature or lower for 0.1 to 1500 hours. Thereby, the curl of the support can be prevented, and the photosensitive material can be better processed. 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. In the present invention, annealed PEN is particularly preferred. This eliminates curl and facilitates silver halide emulsion coating, and at the same time USP 4,84
8893, USP 5,296,886, USP 5,34
7,334 is a narrower cartridge than before, and the tongue part is automatically locked, the door is locked to prevent the light pipe, the usage status is displayed on the cartridge, and the double exposure prevention function is provided. It is easy to load the film into the cartridge cartridge, and the functions of the cartridge become effective. Furthermore, it is possible to prevent the photosensitive material from being jammed in the automatic developing machine during the development processing after photographing, and to prevent curling in the drying section and making it difficult to be accumulated.

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 curl-preventing effect and the industrial productivity is deteriorated. 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 0.1 hours or less, a sufficient effect cannot be obtained, and if the time is 1500 hours or more, the effect is saturated, while 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 the form of a roll or may be carried out while being conveyed in the form of a web. In the case of heat treatment in the form of a roll, it may be carried out by any of a method of heat-treating the roll from room temperature in a constant temperature bath, and a method of winding and heat-treating the roll in a constant temperature during web conveyance. Good. 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 the roll form, the surface shrinkage such as wrinkles due to winding tightness and the cutout of the core portion is likely to occur due to the heat shrinkage stress generated during the heat treatment. For this reason, unevenness is imparted 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 such as preventing the cut edge of the winding core from being exposed by giving a knurl to the end and slightly raising only the end. On the other hand, when the heat treatment is carried out 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 if the pre-heat treatment is carried out in the form of a web, planar defects are less likely to occur as compared with the case of performing it 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, lubricant, 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, with respect to the polyester used as the support in the present invention, various additives are preferably coexistent in order to further enhance the function as the photographic support. 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 to 20% by weight based on the weight of the polyester film.
%, Preferably about 0.05 to 10% by weight. If it is less than 0.01% by weight, the effect of suppressing deterioration of ultraviolet rays cannot be expected. Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2,2 ', 4. 4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,
Benzophenone-based compounds such as 4'-dimethoxybenzophenone, 2 (2'-hydroxy-5-methylphenyl) benzotriazole, 2 (2'-hydroxy 3 ', 5'-di-t-butylphenyl) benzotriazole, 2 (2 ′
Examples thereof include benzotriazole-based UV absorbers such as -hydroxy-3'-di-t-butyl-5'-methylphenyl) benzotriazole and salicylic acid-based UV absorbers such as phenyl salicylate and methyl salicylate.

The preferred aromatic polyester of the present invention has a high refractive index of 1.6 to 1.7, while the gelatin which is the main component of the photosensitive layer coated thereon has a refractive index of 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 depending on the 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 is 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 the support becomes colored as the amount of light increases,
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
0 Kcal / m ² , more preferably 3 to 20 Kcal / m ^2.
Is. The distance between the tip of the internal flame of the burner and the support is 4
It is more effective to make it less than 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 Examined 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 preheated support is subjected to glow discharge treatment. Important processing conditions other than the steam partial pressure, the preheating temperature of the support, and the like 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 to be used is from direct current to several 1000 MHz, preferably 50 Hz to 20 MHz, more preferably 1 KHz, as seen in the prior art.
~ 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 a monomer 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-resin. 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 comprises 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 light-sensitive material of the present invention will be described.
The present invention can be applied to any photosensitive material having the above-mentioned transparent 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, in particular European patent EP 0,35
Those described in 5,660A2 (Japanese Patent Application No. 1-107011) are preferably used.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

[0115]

[Table 4]

[0116]

[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%. . The coated silver amount is not particularly limited, but it is ² g to 10 g / m ²
%, More preferably 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, JP-A-2-33
In addition to the diphenylimidazole type cyan couplers described in No. 144, 3-hydroxypyridine type cyan couplers described in European Patent No. A divalent equivalent having a leaving group, 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).

The magenta coupler preferably contains at least one coupler selected from the following general formula (II) or (III).

[0119]

Embedded image

(In the formula, R ₁ represents a hydrogen atom or a substituent. Z represents a group of non-metal atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms. May have a substituent (including a condensed ring). X represents a hydrogen atom or a group capable of splitting off upon a coupling reaction with an oxidized product of a developing agent.)

[0121]

Embedded image

(In the formula, R ₁₁ represents a substituent, R ₁₂ represents an electron-withdrawing group. M represents an integer of 1 to 5, and when m is 2 or more, R ₁₁ is the same or different. Is good, n is 2
And R ₁₂ may be the same or different. X ₁ represents a group capable of splitting off upon reaction with an oxidized product of an aromatic primary amine color developing agent. R ₁₁ , R ₁₂ or X ₁
In, a dimer or a multimer having a valence of two or more may be bonded to each other to form a dimer or a multimer. ) In the present invention, by using the coupler of the general formula (II) or (III), washing and / or stabilizing bath can be commonly used without impairing the image storability (increased yellow stain or photobleaching), At the same time, it is noteworthy that the processing time could be shortened at the same time.

