JPH09160175A - Silver halide photographic sensitive material and its processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enhance sensitivity and storage stability and to prevent occurrence of roller marks and to enhance developed silver tone and resistance to occurrence of uneven reflection spots even in the case of ultrahigh-speed processing reduced in a replenishing amount. SOLUTION: This photosensitive material has a support made of a polystyrene comprising an at least >=50% syndiotactic structure and hydrophilic colloidal layers including at least one silver halide emulsion layer on this support, and the above hydrophilic colloidal layers contains a polymer comprising >=15mol% repeating units derived from a monomer having at least one kind of acid group selected from carboxylic, phosphoric, and sulfonic acid groups and their salt groups.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a silver halide photographic light-sensitive material and a processing method for processing the light-sensitive material.

[0002]

BACKGROUND OF THE INVENTION In recent years, with respect to the development processing of silver halide photographic light-sensitive materials, it has been increasingly desired to reduce the processing time and the processing waste liquid. For example, in the medical field, regular health checkups,
The spread of medical checkups and the number of inspections including diagnosis in general medical care have increased rapidly, which has led to an increase in the number of X-ray photographs taken, and a demand for further rapid development processing after photography and further reduction of processing waste liquid. Is increasing.

In order to carry out development processing in a short time,
A light-sensitive material having excellent fixability and capable of being dried in a short time after washing with water is required. As a technique for increasing the sensitivity and improving the drying property of an X-ray photographic light-sensitive material, a method of using tabular grains with a high covering power, a method of reducing the amount of gelatin in the emulsion layer, a method of increasing the hardness and suppressing swelling during processing Methods for reducing the drying load are known.

Many techniques for increasing sensitivity using tabular silver halide grains have been disclosed, and examples thereof are disclosed in JP-A Nos. 58-111935, 58-111936 and 58-111936.
-11937, 58-113927, 59-99.
No. 433, etc.

Since these tabular silver halide grains have the same volume and a large surface area as those of so-called normal crystal silver halide grains such as hexahedron and octahedron, the adsorption amount of the sensitizing dye on the grain surface should be increased. Is possible, and as a result, there is an advantage that high sensitivity can be achieved.

Further, JP-A-63-92942 discloses a technique of providing a core having a high silver iodide content inside a tabular silver halide grain, and JP-A-63-151618 discloses a hexagonal tabular silver halide grain. Is disclosed, and the effect of increasing the sensitivity is shown.

However, when a method of reducing the amount of gelatin as a means for reducing the drying load while using these tabular grains or a method of increasing the hardness and suppressing the swelling during the treatment, Sensitometric fluctuations become large due to differences in activity and so stable images cannot be obtained, and roller marks are induced due to deterioration of pressure resistance. Further, the silver color tone after development processing (developed silver color tone) has a yellowish tint, causing unevenness of reflection spots, which is not preferable for diagnosis and it is difficult to use it for medical X-ray photographic light-sensitive materials. These are more prominent when the treatment liquid replenishment amount is reduced and the treatment is performed, which is also a problem in reducing the treatment waste liquid.

[0008]

DISCLOSURE OF THE INVENTION The present invention is directed to a silver halide which is highly sensitive and excellent in preservability, has no roller marks, and is excellent in developed silver tone and unevenness of reflection spots even in ultra-rapid processing with a reduced replenishment amount. An object is to provide a photographic light-sensitive material and a processing method thereof.

