JPH06295011A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide the silver halide photosensitive material which is good in drying property, carry over and fixing drop-out when subjected to rapid development processing with a low replenishing amt. CONSTITUTION:This silver halide photographic sensitive material has silver halide emulsion layers consisting of high silver chloride particles having at least 90mol% average silver chloride content and having locally existing phases of a silver bromide on the surface on a transparent base having >=150mum thickness and having at least one layer of nonphotosensitive hydrophilic colloidal layers on the surface on the side opposite to the silver halide emulsion layers. The hydrophilic colloid binder ratio of the surface coated with the nonphotosensitive hydrophilic colloidal layers and the surface coated with the silver halide emulsion layers of this photographic sensitive material is >=0.3 by weight and the moisture content of the surface provided with the nonphotosensitive hydrophilic colloidal layers after the end of a washing stage at the time of development processing is <=0.2g per 1g hydrophilic colloid binder. The silver halide photographic sensitive material for medical purposes is thus obtd.

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 in particular, the amount of replenisher of developer and fixer per unit area of light-sensitive material when processed by an automatic processor. The present invention relates to a silver halide photographic light-sensitive material for medical use which can be reduced in number and is excellent in rapid processability, and a processing method thereof.

[0002]

2. Description of the Related Art A silver halide photographic light-sensitive material for medical use is generally processed in steps of developing, fixing, washing with water and drying after exposure. Recently, most of them are processed by using an automatic processor (hereinafter, abbreviated as an automatic processor). At this time, the developing solution is placed in the developing tank of the developing machine in a state of being in contact with air, and the photosensitive material is appropriately processed. It has been desired that the developer has high stability when subjected to such processing. Furthermore, it has been desired to reduce the amount of replenisher required per unit area of the light-sensitive material. In the past, it was general to replenish a so-called sheet-shaped photographic light-sensitive material 1 m ² such as a light-sensitive material for X-ray photography or graphic arts with a developing solution and a fixing solution of about 330 ml or more. However, photographic developing and fixing effluents have high chemical oxygen demands (so-called C.O.
D) or biological oxygen demand (so-called BOD), the development and fixing waste liquids are subjected to chemical or biological treatment to be rendered harmless before being discharged. There is. Since a great economic burden is imposed on the treatment of these waste liquids, a treatment method with a small amount of development and fixing replenishment has been desired. On the other hand, high silver chloride content (at least 90%)
The use of a silver halide emulsion (more than mol%) is very advantageous for reducing the developing replenisher amount. This is because in the case of silver bromide, bromine ions are released and accumulate in the developer after development. When the amount of the replenisher is small, the accumulated bromine ions increase and the development suppressing action becomes large, which has a great adverse effect on the photographic performance. On the other hand, in the case of silver chloride, chloride ions are accumulated, but the development inhibiting effect is much smaller than that of bromine ions, and there is substantially no effect. However, no matter how high a silver chloride silver halide emulsion is used to reduce the amount of the developer replenisher, the developer carried out by the light-sensitive material, so-called carryover, accumulates in the fixer and the fixing ability is lowered. For,
Fixing of the photosensitive material is poor. Therefore, conventionally, it has been difficult to reduce the amount of fixing replenisher.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to develop a silver halide photographic light-sensitive material using an automatic processor, and to fix the silver halide photographic material. An object of the present invention is to provide a possible photographic light-sensitive material and a processing method thereof.

[0004]

The above object of the present invention is to provide a silver halide emulsion layer comprising high silver chloride grains having an average silver chloride content of at least 90 mol% and having a silver bromide localized phase on the surface. In a silver halide photographic light-sensitive material having a transparent support having a thickness of 150 μm or more, and having at least one non-light-sensitive hydrophilic colloid layer on the surface opposite to the silver halide emulsion layer. If the weight ratio of the hydrophilic colloid binder between the surface coated with the photosensitive hydrophilic colloid layer (B surface) and the surface coated with the silver halide emulsion layer (A surface) is 0.3 or more. , The surface on which the non-photosensitive hydrophilic colloid layer is coated after the washing step at the development processing (B
The surface water content was 0.2 g or less per 1 g of the hydrophilic colloid binder.

A specific configuration of the present invention will be described in detail. The high silver chloride contained in the photographic emulsion layer of the photographic light-sensitive material used in the present invention contains silver chloride of 90 mol% or more (average value), silver chlorobromide, silver iodochloride, silver iodochlorobromide or chloride. It is silver. The silver iodide content is preferably 1 mol% or less. Particularly preferred is silver chlorobromide or silver chloride containing 96 mol% or more (average value) of silver chloride. The high silver chloride emulsion used in the present invention has a silver bromide localized phase whose silver bromide content is relatively higher than that of the substrate on the surface of the silver halide grain.

A preferred example of such a localized structure may be a thin shell-like structure, but it is particularly one having a localized phase in the form of protrusions on the edges or corners of the crystal surface of the grain, or on the crystal plane. The halogen composition in the localized phase may be 10 mol% or more and 95 mol% or less in terms of silver bromide content.
It is preferably 5 mol% or more and 90 mol% or less. Further, it is preferably 20 mol% or more and 60 mol% or less, and most preferably 30 mol% or more and 60 mol% or less. The remaining silver halide in the localized phase consists of silver chloride, but it is also preferred to include traces of silver iodide. However, as described above, it is not preferable to exceed 1 mol% with respect to the total amount of silver halide. Further, these localized phases preferably account for 0.03 mol% or more and 10 mol% or less, more preferably 0.1 mol% or more and 10 mol% or less of the silver halide constituting all the silver halide grains of the emulsion. It is preferable to occupy mol% or less. The localized phase does not have to consist of a single halogen composition, may have two or more localized phases having distinctly different silver bromide contents, and may have a phase other than the localized phase. The interface may be formed so that the halogen composition changes continuously. In order to form a silver bromide localized phase as described above, a water-soluble silver salt and a water-soluble halogen salt containing a water-soluble bromide are simultaneously mixed with an emulsion containing silver chloride or high silver chloride grains already formed. And deposit it, or convert part of the already formed silver chloride or high silver chloride particles into a silver bromide-rich phase by using the so-called halogen conversion method, or silver chloride or high silver chloride particles. It can also be formed by adding fine grained silver bromide or high silver bromide grains or other sparingly soluble silver salt to crystallize the surface of silver chloride or high silver chloride grains by recrystallization.

Such a manufacturing method is also described in, for example, European Patent Application Publication No. 0,273,430A2. The silver bromide content of the localized phase can be determined by X-ray diffraction (for example, “Chemical Society of Japan, New Experimental Chemistry Course 6, Structural Analysis” Maruzen,
Or an XPS method (for example, "Surface analysis, -IM"
A, Application of Auger electron / photoelectron spectroscopy- "Kodansha)) and the like. Further, the localized phase of silver bromide is observed by an electron microscope and the above-mentioned European Patent Application Publication Nos. 0, 2
It can also be found by the method described in No. 73,430A2. Of these methods, the method of forming a localized silver bromide phase particularly useful in the present invention is a method of forming silver bromide on the surface of a high silver chloride emulsion during chemical ripening. , Add fine grain silver bromide or silver chlorobromide, which has a higher solubility than the chemically ripened silver chloride grains during chemical ripening, to form a localized phase of silver bromide or silver chlorobromide on the high silver chloride grains. Forming is desirable from the viewpoint of high sensitivity and low fog.