Next, the coupler represented by the general formula [II] will be described in detail. Among the coupler skeletons represented by the formula (II), a preferable skeleton is 1H-imidazo [1,2-b] pyrazole,
1H-pyrazolo [1,5-b] [1,2,4] triazole, 1H-pyrazolo [5,1-c] [1,2,4] triazole, 1H-pyrazolo [1,5-d] tetrazole and 1H-pyrazolo [1,5-a] benzimidazole.

Specific examples of the pyrazolotriazole couplers among these couplers are listed below.

[0125]

Embedded image

[0126]

[Chemical 4]

[0127]

Embedded image

[0128]

[Chemical 6]

[0129]

[Chemical 7]

[0130]

Embedded image

[0131]

[Chemical 9]

[0132]

[Chemical 10]

[0133]

[Chemical 11]

[0134]

[Chemical 12]

[0135]

[Chemical 13]

[0136]

Embedded image

[0137]

[Chemical 15]

Examples of the non-color-forming, ethylenic monomer that does not couple with the oxidation product of the aromatic primary amine developing agent include acrylic acid, α-chloroacrylic acid, α-alkylacrylic acid (for example, methacrylic acid), and their compounds. Esters or amides derived from acrylic acids (eg, acrylamide, n-butyl acrylamide, t-butyl acrylamide, diacetone acrylamide, methacrylamide, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, t-butyl acrylate) , Iso-butyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate and β-. Mud carboxymethyl methacrylate),
Methylenedibisacrylamide, vinyl esters (eg vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylonitrile, aromatic vinyl compounds (eg styrene and its derivatives, vinyltoluene, divinylbenzene, vinylacetophenone and sulfostyrene). , Itaconic acid, citraconic acid, crotonic acid, vinylidene chloride, vinyl alkyl ether (eg vinyl ethyl ether),
Maleic acid, maleic anhydride, maleic acid ester, N
-Vinyl-2-pyrrolidone, N-vinylpyridine, and 2- and 4-vinylpyridine. Two or more non-color-forming ethylenically unsaturated monomers used herein can be used together. For example, n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymer color coupler art, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with the solid water-insoluble monomer coupler are the physical properties and / or chemistry of the copolymer formed. Properties such as solubility,
The compatibility of the binder of the photographic colloidal composition, such as gelatin, its flexibility, thermal stability, etc., can be selected to be favorably influenced. The polymer coupler used in the present invention may be water-soluble or water-insoluble, and among them, a polymer coupler latex is particularly preferable.

Specific examples of the coupler represented by formula (III) of the present invention are shown below, but the present invention is not limited thereto.

[0141]

Embedded image

[0142]

[Chemical 17]

[0143]

Embedded image

[0144]

[Chemical 19]

[0145]

Embedded image

[0146]

[Chemical 21]

[0147]

[Chemical formula 22]

The couplers represented by the formulas (II) and (III) of the present invention have a spectral absorption waveform of a dye obtained from the coupler by color development and a spectral dye of a color dye obtained from another coupler used in the same layer. Selected to approximate. With this, color filters with various spectral characteristics, light sources,
The printer suitability in various auto printers of various companies using the density sensor is stably maintained even when the photographing conditions and the exposure amount are changed, and it is possible to supply a print having a constant quality. Furthermore, the formulas (II) and (II
The coupler represented by I) has improved photographic sensitivity and exhibits stable color development processability. Formula (II) of the present invention and
The coupler represented by (III) may be used in any layer in the silver halide photographic material, but is preferably added to the green-sensitive emulsion layer and / or its adjacent layer. The total amount added is 1 × 10 ^{−3 to} 1.0 g / m ² , preferably 5
× 10 ^{−3 to} 0.8 g / m ² , more preferably 1 × 10 ⁻² to
It is 0.5 g / m ² . The method of adding the coupler of the present invention to the light-sensitive material is based on the method of other couplers described later,
The weight ratio of the high-boiling organic solvent used as the dispersion solvent to the magenta coupler is preferably 0 to 3.0, more preferably 0.3 to 2.0, and even more preferably 0.5 to 1.2.

The couplers represented by the formulas (II) and (III) of the present invention can be used with known magenta couplers. As the known magenta coupler, 5-pyrazolone compounds are preferable, and US Pat. No. 4,310,619
No. 4,351,897, European Patent No. 73,63.
6, U.S. Pat. Nos. 3,061,432 and 3,72.
No. 5,067, Research Disclosure No. Two
4220 (June 1984), JP-A-60-33552.
No., Research Disclosure No. 24230
(June 1984), JP-A-60-43659, 6
1-72238, 60-35730, 55-1
No. 18034, No. 60-185951, U.S. Patent Nos. 4,500,630, 4,540,654, 4,556,630, and International Publication WO88 / 0479.
Those described in No. 5 and the like are particularly preferable. In the light-sensitive material of the present invention, a hydrophilic colloid layer for the purpose of improving the sharpness of an image, a dye which can be decolorized by the treatment described in European Patent EP 0,337,490A2, pages 27 to 76, is used. Among them, oxonol-based dyes) are used as photosensitive materials for 680n.
It can be added so that the optical reflection density in m is 0.70 or more. The color photographic light-sensitive material according to the present invention includes a coupler and a European patent EP0,277,589A2.
It is preferred to use color image-storing improving compounds as described in US Pat. In particular, it is preferably used in combination with a pyrazoloazole coupler.