[0009]

The silver halide photographic light-sensitive material according to the present invention which achieves the above object comprises at least 50% or more of the components of the support made of a styrene polymer having a syndioctatic structure. A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on a support, wherein the hydrophilic colloid layer contains a carboxyl group, a phosphoric acid group, a sulfonic acid group and salts thereof. It is characterized by containing a polymer containing 15 mol% or more of a monomer having at least one kind of acid residue selected from

Further, in the method of processing a silver halide photographic light-sensitive material according to the present invention which achieves the above object, (1) at least 50% or more of the components of the support are composed of a styrene polymer having a syndioctatic structure, A silver halide photographic light-sensitive material having a hydrophilic colloid layer containing at least one silver halide emulsion layer on the support, wherein at least one of the hydrophilic colloid layers has a carboxyl group, a phosphate group, A processing step including a developing step, a fixing step and a drying step of a silver halide photographic light-sensitive material containing a polymer containing 15 mol% or more of a monomer having at least one acid residue selected from sulfonic acid groups and salts thereof. And (2) the drying step is performed by a heat roller, and (3) the drying step is performed by infrared radiation. (4) In the method of processing a silver halide photographic light-sensitive material according to claim 2, 3 or 4, the total processing time (Dry to Dry) is less than 45 seconds, (5) claim 2, 3 or 4. In the method for processing a silver halide photographic light-sensitive material, the total processing time (Dry
to Dry) is less than 45 seconds, and the replenishing amount of the developing solution in the developing step and the replenishing amount of the fixing solution in the fixing step are each 200 ml / m ² or less.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. (Support) In the support of the present invention, at least 50% is a styrene polymer having a syndioctatic structure (hereinafter also referred to as polystyrene of the present invention). First, the support (hereinafter, also referred to as a film) will be described. In the present invention, syndiotactic polystyrene (SPS)
A stereoregular structure (tacticity) is mainly a syndiotactic structure, that is, a stereostructure in which a phenyl group or a substituted phenyl group, which is a side chain with respect to a carbon-carbon bond or a main chain to be formed, is alternately located in opposite directions. The main chain of the main chain is polystyrene, which is a racemo chain, or a composition containing the same. If it is a homopolymer of styrene, it is polymerized by the method described in JP-A-62-117708. And other polymers are described in JP-A-1-46912 and 1-17.
It can be obtained by polymerization according to the method described in No. 8505.

The tacticity is quantified by a nuclear magnetic resonance method (13C-NMR method) using isotope carbon. The tacticity measured by 13 C-NMR method is the existence ratio of a plurality of continuous structural units, for example, 2
In the case of three, triad in the case of three, pentad in the case of five, and pentad in the case of five, the styrene-based polymer having a syndiotactic structure referred to in the present invention is usually a racemic diad of 75%. It is preferably 85% or more, preferably 60% or more with racemic triad, preferably 75% or more, or 30% or more, preferably 50% or more with racemic pentad.

Specific monomers of the polymer constituting the syndiotactic polystyrene-based composition include styrene, alkylstyrene such as methylstyrene, halogenated (alkyl) styrene such as chloromethylstyrene and chlorostyrene, alkoxystyrene, A single or a mixture containing vinyl benzoate as a main component. In particular, the copolymer of alkyl styrene and styrene is 50 μm
This is a preferable combination for obtaining a film having the above film thickness.

In the polystyrene of the present invention, the above-mentioned raw material monomers are used as a catalyst for the polymerization, and the method is disclosed in JP-A-5-3204.
No. 48, 4 to 10 (a) (a) transition metal compound and (b) aluminoxane as a main component, or (b) (a) transition metal compound and (c) transition metal compound It can be produced by polymerization using a compound containing a compound capable of reacting to form an ionic complex as a main component.

To produce the polystyrene of the present invention, first the styrenic monomer is thoroughly purified and then polymerized in the presence of any of the above catalysts. At this time, the polymerization method, polymerization conditions (polymerization temperature, polymerization time), solvent and the like may be appropriately selected. Usually, the polymerization is carried out at a temperature of -50 ° C to 200 ° C, preferably 30 ° C to 100 ° C for 1 second to 10 hours, preferably 1 minute to 6 hours. As the polymerization method, any of a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method and the like can be used,
Either continuous polymerization or discontinuous polymerization may be used. Here, in solution polymerization, as a solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, and aliphatic hydrocarbons such as cyclopentane, hexane, heptane, and octane are used alone or in combination of two or more. It can be used in combination. In this case, the monomer / solvent (volume ratio) can be arbitrarily selected. The molecular weight and composition of the polymer may be controlled by a commonly used method. The molecular weight can be controlled by hydrogen, temperature,
It can be performed at a monomer concentration or the like.