An iridium compound is preferably used in the silver halide emulsion of the present invention. As the iridium compound used in the present invention, a water-soluble iridium compound can be used. For example, iridium (III) halide
Compounds, iridium (IV) halide compounds, and iridium complex salts having halogens, amines, oxalates, etc. as ligands, such as hexachloroiridium (III) or (IV) complex salts, hexaammineiridium (III) or ( IV) complex salt, trioxalatoiridium (III) or (IV) complex salt and the like. In the present invention, any of these compounds may be used in any combination of a trivalent compound and a trivalent compound. These iridium compounds are used by dissolving them in water or a suitable solvent, and they are generally used to stabilize the solution of the iridium compound, that is, a hydrogen halide aqueous solution (for example, hydrochloric acid, hydrobromic acid, hydrofluoric acid, etc.). , Or an alkali halide (eg KCl, NaCl, KBr, NaB
r etc.) can be used. Instead of using water-soluble iridium, it is also possible to add and dissolve another silver halide grain which has been previously doped with iridium when preparing the silver halide grain. The total addition amount of the iridium compound according to the present invention is 1 × 10 ⁻⁸ mol, preferably 1 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol, per 1 mol of finally formed silver halide, More preferably, it is 5 × 10 ⁻⁸ to 1 × 10 ⁻⁶ mol. The addition of these compounds can be appropriately carried out at the time of producing the silver halide emulsion and at each stage before coating the emulsion, but in particular, it can be added at the time of grain formation and incorporated into the silver halide grains. preferable. Specific compounds include primary iridium (III) chloride, primary iridium (III) bromide, secondary iridium (IV) chloride, sodium hexachloroiridium (III) salt, hexachloroiridium (III) salt, hexaamineiridium ( Preferred are halogen amines such as IV) salts, trioxalite iridium (III) salts, trioxalatoiridium (IV) salts, and oxalate complex salts.

The silver halide grains used in the present invention include
Metal ions other than silver and iridium ions (for example, metal ions of Group VIII of the periodic table, transition metal ions of Group II,
It is more preferable to contain a group IV lead ion, a group I metal ion, a copper ion or the like) or a complex ion thereof in order to more effectively exert the effects of the present invention under various conditions. The metal ions or complex ions thereof may be contained in the entire silver halide grains, the above-described silver bromide localized phase, or any other phase. Among the above metal ions or complex ions thereof, those selected from iridium ion, palladium ion, rhodium ion, zinc ion, iron ion, platinum ion, gold ion, copper ion and the like are particularly useful. It is often the case that these metal ions or complex ions are used in combination, rather than being used alone, to obtain desirable photographic properties. In particular, it is necessary to change the added ionic species and the added amount between the localized phase and other parts of the particle. Is preferred.

In order to incorporate a metal ion or a complex ion into the localized phase of the silver halide grain and / or the other portion of the grain, the metal ion or the complex ion is formed before, during or after the formation of the silver halide grain. It may be added directly to the reaction vessel during the subsequent physical ripening, or may be added in advance in the addition solution of the water-soluble halogen salt or water-soluble silver salt. When the localized phase is formed of fine grain silver bromide or high silver bromide, it is added to silver bromide or high silver bromide fine grains by the same method as above, and then added to silver chloride or high silver chloride emulsion. You may.

The size of the silver halide grains used in the present invention is such that the diameter corresponding to the projected area circle is not larger than 0.3 μm,
It is preferably 0.28 μm or less. This is desirable because the particles having a small size can obtain high covering power.

The size distribution of silver halide grains may be wide or narrow, but so-called monodisperse emulsions are better in terms of photographic characteristics such as latent image stability and pressure resistance, and processing stability such as developer pH dependency. preferable. The value S / d obtained by dividing the standard deviation S of the diameter distribution when the projected area of silver halide grains is converted into a circle by the average diameter is preferably 20% or less, more preferably 15% or less.

The silver chloride, silver chlorobromide or silver chloroiodobromide emulsion used in the present invention is described in "Chemistry and Physics of Photography" by P. Glafkides (Graphkide) (Paul Montel, 1967).
), GF Duffin, "Photoemulsion Chemistry"
(Focal Press, 1966), VL Zelikman
(Zeulicmann) et al. "Preparation and coating of photographic emulsions"
(Focal Press Co., 1964) and the like. That is, the acidic method,
Either a neutral method or an ammonia method may be used, but the acidic method and the neutral method are particularly preferable in the present invention in terms of reducing fog. To obtain a silver halide emulsion by reacting a soluble silver salt with a soluble halogen salt, any one of so-called one-side mixing method, simultaneous mixing method or a combination thereof may be used. It is also possible to use a so-called reverse mixing method in which grains are formed under the condition of excess silver ions. In order to obtain the monodisperse grain emulsion preferred in the present invention, it is preferable to use the simultaneous mixing method. As one form of the simultaneous mixing method, it is more preferable to use a method of keeping the silver ion concentration in the liquid phase where silver halide is produced constant, that is, a so-called controlled double jet method. By using this method, it is possible to obtain a silver halide emulsion suitable for the present invention, which has a regular silver halide crystal shape and a narrow grain size distribution.

In the course of such grain formation or physical ripening of silver halide, a cadmium salt, a zinc salt, a lead salt, a thallium salt, or the iridium salt or its complex salt, a rhodium salt or its complex salt, an iron salt as described above. Alternatively, its complex salt may coexist. During or after grain formation silver halide solvents (eg, as known, ammonia, thiocyanates, U.S. Pat. No. 3,271,1).
57, JP-A-51-12360, JP-A-53-82.
408, JP-A-53-144319, JP-A-54-
No. 100717 or thioethers and thione compounds described in JP-A No. 54-155828, etc. may be used. When used in combination with the above-mentioned method, the present invention has a regular silver halide crystal shape and a narrow grain size distribution. A preferable silver halide emulsion can be obtained. In order to remove the soluble salt from the emulsion after physical ripening, Nudel water washing, flocculation sedimentation method, ultrafiltration method or the like can be used. The emulsion used in the present invention can be chemically sensitized by sulfur sensitization, selenium sensitization, reduction sensitization, noble metal sensitization, etc., alone or in combination. That is, active gelatin or a compound containing a sulfur compound capable of reacting with silver ions (for example, thiosulfate, thiourea compound, mercapto compound,
Sulfur sensitization using a rhodanine compound, etc.), reducing substances (such as stannous salts, amines, hydrazine derivatives,
Reduction sensitization using formamidinesulfinic acid, silane compounds, etc., and metal compounds (eg, the above-mentioned gold complex salts, platinum, iridium, palladium, rhodium, iron, etc., Group VIII metal salts or complex salts thereof, etc.) Noble metal sensitization method using a) can be used alone or in combination. In the emulsion of the present invention, sulfur sensitization or selenium sensitization is preferably used, and gold sensitization is preferably used in combination with these. In addition, in these chemical sensitization,
The presence of a hydroxyazaindene compound or a nucleic acid is preferable for controlling sensitivity and gradation.