That is, the compound (F) and // which chemically bond 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 of the sample is 25 ° C. 6
0RH% After left 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 term "photographic layer" as used herein refers to a laminated hydrophilic colloid group layer containing 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 (dimethylolurea, methyloldimethylhydantoin, 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 light-sensitive materials. In particular, a color negative film, a color reversal film, a negative film for movies, a positive film for movies, and the like can be mentioned, but the application to color negative films and color reversal films is particularly preferable.

EXAMPLES The present invention will be described in more detail with reference to specific examples, but the invention is not limited to the examples as long as the gist of the invention is not exceeded. Example 1 1) Support The support used in this example was prepared by the following method. 100 parts by weight of commercially available polyethylene-2,6-naphthalate polymer and Tinuvin as an ultraviolet absorber
P. 2 parts by weight of 326 (manufactured by Geigy) was dried by a conventional method, melted at 300 ° C., extruded from a T-die and longitudinally stretched 3.0 times at 140 ° C., and then at 130 ° C. for 3. The film was transversely stretched 0 times and further heat-set at 250 ° C. for 6 seconds to obtain a PEN film having a thickness of 90 μm. Furthermore, by winding a part of it around a stainless steel core with a diameter of 20 cm,
A thermal history of 110 ° C. for 48 hours was given.

2) Coating of Undercoat Layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, glow discharge treatment, and flame treatment on both sides thereof,
An undercoat liquid having the following composition was applied to each surface to form an undercoat layer on the high temperature surface side during stretching. For the corona discharge treatment, use a solid state corona treatment machine 6KVA model manufactured by Pillar Co.
A 0 cm wide support is treated at 20 m / min. At this time, the object to be processed is 0.375 KV from the current and voltage readings.
・ A · min / m ² was processed. The discharge frequency during the treatment was 9.6 KHz, and the gap clearance between the electrode and the dielectric roll was 1.6 mm. UV discharge treatment
Discharge treatment was performed while heating at 75 ° C. Further, the glow discharge treatment was performed by irradiating with a cylindrical electrode of 3000 W for 30 seconds.

Gelatin 3 g Distilled water 25 cc Sodium α-sulfodi-2-ethylhexyl succinate 0.05 g Formaldehyde 0.02 g Salicylic acid 0.1 g Diacetyl cellulose 0.5 g p-Chlorophenol 0.5 g Resorcin 0.5 g Cresol 0.5 g ( CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.2 g trimethylolpropane triazine 0.2 g trimethylolpropane tristoluene diisocyanate 0.2 g methanol 15 cc acetone 85 cc formaldehyde 0.01 g acetic acid 0.01 g concentrated hydrochloric acid 0.01 g

3) Coating of Back Layer After the undercoating, an antistatic layer having the following composition, a magnetic recording layer and a sliding layer having the following composition were provided as a back layer on one surface of the support. 3-1) Coating of antistatic layer 3-1-1) Preparation of conductive fine particle dispersion liquid (tin oxide-antimony oxide composite dispersion liquid) 230 parts by weight of stannic chloride hydrate and antimony trichloride 2
3 parts by weight was dissolved in 3000 parts by weight of ethanol to obtain a uniform solution. A 1N aqueous sodium hydroxide solution was added dropwise to this solution until the pH of the solution became 3, to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The obtained coprecipitate was left at 50 ° C. for 24 hours to obtain a reddish brown colloidal precipitate.

The reddish brown colloidal precipitate was separated by centrifugation. To remove excess ions, water was added to the precipitate and washed by centrifugation. This operation was repeated 3 times to remove excess ions. Colloidal precipitate from which excess ions have been removed 2
100 parts by weight of water was redispersed in 1500 parts by weight of water, and sprayed in a baking furnace heated to 650 ° C. to obtain a bluish average particle diameter of 0.0
A fine powder of 05 μm tin oxide-antimony oxide composite was obtained. The specific resistance of this fine particle powder was 5 Ω · cm. A mixed solution of 40 parts by weight of the fine particle powder and 60 parts by weight of water was adjusted to pH 7.0 and roughly dispersed by a stirrer, and then a horizontal sand mill (trade name: Dynomill; WILLYA.BACHO).
It was prepared by dispersing with FENAG) until the residence time reached 30 minutes. The average particle size of the secondary aggregate at this time is about 0.04.
μm.

