JPH0659406A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the rapid development processing method small in fatigue of a fixing solution due to processing and good in clearing in fixing. CONSTITUTION:The photosensitive material has a nonphotosensitive gelatin layer of >=0.5mum thickness on the side of a support reverse to a silver halide emulsion layer and a hydrophobic polymer layer on its outside and both layers do substantially not swell at the time of processing, and it is processed in an automatic developing machine provided with rinse rollers and a rinse bath between a developing step and a fixing step.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide black-and-white photographic light-sensitive material which has a reduced processing fatigue of a fixing solution and is excellent in rapid processability.

[0002]

2. Description of the Related Art In recent years, the delivery period has been shortened in the printing and platemaking industry.
There is an increasing demand for reduction of processing time in order to improve work efficiency. The fixing time is preferably 19 seconds or less in order to achieve a total processing time of 60 seconds or less. When processing a large-sized photosensitive material such as a scanner film, a return film and a facsimile film used in the plate making field, there is a case where the central portion of the photosensitive material is insufficiently fixed especially in a fixing time of 19 seconds or less. In addition, the washing time becomes short, so that the washing performance may be poor and the image storability may be poor.

As a countermeasure against this, it is conceivable to reduce the amount of silver halide in the light-sensitive material, but generally, the maximum density is lowered. Particularly in the field of printing photosensitive materials, there is a reduction work, and the amount of silver is preferably 2.0 g / m ² or more, and there is a limit to the reduction of the amount of silver. Further, as the fixing speed improving means, there is an increase in the fixing temperature and an increase in the agitation amount in the fixing tank. However, if uneven fixing is likely to occur excessively and the fixing temperature is excessively increased, odor and liquid evaporation problems occur. Occurs, which causes a problem that the vaporized sulfurous acid gas corrodes indoor equipment.

There is also a method of increasing the circulation amount of the fixing solution. In this case, the fixing property is improved in the vicinity of the solution outlet,
The effect diminishes in the central part. In order to improve the fixing property in the central portion, it is necessary to considerably increase the circulation amount, and it becomes excessive at both ends, resulting in energy waste.

On the other hand, from the viewpoint of the composition of the fixing solution, it is common to increase the concentration of the fixing agent (usually thiosulfate) in order to increase the fixing speed, but (a) the thiosulfate concentration is 2 mol / mol. On the other hand, if it is more than 1 liter, fixing is suppressed. (B) Washing time is shortened due to rapid processing. Therefore, if the concentration of the fixing agent is high, the washing property is deteriorated, the amount of residual hypo is increased, and the image storability is deteriorated. . (C) The pollution load of the fixer and washing water increases. (D) There is a limit in practical use due to restrictions such as difficulty in concentrating the fixing solution and high cost.

It has also been investigated to use an organic compound instead of thiosulfate as a fixing agent. U.S. Pat. No. 4,378,424, JP-A-57-150842 and the like describe the use of the mesoionic compound 1,2,4-triazolium-3-thiolate as a fixing agent in place of the thiosulfate. Only the embodiment using only the mesoionic compound is described.

Further, JP-A-1-201659 discloses that a mesoionic thiolate compound is added as a bleaching accelerator to a bleaching bath or a bleach-fixing bath.
-44355 discloses the use of a bleaching solution using diethylenetoariminepentaacetic acid ferric salt and fixing containing a 1,2,4-triazolium-3-thiolate compound in the processing of color light-sensitive materials. However, there is no description of use as a fixing solution for rapid processing of black-and-white silver halide light-sensitive materials that does not use a bleaching solution as in the present invention, and no mention is made of the effects intended by the present invention.

Other mesoionic compounds are also US Pat. Nos. 4,003,910 and 4,675,2.
No. 76, No. 4,624,913, No. 4,631,25
3, JP-A Nos. 62-217237 and 64-3641.
No. 60-144737, No. 62-253161.
No. 62-287239, No. 61-176920.
No. 62-96943 and JP-A No. 1-154056, all of which are added to a photographic light-sensitive material or to a developing solution, and the effects intended by the present invention are disclosed. I didn't say anything.

[0009]

SUMMARY OF THE INVENTION With respect to the above problems, it is an object of the present invention to provide a rapid processing method for silver halide photographic light-sensitive materials. Still another object of the present invention is to provide a fixing method for rapid processing, which has good fixing property even in rapid processing.

[0010]

The object of the present invention is to provide a support on which a silver halide emulsion layer is coated. On the surface opposite to the surface of the silver halide emulsion layer, 0.5 .mu. The non-photosensitive gelatin layer having the above thickness, and the hydrophobic polymer layer at a position farther from the support than the non-photosensitive gelatin layer, the non-photosensitive gelatin layer and the hydrophobic polymer layer are substantially In a method for processing a non-swelling light-sensitive material by using an automatic developing machine, the halogen is characterized by processing by using an automatic developing machine having a rinse tank and a rinse roller between the developing step and the fixing step. It was achieved by the processing method of silver halide sensitive material.

The present invention will be described in detail below. It is known that a factor of fatigue of the fixing solution due to photographic processing is bringing the developing solution into the fixing tank. The developer is swelled and absorbed into the gelatin film, and the developer is attached to the surface. By bringing the back surface side into non-swelling, the carry-in of the developing solution was slightly reduced, but the rate of surface adhesion was large and the effect was not sufficient. Further, although there was some effect by treating a photosensitive material having a normal swelling back surface with an automatic developing machine having a rinse tank and a rinse roller, the developer sucked by the swelling was removed by the rinse. I couldn't do that.

When the back side surface is a hydrophilic gelatin layer, the developer adhered to the surface could not be completely removed even after rinsing because the surface was hydrophilic. However, when a photosensitive material whose surface was covered with a hydrophobic polymer as in the present invention was processed by an automatic developing machine having a rinse tank and a rinse roller, the developer brought in on the back surface side could be completely removed. . This is larger than the sum of the effects of the hydrophobic polymer backing material and the rinse alone, and thus the deterioration of fixing loss due to processing fatigue is reduced. As a result, the amount of replenishment is small and the fixing loss is good even with a short fixing time, which enables rapid processing and a low replenishment amount.

(Specific Structure of the Invention) First, a non-photosensitive hydrophilic colloid layer (hereinafter referred to as a back layer) on the opposite surface of the emulsion layer of the present invention is described. The back layer of the present invention is a layer using a hydrophilic colloid as a binder. As the hydrophilic colloid used for the back layer, a binder for the photographic layer on which the silver halide emulsion layer is coated is used from the viewpoint of curling. Those having a close moisture absorption rate and moisture absorption rate are preferable. The most preferable hydrophilic colloid used for the binder of the back layer of the present invention is gelatin.

As the gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives and modified gelatin, which are generally used in the art, can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used.

As a hydrophilic colloid other than gelatin, proteins such as colloidal albumin and casein, viewpoints, sugar derivatives such as sodium alginate and starch derivatives, cellulose compounds such as carboxymethyl cellulose and hydroxymethyl cellulose, polyvinyl alcohol, poly-N
Examples thereof include synthetic hydrophilic compounds such as vinylpyrrolidone and polyacrylamide.

In the case of a synthetic hydrophilic compound, other components may be copolymerized, but if the amount of the hydrophobic copolymerization component is too large, the moisture absorption amount and the moisture absorption speed of the back layer will be small, which is not suitable from the viewpoint of curling. is there. These hydrophilic colloids may be used alone or in combination of two or more.

In the back layer of the present invention, other than the binder,
A photographic additive such as a matting agent, a surfactant, a dye, a cross-linking agent, a thickener, an antiseptic, a UV absorber, and inorganic fine particles such as colloidal silica may be added. Regarding these additives, for example, the description of Research Disclosure Vol. 176, Item 17643 (December 1978) can be referred to.