Next, the non-photosensitive hydrophilic colloid layer (hereinafter referred to as the back layer) of the present invention will be 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 gelatin, so-called lime-processed gelatin, acid-processed gelatin, enzyme-processed gelatin, gelatin derivatives, modified gelatin, and the like commonly used in the art can be used. Among these gelatins, lime-processed gelatin and acid-processed gelatin are most preferably used.

As hydrophilic colloids other than gelatin, colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as 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 the 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 rate of the back layer become small, which is unsuitable from the viewpoint of curling. 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 preferably about 0.2 μ to 20 μ, and particularly preferably 0.5 μ to 10 μ. When the back layer consists of two or more layers, the sum of the thickness of all back layers is
The thickness of the back layer of the silver halide photographic light-sensitive material of the present invention.

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.

The back layer of the present invention may be composed of one layer or two or more layers. When the back layer is a single layer, it is preferable to provide the hydrophobic polymer layer of the present invention as an adjacent layer at a position far from the support of the back layer. When the back layer is composed of two or more layers, it is preferable to provide the hydrophobic polymer layer of the present invention as an adjacent layer located at a position far from the support of at least one layer of the back layer.

The total amount of hydrophilic colloids in the back layer of the present invention is 0.3 of the total amount of hydrophilic colloids on the surface (A-side) on which the silver halide emulsion layer is coated (total emulsion surface hydrophilic colloids). More than double (weight ratio). The proper value of the total hydrophilic colloid of the back layer / the total hydrophilic colloid of the emulsion surface (weight ratio) varies depending on the total amount of the hydrophilic colloid of the silver halide photographic light-sensitive material, the coated silver amount, and the thickness of the support. If the value is too small, the curl becomes poor.

The silver halide photographic light-sensitive material of the present invention has a water content of 0.2 g or less per 1 g of the hydrophilic colloid after the completion of the water washing step during the development processing of the back surface.

There is no particular limitation on the means for controlling the water content per 1 g of the hydrocolloid after development on the back surface of the silver halide photographic light-sensitive material of the present invention to 0.2 g or less. However, by controlling the amount of hydrocolloid on the back side and the amount of crosslinking agent added on the back side, the water content per 1 g of hydrocolloid cannot be reduced to 0.2 g or less without deteriorating curling. It is preferable to apply the hydrophobic polymer layer of the invention to prevent the back layer located closer to the support than this layer from swelling and reduce the water content after the development treatment.

Next, hydrophobic polymer layer (polymer layer)
I will describe. The water content of surface B of the silver halide photographic light-sensitive material of the present invention at the end of the washing step can be controlled to 0.2 g or less per 1 g of the hydrocolloid by this polymer layer. As the binder of the polymer layer, a hydrophobic polymer is used to prevent the back layer from swelling in the treatment liquid. There are no restrictions on the materials as long as these conditions are satisfied. Specific examples of the binder for the polymer layer include polyethylene,
Fluorine resin such as polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyvinyl acetate, urethane resin, urea resin, melamine resin, phenol resin, epoxy resin, tetrafluoroethylene, polyvinylidene fluoride, butadiene rubber,
Rubbers such as chloroprene rubber and natural rubber, esters of acrylic acid or methacrylic acid such as polymethylmethacrylate and polyethylacrylate, polyester resins such as polyethylene phthalate, polyamide resins such as nylon 6 and nylon 66, cellulose resins such as cellulose triacetate. , Water-insoluble polymers such as silicone resins, or derivatives thereof. 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.

If desired, photographic additives such as a matting agent, a surfactant, a dye, a slipping agent, a cross-linking agent, a thickener and a UV absorber may be added to the polymer layer of the present invention. . Regarding these additives as well, the description in Research Disclosure Vol. 176, Item 17643 (December 1978) and the like 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, it is necessary to determine the thickness of the polymer layer 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 polymer.

It is preferable that the surface A of the present invention has a layer (hereinafter referred to as a dyed layer) which is substantially decolorized by the development processing. The dyeing layer preferably used in the present invention is a hydrophilic colloid layer containing a dye or other coloring substance that is decolorized or dissolved and removed in the development processing step. As a method for dyeing a dyeing layer, US Pat. Nos. 3,455,693 and 2,
548,564, 4,124,386, 3,6
25,694, JP-A-47-13935, 55-
No. 33172, No. 56-36414, No. 57-161.
No. 853, No. 52-29727, No. 61-19814.
No. 8, No. 61-177447, No. 61-217039.
No. 61-219039 and the like, a method of adsorbing a dye to a mordant, JP-A-61-213839 and 63.
-208846, 63-296039, JP-A-1
-158439, etc., using a diffusion resistant dye,
A method of emulsifying and dispersing a dye dissolved in an oil in the form of oil droplets, as described in Japanese Patent Application No. 1-142688, US Pat. No. 2,719,
088, 2,496,841 and 2,496,8
43, JP-A-60-45237, and JP-A-3-574.
Method of adsorbing the dye described in No. 8 or the like on the surface of an inorganic substance, method of adsorbing the dye described in JP-A-2-298939 to a polymer, JP-A-56-12639 or 55-15
No. 5350, No. 55-155351, No. 63-278.
38, 63-197943, European Patent No. 15,6.
01, 274,723, 276,566, 299,435, World Patent (WO) 88/04794.
And JP-A-2-264936, there is a method using a water-insoluble dye solid. Among these methods, the method of dispersing the dye as a solid (as a fine crystal dispersion) is preferable from the viewpoint of fixing the dye in the specific layer and reducing the residual color after the development processing.

Since the fine crystal dispersion preferably used in the present invention has insufficient solubility of the dye itself, it cannot exist in a molecular state in the intended colored layer, and the diffusion in the layer is substantially impaired. It is meant to exist as a solid of possible size. Regarding the preparation method, International Publication (WO) 88/047
No. 94, European Patent Publication (EP) 0276566A
No. 1, JP-A-63-197943 and the like, it is generally ball milled and stabilized with a surfactant and gelatin. The particle size of the microcrystals of the dye preferably used in the present invention is preferably 1.0 μm or less, more preferably 0.5 μm or less. The amount of the dye used is 5 mg / m ^{2 to} 300 mg / m ² , particularly 10 mg / m ² to 1
It is preferably 50 mg / m ² .

As the binder for the dyeing layer in the present invention, the same binders as those for the emulsion layer and the protective layer can be used. The amount of binder in the dyed layer of the present invention is 0.02 to 2.
5 g / m ^2, more preferably from 0.05 to 2 g / m ² is desirable.