3-1-2) Coating of Conductive Layer The following formulation was applied so that the dry film thickness would be 0.2 μm,
It was dried at 115 ° C. for 60 seconds. Conductive fine particle dispersion liquid prepared in 3-1-1) 20 parts by weight Gelatin 2 parts by weight Water 27 parts by weight Methanol 60 parts by weight p-Chlorophenol 0.5 parts by weight Resorcin 2 parts by weight Polyoxyethylene nonylphenyl ether 0. 01 parts by weight

The resistance of the obtained conductive film is 10 ^8.0 (100
V) and had excellent antistatic performance.

3-2) Coating of magnetic recording layer Magnetic substance Co-deposited γ-Fe ₂ O ₃ (long axis 0.14 μm,
Uniaxial needle shape with 0.03 μm, specific surface area 41 m ² / g, saturation magnetization 89 emu / g, surface treated with 2% by weight of Fe ₂ O ₃ each with aluminum oxide and silicon oxide, coercive force 930 Oe , Fe ^{+ 2} / Fe ⁺³ ratio is 6/94) 110
220 g of water and 150 g of a silane coupling agent of poly (polymerization degree 16) oxyethylenepropyl trimethoxysilane were added to 0 g, and kneaded well in an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for one day to remove water, and then heated at 110 ° C. for 1 hour for treatment to prepare surface-treated magnetic particles. Further, the following formulation was used, and the mixture was kneaded again in an open kneader.

The above-mentioned surface-treated magnetic particles 1000 g Diacetyl cellulose 17 g Methyl ethyl ketone 100 g Cyclohexanone 100 g Furthermore, 200 with a sand mill (1/4 G) with the following formulation.
Finely dispersed at rpm for 4 hours.

The above kneaded product 100 g Diacetyl cellulose 60 g Methyl ethyl ketone 300 g Cyclohexanone 300 g

Further, diacetyl cellulose and C ₂ H ₅ C (CH ₂ OCONH-C ₆ H ₃ (C
The H ₃₎ NCO) ₃ was added 20 wt% based on the binder. The obtained liquid was diluted with equal amounts of methyl ethyl ketone and cyclohexanone so that the viscosity was about 80 cp.
The coating was carried out on the above conductive layer with a bar coater, and the film thickness was 1.2 μm. Amount of magnetic material 0.6g / m
^It was applied so as to be ² . Silica particles (0.3 μm) as a matting agent and aluminum oxide (0.5 μm) as an abrasive.
Was added so as to be 10 mg / m ² , respectively. Drying was performed at 115 ° C. for 6 minutes (the temperature of the rollers and the conveying device in the drying zone are 115 ° C.). When using a blue filter in Status M of X- write, increment of the color density of D ^B of the magnetic recording layer was about 0.1. The saturation magnetization moment of the magnetic recording layer is 4.2 emu / m.
² , the coercive force was 923 Oe, and the squareness ratio was 65%.

3-3) Preparation of Sliding Layer The following prescription liquid was applied so that the coating amount of the solid content of the compound was as follows, and dried at 110 ° C. for 5 minutes to obtain a sliding layer. Diacetyl cellulose 25 mg / m ² C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ COOC ₄₀ H ₈₁ compound a 6 mg / m ² C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H compound b 9 mg / m ² Compound a / compound b (6: 9) was xylene and propylene glycol monomethyl ether (volume ratio 1:
1) is heated to 105 ° C in the same amount of the solution and dissolved, and this solution is added to 1
0 times the amount of propylene glycol monomethyl ether (2
5 ° C.) to give a fine dispersion. After further diluting in 5 times the volume of acetone, high pressure homogenizer (200 atm)
Was re-dispersed to form a dispersion (average particle diameter 0.01 μ), and then added and used. The obtained sliding layer has a dynamic friction coefficient of 0.06 (stainless steel balls of 5 mmφ, load 10).
0g, speed 6cm / minute), static friction coefficient 0.07
(Clip method) and has excellent characteristics. The sliding property with respect to the emulsion surface, which will be described later, also had a dynamic friction coefficient of 0.12.

4) Coating of Photosensitive Layer Next, each layer having the following composition was multilayer coated on the side opposite to the back layer obtained above to prepare a color reversal photographic film. (Photosensitive layer composition) The reverse color emulsion layer of Sample 101 of Example 1 described in JP-A-2-854 was coated. With respect to the layer structure of the emulsion layer, the first layer is an antihalation layer, the second layer is an intermediate layer, the third to fifth layers are red-sensitive emulsion layers, and the seventh to ninth layers.
The layers are green-sensitive emulsion layers, the 11th to 13th layers are blue-sensitive emulsion layers, the 14th to 15th layers are protective layers, and the 6th and 10th layers are intermediate layers.