Further, the polystyrene of the present invention includes polystyrene obtained by copolymerizing another monomer copolymerizable therewith to the extent that the effect of the present invention is not impaired.

When the polystyrene of the present invention is used for forming a film, the weight average molecular weight is preferably 10,000 or more, more preferably 30,000 or more. If the weight average molecular weight is less than 10,000, the film may not be excellent in strength properties and heat resistance. The upper limit of the weight average molecular weight is not particularly limited, but it is 150
If it is 0000 or more, particularly 3,000,000 or more, breakage may occur due to an increase in the drawing tension, and a value less than that is preferable.

From the above viewpoints, the molecular weight of the polystyrene of the present invention is not limited as long as it is formed into a film, but the weight average molecular weight is preferably 10,000 to 3,000,000, and particularly preferably 30,000 to 15,000,000. .

The molecular weight distribution at this time (number average molecular weight /
The weight average molecular weight) is preferably 1.5 to 8. This molecular weight distribution can be adjusted by mixing different molecular weights. Further, in the polystyrene film of the present invention, syndiotactic polystyrene pellets are dried at 120 to 180 ° C. for 1 to 24 hours under vacuum or under an atmospheric pressure or an inert gas atmosphere such as nitrogen. The target moisture content is not particularly limited, but is 0.05% or less, preferably 0.01% or less, from the viewpoint of preventing reduction in mechanical strength and the like due to hydrolysis.
More preferably, it is 0.005% or less. However, these methods are not particularly limited as long as the purpose is achieved.

[Polymerization Example] SPS pellets were prepared according to JP-A-3-131843. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. Internal volume 5
Glass container in copper sulfate pentahydrate of 00ml (CuSO ₄ ·
5H ₂ O) 17.8 g (71 mmol) purified benzene 2
00 ml and 24 ml of trimethylaluminum were added, and the catalyst was adjusted by stirring at 40 ° C. for 8 hours. This was placed under an argon gas flow. After filtering through 3 glass filters, the filtrate was freeze-dried. This was taken out and placed in a 2-liter stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein and heated to 90 ° C.

Into this, 1 liter of purified styrene was added, and further 70 ml of purified p-methylstyrene was added, and the polymerization reaction was continued at this temperature for 8 hours. After that, the mixture was cooled to room temperature, 1 liter of methylene chloride was added, and a methanol solution of sodium methylate was added with stirring to deactivate the catalyst. The content was gradually dropped into 20 liters of methanol, filtered through a glass filter, washed with methanol three times, and then dried.
Using 1,2,4-trichlorobenzene as a catalyst, 135
The weight average molecular weight of this polymer determined from the results of GPC (gel permeation chromatography) measurement calibrated with standard polystyrene at ℃ was 415,000.

The melting point of this polymer is 13 at 245 ° C.
It was confirmed from the C-NMR measurement that the polymer obtained had a syndiotactic structure. This was pelletized with an extruder and then dried at 130 ° C.

The SPS film of the present invention is preferably SPS alone made from styrene, but as a film further containing SPS, SPS has a styrene-based heavy chain having an isotactic structure in which the main chain is a meso chain. The crystallization rate can be controlled by mixing the coalescence (IPS), and a stronger film can be obtained. When mixing SPS and IPS,
The ratio depends on the stereoregularity of each other, but is preferably 50:50 to 98: 2, but particularly 100%.
It is preferably SPS.

The support may contain inorganic fine particles, an antioxidant, a UV absorber, an antistatic agent, a dye, a pigment, a dye, etc., in order to impart functionality, within a range not impeding the object of the present invention. Is possible.