The sensitizing dye used in the present invention is disclosed in JP-A-3-11.
336, JP-A-64-40939, Japanese Patent Application No. 2-26
No. 6934, No. 3-121798, No. 3-22874
The sensitizing dyes described in No. 1, No. 3-228741, No. 3-266959 and No. 3-311498 can be preferably used. 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).
Disclosure) Volume 176, 17643 (issued in December 1978), page 23, IV, paragraph J, or the aforementioned Japanese Patent Publication No. 49-2.
5500, 43-4933, JP-A-59-190.
32, 59-192242 and the like.
The content of the sensitizing dye used in the present invention depends on the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the halogen compound emulsion, the type of the antifoggant compound, and the like. It is desirable to select the optimum amount accordingly, and the method of testing is well known to those skilled in the art for the selection. Usually, it is preferably used in the range of 10 ^-7 mol to 1 × 10 ^-2 mol, particularly 10 ^-6 mol to 5 × 10 ^-3 mol, per mol of silver halide.

As the support of the photographic light-sensitive material of the present invention,
It must have a thickness of 150 μm or more. This is essential from the viewpoint of handleability when observing on a medical Schaukasten. A polyethylene terephthalate film is preferable as the material, and it is particularly preferable that the film is colored in blue, but it may not be colored in blue. The support is preferably subjected to a corona discharge treatment, a glow discharge treatment, or an ultraviolet irradiation treatment for improving the adhesion to the hydrocolloid layer. Alternatively, an undercoat layer made of styrene-butadiene-based latex, vinylidene chloride-based latex or the like may be provided, and a gelatin layer may be further provided thereon. An undercoat layer using an organic solvent containing a polyethylene swelling agent and gelatin may be provided. By applying a surface treatment to these undercoat layers, the adhesion with the hydrocolloid layer can be further improved.

The total coating amount of gelatin on the silver halide emulsion layer side of the support of the present invention is preferably 3.5 g / m ² or less, more preferably 3.3 g / m ² or less,
Further, it is preferably 3.0 g / m ² or less. The coated Ag amount per one side of the silver halide emulsion of the present invention is 2.6 g.
/ M ² or less, preferably 2.3 g / m ² or less, and more preferably 2.0 g / m ² or less. Further, the weight ratio of silver and gelatin in the silver halide emulsion layer is an important factor from the viewpoint of suitability for rapid processing. If the ratio of silver and gelatin in the silver halide emulsion layer is increased, the silver halide photographic light-sensitive material will peel off due to the protrusions on the roller when processed by an automatic processor, making it difficult to see the image. Occurs. From this viewpoint, the weight ratio of silver to gelatin in the silver halide emulsion layer is preferably 1.8 or less, more preferably 1.4 or less, and further preferably 1.2 or less.

As various additives and the like used in the photographic light-sensitive material of the present invention, those described in the following relevant parts can be used. Item This section 1) Chemical sensitization method JP-A-2-68539, page 10, upper right column, line 13 to upper left column, line 16; Japanese Patent Application No. 3-105035. 2) Antifoggant and stabilizer JP-A-2-68539, page 10, lower left column, line 17 to page 11 upper left column, line 7 and page 3 lower left column, line 2 to page 4 lower left column . 3) Color tone improving agent JP-A-62-276539, page 2, lower left column, line 7 to page 10, lower left column, line 20; JP-A-3-94 249, page 6, lower left column, line 15 to Page 11, right upper column, line 19 4) Surfactant, antistatic JP-A-2-68539, page 11, upper left column, line 14 agent to page 12, upper left column, line 9 5) Matting agent, slipping agent, JP-A-2-68539, page 12, upper left column, line 19 plasticizer to same upper right column, line 10; page 14 lower left column, line 10 to lower right column, line 1 . 6) Hydrophilic Colloid JP-A-2-68539, page 12, upper right column, line 11 to left lower column, line 16 7) Hardener JP-A-2-68539, page 12, lower left column, line 17 to page 13, upper right column, line 6 8) Polyhydroxybenze JP-A-3-39948, page 11, upper left column to the same, page 12, lower left column, EP Patent No. 452772A. 9) Layer structure JP-A-3-198041.

The developing agent preferably used in the developing solution of the present invention is a dihydroxybenzene type developing agent. As the dihydroxybenzene type developing agent, hydroquinone,
Chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3
-Dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2,5-dimethylhydroquinone, potassium hydroquinone monosulfonate, etc., but hydroquinone is particularly preferable. The developing agent is usually preferably used in an amount of 0.05 mol / liter to 0.8 mol / liter. In the present invention, in particular, the dihydroxybenzene-based developing agent
It is preferable to use -phenyl-3-pyrazolidones or p-aminophenols together.

Examples of 1-phenyl-3-pyrazolidones include 1-phenyl-3-pyrazolidone and 1-phenyl-
4,4-dimethyl-3-pyrazolidone, 1-phenyl-
4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-
Examples include pyrazolidone and 1-phenyl-5-methyl-3-pyrazolidone. As p-aminophenols,
There are N-methyl-p-aminophenol, N- (β-hydroxyethyl) -p-aminophenol, N- (4-hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol and the like. However, among them, N-methyl-p-aminophenol is preferable.

When a dihydroxybenzene type developing agent and an auxiliary developing agent such as 1-phenyl-3-pyrazolidone or p-aminophenol are used in combination, the former is 0.05 mol / liter to 0.5 mol / Liter, the latter 0.001 to 0.06 mol / liter (especially 0.0
It is preferably used in an amount of 03-0.06 mol / liter).

As the sulfite, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.04 mol / liter or more, and particularly preferably 0.15 mol / liter or more. The upper limit is 1.0 mol /
It is preferably up to liter, particularly up to 0.65 mol / liter.

As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.04 mol / liter or more, and particularly preferably 0.15 mol / liter or more. The upper limit is preferably 1.0 mol / liter, particularly 0.65.

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, methanol and other organic solvents: 1-phenyl-
5-Mercaptotetrazole, mercapto-based compounds such as 2-mercaptobenzimidazole-5-sulfonic acid sodium salt, may contain an antifoggant such as indazole-based compounds such as 5-nitroindazole, if necessary, toning agents, Surfactants, antifoaming agents, water softeners, hardeners, JP-A-56-106244, JP-A-61-26
The amino compounds described in 7759 and JP-A-2-208652 may be included.

In the present invention, as a silver stain preventing agent in a developing solution, JP-B-56-46585 and JP-B-62-4702 are used.
Japanese Patent Publication No. 62-4703, US Pat. No. 4,254,
No. 215, No. 3,318,701, Japanese Patent Publication No. 58-20
No. 3439, No. 62-56959, No. 62-1782.
47, Japanese Patent Application Laid-Open No. 1-20249, Japanese Patent Application No. 3-949.
The compounds described in No. 55, No. 3-112275 and No. 3-233718 can be used. A method for preparing a treating agent used in the present invention is disclosed in JP-A-61-177132.
Japanese Patent Application No. 3-134666, Japanese Patent Application Laid-Open No. 3-67258.
The method described in the publication can be used. Japanese Patent Application No. 4-541 discloses a method of replenishing a developing solution as a processing method of the present invention.
The method described in No. 31 can be used.