As an automatic developing processor used for processing this light-sensitive material, a modified product of a processor RF0506V for color reversal film manufactured by Hope was used. Fuji Photo Film, processing manual CR for processing liquid and processing process
Followed -56p. For the modified part of RF0506V, the photosensitive material was processed by changing the crossover roller portion of the stabilizing bath which is the final bath to the materials and nip pressures shown in Table 6 below.

To change the nip pressure, both ends of the nip roller were stretched and adjusted with a coil spring. For the measurement of the nip pressure, the sensitive material was attached to the nip roller, the sensitive material was joined to the tip of a spring-type weight meter, and the number of grams (g) at which the sensitive material started to move from the nip roller was determined by pulling. The coil spring was adjusted to set a predetermined nip pressure. The set level was set at ± 20 g.

With respect to the above-mentioned sensitive materials and their treatments, the passage of the sensitive material, the magnetic characteristics and the processing stain were evaluated as follows. The evaluation of the passage of the photosensitive material was carried out by passing 30 pieces of the 1-meter-long photosensitive material, and the place where there was no break and no meandering was marked with ◯. When even one fold was broken, it was evaluated as ×, and when bent, it was evaluated as Δ. The evaluation of the processing stain is made by visual judgment of the processed photosensitive material, and Δ is the stain but is within the allowable range. ○ is not dirty. X was evaluated as being dirty. The magnetic properties were evaluated by measuring the coercive force, the saturation magnetization, and the squareness of the coated material using VSMP10-15P manufactured by Toei Industry Co., Ltd. After slitting the film to a width of 35 mm, the head gap was 5 μm from the coated surface side of the magnetic recording layer, and the number of turns was 20.
After the FM signal was recorded at a feed speed of 100 mm / s using a head capable of inputting / outputting 00, the signal was read at the same head and the same speed to determine 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. When this error rate is less than 10 ⁻⁴ , there is no practical problem. 10 ^-4 to 10 ^-3 are within the allowable range although there are reading errors. If the error rate exceeds 10 ⁻³ , it becomes a problem.

[0173]

[Table 6]

[0174]

[Table 7]

According to Table-6, PP and P of Samples 1-28
For E, PMP, and PVC rollers, the nip pressure is 100 g or more in order to obtain good passage of the photosensitive material, and 100 g or more in terms of processing stains (Δ is an allowable range). On the other hand, when the error rate of the magnetic property is 10 ⁻⁴ or less, only 300 g or less can be obtained. Therefore, with respect to these three evaluation items, the nip pressure between 100 and 300 g was all within the allowable range.
Further, when the roller nip pressure was 500 g, deterioration of the film quality of the emulsion layer was observed. Therefore, the nip pressure 100 to 300
By setting to g, in the case of the magnetic coating sensitive material, the magnetic permeability,
Improves magnetic properties and processing stains. On the other hand, sample 2
9-70 PTFE, PFA, UHMPE, HDPE,
For rollers made of PUDF and PBT, 50 to 500
Even with a nip pressure of g, the photosensitive material was excellent in passability, and the error rate of the magnetic characteristics was good if the nip pressure was 400 g or less. Furthermore, processing stains disappeared at any nip pressure. Therefore, when the magnetic recording coating sensitive material is treated with a normal roller material, if the nip pressure is 100 g or more and 300 g or less, or if the specific material of the present invention is used, magnetic properties, passage characteristics, and processing stains are good. become. Further, the processed photosensitive material is contaminated with dirt, and if it adheres, the magnetically recorded information cannot be read out well. 50-
PTFE, PFA, UHM for 500g nip pressure
PE, PVMPE, HDPE rollers prove to be advantageous.

Example 2 In Example 1, the photosensitive material in which the amount of the magnetic material was changed was adjusted so that the roller material was UHMPE (ultra high molecular weight polyethylene resin) and the nip pressure was 250 g. . Except for this, the light-sensitive material was prepared and processed in the same manner as in Example 1 above. Here, X-rite manufactured by X-rite was used for various samples in which the amount of the magnetic material was changed.
The blue transmission density was measured using a densitometer STATUS-A, and the error rate of the magnetic characteristics was determined in the same manner as in Example 1.

Sample No. Amount of magnetic material Blue transmission density Magnetic characteristic error rate 1 0.08 g / m ² 0.18 4.3 × 10 ⁻³ 2 0.15 g / m ² 0.18 0.1 3 0.3 g / m ² 0 .18 0.05 4 0.6 g / m ² 0.18 0.01 5 0.9 g / m ² 0.18 0.001 6 1.2 g / m ² 0.19 0.0001 7 1. 8 g / m ² 0.23 0.0001 8 2.4 g / m ² 0.29 0.0001

From the error rate of the magnetic characteristics, the amount of the magnetic substance is required to be 0.15 g / m ² or more, and from the viewpoint of the blue transmission density, 1.2 g / m ² or less is required. When the amount of the magnetic substance exceeds 1.8 g / m ² , the color reversal film becomes yellow and unsightly. Moreover, when this was printed on reverse color paper, unsightly grain was seen in the sky and skin in the photograph. Next, a waterproof tape was applied to the back side of each of these films, immersed in a 3% sodium hypochlorite solution at 40 ° C. for 30 minutes, washed with hot water to remove the emulsion layer, and dried. After that, when the blue transmission density was measured, sample No. 7,8
Had a concentration of 0.17, 0.23. Therefore, the transmission density is 0.17 when the magnetic recording layer is installed without the emulsion layer.
It turns out that the above cannot be used.