A known method can be applied as a method of extruding at the time of film formation, but it is preferable to extrude with a T die, for example.
Syndiotactic polystyrene pellets 280-3
An unstretched film is produced by melting and extruding at 50 ° C. and cooling and solidifying while applying static electricity on a casting roll.

Next, this unstretched film is biaxially stretched to obtain 2
Orient the axis. As a stretching method, a known method, for example, a sequential biaxial stretching method in which longitudinal stretching and transverse stretching are sequentially performed, a sequential biaxial stretching method of transverse stretching / longitudinal stretching, a transverse / longitudinal / longitudinal stretching method, a longitudinal / transverse stretching method. -A longitudinal stretching method, a longitudinal-longitudinal-transverse stretching method, a simultaneous biaxial stretching method or the like can be adopted and can be appropriately selected according to various characteristics such as required mechanical strength and dimensional stability. .

In general, a sequential biaxial stretching method is preferred in which stretching is carried out first in the longitudinal direction and then in the width direction, and in this case,
The stretching ratio in the longitudinal and transverse directions is 2.5 to 6 times, and the longitudinal stretching temperature depends on the glass transition temperature (Tg) of the polymer.
Stretching is usually performed in a temperature range of (Tg + 10) ° C. to (Tg + 50) ° C. In the case of a syndiotactic polystyrene film, it is preferably performed at 110 to 150 ° C. The stretching temperature in the width direction is preferably slightly higher than that in the longitudinal direction and is preferably 115 to 160 ° C. Next, this stretched film is heat-treated. The heat treatment temperature in this case can be appropriately changed depending on the application. For shrink-wrapping applications that require a high shrinkage rate, 150 ° C or lower, and for photographic, printing, medical applications that require dimensional stability, 1 depending on the purpose.
Temperatures of 50-270 ° C are adopted.

The heat treatment time is not particularly limited, but is usually 1
Seconds to 2 minutes are adopted. Longitudinal heat relaxation, if necessary
It goes without saying that lateral heat relaxation treatment or the like may be performed.
After this, the film may be rapidly cooled and wound up.
g to a heat treatment temperature for 0.1 minute to 1500 hours, and then slowly wound into a large-diameter core and further between 40 ° C. and Tg.
Cooling at an average cooling rate of 0.01 to −20 ° C./min is preferable in that it has an effect of making it difficult for the support to be wound around. Of course, the heat treatment between 40 ° C. and Tg is 0.1 from winding the support to cutting the product after coating the emulsion.
It is preferably carried out by placing in a constant temperature bath for 1 minute to 1500 hours.

In addition to the above film forming method, an easy sliding method, an adhesive method,
In order to impart various properties such as antistatic performance, it is also possible to produce an SPS laminated film in which an SPS support having the above-mentioned properties and the like is laminated on at least one surface of the SPS support. The lamination method is such that the resin is melted in a laminar flow and then extruded from a die or cooled and solidified S.
It is obtained by extrusion laminating molten SPS onto a PS unstretched support or an SPS uniaxially stretched support, and then stretching and heat-setting in both the longitudinal and transverse directions or in the direction perpendicular to the uniaxial stretching direction. Extrusion conditions, stretching temperature, stretching ratio, heat setting temperature, etc. of the SPS resin are slightly different depending on the combination of the SPS laminated supports, but they may be finely adjusted to select the optimum conditions and do not make a great change. Needless to say, the laminate may be composed of two or more layers, and may be a combination of the same type of polymers (including a combination of copolymerized polymers) or a different type of polymers. The above-mentioned film forming method can be appropriately changed according to its use and purpose, and the present invention is not limited to these methods for any reason.

The thickness of the thus obtained syndiotactic polystyrene-based stretched film varies depending on the application, but when it is used in a silver halide photographic light-sensitive material, it has the same thickness as a conventional support. However, it can be used even if it is thinner than usual, and it can be widely used in the present invention. Generally, it can be used in a range of 80 to 300 μm, preferably 80 to 200 μm.