In the developer used in the present invention, boric acid described in JP-A-62-186259, saccharides (for example, saccharose) and oximes (for example, described in JP-A-60-93433) are used as buffers. Acetoxime), phenols (for example, 5-sulfosalicylic acid) and the like are used. The processing method of the present invention can be carried out in the presence of polyalkylene oxide, but in order to contain polyalkylene oxide in the developing solution, the average molecular weight is from 1000 to 60.
It is preferable to use polyethylene glycol of 00 in the range of 0.1 to 10 g / liter.

The fixing solution may contain a water-soluble aluminum compound as a hardening agent in addition to the fixing agent. Further, if necessary, an acidic aqueous solution containing acetic acid and a dibasic acid (eg tartaric acid, citric acid or a salt thereof), preferably pH 3.
It has 8 or more, more preferably 4.0 to 6.5. Examples of the fixing agent include sodium thiosulfate and ammonium thiosulfate, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed and is generally about 0.1 to about 5 mol / liter. The water-soluble aluminum salt, which mainly acts as a hardening agent in the fixing solution, is a compound generally known as a hardening agent for an acidic hardening fixing solution, and examples thereof include aluminum chloride, aluminum sulfate and potassium alum.

As the above-mentioned dibasic acid, tartaric acid or its derivative, citric acid or its derivative can be used alone or in combination of two or more kinds. 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. Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium sodium tartrate, ammonium tartrate, potassium ammonium tartrate, and the like can be given. Examples of citric acid or its derivative effective in the present invention include citric acid, sodium citrate, potassium citrate, and the like. If desired, the fixer may contain preservatives (eg, sulfite, bisulfite),
A pH buffering agent (eg, acetic acid, boric acid), a pH adjusting agent (eg, Annimore, 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.

Regarding the roller transport type automatic developing machine, US Pat. Nos. 3,025,779 and 3,545,971 are applicable.
And the like, and is simply referred to as a roller conveyance type processor in this specification. 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. . Replenishing amount of washing water is 1200 ml / m ²
The following may be included (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 for reducing the replenishment amount, a multi-stage countercurrent system (for example, two-stage, three-stage) has been known for a long time.

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. RT for wash bath or stabilizing bath
Kreiman J.Image.Tech.Vol.10 No.6 242 (1
984), isothiazoline compounds, Research Disclosure (RD) Volume 205, No.
20526 (May, 1981), isothiazoline compounds, Vol. 228, No. 22845 (1).
983, April issue), isothiazoline compounds described in JP-A-61-115154, JP-A-62-20.
The compounds described in No. 9,532 are used as antibacterial agents (Micr
obiocide) can also be used together. 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 61), LEWest "Watet Quallity Criteria" Photo
Sci & Eng.vol. 9 No.6 (1965), MW Beach "M
icrobiological Growths in Motion Picture Processin
g "SMPTE Journal Vol. 85 (1976), RO.Deegan
"Photo Processing Wash Water Biocides" J. Imaging T
ech. vol.10 No. 6 (1984).

When washing with a small amount of washing water in the method of the present invention, JP-A-63-18350 and JP-A-62-
It is more preferable to provide a squeeze roller and a crossover rack cleaning tank described in No. 287,252.
Furthermore, a part or all of the overflow liquid from the washing or stabilizing bath of the present invention, which is produced by supplementing the washing or stabilizing bath with antifungal water according to the treatment, is disclosed in JP-A-60 / 1985.
As described in JP-A-235,133 and JP-A-63-129,343, it can also be used for a processing solution having a fixing ability which is 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-63-163456 may be installed in a water washing tank to prevent contamination by dyes eluted from the light-sensitive material.

The photosensitive material of the present invention has a total processing time of 15 seconds to
It shows excellent performance in rapid development processing by an automatic processor, which is 60 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. In the present invention, the light-sensitive material is developed, fixed, and then washed with water or stabilized. Here, in the water washing step, water saving treatment can be performed by using a countercurrent water washing method of two or three stages. Further, when washing with a small amount of washing water, it is preferable to provide a squeeze roller washing tank. Further, a part or the whole of the overflow solution from the washing bath or the stabilizing bath can be used as the fixing solution as described in JP-A-60-235133. This is more preferable because the amount of waste liquid is reduced. In the present invention, the photosensitive material which has been developed, fixed and washed with water is dried through a squeeze roller. Drying at 40 ° C to 80 ° C for 4 seconds to 3
It takes 0 seconds. With the total processing time in the present invention, after inserting the tip of the film into the insertion port of the automatic developing machine, a developing tank, a transition portion, a fixing tank, a transition portion, a washing tank, a transition portion,
It is the total time for the leading edge of the film to come out of the drying outlet after passing through the drying section. Since the silver halide light-sensitive material of the present invention can reduce the amount of gelatin used as the binder of the emulsion layer and the protective layer without impairing the pressure fog, the total processing time is 15 to 60 seconds. Development processing can be carried out without impairing the speed, fixing speed, and drying speed. Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited thereto.

[0051]

【Example】

Example 1 1. Preparation of photographic material A backing layer having the following formulation and a polymer layer were simultaneously coated on one surface of a 180-μm-thick blue-colored polyethylene terephthalate support having undercoat layers coated on both sides, and dried at 50 ° C. for 5 minutes. . 1) Back layer Gelatin 3.0 g / m ² Sodium dodecylbenzene sulfonate 10 mg / m ² Sodium polystyrene sulfonate 20 mg / m ² N, N′-ethylenebis- (vinyl sulfone acetamide) 40 mg / m ² Ethyl acrylate latex (average) Particle size 0.1 μm) 1.0 g / m ² 2) Polymer layer (methyl methacrylate): (styrene) 1 g / m ² : (2 ethylhexyl acrylate): (methacrylic acid) = 63: 9: 27: 1 polymethyl methacrylate Fine particles (average particle size 2.5μ) 50mg / m ²

Subsequently, a dye layer having the following formulation, a silver halide emulsion layer, and a surface protective layer for the emulsion layer were simultaneously coated on the opposite side of this sample in the order close to the support and dried to obtain a photographic material. 3) Dye layer Gelatin 0.5 g / m ² Dye- [1] 75 mg / m ²

[0053]

[Chemical 2]

Phosphoric acid 15 mg / m ² Sodium dodecylbenzene sulfonate 15 mg / m ² Sodium polystyrene sulfonate 15 mg / m ² * Preparation method of Dye 1 The preparation method of the present invention is based on the method of JP-A-63-197943. It was That is, water (434 ml) and
Triton X-200R Surfactant (TX-200R)
(53 g) (sold by Rohm & Haas) and a 6.7% solution were placed in a 1.5 liter screw cap bottle. To this was added 20 g of the dye and zirconium oxide (ZrO ₂ ) beads (800 ml) (2 mm diameter), the bottle was capped tightly, placed in a mill and the contents crushed for 4 days. 12.5% gelatin aqueous solution (16
0 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.