Example 3 (1) Support Material and the Like 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 an 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) Bag 1st 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 23. Compound of 0.1 g / m ²

[0183]

[Chemical formula 23]

Compound shown in Chemical formula 24 below 0.02 g / m ² poly (ethyl acrylate) (average diameter 0.08 μm) 1 g / m ²

[0185]

[Chemical formula 24]

(B) Back second layer 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) Back third layer 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 Sojiumuji (2-ethylhexyl) sulfosuccinate compounds described isocyanate 0.01 g / m ² the following formula 25 0.01 g / m ²

[0188]

[Chemical 25]

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. Sample 101 with heat-treated PEN support and sample 102 with TAC support
And A sample 103 was the PEN support that had not been subjected to the heat treatment (4).

(5) Preparation of Photosensitive Layer Each layer having the composition shown below was coated in multiple layers to prepare each sample as a color negative film. (Photosensitive layer composition) The main materials used for each layer are classified as follows; ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling point organic solvent ExY: Yellow coupler H: Gelatin Curing agent ExS: Sensitizing dye The numbers corresponding to the respective components indicate the coating amount expressed in units of g / m ² , and for silver halide, the coating amount in terms of silver. However, with respect to the sensitizing dye, the coating amount is shown in mol unit per mol of silver halide in the same layer.

First Layer (Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.60 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse Dye ExF-2 0.030 Solid Disperse Dye ExF-3 0.040 HBS-1 0.15 HBS- 2 0.02

Second layer (intermediate layer) Silver iodobromide emulsion M Silver 0.065 ExC-2 0.04 Polyethyl acrylate latex 0.20 Gelatin 1.04

Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion A Silver 0.25 Silver iodobromide emulsion B Silver 0.25 ExS-1 6.9 × 10 ^-5 ExS-2 1.8 × 10 ^-5 ExS-3 3.1 × 10 ^-4 ExC-1 0.17 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 0.87

Fourth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Silver Iodobromide Emulsion C Silver 0.70 ExS-1 3.5 × 10 ^-4 ExS-2 1.6 × 10 ^-5 ExS-3 5.1 × 10 ^-4 ExC-1 0.13 ExC-2 0.060 ExC-3 0.0070 ExC-4 0.090 ExC-5 0.015 ExC-6 0.0070 Cpd-2 0.023 HBS-1 0.10 Gelatin 0.75

Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion D Silver 1.40 ExS-1 2.4 × 10 ^-4 ExS-2 1.0 × 10 ^-4 ExS-3 3.4 × 10 ^-4 ExC-1 0.10 ExC-3 0.045 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 HBS-1 0.22 HBS-2 0.050 Gelatin 1.10

Sixth layer (intermediate layer) Cpd-1 0.090 Solid disperse dye ExF-4 0.030 HBS-1 0.050 Polyethyl acrylate latex 0.15 Gelatin 1.10

Seventh Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide Emulsion E 0.15 Silver iodobromide Emulsion F Silver 0.10 Silver iodobromide Emulsion G Silver 0.10 ExS-4 3.0 × 10 ^-5 ExS-5 2.1 × 10 ^-4 ExS-6 8.0 × 10 ^-4 ExM-2 0.33 ExM-3 0.086 ExY-1 0.015 HBS-1 0.30 HBS-3 0.010 Gelatin 0.73

Eighth Layer (Medium-Sensitivity Green Sensitive Emulsion Layer) Silver Iodobromide Emulsion H Silver 0.80 ExS-4 3.2 × 10 ^-5 ExS-5 2.2 × 10 ^-4 ExS-6 8.4 × 10 ^-4 ExC-8 0.010 ExM-2 0.10 ExM-3 0.025 ExY-1 0.018 ExY-4 0.010 ExY-5 0.040 HBS-1 0.13 HBS-3 4.0 × 10 ^-3 Gelatin 0.80

Ninth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion I Silver 1.25 ExS-4 3.7 × 10 ^-5 ExS-5 8.1 × 10 ^-5 ExS-6 3.2 × 10 ^-4 ExC-1 0.010 ExM-1 0.020 ExM-4 0.025 ExM-5 0.040 Cpd-3 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

10th layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Eleventh layer (low sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion J Silver 0.09 Silver iodobromide emulsion K Silver 0.09 ExS-7 8.6 × 10 ^-4 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.22 ExY-3 0.50 ExY-4 0.020 Cpd-2 0.10 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 1.20