A polymer latex may be further added to the back layer of the present invention. The polymer latex used in the present invention is an aqueous dispersion of a water-insoluble polymer having an average particle size of 20 mμ to 200 mμ, and the preferable amount is 0.01 to 1.0 in terms of dry weight ratio to 1.0 of the binder, and particularly preferable. Is 0.1 to 0.8. Preferable examples of the polymer latex used in the present invention have acrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester, or methacrylic acid alkyl ester, hydroxyalkyl ester or glycidyl ester as a monomer unit and have an average molecular weight of 10 It is a polymer of 10,000 or more, particularly preferably 300,000 to 500,000, and a specific example is represented by the following formula.

[0019]

[Chemical 1]

The back layer of the present invention may be one layer or two or more layers. The thickness of the back layer of the present invention is not particularly limited, but from the viewpoint of curling, it is 0.2 μm to 20 μm.
It is preferably about 0.5 μm to 10 μm. When the back layer is composed of two or more layers, the sum of the thicknesses of all the back layers is the thickness of the back layer of the silver halide photographic light-sensitive material of the present invention.

The back layer of the present invention is substantially non-swelling in the processing liquid. The term “substantially non-swelling in the processing liquid” means that the thickness of the back layer after the water washing step during the development processing is 1.05 times or less than the thickness of the back layer after the drying step.

Since the back layer of the present invention uses a hydrophilic colloid such as gelatin as a binder, it swells in the processing liquid originally. However, in the present invention, a hydrophobic polymer layer (hereinafter referred to as a polymer layer) coated on this layer can be substantially unswelled in the processing liquid.

The method for applying the back layer of the present invention is not particularly limited. Conventionally known methods for coating a hydrophilic colloid layer of a silver halide photographic light-sensitive material can be used. For example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, or US Pat.
Extrusion coating method using a hopper described in 681294, or US Pat. Nos. 2,761,418 and 3,
The multilayer simultaneous coating method described in No. 508947 and No. 2761791 can be used.

Next, the hydrophobic polymer layer (polymer layer) of the present invention will be described. The polymer layer of the present invention is substantially non-swelling in the processing liquid. "Substantially non-swelling in the processing liquid"
The term "means that the thickness of the polymer layer after the washing step during the development treatment is 1.05 times or less the thickness of the polymer layer after the drying step.

The binder for the polymer layer of the present invention is not particularly limited as long as the polymer layer and the back layer are "substantially non-swelling in the processing liquid". Specific examples of the binder for the polymer layer include polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene, and polyfluorine. Fluorinated resins such as vinylidene chloride, rubbers such as butadiene rubber, chlorobrene rubber, natural rubber, esters of acrylic acid or methacrylic acid such as polymethylmethacrylate and polyethylacrylate, polyester resins such as polyethylene phthalate, nylon 6, nylon Polyamide resin such as 66, cellulose resin such as cellulose triacetate,
Mention may be made of water-insoluble polymers such as silicone resins or derivatives thereof.

Of these, particularly preferable are acrylic oxygen resins and urethane resins. Further, as a binder for the polymer layer, a homopolymer composed of one kind of monomer or a copolymer composed of two or more kinds of monomers may be used. These may be used alone or in combination of two or more.

In the polymer layer of the present invention, a photographic additive such as a matting agent, a surfactant, a dye, a slipping agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica may be added, if necessary. May be added. For these additives, Research Disclosure, Vol. 176, 176
The description in item 43 (December 1978) can be referred to.

The polymer layer of the present invention may be one layer or two or more layers. The thickness of the polymer layer of the present invention is not particularly limited. However, if the thickness of the polymer layer is too small, the water resistance of the polymer layer will be insufficient and the back layer will swell in the treatment liquid, which is inappropriate. On the contrary, when the thickness of the polymer layer is too large, the water vapor permeability of the polymer layer becomes insufficient, and the moisture absorption / desorption of the hydrophilic colloid layer of the back layer is impeded, resulting in poor curling. Of course, the thickness of the polymer layer also depends on the physical properties of the binder used. Therefore, the polymer layer thickness needs to be determined in consideration of both of them. The preferred thickness of the polymer layer depends on the binder species of the polymer layer, but is 0.05 to 10 μm.
m, more preferably 0.1 to 5 μm.

When the polymer layer of the present invention comprises two or more layers, the sum of the thicknesses of all the polymer layers is the thickness of the polymer layer of the silver halide photographic light-sensitive material of the present invention.

The method of applying the polymer layer of the present invention is not particularly limited. After coating and drying the back layer, a polymer layer may be coated on the back layer and then dried, or the back layer and the polymer layer may be coated simultaneously and then dried. The polymer layer may be dissolved in a solvent for the binder of the polymer layer and applied in a solvent system, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

The silver halide used in the present invention may be any of silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, silver chloroiodobromide and the like. . In the present invention, of the above silver halides, silver chloroiodobromide, silver chlorobromide and silver iodobromide are preferred. More preferably, the silver iodide content is 0 to
Silver chlorobromide or silver chloroiodobromide containing 1 mol% is advantageously used.

The average grain size of silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), and particularly preferably 0.5 μm or less. The particle size distribution is basically not limited, but it is preferably monodisperse.
The monodispersion as used herein means that at least 95% by weight or the number of particles is composed of a particle group having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion are cubic,
It may have a regular crystal such as an octahedron, or may have an irregular crystal such as a sphere or a plate, or may have a composite form of these crystal forms. It may be. The silver halide grains may have a uniform phase in the inside and the surface layer, or may have a simple phase. 2 formed separately
A mixture of two or more silver halide emulsions may be used.

The silver halide emulsion layer may be a single layer or multiple layers (two layers, three layers, etc.). In the case of multiple layers, different silver halide emulsions are used. They may be used or the same may be used. In the silver halide emulsion used in the present invention, a cadmium salt, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof and the like may coexist in the process of forming silver halide grains or physically ripening.

In the present invention, it is preferable to use a water-soluble rhodium salt, typically rhodium chloride, rhodium trichloride, rhodium ammonium chloride and the like. Furthermore, these complex salts can also be used. The addition time of the rhodium salt is limited before the completion of the first ripening at the time of emulsion production, and is preferably added during grain formation. The addition amount is 1 mol to 1 mol of silver, 1 × 10 ⁻⁸ mol or more. The range of ^{x10 -6} mol or less is preferable.

Particularly suitable silver halide for use in the present invention is prepared in the presence of 10 ^-8 to 10 ^-5 mol of iridium salt or its complex salt per mol of silver. In the above, it is desirable to add the above-mentioned amount of iridium salt before the physical ripening in the production process of the silver halide emulsion, especially at the time of grain formation. The iridium salt used here is a water-soluble iridium salt or iridium complex salt, such as iridium trichloride, iridium tetrachloride, hexachloroiridium (I
Examples thereof include potassium II) acid, potassium hexachloroiridium (IV) acid, and ammonium hexachloroiridium (III) acid.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, 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. , Polyvinyl alcohol partial acetal, poly-
N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole,
A wide variety of synthetic hydrophilic polymeric substances such as polyvinylpyrazole and other single or copolymers can be used.

The silver halide emulsion used in the present invention may not be chemically sensitized, but may be chemically sensitized. As a method of chemically sensitizing a silver halide emulsion, sulfur sensitization, selenium sensitization, reduction sensitization and noble metal sensitization are known, and any of these may be used alone or in combination. You may feel. Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, which uses a gold compound, mainly a gold complex salt.
Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained.

As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. As a reduction sensitizer, first tin salt,
Amines, formamidinesulfinic acid, silane compounds and the like can be used.

As the selenium sensitizer, the selenium compounds disclosed in conventionally known patents can be used. That is, usually, an unstable selenium compound and / or a non-unstable selenium compound is added at a high temperature, preferably 40
It is used by stirring the emulsion at a temperature of ℃ or more for a certain period of time. As the unstable selenium compound, Japanese Patent Publication No. 44-157
No. 48, Japanese Patent Publication No. 43-13489, Japanese Patent Application No. 2-130
It is preferable to use the compounds described in Japanese Patent Application No. 976 and Japanese Patent Application No. 2-229300.