4) Silver halide emulsion layer a) Preparation of silver halide emulsion A 32 g of gelatin was added to 900 ml of distilled water and dissolved at 40 ° C., pH was adjusted to 3.8 with sulfuric acid, and sodium chloride 3 was added. 0.3 g was added. A solution prepared by dissolving 32 g of silver nitrate in 200 ml of distilled water and a solution prepared by dissolving 11 g of sodium chloride and K ₂ IrCl ₆ in 200 ml of distilled water in an amount of 4.4 × 10 ⁻⁸ mol per mol of silver halide were prepared at 40 ° C. The mixture was added and mixed under the conditions for 2 minutes. Further, a solution prepared by dissolving 64 g of silver nitrate in 280 ml of distilled water and sodium chloride 21.6
and 275 ml of distilled water were added and mixed at 40 ° C. for 5 minutes. Subsequently, a solution prepared by dissolving 64 g of silver nitrate in 280 ml of distilled water and sodium chloride 22.4.
g, K ₄ Fe (CN) ₆ .3H ₂ O dissolved in 285 ml of distilled water in an amount of 1 × 10 ⁻⁴ mol per mol of silver halide was added at 40 ° C. for another 5 minutes. Add and mix. When the obtained emulsion was observed with an electron microscope, it was an emulsion consisting of cubic grains having a grain size equivalent to a projected area circle of about 0.27 μm and a coefficient of variation of grain size distribution of 10%.

54 g of gelatin after desalting with this emulsion,
Phenoxyethanol (2.6 g) was added, pAg was adjusted to 7.9 with sodium chloride at pH 6.7, and chemical sensitization was performed at 58 ° C. according to the following procedure. First, the average particle size is 0.
1.1 mol% of a silver halide having a thickness of 05 μm was added in an amount corresponding to 1.1 mol% of silver halide, and then 7.2 mg of compound (1), 9.2 mg of chloroauric acid, 1.3 mg of triethylthiourea, and selenium sensitization. Add agent (A) 0.72 mg, and further add 0.29 g of nucleic acid,
Finally 4-hydroxy-6-methyl-1,3,3a, 7
-Tetrazaindene (162 mg) was added, and the mixture was rapidly solidified to give Emulsion A.

Compound (1)

[0058]

[Chemical 3]

Selenium sensitizer (A)

[0060]

[Chemical 4]

B) Preparation of Silver Halide Emulsions B to D Sodium chloride and potassium bromide for forming the silver halide emulsion A were changed to sodium chloride and potassium bromide, and the amounts were adjusted appropriately to change the grain forming temperature. An emulsion having the halogen composition and grain size shown in Table 1 was obtained. After the desalting treatment, emulsions A to D were prepared in the same manner as Emulsion A. c) Preparation of silver halide emulsion E 32 g of gelatin was dissolved in 1 liter of distilled water, and 0.2 g of potassium bromide, 3 g of sodium chloride and N, N-dimethylimidazolidine-2- were placed in a container heated at 38 ° C. After adding 4.6 ml of thione (1% aqueous solution), 444 ml of an aqueous solution containing 80 g of silver nitrate, 45 g of potassium bromide, 5.5 g of sodium chloride and 4. mol per mol of finished silver halide.
452 ml of an aqueous solution containing 4 × 10 ⁻⁸ mol of K ₂ IrCl ₄
By the double jet method over about 20 minutes,
A core portion of 20 mol% silver chloride was prepared, and then 400 ml of an aqueous solution containing 80 g of silver nitrate and 44.8 g of potassium bromide,
Sodium chloride 5.5g, K ₄ Fe (CN) ₆ / 3H ₂ O
Was added to 415 ml of an aqueous solution containing 1 × 10 ⁻⁴ mol per mol of finished silver halide by the double jet method over about 25 minutes to form a shell portion of 20 mol% silver chloride, and the average grain size (projection Cubic monodisperse silver chlorobromide grains having an area diameter of 0.21 μm (variation coefficient of projected area diameter: 10
%) Was prepared.

After desalting this emulsion, 54 g of gelatin,
2.6 g of phenoxyethanol was added, pH 6.5, p
It was adjusted to Ag 8.5. Then, the temperature was raised to 65 ° C., 2 mg of sodium thiosulfate was added, 2 minutes after that, 5 mg of chloroauric acid was added, and 80 minutes later, 4-hydroxy-6-methyl-1,
Emulsion E was prepared by adding 512 mg of 3,3a, 7-tetrazaindene and then rapidly cooling to solidify.

D) Preparation of emulsion coating solutions The following chemicals were added to emulsions A to E per mol of silver halide to prepare emulsion coating solutions.

(Formulation of emulsion coating solution)

B. Spectral sensitizing dye [2] 5.5 × 10 ⁻⁵ mol. Supersensitizer [3] 3.3 × 10 ⁻⁴ mol c. Polyacrylamide (molecular weight 40,000) 9.2 g d. Trimethylolpropane 1.4 g e. Poly (ethyl acrylate / methacrylic acid) latex 22g Spectral sensitizing dye [2]

[0066]

[Chemical 5]

Supersensitizer [3]

[0068]

[Chemical 6]

The coating silver amount of this emulsion coating solution was 1.85 g /
A silver halide emulsion layer was prepared by coating so that the coating amount of m ² and gelatin was 1.27 g / m ² .

5) Surface protective layer of emulsion layer The container was heated to 40 ° C. and the following chemicals were added to prepare a surface protective layer coating solution. I. Gelatin 100 g b. Polyacrylamide (molecular weight 40,000) 12.3 g c. Sodium polystyrene sulfonate (molecular weight 600,000) 0.6 g d. Polymethylmethacrylate fine particles (average particle size 2.5 μm) 2.7 g e. Sodium polyacrylate 3.7 g f. t-octylphenoxyethoxyethanesulfonic acid sodium salt 1.5 g. _{C 16 H 33 O- (CH 2} CH 2 O) 10 -H 3.3g Ji. C ₈ F ₁₇ SO ₃ K 84 mg Re. _{C 8 F 17 SO 2 N (} C 3 H 7) (CH 2 CH 2 O) 4 (CH 2) 4 -SO 3 Na 84mg j. NaOH 0.2 g ru. Methanol 78cc. 1,2-Bis (vinylsulfonylacetamide) Prepared to be 2.5% by weight based on the total gelatin amount of the emulsion layer and the surface protective ethane layer. Wa. Compound (4) 52 mg

[0071]

[Chemical 7]

The surface protective layer of the emulsion layer was prepared by coating the surface protective layer coating solution so that the coating amount of gelatin was 1.23 g / m ² .

2. Preparation of developer Concentrated developer A Hydroquinone 20 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.5 g Potassium sulfite 50 g Potassium carbonate (monohydrate) 25 g Diethylene glycol 10 g Potassium bromide 1 g Diethylenetriaminepentaacetic acid 2 g 5-Methylbenztriazole 0.1 g 2-Mercaptoimidazole-5-sulfonic acid 0.3 g 2,3,5,6,7,8-hexahydro-2-oxo- (1H) -quinazoline 0.3 g Sodium ascorbate 7 g Add 1 liter of water (adjust to pH 10.0 with potassium hydroxide) 3. Preparation of fixer Sodium thiosulfate 185 g Ethylenediaminetetraacetic acid disodium dihydrate 0.025 g Sodium metabisulfite 22 g Water was added to 1 liter (pH adjusted to 5.5 with sodium hydroxide).