12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion L Silver 1.00 ExS-7 4.0 × 10 ^-4 ExY-2 0.10 ExY-3 0.10 ExY-4 0.010 Cpd-2 0.10 Cpd-3 1.0 × 10 ^-3 HBS-1 0.070 Gelatin 0.70

Thirteenth layer (first protective layer) UV-1 0.19 UV-2 0.075 UV-3 0.065 HBS-1 5.0 x 10 ^-2 HBS-4 5.0 x 10 ^-2 Gelatin 1.8

14th layer (second protective layer) Silver iodobromide emulsion M Silver 0.10 H-1 0.40 B-1 (diameter 1.7 μm) 5.0 × 10 ^-2 B-2 (diameter 1.7 μm) 0.15 B-3 0.05 S-1 0.20 Gelatin 0.70

Further, in order to improve storage stability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property, each layer may be provided with W-1 to W-3, B-4 to B-. 6, F
-1 to F-17 and iron salt, lead salt, gold salt, platinum salt,
It contains a palladium salt, an iridium salt, and a rhodium salt.

[0207]

[Table 8]

In Table 8 above, (1) Emulsions J to L were prepared according to the examples of JP-A-2-91938.
It is reduction-sensitized during grain preparation using thiourea dioxide and thiosulfonic acid. (2) Emulsions A to I were prepared according to the examples of JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization are performed in the presence of the spectral sensitizing dye described in each photosensitive layer and sodium thiocyanate. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the examples of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed in the tabular grains by using a high voltage electron microscope. (5) Emulsion L is a double structure grain containing an internal high iodine core described in JP-A-60-143331.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of an aqueous solution of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The contents were dispersed for 2 hours. A BO type vibrating ball mill manufactured by Chuo Koki was used for this dispersion. After the dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the dye fine particles were 0.24 μm, 0.45 μm and 0.52 μm, respectively.
ExF-5 is a microprecipitation described in Example 1 of European Patent Application Publication (EP) 549,489A.
It was dispersed by the dispersion method. The average particle size was 0.06 μm.

[0211]

[Chemical formula 26]

[0212]

[Chemical 27]

[0213]

[Chemical 28]

[0214]

[Chemical 29]

[0215]

Embedded image

[0216]

[Chemical 31]

[0219]

Embedded image

[0218]

[Chemical 33]

[0219]

Embedded image

[0220]

Embedded image

[0221]

Embedded image

[0222]

Embedded image

[0223]

[Chemical 38]

[0224]

[Chemical Formula 39]

[0225]

[Chemical 40]

[0226]

Embedded image

[0227] The light-sensitive material prepared as described above is set to 24 mm.
The width is cut into 160 cm, and two perforations of 2 mm square are provided at a distance of 5.8 mm at a position 0.7 mm from one side width direction of the photosensitive material. A device in which these two sets are provided at intervals of 32 mm is prepared, and is shown in US Pat. No. 5,296,887, FIG. 1-FIG. It was housed in the plastic film cartridge described in 7. An FM signal was recorded on this sample at a feed rate of 100 mm / s during the above-mentioned perforation of the photosensitive material by using a head gap of 5 μm from the coated surface side of the magnetic recording layer and a turnable number of 2000. FM
After recording the signal, the emulsion surface was exposed uniformly for 1000 cms and each processing was performed by the methods described below, and then the emulsion 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. The ratio of the number of error bits to the number of input bits is shown in Table 9 below. When this error rate is less than 10 ⁻⁴ , there is no practical problem. 10 ^-4 to 10 ^-3 are within the allowable range although there are reading errors. If the error rate exceeds 10 ⁻³ , it becomes a problem.

Details of the processing executed will be described below. The sample described above was subjected to a gray exposure of 1000 cms at a color temperature of 4800 K, and was processed by the following processing steps and processing solutions by an automatic processor CO509V for color negative film manufactured by Hope. The final treatment liquid was changed in salt concentration and additives as shown below, and each treatment was sequentially performed.

(Processing process) Process processing time Processing temperature Color development 2 minutes 00 seconds 40.0 ° C Bleach 30 seconds 38.0 ° C Settlement 1 minute 00 seconds 38.0 ° C Final processing (1) 15 seconds 38.0 ° C Final processing (2) 15 seconds 38.0 ℃ Final treatment (3) 15 seconds 38.0 ℃ Dry 1 minute 55 ℃ * The final bath is the countercurrent method from (3) to (1)

The composition of the processing liquid is shown below. (Color developer) Tank solution (g) Diethylenetriaminepentaacetic acid 5.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 2.0 Potassium iodide 1.2 mg Hydroxylamine sulfate 2.0 N, N- (Disulfonatoethyl) hydroxylamine 5.0 4- [ N-Ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 7.0 Water was added to 1.0 liter pH (adjusted with potassium hydroxide and sulfuric acid) 10.00