The photographic light-sensitive material of the present invention is disclosed in JP-A-60-140340 and JP-A-60-140340 for the purpose of promoting high sensitivity and high contrast.
The compounds described in 1-167939 can be added. These may be used alone or in combination of two or more. The light-sensitive material of the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroindazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptothiadiazoles, aminotriazoles, benzothiazoles, nitrobenzotriazoles. , Etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetrazaine) Dens), pentaazaindene, etc .; many known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. It may be added compound. Among these, preferred are benzotriazoles (for example, 5-methylbenzotriazole) and nitroindazoles (for example, 5-nitroindazole). Further, these compounds may be contained in the treatment liquid.

The photosensitive silver halide emulsion of the present invention may be spectrally sensitized with a sensitizing dye into blue light, green light, red light or infrared light having a relatively long wavelength. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holoholer cyanine dye, a styryl dye, a hemicyanine dye, an oxonol dye, a hemioxonol dye and the like can be used.

Useful sensitizing dyes for use in the present invention are, for example, the RESEARCH DISCLOSURR Item.
17643 IV-A (December 1978 p. 2
3), Item 1831X of the same item (p. 4, August 1978).
37) or the literature cited. In particular, a sensitizing dye having a spectral sensitivity suitable for the spectral characteristics of various scanner light sources can be advantageously selected.

For example, as for A) an argon laser light source, JP-A-60-1
No. 62247, JP-A-2-48653, US Pat.
161,331, simple merocyanines described in West German Patent 936,071, and B) helium-neon laser light source are disclosed in JP-A Nos. 50-62425 and 54-1.
Nos. 8726 and 59-102229, for the trinuclear cyanine dyes and C) LED light source, Japanese Patent Publication No. 48-
No. 42172, No. 51-9609, No. 55-3981.
No. 8 thiacarbocyanines described in JP-A-62-284343 and D) tricarbocyanines described in JP-A-59-191032 and JP-A-60-80841 for semiconductor laser light sources. , JP-A-59-19
The dicarbocyanines containing a 4-quinoline nucleus described in 2242 are advantageously selected.

These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used especially for the purpose of supersensitization. Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance that does not substantially absorb visible light and exhibits supersensitization may be included in the emulsion. Useful sensitizing dyes, combinations of dyes exhibiting supersensitization, and substances exhibiting supersensitization are described in Research Disclosure (Research).
Disclosure) Volume 176 17643 (197)
(December 8th, 2012) Page 23, Item IV, J.

The content of the sensitizing dye of the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization,
It is desirable to select the optimum amount according to the relationship between the layer containing the compound and the silver halide emulsion, the kind of the antifoggant compound, etc. The test method for the selection is well known to those skilled in the art. Normally, it is preferably 10 ^-7 to 1 × 10 ^-2 mol, especially 1 mol per mol of silver halide.
It is used in the range of 0 ⁻⁶ to 5 × 10 ⁻³ mol.

Gelatin is used as the binder for the silver halide emulsion layer and the protective layer of the present invention, 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, polyvinyl alcohol partial acetal, poly-N-
Polysaccharide synthetic hydrophilic polymer substances such as vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers can be used.

As the gelatin, acid-treated gelatin may be used in addition to lime-processed gelatin, and gelatin hydrolyzate and gelatin enzyme-decomposed product may also be used. In the present invention, the coating amount of gelatin as a binder is preferably as small as possible in order to obtain rapid processing suitability and dimensional stability improvement. In particular, the gelatin coating amount of the protective layer greatly affects the developing rate and the fixing rate, and the total gelatin coating amount including the silver halide emulsion layer affects the drying rate and dimensional stability. Therefore, the gelatin coating amount of the protective layer of the present invention is 1.0 g / m ² or less, and preferably 0.
15 to 0.5 g / m ² , and the total gelatin coating amount on the side of the emulsion layer on the support including the silver halide emulsion layer is 5 g / m ² or less, preferably 1.5 to 4. 0 g / m
^{Is 2} .

The swelling ratio of the hydrophilic colloid layer on the emulsion layer side including the emulsion layer and the protective layer of the silver halide photographic light-sensitive material of the present invention may be 200% or less. Preferably 50 to 1
50%. It has been found that when the swelling ratio exceeds 200%, not only does the strength of the wet film decrease, but jamming easily occurs in the drying section of the automatic processor. Also,
When the swelling ratio is less than 50%, the developing speed and the fixing speed become slow, which adversely affects the photographic properties.

The swelling ratio of the hydrophilic colloid layer in the present invention is determined by measuring the thickness (d ₀ ) of the hydrophilic colloid layer including the emulsion layer and protective layer in the silver halide photographic light-sensitive material. Photosensitive material in distilled water at 25 ℃ 1
It is immersed for a minute, and the swollen thickness (Δd) is measured, and the swelling rate (%) = Δd ÷ d ₀ × 100 is calculated.
The thickness can be measured by the same principle as the electric micrometer described in JIS B7536.

For example, it can be measured with an electronic micrometer (K306 type) manufactured by Anritsu Electric Co., Ltd.

As a specific method for arbitrarily controlling the swelling ratio of the hydrophilic colloid layer including the silver halide emulsion layer and the protective layer in the present invention, an inorganic or organic gelatin hardener is used alone or in combination. There is a way.
For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis-
(Β- (vinylsulfonyl) propionamide) etc.)
Active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-morpholin, carbonyl-3-pyridinio) methanesulfonate, etc. ) Haloamidinium salts (1- (1
-Chloro-1-pyridinomethylene) pyrrolidinium, 2
-Naphthalene sulfonate, etc.) alone or in combination. Among them, JP-A-53-4122
0, 53-57257, 59-162546, 6
The active vinyl compounds described in 0-80846 and the active halogen compounds described in US Pat. No. 3,325,287 are preferred.

Typical compounds of the gelatin hardening agent are shown below.

[0054]

[Chemical 2]

[0055]

[Chemical 3]

[0056]

[Chemical 4]

In the present invention, for the purpose of improving pressure resistance without impairing sensitivity, a silver halide emulsion layer and / or
Alternatively, it is preferable to add colloidal silica and a polyhydroxybenzene compound to layers other than the emulsion layer. The colloidal silica (colloidal silica) used in the present invention has an average particle diameter of 5 mμ to 1000 mμ, preferably 5 mμ to 5 μm.
It is 00 mμ, the main component is silicon dioxide, and may contain alumina or sodium aluminate as a minor component. Further, these colloidal silica may contain, as a stabilizer, an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia, or an organic base such as tetramethylammonium ion.

These colloidal silicas are disclosed in JP-A-53-112732, JP-B-57-009051 and JP-B-57-051653. Specific examples of colloidal silica include Snowtex 20 (SiO ₂ / Na ₂ O ≧ 5) from Nissan Kagaku (Tokyo, Japan).
7), Snowtex 30 (SiO ₂ / Na ₂ O ≧ 5
0), Snowtex C (SiO ₂ / Na ₂ O ≧ 10
0), Snowtex O (SiO ₂ / Na ₂ O ≧ 50
0), etc. are marketed. Here, (SiO
₂ / Na ₂ O is the content weight ratio of silicon dioxide (SiO ₂ ) and sodium hydroxide in terms of sodium hydroxide converted into Na ₂ O, and each is the value described in the catalog. .

The colloidal silica used in the present invention is preferably used in a dry weight ratio of 0.05 to 1 with respect to the gelatin used as the binder of the layer to be added.
0, particularly preferably 0.1 to 0.6. The polyhydroxybenzene compound used in the present invention is Japanese Patent Application No.
The compounds described on page 37 line 10 line 10 to page 64 line 10 can be used.