4. Evaluation of photographic material While keeping the photographic material at 25 ° C and 65% RH temperature and humidity, it was left for 7 days after coating, and the transmission blackening density was 1.0 at 10 ^-7 seconds using a semiconductor laser having a wavelength of 780 nm. The scanning exposure was performed so that After exposure, the drive motor and gear of FPM-2000 manufactured by Fuji Photo Film Co., Ltd. were modified by the above-mentioned developing and fixing solution to speed up the transportation speed, and at the developing temperature of 35 ° C., including fixing, washing and drying. 30
Seconds processing.

A) Water content after development of back layer The silver halide emulsion layer of the photographic material and its surface protective layer and dye layer are removed using an aqueous solution of sodium hypochlorite, and the development treatment is carried out under the above-mentioned conditions. And weight W after the washing process
₁ (g) is measured. Next, this sample was placed in a vacuum dryer (square vacuum dryer DP41 manufactured by Yamato Scientific Co., Ltd.),
5 Torr Weight after drying at 105 ℃ for 24 hours W
₂ (g) is measured. W ₁ , W ₂ , sample area S (m ² ),
From the gelatin coating amount X (g / m ² ) of the back layer, the water content is calculated by the following formula. The water content after the development of the back layer _{= (W 1 -W 2) /} (S
XX) Further, while supplementing the developing solution and the fixing solution at 80 ml / m ² each, the exposed photographic material having a size of 0.257 m × 0.364 m was exposed under an atmosphere of 25 ° C. and 60% RH. 1,500 sheets were run.

B) Evaluation of Dryability The degree of dryness immediately after the treatment is classified into the following three levels. Of these, the practically acceptable level is ◯ level. ○: It is completely dry. The photographic material is warm. △: Slightly tightened. The temperature of the photographic material is about room temperature. ×: It is tight. Photographic materials adhere to each other.

C) Estimation of carry-over amount The weight W ₁ of a photographic material of 0.257 m × 0.364 m was measured and then passed through only the developing tank of the FPM2000 automatic developing machine. Then, the weight W _{2 of the} photographic material was measured and the carry-over amount was obtained from the following formula. Carry over amount = (W ₁ −W ₂ ) ÷ (0.257 ×
0.364) (g / m ² )

D) Evaluation of fixing loss After the above-mentioned running processing, an unexposed photographic material (0.25
(7 m × 0.364 m size) was processed and the fixing loss was evaluated. The fixing loss was evaluated on a 5-point scale. 5 indicates a state in which there is no residual silver, 4 indicates a color as silver sulfide when immersed in a sodium sulfide solution, and there is some residual silver, but it is practically acceptable. 3 indicates that slight residual silver is visually observed. Level, which is practically unacceptable in the state of being set, 2 and 1 indicate that the fixing loss is poor. The obtained results are shown in Table-1.

[0079]

[Table 1]

As is clear from Table 1, the present invention is effective in terms of fixing property and drying property. Further, when the gelatin amount ratio between the back surface and the emulsion surface is less than 0.3, the curl is seriously deteriorated, and conveyance failure occurs during scanning exposure with a semiconductor laser (the gelatin amount ratio between the back surface and the emulsion surface is 0. .3 or more).

[Procedure amendment]

[Submission date] January 7, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction content]

Next, hydrophobic polymer layer (polymer layer)
I will describe. The water content of surface B of the silver halide photographic light-sensitive material of the present invention at the end of the washing step can be controlled to 0.2 g or less per 1 g of the hydrocolloid by this polymer layer. As the binder of the polymer layer, a hydrophobic polymer is used to prevent the back layer from swelling in the treatment liquid. As long as these conditions are met, there are no restrictions on the material,
Acrylic resins are preferred. The acrylic resin preferably used as the binder of the polymer layer of the present invention means at least one type of -C-C as a repeating unit in the molecule.
(R ₁ ) A polymer compound having COOR ₂ . Here, R ₁ represents an alkyl group having 1 to 5 carbon atoms, halogen, carboxymethyl group, and R ₂ represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms. Specific examples of these include methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate,
Isobutyl acrylate, amyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, lauryl acrylate, methyl methacrylate, methyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, amyl methacrylate, Examples thereof include n-hexyl methacrylate, 2-ethylhexyl methacrylate, and lauryl methacrylate. The acrylic resin preferably used in the present invention can be copolymerized with one or more copolymerizable vinyl monomers. Specific examples of these vinyl monomers include, but are not limited to, the following. Ethylene, propylene, 1-butene, isobutene, vinyl chloride, vinylidene chloride, styrene, α-methylstyrene,
Chloromethylstyrene, vinyl ketone, monoethylenically unsaturated ester of aliphatic acid (eg vinyl acetate, allyl acetate), substituted alkyl ester of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid (eg 2-hydroxymethyl acrylate, 2 -Hydroxyethyl methacrylate, 3-hydroxypropyl acrylate, 3
-Hydroxypropyl methacrylate, 2-N, N-dimethylaminoethyl methacrylate, glycidyl methacrylate, amides of ethylenically unsaturated monocarboxylic or dicarboxylic acids (eg N, N-dimethylacrylamide, N-methylolacrylamide, N-methoxy) Examples thereof include methyl acrylamide, N, N-diethyl acrylamide, etc., monoethylenically unsaturated compounds (eg, acrylonitrile, methacrylonitrile), dienes (eg, butadiene, isoprene) and the like. If necessary, these acrylic resins may be copolymerized with an acid component such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, citraconic acid, crotonic acid, fumaric acid, maleic anhydride. .

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction content]

As the preservative of sulfite used in the present invention, sodium sulfite, potassium sulfite, lithium sulfite,
Examples include ammonium sulfite, sodium bisulfite, potassium metabisulfite, and formaldehyde sodium bisulfite. The sulfite content is preferably 0.04 mol / liter or more, and particularly preferably 0.15 mol / liter or more. The upper limit is preferably 1.0 mol / liter, particularly 0.65.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction content]

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.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0042

[Correction method] Change

[Correction content]

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-
Mercapto-benzimidazole-5-sulfonic acid sodium salt and other mercapto-based compounds, may contain an antifoggant such as 5-nitroindazole and other indazole-based compounds, if necessary, further toning agents, surfactants, antifoaming agents , Water softener, hardener, JP-A-56-106244
JP-A-61-267759 and JP-A-2-208.
The amino compound described in No. 652 may be included.