(Bleaching Solution) Tank Solution (g) 1,3-Diaminopropanetetraacetic Acid Ammonium Ferric Acid Monohydrate 150.0 1,3-Diaminopropanetetraacetic Acid 3.0 Ammonium Bromide 80.0 Ammonium Nitrate 17.5 Ammonia Water (27%) 10.0 Acetic acid (98%) 50.0 Potassium carbonate 10.0 Add water to 1.0 liter pH (adjust with ammonia water and acetic acid) 4.3

(Fixer) (Unit: g) Ethylenediaminetetraacetic acid disodium salt 1.7 Sodium sulfite 16.0 Sodium bisulfite 11.0 Ammonium thiosulfate aqueous solution (700 g / liter) 210.0 mL Ammonium thiocyanate 150.0 Thiourea 1.8 1.0 liter pH 6.5 with addition of water

(Final Treatment Solution) (Unit: g) Stabilizing Solution A Surfactant 0.5 [C ₁₀ H ₂₁ -O- (CH ₂ CH ₂ O) ₁₀ -H] Polymaleic acid (average molecular weight 2000) 0.5 1,2- Benzisothiazolin-3-one 0.02 Hexamethylenetetramine 3.0 Water added 1.0 liter pH 8.5

This time, samples 101, 102 and 103 were treated with the same materials and nip pressures as in Example 1 for the nip rollers at the crossover portions of the color developing solution and the bleaching solution, and the error rate of magnetic recording was determined. In addition, in the same manner as in Example 1, the light-sensitive material passing property and the processing stain were evaluated. The results are summarized in Table 9 and Table 10 below. However, samples 102 and 10
For No. 3, the characteristics of the roller material were PVC and UHMPE.

[0235]

[Table 9]

[0236]

[Table 10]

[0237]

[Table 11]

From the results shown in Table 9 above, in Sample 101,
In general, the magnetic error rate is higher than in Table 6, and the passage of the photosensitive material and the processing stain are poor. It is presumed that this is because the roller portion of the bleaching solution was largely soiled in the bleaching-processed area without color washing after color development. However, the general tendency was the same as in Example 1. That is, in Samples 1 to 28,
When the nip pressure is 100 g or more and 300 g or less, the photosensitive material passing property, the magnetic property, and the processing stain are improved. On the other hand, samples 29 to 70
When the roller material is selected as shown in, the selection range of the nip pressure is widened, and the magnetic characteristics, the passage of the photosensitive material, and the processing stain are improved. As shown in Table-10, the difference in roller material is not large in the support of TAC or PEN without annealing.
Regarding a wide roller nip pressure range, the magnetic error rate, the passage of the photosensitive material, and the processing stain are not so good. That is,
PEN with good PEN support and annealed PEN
However, it can be seen that all evaluation items can be satisfied in the wide roller nip pressure range.

[0239]

According to the present invention, a photosensitive material having a transparent magnetic recording layer can be processed by an automatic processor without degrading the S / N ratio of magnetically recorded information. A method and processing device can be provided. Furthermore, it is possible to provide a processing method or a processing apparatus for a silver halide photographic light-sensitive material, which prevents generation of processing stains and maintains the beauty of a transmitted image.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location G03C 7/407

Claims (8)

[Claims] 1. A silver halide color photographic light-sensitive material having, on a transparent support, at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer, and a magnetic recording layer containing ferromagnetic fine powder. A method for processing a silver halide color photographic light-sensitive material, characterized in that the roller nip pressure when processed by an automatic processor having a crossover roller is 100 to 300 g. 2. The method of processing a silver halide color photographic light-sensitive material according to claim 1, wherein the transparent support is annealed polyethylene naphthalate. 3. A silver halide color photographic light-sensitive material having, on a transparent support, at least one red-sensitive layer, green-sensitive layer and blue-sensitive layer, and a magnetic recording layer containing ferromagnetic fine powder. When processing with an automatic processor having a crossover roller, the material of the roller is polybutylene terephthalate, ultra high density polyethylene resin, ultra high molecular weight polyethylene, polytetrafluoroethylene resin, polytetrafluoroethylene perfluoroalkoxyethylene resin A processing device for a silver halide color photographic light-sensitive material, which is selected from a polyvinylidene fluoride resin, or is obtained by coating the above fluorinated polymer material on another material. 4. The processing apparatus for silver halide color photographic light-sensitive material according to claim 3, wherein the roller nip pressure during processing by the automatic processor is 50 to 400 g. 5. A silver halide color photographic light-sensitive material processing apparatus according to claim 3, wherein said silver halide color photographic light-sensitive material is coated with a color negative emulsion or a color reversal emulsion. . 6. The processing device for a silver halide color photographic light-sensitive material according to claim 3, wherein the magnetic recording layer has a blue filter density of 0.15 or less. 7. The automatic processor has a mechanism for reading information carried on an unprocessed silver halide light-sensitive material and determining processing conditions based on the read information. 4. The processing device for silver halide color photographic light-sensitive material according to claim 3. 8. The apparatus for processing a silver halide color photographic light-sensitive material according to claim 3, wherein the transparent support is annealed polyethylene naphthalate.