(Acid Polymer) The acid polymer used in the present invention will be specifically described below. The basic structure of the acid polymer is basically any polymer as long as it contains at least 15 mol% of a monomer having at least one of a carboxyl group, a phosphoric acid residue and a sulfonic acid residue. Subject to invention. The simplest structure is a homopolymer obtained by polymerizing a monomer having an acid residue having a vinyl carboxyl group, a phosphoric acid residue, a sulfonic acid residue or a salt thereof. That is,
It is a polymer containing 100% of the above monomers. Specifically, acrylic acid, methacrylic acid, α-chloroacrylic acid, acrylamidoacetic acid, 3-acrylamidopropionic acid, 4-acrylamidobutyric acid, acrylamidoacetic acid, methacrylamide acetic acid, 3-methacrylamide propionic acid, itaconic acid, crotonic acid. , 2-acrylamido-2-methylpropanesulfonic acid (AMPS), p-
Styrene sulfonic acid, 3-acrylamido propane sulfonic acid, 3-acryloyloxy propane sulfonic acid,
Examples thereof include polymers of vinyl sulfonic acid and salts thereof, and polymers of the monomers shown below.

[0032]

Embedded image Further, a polymer obtained by copolymerizing the acid residue-containing monomer with another monomer having no acid residue is also used in the present invention as long as the acid residue-containing monomer unit is 15 mol% or more. , More preferably 30 mol% or more, particularly preferably 50 mol% or more.

Other monomers include acrylic acid esters, acrylamides, methacrylamides, vinyl esters, vinyl ketones, allyl compounds, olefins, vinyl ethers, N-vinyl ethers, N.
-Vinyl amides, vinyl heterocyclic compounds, maleic acid esters, itaconic acid esters, fumaric acid esters, crotonic acid esters and the like.

Specific examples will be shown below. That is, methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, octyl acrylate, diethylene glycol monoacrylate, trimethylolethane monoacrylate, 3-methoxybutyl acrylate, ω-methoxy polyethylene glycol acrylate (addition Number of moles n
= 9), 1-bromo-2-methoxyethyl acrylate, p-chlorophenyl acrylate, methyl methacrylate, ethyl methacrylate, acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl acrylamide, Nn-propyl acrylamide, N
-Tert-butyl acrylamide, hexyl acrylamide, octyl acrylamide, methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether,
Butyl vinyl ether, 2-ethylbutyl vinyl ether, vinyl acetate, vinyl propionate, vinyl pyridine, N-vinyl-2-methylimidazole, N-
Vinyltriazole, N-vinylpyrrolidone, ethylene, propylene, 1-butene, 1-heptene, 1-octene, dioctyl itaconate, dihexyl maleate,
Styrene, methyl styrene, dimethyl styrene, benzyl styrene, chloromethyl styrene, chlorostyrene,
Methyl vinyl benzoate, vinyl chlorobenzoate, acrylonitrile, methacrylonitrile, vinyl chloride and the like can be mentioned.

Among these monomers, methacrylic acid esters, acrylic acid esters and styrenes are preferable. In addition, the acid polymer used in the present invention may be any polymer having any structure, such as a polycondensation polymer and a graft polymer, as long as the requirements of the present invention are satisfied.