In the present invention, the coefficient of dynamic friction of the outermost layer is preferably 0.35 or less. The dynamic friction coefficient (μk) in the present invention can be determined by the same principle as the friction coefficient test method described in JIS K7125. 25
After leaving the silver halide light-sensitive material for 1 hour or more under the condition of 60 ° C. RH and sapphire needle (eg diameter 0.5 to 5 m
m) constant load (contact force; Fp example 50-200g)
The surface of the silver halide light-sensitive material is slid at a constant speed (for example, 20 to 100 cm / min), the tangential force (Fk) at that time is measured, and it is determined by the following formula 1.

[0061]

[Equation 1]

For example, a surface quality measuring device (H
EIDON-14 type). In the present invention, it is preferable to use a so-called slipping agent in order to set the dynamic friction coefficient of the outermost layer to 0.35 or less. Typical examples of the slip agent used in the present invention are, for example, US Pat. No. 3,042,522 and British Patent No. 955,061.
U.S. Pat. Nos. 3,080,317 and 4,044.
927, 4,047,958, 3,489,5
67, British Patent No. 1,143,118, etc., silicone-based lubricants, US Pat. No. 2,454,043,
2,732,305, 2,976,148, 3,206,311 and German Patent Nos. 1,284,295.
No. 1,284,294, etc., higher fatty acid-based compounds,
Alcohol-based and acid amide-based lubricants, British Patent Nos. 1 and 26
3,722, U.S. Pat. No. 3,933,516 and other metallic soaps, U.S. Pat. Nos. 2,588,765, 3,121,060, British Patent 1,198,387.
And the like, and the taurine-based lubricants described in U.S. Pat. Nos. 3,502,473 and 3,042,222, the colloidal silica, and the like.

As the slip agent of the present invention, there is disclosed in JP-A-60-1.
The alkyl polysiloxane described in 88945, liquid paraffin in a liquid state at room temperature, and an anionic surfactant are preferable. The coating amount of the lubricant is 0.01 to 1.0 by weight ratio with respect to the binder amount of the outermost layer, and preferably 0.50.
~ 0.5. It is particularly preferably 0.01 to 0.1.

When an anionic surfactant is used, it is 0.001 to 0.5 g / m ² , especially 0.01 to 0.2 g.
/ M ² is preferable. The dynamic friction coefficient (μ _K ) is 0.35 or less, preferably 0.35 to 0.10.

In the present invention, the protective layer preferably comprises two or more layers. When the silver halide light-sensitive material is stored under low humidity conditions, it has a drawback that the film of the hydrophilic colloid layer becomes brittle. For the purpose of improving this, it is preferable that a polymer latex having a glass transition point (hereinafter referred to as Tg) of 20 ° C. or less is contained in the emulsion layer and / or the protective layer. In particular, when the number of protective layers is two or more, inclusion in the intermediate layer between the emulsion layer and the outermost layer does not impair the film strength in the developing solution and the brittleness of sensitive materials under high humidity conditions. Is preferable in terms of improving

The polymer latex contained in the protective layer of the present invention is, for example, US Pat. No. 2,772,1.
No. 66, No. 3,325, 286, No. 3,411, 91
No. 1, No. 3,311,912, No. 3,525,620
Issue, Research Disclosure
Disclosure) No. 195 19551
(July 1980) and the like, hydrates of vinyl polymers such as acrylic acid esters, methacrylic acid esters, and styrene.

Preferred polymer latexes having a Tg of 20 ° C. or lower are homopolymers of alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate, or copolymers of alkyl acrylates with acrylic acid and N-methylol acrylamide (preferably Is up to 30% by weight of a copolymerization component such as acrylic acid), a homopolymer of butadiene or a copolymer of butadiene and one or more of styrene, butoxymethyl acrylamide, acrylic acid, vinylidene chloride-methyl acrylate acrylic acid ternary Examples thereof include copolymers.

The Tg of the polymer latex can be determined by the method of differential scanning calorimetry (DSC). The preferred range of the average particle size of the polymer latex used in the present invention is 0.005 to 1 μm, and particularly 0.02 to 0.1 μm. The amount of the polymer latex added is 5 to 200%, especially 10 to 100% based on the weight of the hydrophilic colloid in the layer to be added.
Is preferred.

The non-photosensitive hydrophilic colloid layer dyed with a dye on the upper and / or lower part of the emulsion layer in the present invention (hereinafter referred to as a dyed layer) means halation prevention, improved safelight safety, and good front / back distinction. For the purpose of emulsification, a dyeing layer is coated on the upper and / or lower part of the emulsion layer. This hydrophilic colloid layer to be dyed usually contains a dye. This dye needs to satisfy the following conditions. (1) It has a proper spectral absorption according to the purpose of use. (2) Photochemically inactive. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog. (3) It should not be decolorized in the course of photographic processing or be dissolved in a processing solution or washing water to leave no harmful coloring on the photographic light-sensitive material after processing. (4) Do not diffuse from the dyed layer to other layers. (5) It has excellent stability over time in a solution or photographic material and should not discolor or fade.

As a dyeing method satisfying these conditions,
U.S. Pat. Nos. 3,455,693 and 2,548,56
No. 4, No. 4,124,386, No. 3,625,694
Nos. 47-13935, 55-33172, 56-36414, 57-161853 and 52-2.
9727, 61-198148, 61-17744.
7, a method of adsorbing the dyes described in JP-A-61-217039 and JP-A-61-219039 on a mordant, JP-A-61-2.
13839, 63-208846, 63-2960.
39, a method of using a diffusion-resistant dye described in JP-A-1-158439, a method of emulsifying and dispersing a dye dissolved in an oil described in Japanese Patent Application No. 1-142688 into oil droplets, US Pat.
719,088, 2,496,841, 2,4
96,843, JP-A-60-45237, Japanese Patent Application No. 1-
A method of adsorbing the dye described in 139691 etc. on the surface of an inorganic material, a method of adsorbing the dye described in Japanese Patent Application No. 11-19851 to a polymer, JP-A-56-12639 and JP-A-55-
155350, 55-155351, 63-278.
38, 63-197943, European Patent No. 15,60.
1, 274, 723, 276, 566, 299,
435, World Patent (WO) 88/04794, Japanese Patent Application No. 1
There is a method using a water-insoluble dye solid described in -87367 and the like. Among these methods, the method in which the dye is dispersed as a solid is preferable from the viewpoint of fixing the dye in the specific layer and reducing the residual color after the development processing.

The dye used in the dyeing layer of the present invention is at least 1 selected from the group consisting of the following general formulas (I) to (V).
Microcrystalline dispersions of individual compounds are preferred. General formula (I)

[0072]

[Chemical 5]

Formula (II)

[0074]

[Chemical 6]

Formula (III)

[0076]

[Chemical 7]

General formula (IV)

[0078]

[Chemical 8]

General formula (V)

[0080]

[Chemical 9]

(In the formula, A and A ′ may be the same or different and each represents an acidic nucleus, B represents a basic nucleus, and X represents
And Y may be the same or different and each represents an electron-withdrawing group. R represents a hydrogen atom or an alkyl group, R ₁ and R ₂ each represent an alkyl group, an aryl group, an acyl group or a sulfonyl group, and R ₁ and R ₂ may be linked to form a 5- or 6-membered ring. Good. R ₃ and R ₆ each represent a hydrogen atom, an alkyl group, a hydroxy group, a carboxyl group, an alkoxy group or a halogen atom, and R ₄ and R ₅ each represent a hydrogen atom or R ₁ and R ₄ or R ₂ and R ₃ are linked. Then 5 or 6
Represents a non-metal atom necessary to form a member ring. L ₁ , L
₂ and L ₃ each represent a methine group. m represents 0 or 1, n and q each represent 0, 1 or 2, and p is 0 or 1.
When p is 0, R ₃ represents a hydroxy group or a carboxyl group, and R ₄ and R ₅ represent a hydrogen atom.