[Procedure Amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0052

[Correction method] Change

[Correction content]

Subsequently, a dye layer having the following formulation, a silver halide emulsion layer, and a surface protective layer for the emulsion layer were simultaneously coated on the opposite side of this sample in the order close to the support and dried to obtain a photographic material. 3) Dyeing layer Gelatin 0.5 g / m ² Dye- [1] 75 mg / m ²

[Procedure correction 6]

[Document name to be amended] Statement

[Correction target item name] 0055

[Correction method] Change

[Correction content]

4) Silver halide emulsion layer a) Preparation of silver halide emulsion A 32 g of gelatin was added to 900 ml of distilled water and dissolved at 40 ° C., pH was adjusted to 3.8 with sulfuric acid, and sodium chloride 3 was added. 0.3 g was added. A solution prepared by dissolving 32 g of silver nitrate in 200 ml of distilled water and a solution prepared by dissolving 11 g of sodium chloride and K ₂ IrCl ₆ in 200 ml of distilled water in an amount of 4.4 × 10 ⁻⁸ mol per mol of silver halide were prepared at 40 ° C. The mixture was added and mixed under the conditions for 2 minutes. Further, a solution prepared by dissolving 64 g of silver nitrate in 280 ml of distilled water and sodium chloride 21.6
and 275 ml of distilled water were added and mixed at 40 ° C. for 5 minutes. Subsequently, a solution prepared by dissolving 64 g of silver nitrate in 280 ml of distilled water and sodium chloride 22.4.
g, K ₄ Fe (CN) ₆ .3H ₂ O dissolved in 285 ml of distilled water in an amount of 1 × 10 ⁻⁴ mol per mol of silver halide was added at 40 ° C. for another 5 minutes. Add and mix. When the obtained emulsion was observed by an electron microscope, it was an emulsion composed of cubic grains having a grain size of a projected area circle diameter of about 0.21 μm and a coefficient of variation of grain size distribution of 10%.

[Procedure Amendment 7]

[Document name to be amended] Statement

[Correction target item name] 0061

[Correction method] Change

[Correction content]

B) Preparation of Silver Halide Emulsions B to D Sodium chloride and potassium bromide for forming the silver halide emulsion A were changed to sodium chloride and potassium bromide, and the amounts were adjusted appropriately to change the grain forming temperature. A monodisperse cubic emulsion having a halogen composition shown in Table 1 and a grain size of 0.21 μm was obtained. After the desalting treatment, the same preparation as in Emulsion A was carried out, and Emulsion B to
D. c) Preparation of silver halide emulsion E 32 g of gelatin was dissolved in 1 liter of distilled water, and 0.2 g of potassium bromide, 3 g of sodium chloride and N, N-dimethylimidazolidine-2- were placed in a container heated at 38 ° C. After adding 4.6 ml of thione (1% aqueous solution), 444 ml of an aqueous solution containing 80 g of silver nitrate, 45 g of potassium bromide, 5.5 g of sodium chloride and 4. mol per mol of finished silver halide.
452 ml of an aqueous solution containing 4 × 10 ⁻⁸ mol of K ₂ IrCl ₄
By the double jet method over about 20 minutes,
A core portion of 20 mol% silver chloride was prepared, and then 400 ml of an aqueous solution containing 80 g of silver nitrate and 44.8 g of potassium bromide,
Sodium chloride 5.5g, K ₄ Fe (CN) ₆ / 3H ₂ O
Was added to 415 ml of an aqueous solution containing 1 × 10 ⁻⁴ mol per mol of finished silver halide by the double jet method over about 25 minutes to form a shell portion of 20 mol% silver chloride, and the average grain size (projection Cubic monodisperse silver chlorobromide grains having an area diameter of 0.21 μm (variation coefficient of projected area diameter: 10
%) Was prepared.

[Procedure Amendment 8]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction content]

2. Preparation of developer Hydroquinone 20 g 1-Phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 2.5 g Potassium sulfite 50 g Potassium carbonate (monohydrate) 25 g Diethylene glycol 10 g Potassium bromide 1 g Diethylenetriaminepentaacetic acid 2 g 5-Methylbenz Triazole 0.1 g 2-mercaptoimidazole-5-sulfonic acid 0.3 g 2,3,5,6,7,8-hexahydro-2-oxo- (1H) -quinazoline 0.3 g sodium ascorbate 7 g 1 liter (pH adjusted to 10.0 with potassium hydroxide) 3. Preparation of fixer Sodium thiosulfate 185 g Ethylenediaminetetraacetic acid disodium dihydrate 0.025 g Sodium metabisulfite 22 g Water was added to 1 liter (pH adjusted to 5.5 with sodium hydroxide).

[Procedure Amendment 9]

[Document name to be amended] Statement

[Correction target item name] 0075

[Correction method] Change

[Correction content]

A) Water content after development of back layer The silver halide emulsion layer of the photographic material and its surface protective layer and dye layer are removed using an aqueous solution of sodium hypochlorite, and the development treatment is carried out under the above-mentioned conditions. And weight W after the washing process
₁ (g) is measured. Next, this sample was placed in a vacuum dryer (square vacuum dryer DP41 manufactured by Yamato Scientific Co., Ltd.),
5 Torr Weight after drying at 105 ℃ for 24 hours W
₂ (g) is measured. W ₁ , W ₂ , sample area S (m ² ),
From the gelatin coating amount X (g / m ² ) of the back layer, the water content is calculated by the following formula. The water content after the development of the back layer _{= (W 1 -W 2) /} (S
XX) Thereafter, the above-mentioned exposed photographic material having a size of 0.257 m × 0.364 m was replenished with 80 ml / m ^{2 of} the above-mentioned developing solution and fixing solution at 25 ° C. in an atmosphere of 60% RH. 1,500 sheets were run.

[Procedure Amendment 10]

[Document name to be amended] Statement

[Correction target item name] 0076

[Correction method] Change

[Correction content]

B) Evaluation of Dryability The degree of dryness immediately after the treatment is classified into the following three levels. Of these, the practically acceptable level is ◯ level. The drying temperature was set to 55 ° C. ○: It is completely dry. The photographic material is warm. △: Slightly tightened. The temperature of the photographic material is about room temperature. ×: It is tight. Photographic materials adhere to each other.

Claims (2)

[Claims] 1. A transparent support having a silver halide emulsion layer having an average silver chloride content of at least 90 mol% and comprising high silver chloride grains having a silver bromide localized phase on the surface and having a thickness of 150 μm or more. In a silver halide photographic light-sensitive material having the above and at least one non-photosensitive hydrophilic colloid layer on the surface opposite to the silver halide emulsion layer, the non-photosensitive hydrophilic colloid layer is coated. And the surface of the coated silver halide emulsion layer has a hydrophilic colloid binder ratio of 0.3 or more by weight, and the non-photosensitive hydrophilic colloid layer is coated after the washing step during development processing. Water content of the surface is 0.2g per 1g of hydrophilic colloid binder
A silver halide photographic light-sensitive material characterized by the following: 2. When the silver halide photographic light-sensitive material according to claim 1 is image-exposed and processed by a roller-conveying type automatic processor having a total processing time of 15 to 60 seconds, and A photographic image forming method comprising replenishing a replenisher for a developing solution and a fixing solution at a ratio of 100 ml or less per 1 m ^{2 of a} silver halide photographic light-sensitive material.