Specific examples of the acid polymer used in the present invention are shown below. That is, acrylic acid / methacrylic acid copolymer, acrylic acid / methyl acrylate copolymer, acrylic acid / butyl methacrylate copolymer, acrylic acid / 2
-Hydroxyethyl acrylate copolymer, acrylic acid / acrylamide copolymer, acrylic acid / ethyl acrylate / butyl methacrylate copolymer, polymethacrylic acid, methacrylic acid / methyl acrylate copolymer, methacrylic acid / butyl methacrylate copolymer, Methacrylic acid / 2-hydroxyethyl acrylate copolymer, methacrylic acid / acrylamide copolymer, methacrylic acid / ethyl acrylate / 2-hydroxyethyl acrylate copolymer, AMPS / methyl acrylate copolymer, AMPS / butyl methacrylate copolymer Coalescence, AMP
S / 2-hydroxyethyl acrylate copolymer, AM
PS / acrylamide copolymer, AMPS / ethyl acrylate / butyl methacrylate copolymer, maleic acid / styrene copolymer, isobutylene maleate copolymer, acrylic acid block copolymer on polyvinyl alcohol, acrylic acid on polyvinyl alcohol Examples thereof include graft copolymers, gelatin modified products such as maleylated gelatin and succinylated gelatin, and cellulose modified products such as carboxymethyl cellulose.

The methods for synthesizing these acid polymers are described in British Patent No. 1211039, Japanese Patent Publication No. 4-29195, British Patent No. 941395, US Pat. Nos. 3,227,672, 3,290,417, 3,262,919, and No. 32.
No. 45932, No. 2681897, No. 32302
No. 75, John, C, Petropoulos, et al. "Official Digest" (John C. Petropou
Los et al: Official Digest)
33, 719-736 (1961), Shunsuke Murahashi et al., "Synthetic Polymers" 1, 246-290, 31-108. The polymerization initiator, concentration, polymerization temperature, reaction time, etc. can be widely and easily changed according to the purpose.

For example, the polymerization is generally carried out at 20 to 180 ° C, preferably 40 to 120 ° C. The polymerization reaction is usually 0.0 with respect to the monomer to be polymerized.
It is carried out using 5 to 5% by weight of a radical polymerization initiator.
Examples of the initiator include azobis compounds, peroxides, hydroperoxides, redox catalysts, and the like, for example,
Potassium persulfate, tert-butyl peroctoate,
Examples thereof include benzoyl peroxide, isopropyl percarbonate, 2,4-dichlorobenzoyl peroxide, methyl ethyl ketone peroxide, cumene hydroperoxide, dicumyl peroxide, and azobisisobutyronitrile.

The molecular weight of the acid polymer used in the present invention is preferably 5 × 10 ³ or more, particularly preferably
1 × 10 ⁴ to 5 × 10 ⁶ (all are weight average molecular weights)
It is.

In the case of a silver halide photographic light-sensitive material having two or more hydrophilic colloid layers (silver halide emulsion layer and other hydrophilic colloid layers), the acid polymer is incorporated in all hydrophilic colloid layers. It may be added to at least one layer, and may not be added to other layers. The amount of the acid polymer in each layer when the acid polymer of the present invention is contained in two or more hydrophilic colloid layers can be optionally changed. For example, when the silver halide photographic light-sensitive material according to the present invention has at least one light-sensitive silver halide emulsion layer and a protective layer, it may be contained in both of them, or may be contained in either one of them. .

In the present invention, the neutralization ratio of the acid polymer preferably used may vary depending on the kind and amount of the hydrophobic monomer or the structure of the repeating unit having a carboxyl group and the like. Depending on the sum, a salt structure may be taken, or all the acid residues may take an acid structure. Basically, set the neutralization rate based on the range in which the acid polymer becomes soluble when mixed with a hydrophilic colloid as a guide, or add an alkali etc. at the time of dissolution to solubilize it. do it.

The neutralizing alkali may be of any type as long as it can form a salt with the acid polymer. As an example, potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonia and the like can be mentioned. These alkalis may be used alone or in an appropriate combination as a mixture.