However, general formulas (I), (II) and (II
The compounds represented by I), (IV) and (V) contain at least a dissociative group having a pKa in the range of 4 to 11 in a mixed solution of water and ethanol in a volume ratio of 1: 1 in one molecule. I have one.

Specific examples of the dyes used in the present invention will be given below, but the present invention is not limited to these.

[0084]

[Chemical 10]

[0085]

[Chemical 11]

[0086]

[Chemical 12]

[0087]

[Chemical 13]

The dye used in the present invention is the international publication WO8.
8/04794, European Patent Publication EP 02747
23A1, 276, 566, 299, 435
No. 52-92716, 55-155350.
No. 55, No. 55-155351, No. 61-205934.
No. 48-68623, US Pat. No. 2,527,583.
Nos. 3,468,897, 3,746,539, 39
No. 33798, No. 4130429, No. 4040841
No. 1, Japanese Patent Application No. 1-50874, No. 1-103751,
It can be easily synthesized according to the method described in JP-A-1-307363 and the like.

Since the dye itself in the microcrystalline dispersion of the present invention is insufficient in solubility, it cannot exist in a molecular state in the intended colored layer and substantially cannot diffuse in the layer. The state of existence as a solid of size is meant. The preparation method is described in International Publication (WO) 88/04794, European Patent Publication (EP) 0276566A1, JP-A-63-197943 and the like, but it is ball milled and stabilized with a surfactant and gelatin. It is common.

The particle size of the microcrystals of the dye used in the present invention is preferably 1.0 μm or less, more preferably 0.5 μm or less. The amount of dye used is 5 mg / m ^{2 to} 3
00 mg / m ² , especially 10 mg / m ^{2 to} 150 mg / m
It is preferably ² .

As the binder for the dyeing layer in the present invention, it is preferable to use the same binder as that for the emulsion layer and the protective layer. The gelatin coating amount of the dyed layer is the total gelatin coating amount used in the present invention (not including the BC layer), that is, 10 g.
The amount necessary for controlling the amount to be / m ² or less can be appropriately used. It is preferably 0.05 to 2.0 g / m ² .

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material of the present invention is described in JP-A-3-109542 P-5.
9 From the 1st line to the line of P-60 18th, various interfaces for various purposes such as coating aid, antistatic, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, contrast enhancement, sensitization). An activator may be included. The photographic light-sensitive material of the present invention may contain a matting agent such as silica, magnesium oxide and polymethylmethacrylate in the photographic emulsion layer and other hydrophilic colloid layers for the purpose of preventing adhesion.

The light-sensitive material of the present invention may contain a dispersion of a water-soluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate,
Glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with these, acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid It is possible to use a polymer having a monomer component of a combination of a hydroxyalkyl (meth) acrylate, a sulfoalkyl (meth) acrylate, and styrenesulfonic acid.

As the support of the light-sensitive material of the present invention, polyethylene-coated paper, polyethylene paper, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate and the like can be used, but polyethylene terephthalate film is most preferable. These supports may be subjected to corona treatment by a known method, or may be subjected to undercoating processing by a known method, if necessary.

A waterproof layer containing a polyvinylidene chloride-based polymer may be provided in order to improve the so-called dimensional stability, in which the dimension changes with changes in temperature and humidity.

The developing agent used in the developing solution used in the present invention is not particularly limited, but it is preferable to contain dihydroxybenzenes from the viewpoint of easily obtaining good halftone dot quality, and hydroquinone is used as the dihydroxybenzene developing agent. ,
Chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3
-Dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, etc., but hydroquinone is particularly preferable.

Preservatives for sulfite used in the present invention include sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.25 mol / liter or more, and particularly preferably 0.4 mol / liter or more. The upper limit is 2.
It is preferably up to 5 mol / liter, particularly up to 1.2.

Alkaline agents used to set the pH include sodium hydroxide, potassium hydroxide, sodium carbonate,
It contains a pH adjusting agent such as potassium carbonate and a buffering agent.

As additives used in addition to the above components, compounds such as boric acid and borax, development inhibitors such as sodium bromide, potassium bromide and potassium iodide; ethylene glycol, diethylene glycol, triethylene glycol, dimethylformamide. , Methyl cellosolve, hexylene glycol, ethanol, organic solvents such as methanol: 1-phenyl-5-mercaptotetrazole, 2-
Antifoggants such as mercapto-based compounds such as mercaptobenzimidazole-5-sulfonic acid sodium salt, indazole-based compounds such as 5-nitroimidazole, and benztriazole-based compounds such as 5-methylbenztriazole, or black potter (black pepper) prevention Agent;
May also be contained, and if necessary, toning agents, surfactants, defoaming agents, water softeners, hardeners, JP-A-56-106.
No. 244, JP-A-61-267,759 and Japanese Patent Application No. 1-
The amino compound described in No. 29418 may be included.

The developer used in the present invention contains a compound described in JP-A-56-24347 as a silver stain inhibitor.
Compounds described in JP-A-62-212,651 as development unevenness preventing agents, and JP-A-61-267,7 as dissolution aids.
The compound described in No. 59 can be used. The developing solution used in the present invention contains, as a buffer, Japanese Patent Application No. 61-28.
708, boric acid, saccharides (for example, sucrose) described in JP-A-60-93433, oximes (for example,
Acetoxime), phenols (for example, 5-sulfosalicylic acid) and the like are used.

The developing solution used in the present invention is described in JP-A-61-161.
It is preferable to store the packaging material having low oxygen and moisture permeability described in No. 73147. The replenishing system described in JP-A-62-91939 can be preferably used as the developing solution used in the present invention.

In addition to the fixing agent, the fixing solution contains a hardener,
A water-soluble aluminum compound may be included. It is known and widely used to incorporate a water-soluble aluminum compound in a fixing solution in order to harden the film surface of a light-sensitive material and improve the drying property. However, the water-soluble aluminum compound slows the fixing speed due to the film hardening action, and it is difficult to achieve both the drying property and the fixing property. Further, in order for the water-soluble aluminum compound to exist stably in the fixing solution, the pH of the fixing solution is
The value must be kept low, and there are problems such as the odor caused by acetic acid and SO ₂ gas in the fixing solution, and the rustiness of the developing machine.

In the present invention, since the back side of the light-sensitive material is substantially non-swelling, the drying load is greatly reduced, and a very small amount of the water-soluble aluminum compound was able to obtain desirable results. Further, as the fixing agent, ammonium thiosulfate has been conventionally used because of its high fixing speed, but there was a problem of odor due to generation of NH ₃ gas. In the present invention, the fixing speed is improved, and the fixing agent is N
More preferable results were obtained by using mainly sodium thiosulfate, which does not have the problem of H ₃ gas.

Examples of the water-soluble aluminum compound include aluminum chloride, aluminum sulfate, potassium alum and the like, and the preferable addition amount is 0 to 0.01 mol / l.
More preferably, it is 0 to 0.005 mol / l. As the fixing agent, sodium thiosulfate is preferable, and when used in combination with ammonium thiosulfate, ammonium ion (mol / l) is 20% of sodium ion (mol / l).
It is preferably the following or less, and more preferably 10% to 0%.

The pH of the fixing solution is preferably 5.0 or higher, more preferably 5.0 to 7.0. As the dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more as the dibasic acid in the fixing solution. It is effective that these compounds are contained in an amount of 0.005 mol or more per liter of the fixing solution, and particularly 0.01 mol / liter to 0.03 mol / liter is particularly effective.

Specific examples include tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like.

The fixing solution used in the present invention includes Japanese Patent Application No.
It is preferable to use the mesoionic compound described in -144226 together. The methyl ion compound is 1 × 10 ^-5 mol /
Liter to 10 mol / liter, especially 1 × 10 ⁻³ mol / liter
It is preferably used in the fixer or fixer replenisher in the range of 1 to 3 mol / liter.

Here, when the halogen composition of the silver halide emulsion in the light-sensitive material to be processed is silver iodobromide, it is 0.5-2.
It is preferably used in mol / liter, and in the case of silver bromide, silver chlorobromide, or high silver chloride emulsion (silver halide containing 80 mol% or more of silver chloride), 0.05 to 1 mol / liter It is preferable to use in the range of. If desired, the fixer may contain preservatives (eg, sulfite, bisulfite),
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, ammonia, sulfuric acid), an image preservation improving agent (eg, potassium iodide), and a chelating agent can be included. Since the pH of the developing solution is high, the pH buffer is used in an amount of 10 to 40 g / liter, more preferably about 18 to 25 g / liter.

For washing water, an antifungal agent (for example, "Chemistry of antibacterial and antifungal" by Horiguchi, JP-A-62-115154) can be used.
Compound), a water washing accelerator (such as sulfite), and a chelating agent. According to the above method, the developed and fixed photographic material is washed with water and dried.
Washing with water is carried out in order to almost completely remove the silver salt dissolved by fixing, and preferably at about 20 ° C. to about 50 ° C. for 5 seconds to 3 minutes.

Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 3,545,971.
In the present specification, it is simply referred to as a roller conveyance type processor. The roller conveyance type processor comprises four steps of developing, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, stopping step), but it is most preferable to follow these four steps. .

It is preferable to provide a rinse roller and a rinse tank for washing the rinse roller between the developing step and the fixing step of the automatic developing machine. The rinsing roller has one pair or two pairs of opposing rollers, and the rinsing tank is preferably running water or water, and the overflow liquid from the fixing tank may be introduced into the rinsing tank to use the fixing waste liquid as the rinsing liquid. Replenishment amount of rinse water is 20 ~ 500ml / m ²
And may be 50 to 300 ml / m ² . An acid, a sulfite or the like can be added to the rinse liquid. The rinse liquid may be circulated in the rinse tank, or may be applied as a shower from above the rinse roller.

In order to improve the fixing performance within the fixing solution temperature and time limited in the fixing step, the stirring amount of the fixing solution relative to the emulsion surface of the light-sensitive material (hereinafter simply referred to as the emulsion surface) is raised. It is effective to do it. In order to increase the relative agitation amount of the fixing solution, simply increasing the circulation amount of the solution locally causes the intensity of the agitation effect in the direction in which the photosensitive material is conveyed. In order to exert its effect on the entire emulsion surface, it is necessary to pass the light-sensitive material itself through the fixing solution faster. That is, there are optimum values for the liquid circulation speed, the circulation amount, and the line speed. As the optimum value, the fixing liquid circulation speed is 50 to 200 m / min, the circulation amount is 70 to 200% of the tank capacity of the fixing tank, and the line speed is 15 m.
/ Sec or more and 60 mm / sec or less.

In the washing process, the replenishing amount of the washing water is 1
It may be 200 ml / m ² or less (including 0). The case where the replenishment amount of the washing water (or the stabilizing solution) is 0 means a washing method by a so-called accumulated water washing method. As a method of reducing the replenishment amount, a multistage countercurrent method (for example, 2
Stages, 3 stages, etc.) are known.

Good processing performance can be obtained by combining the following techniques with the problems that occur when the replenishing amount of washing water is small. For the washing bath or stabilizing bath, R.
T. Kreiman, J. Image, Tech. V
ol. 10 No. 6242 (1984), isothiazoline compounds, Research Disclosure (RD) Vol. 205, No. 6 20526 (1981
, May issue), isothiazoline compounds, Vol. 228, No. 22845 (April, 1983 issue)
Isothiazoline compounds described in JP-A-61-161
No. 15,154, compounds described in JP-A No. 62-209,532 and the like are used as antibacterial agents (Microbiocid).
It can also be used together as e). Others, "The Chemistry of Antibacterial and Antifungal", Hiroshi Horiguchi, Sankyo Publishing (SHO 57), "Handbook of Antibacterial and Antifungal Technology", Japan Society of Antibacterial and Antifungal, Hakuhodo (Showa 6)
1), L.S. E. West “Water Quallit
y Criteria "Photo Sci & En
g. Vol. 9 No. 6 (1965), M.A. M. Be
ach “Microbiological Grow
ths in Motion Picture Pro
cessing "SMPTE Journal Vo
l. 85 (1976), R.I. O. Deegan “Pho
to Processing Wash Water
Biosides "J.Imaging Tech.V
ol. 10 No. 6 (1984).

When washing with a small amount of washing water in the method of the present invention, JP-A-63-18,350 and JP-A-62-2 are used.
It is more preferable to provide a squeeze roller and a crossover rack cleaning tank described in No. 87,252. Further, a part or all of the overflow solution from the washing or stabilizing bath of the present invention, which is produced by replenishing the washing or stabilizing bath with antifungal water depending on the treatment, is disclosed in JP-A-60-
No. 235,133 and JP-A No. 63-129,343, it can also be used for a processing solution having a fixing ability as a processing step before that. Further, a water-soluble surfactant or a defoaming agent is added to prevent unevenness of water bubbles, which is likely to occur when washing with a small amount of washing water, and / or to prevent transfer of a treating agent component attached to a squeeze roller to a treated film. You may add.

Further, the dye adsorbent described in JP-A-63-163,456 may be installed in the washing tank to prevent contamination by the dye eluted from the light-sensitive material. The light-sensitive material of the present invention exhibits excellent performance in rapid development processing by an automatic processor having a total processing time of 15 seconds to 90 seconds. In the rapid development process of the present invention, the temperature and time for development and fixing are each 25 seconds or less at about 25 ° C to 50 ° C, preferably 30 ° C to 40 ° C for 4 seconds to 15 seconds.

The total processing time in the present invention means that after the front end of the film is inserted into the insertion port of the automatic developing machine, the film is passed through the developing tank, the transition portion, the fixing tank, the transition portion, the washing tank, the transition portion and the drying portion. It is the total time until the leading edge of the film emerges from the drying outlet. In the present invention, for the purpose of improving the dimensional stability associated with the development processing, it is preferable to use an automatic processor that controls the drying temperature based on the environmental temperature and humidity conditions described in JP-A-3-174156.

[0118]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Example 1 A 100 μm-thick polyethylene terephthalate support having both surfaces coated with a subbing layer was simultaneously coated with a back layer and a polymer layer having the following formulations in order from the support in the order close to the support.
And dried for 5 minutes. (1) Back layer formulation Gelatin 3.0 g / m ² Polymethylmethacrylate fine particles (average particle size 3 μm) 50 mg / m ² Sodium dodecylbenzene sulfonate 10 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² N, N′-ethylene Bis- (vinyl sulfone acetamide) 40 mg / m ² Ethyl acrylate latex (average particle size 0.1 μm) 1.0 g / m ² (2) Polymer layer formulation Binder (type is as shown in Table-1) (Table-1) Poly Methyl methacrylate fine particles (average particle size 3 μm) 10 mg / m ² C ₅ F ₁₇ SO ₃ K 5 mg / m ² (distilled water is used as the solvent for the coating liquid)

Then, (3) dyeing layer (4) emulsion layer (5) protective layer lower layer and (6) protective layer upper layer having the following compositions were simultaneously coated on the surface opposite to the support. (3) Dyeing layer Gelatin 1.0 g / m ² * Compound example (dye III-5) 0.075 〃 * Compound example (dye III-3) 0.070 〃 phosphoric acid 0.015 〃 sodium dodecylbenzene sulfonate 0.015〃 Sodium polystyrene sulfonate 0.025〃 1,1'-bis (vinylsulfonyl) methane 0.030〃 * Method for preparing coating solutions of compound examples III-5 and III-3 The method of JP-A-63-197943 was applied.

That is, water (434 ml) and Triton X-200R surfactant (TX-200).
R) (53g) (sold by Rohm & Haas)
And a 6.7% solution of was placed in a 1.5 liter screw cap bottle. To this, 20 g of dye and zirconium oxide (ZrO
₂ ) Add beads (800 ml) (2 mm diameter), close the lid of this bottle tightly, place in the mill,
The contents were ground for 4 days.

The contents were treated with a 12.5% aqueous gelatin solution (1
60 g) and placed on a roll mill for 10 minutes to reduce foam. The resulting mixture was filtered to remove ZrO ₂ beads. Since the fine particles having an average particle size of about 0.3 μm were left as they were, the particles were classified by a centrifugal separation method so that the particle size was 1 μm or less.

[0122]

[Chemical 14]

(4) Emulsion Layer Preparation of Emulsion Liquid I Water 1000 ml Gelatin 20 g Sodium chloride 20 g 1,3-Dimethylimidazolidine-2-thione 20 mg Sodium benzenesulfonate 6 mg II liquid Water 400 ml Nitrate 100 g III liquid water 400 ml Sodium chloride 30 0.5 g Potassium bromide 14 g Potassium hexachloroiridium (III) ate (0.001% aqueous solution) 15 ml Ammonium hexabromorhodium (III) ate (0.001% aqueous solution) 1.5 ml Keep at 38 ° C., pH = 4.5 Solution I and solution II and III
The solution was added simultaneously with stirring for 10 minutes, and
16 μm core particles were formed. Subsequently, solutions IV and V described below were added over 10 minutes. Further, 0.15 g of potassium iodide was added to complete grain formation. IV solution Water 400 ml Silver nitrate 100 g V solution Water 400 ml Sodium chloride 30.5 g Potassium bromide 14 g K ₄ Fe (CN) ₆ 1 × 10 ⁻⁵ mol / mol Ag After that, washing with water by a flocculation method according to a conventional method, 40 g of gelatin was added.

This emulsion had a pH of 5.3 and a pAg of 7.
Adjust to 5, sodium thiosulfate 5.2mg, chloroauric acid 10.0mg and N, N-dimethyl selenourea 2.0m
g, 8 mg of sodium benzenesulfonate and 2.0 mg of sodium benzenesulfinate were added, and chemical sensitization was performed at 55 ° C. to obtain optimum sensitivity, and finally silver chloride 80
A silver iodochlorobromide cubic grain emulsion having an average grain size of 0.20 μm and containing mol% was prepared.

Then, a sensitizing dye was added at 5 × 10 ⁻⁴ mol / mol Ag for ortho-sensitization. Further, as antifoggants, hydroquinone and 1-phenyl-5-mercaptotetrazole were added to 2.5 g and 50 m, respectively, per mol of Ag.
g, colloidal silica (Nissan Chemical's Snowtex C,
An average particle size of 0.015 μm) was added to gelatin in an amount of 30% by weight, polyethyl acrylate latex (0.05 μm) was used as a plasticizer in an amount of 40% by weight of gelatin, and a hardening agent was 1,1′-bis ( Vinylsulfonyl) methane was added so that the swelling ratio on the emulsion side would be 1.50.

[0126] was coated with the coating solution Ag3.0g / m ^2, so as to become a gelatin 1.5g / m ^2.

[0127]

[Chemical 15]

(5) Protective layer lower layer formulation Gelatin per m ² 0.25 g Sodium benzenesulfonate 4 mg 1,5-Dihydroxy-2-benzaldoxime 25 mg Polyethyl acrylate latex 125 mg (6) Protective layer upper layer formulation Gelatin per m ² Gelatin 0.25 g Silica matting agent having an average of 2.5 μm 50 mg Compound (gelatin dispersion of slipping agent) 30 mg Colloidal silica (Snowtex C manufactured by Nissan Kagaku Co., Ltd.) 30 mg Compound-5 mg Sodium dodecylbenzenesulfonate 22 mg Dynamic friction coefficient of this sample is 0 .22 ± 0.03 (2
5 ℃ 60RH, Sapphire needle φ = 1mm, load 100
g, speed 60 cm / min).

[0129]

[Chemical 16]

These samples differ only in the back surface side and are common in the emulsion surface side. 25 samples obtained in this way
After storing in an atmosphere of 60 ° C RH for 1 week, the following evaluation was performed. (1) Swelling degree of treatment liquid of back layer and polymer layer Measurement of film thickness d of the back layer and polymer layer after washing with water: The sample after the washing with water of the following developing treatment is freeze-dried with liquid nitrogen. . By observing the section with a scanning electron microscope, d is determined for each of the back layer and the polymer layer.

Film thickness d _{0 of the} back layer and polymer layer after drying
Measurement of: d ₀ of each of the back layer and the polymer layer is obtained by observing a section of the sample after the completion of the drying step of the development processing described below with a scanning electron microscope.

(2) Running Test A running test was performed using each of the samples thus obtained. As the automatic processor, FG-360A manufactured by Fuji Photo Film Co., Ltd. was used. The sample was post-exposed to 50% blackening exposure, and the value obtained by dividing the tank capacity of the fixing tank of the automatic processor + the reduced replenishment amount (ml) by the number of processing m ² was 150 ml.
The test piece was crushed and run until it reached / m ² .
The reduced replenishment amount is the replenishment amount that is reduced by the treatment in order to keep the liquid level in the fixing tank constant. The fixing gap was evaluated by the transparency when the unexposed quartet size was processed after this crushing running. The evaluation criteria are as follows.

5: Totally transparent 4: 99% or more area is transparent 3: 95% or more area is transparent 2: 50% or more area is transparent 1: All surface is opaque

(3) Evaluation of sensitometry After performing Xe flash exposure for 10 ⁻⁶ seconds through an interference filter having a peak at 488 nm and a continuous wedge, development processing was performed. Sensitivity gives fog + density 1.5
Calculated from ogE.

A developer having the following composition was used, and the replenishing rate was 200 ml / m ² . (Developer) 1,2-dihydroxybenzene-3,5-sodium disulfonate 0.5 g Diethylenetriamine-pentaacetic acid 2.0 g Sodium carbonate 5.0 g Boric acid 10.0 g Potassium sulfite 85.0 g Sodium bromide 6.0 g Diethylene glycol 40.0 g 5-methylbenzotriazole 0.2 g hydroquinone 30.0 g 4-hydroxymethyl-4-methyl-1-phenyl-3-pyrazolidone 1.6 g 2,3,5,6,7,8-hexahydro-2- Thioxo-4- (1H) -quinazolinone 0.05 g 2-Mercaptobenzimidazole-5-sodium sulfonate 0.3 g Potassium hydroxide was added and water was added to 1 liter to pH.
Was adjusted to 10.7.

A fixing solution having the following composition was used. (Fixer-1) Sodium thiosulfate 1.0 mol / l 1,4,5-Trimethyl-1,2,4-triazolium-3-thiolate 0.1 mol / l Sodium bisulfite 30 g / l EDTA.4 acetic acid Disodium salt 0.02 g / liter Adjusted to pH = 6.0 with sodium hydroxide (fixing solution-2) Ammonium thiosulfate 1.0 mol / liter 1,4,5-trimethyl-1,2,4-triazolium- 3-thiolate 0.1 mol / liter sodium bisulfite 30 g / liter EDTA.4 acetic acid disodium salt 0.02 g / liter acetic acid (90%) 30 g / liter aluminum sulfate (27%) 20 g / liter pH with sodium hydroxide = Adjusted to 4.8

The automatic processor was processed under the following conditions. Developer temperature, time 38 ° C, 20 ″ Fixer temperature, time 38 ° C, 19 ″ Rinse water flow rate ^* 300 ml / min Line speed 13 mm / sec * Rinse water flow rate is only while the photosensitive material is passing through the rinse part. Was supplied to the rinse tank (volume 300 ml). Also, as a comparative example, the experiment was performed under the condition that the rinse water was not flown (the rinse tank was empty).

The results obtained are shown in Table 1. As is clear from Table 1, the samples of the present invention were
It can be seen that fixing fatigue is small and fixing loss is good.

[0139]

[Table 1]

Example 2 An undercoat layer having the following composition, the first layer and the second layer, were formed on both surfaces of a biaxially stretched polyethylene terephthalate support (thickness: 100 μm).
After applying the layer, a conductive layer having the following composition (surface resistivity: 2 × 10 ¹⁰ Ω at 25 ° C. and 10% RH), a back layer and a polymer layer were simultaneously applied to one surface.

<First Layer of Undercoat Layer> Aqueous dispersion of copolymer of vinylidene chloride / methyl methacrylate / acrylonitrile / methacrylic acid (90/8/1/1 by weight ratio) 15 parts by weight 2,4- Dichloro-6-hydroxy-s-triazine 0.25 part by weight Polystyrene fine particles (average particle size 3 μm) 0.05 part by weight Compound-6 0.20 part by weight Water is added 100 parts by weight Further, 10% by weight of KOH is added. In addition, after the pH of the coating solution was adjusted to 6, the drying film was dried at a temperature of 180 ° C. for 2 minutes to give a dry film thickness of 0.1.
It was applied so as to be 9 μm. Gelatin 1 part by weight methylcellulose 0.05 part by weight compound -7 0.02 part by weight <Second layer undercoat _{layer> C 12 H 25 O (CH} 2 CH 2 O) 10 H 0.03 part by weight compound -8 3. 5 × 10 ^-2 parts by weight Acetic acid 0.2 parts by weight Water was added to 100 parts by weight This coating solution was applied at a drying temperature of 170 ° C. for 2 minutes so that the dry film thickness was 0.1 μm. <Conductive layer> SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 300 mg / m ² gelatin (Ca ^** content 30 ppm) 170 mg / m ² compound-8 7 mg / m ² dodecylbenzenesulfonic acid Sodium 10 mg / m ² Dihexyl-α-sulfosuccinate sodium salt 40 mg / m ² Polystyrenesulfonic acid sodium salt 9 mg / m ²

[0142]

[Chemical 17]

<Back Layer Formulation> Gelatin 2.5 mg / m ² Polymethylmethacrylate fine particles (average particle size 3 μ) 50 mg / m ² Sodium dodecylbenzene sulfonate 10 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² N, N ′ -Ethylene bis- (vinyl sulfone acetamide) 25 mg Ethyl acrylate latex (average particle size 0.1 µ) 1.0 g / m ² <Polymer layer formulation> Polymer layer thickness (polymer type is shown in Table 2) 1.0 µm Polymethyl Methacrylate fine particles (average particle size 3 μ) 10 mg / m ² C ₈ F ₁₇ SO ₃ K 5 mg / m ² (distilled water was used as the solvent for the coating flow) A sample without a polymer layer was also prepared as a comparative example.

Then, a dye layer, an emulsion layer and a protective layer lower layer / protective layer upper layer having the following compositions were simultaneously coated on the surface opposite to the support. <Dyeing layer> Gelatin 1.5 g / m ² * Compound example (dye III-5) (same as in Example 1) 0.050 g / m ² * Compound example (dye III-3) (〃) 0.070 g / m ² * compound example (dye III-6) 0.070g / m ² phosphate 0.020 g / m ² sodium dodecylbenzenesulfonate 0.015 g / m ² polystyrene sulfonic acid sodium 0.020 g / m ² 1,1' Bis (vinylsulfonyl) methane 0.030 g / m ² * Coating solutions of compound examples III-5, III-3 and III-6 were prepared in the same manner as in Example 1.

[0145]

[Chemical 18]

80 mg of a sensitizing dye was added to the emulsion of Example 1 per 1 mol of Ag, and then 4,4'-bis (4,6-dinaphthoxy-pyrimidin-2-ylamino) was used as a supersensitizer and a stabilizer. -Stilbene disulfonic acid disodium salt and 2,5-dimethyl-3-allyl-benzothiazole iodo salt were added in an amount of 300 m / mol Ag, respectively.
g and 450 mg were added, and infrared sensitization was performed. Further, an antifoggant, a plasticizer, a hardener, and colloidal silica were used in Example 1.
In addition to the same as above, Ag 3.0 g / m ² , gelatin 1.2 g
It was applied so as to be / m ² . A lower layer and an upper layer of a protective layer having the following composition were simultaneously coated thereon. (Lower layer of protective layer) Gelatin 0.25 g / m ² compound-9 20 mg / m ² compound-10 10 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² polyethyl acrylate latex (0.05 μ) 150 mg / m ² (protection Layer Upper layer) Gelatin 0.25 g / m ² polymethylmethacrylate fine particles (average particle size 3.4 μ) 60 mg / m ² colloidal silica (Nissan Chemical Snowtex C) 30 mg / m ² compound- (gelatin dispersion of lubricant) 30 mg / m ² sodium dodecylbenzene sulfonate 40 mg / m ² Compound example III-3 50 mg / m ² compound-11 10 mg / m ²

[0147]

[Chemical 19]

A running test was carried out in the same manner as in Example 1 using each of the samples thus obtained. As the automatic developing machine, FG-360A manufactured by Fuji Film Co., Ltd. was modified and used. The modified point was to change the gear ratio of the drive motor to increase the line speed. The rinsing roller was removed between development and fixing, and a guide plate was installed instead. The circulation speed of the fixer was variable. The automatic processor was set under the following conditions for processing.

Developer temperature, time 38 ° C., 15 ″ Fixer temperature, time 38 ° C., 14 ″ Line speed 17 mm / sec Circulating speed of fixing solution (m / min) and circulating amount at that time (% of tank capacity) ( 1) 40% at 30 m / min (2) 130% at 100 m / min The developer used was the same as in Example 1, and the fixer used was Fixer-1 used in Example 1. For sensitometry, the interference filter of Example 1 was changed to a filter having a peak at 780 nm for exposure. The results are shown in Table 2.
As is clear from Table 2, the samples of the present invention are excellent even in rapid processing without the deterioration of fixing loss due to running.

[0150]

[Table 2]

[0151]

According to the present invention, the fatigue of the fixing solution is reduced when the processing is performed by using the automatic developing machine, and the good fixing performance is obtained even in the rapid processing.

Claims (4)

[Claims] 1. A silver halide emulsion layer is coated on a support, and a non-photosensitive gelatin layer having a thickness of 0.5 μm or more is provided on the surface opposite to the surface of the silver halide emulsion layer. Have,
An automatic developing machine is used for a light-sensitive material having a hydrophobic polymer layer at a position farther from the support than the non-light-sensitive gelatin layer, and the non-light-sensitive gelatin layer and the hydrophobic polymer layer are substantially non-swelling during processing. The method for processing a silver halide photosensitive material is characterized in that the processing is carried out by using an automatic developing machine having a rinse tank and a rinse roller between the developing step and the fixing step. 2. A non-photosensitive hydrophilic colloid layer dyed with a dye is provided on the upper and / or lower part of the silver halide emulsion layer of the light-sensitive material.
The processing method described in. 3. The fixing solution used in the treatment has ammonium ions (mol / liter) of 20% or less of sodium ions (mol / liter) and the water-soluble aluminum salt in the fixing solution is 0.01 mol / liter or less. , P of fixer
H is 5.0 or more, The processing method of Claim 1 or 2 characterized by the above-mentioned. 4. The fixing time in an automatic processor is 19 seconds to 5 seconds.
Second, the circulation speed of the fixing solution is 50 to 200 m / min, the circulation amount per minute is 70 to 200% of the tank capacity of the fixing tank, and the line speed is 15 to 60 mm / second. The processing method according to claim 3.