The hydrophilic colloid to be mixed with the acid polymer is not particularly limited, and gelatin, for example, alkali-treated or acid-treated prepared from bones, skins of cow, pig, whale, fish etc. as a raw material is used. , Enzyme-treated gelatin, etc. can be used. In addition, gelatin modified by chemical modification, graft copolymerization, etc., gelatin modified by enzyme modification, etc., and gelatin graft-copolymerized with vinyl monomers and the like can be used. The molecular weight of gelatin is not particularly limited, and it can be used usually in the range of several hundred thousand to several thousand. Other than gelatin, for example, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose and cellulose sulfates; sugar derivatives such as sodium alginate, dextran and starch derivatives; chitin and its derivatives such as chitin, chitosan and hydroxyalkyl chitosan. ; Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N
-Various kinds of synthetic hydrophilic polymer substances such as vinylpyrrolidone, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and other single or copolymers can be used.

(Automatic Developing Machine) An automatic developing machine (also referred to as a developing machine) used in the processing method of the present invention will be described.
However, for the purpose of explanation, the following description will be made on a substantially three-tank automatic developing machine having a developing tank, a fixing tank, and a stabilizing tank.

FIG. 1 is a schematic diagram of an automatic processor. Since the fixing tank has the same configuration as the developing tank 1A, hereinafter, when the processing tank is described, both the developing tank 1A and the fixing tank 1B are referred to. It should be noted that, in the figure, a conveying means for conveying the photosensitive material is omitted for easy understanding of the configuration.

The processing tank of the automatic processor which is preferably used in the present invention is a processing section for processing a photosensitive material and a processing agent called a chemical mixer tank (hereinafter, CM tank) which is connected to the processing section by a pump and a pipe. (Concentrated liquid, tablets, etc.) Kit dissolution part. The cylindrical filter is replaceably provided below the CM tank near the pipe that goes to the processing tank, and has a function of removing insoluble matter in the processing liquid, such as paper waste.

The circulation system is composed of a circulation pipe forming a liquid circulation passage, a circulation pump, a processing tank and the like. The other end of the circulation pipe communicating with the discharge side of the circulation pump penetrates the lower wall of the CM tank and communicates with the CM tank. With such a configuration, when the circulation pump operates, the processing liquid is sucked from the CM tank and discharged to the processing unit. The replenishment amount can be adjusted by the discharge amount of the processing liquid from the circulation pump. 200ml /
m ² or less, particularly preferably 180 ml / m ² or less. The rod-shaped heater is arranged so as to be immersed in the CM tank. This heater is for heating the CM tank to facilitate dissolution of the tablets.

The processing amount information detecting means is provided at the entrance of the developing machine and is used for detecting the processing amount of the photosensitive material to be processed. The processing amount information detecting means includes a plurality of detecting members arranged in the left-right direction and functions as an element for detecting the width of the photosensitive material and counting the detected time. Since the conveying speed of the photosensitive material is mechanically set in advance, the processing area of the photosensitive material can be calculated from the width information and the time information. The processing amount information detecting means may be any means that can detect the width and the transport time of the photosensitive material, such as an infrared sensor, a microswitch, and an ultrasonic sensor. Furthermore, as the information to be detected, in the above description, it is not limited to these, but is processed.
The value may be a value proportional to the processed amount of the photosensitive material that has been processed or is being processed, and may be the concentration of the processing solution contained in the processing tank or a change in the concentration. Further, it is not necessary to provide the processing amount information detecting means for each processing tank, developing tank, fixing tank, and washing tank, and it is preferable to provide one processing amount information detecting means for one automatic developing machine.

The treatment agent supply section is controlled by the treatment agent supply control means described later, and works together with the supply signal emitted from the treatment agent supply control means to prepare the treatment liquid from the concentrated liquid or the tablets.

The processing agent supply control means controls the processing agent supply means, and processing amount information of the photosensitive material detected by the processing amount information detecting means (processing area in this embodiment).
When the value reaches a predetermined constant value, a processing agent supply signal is issued to the processing agent supply means. The treatment agent supply control means may control the treatment agent supply means so as to supply a necessary treatment agent amount to the CM tank according to the treatment amount information. The drying process of the automatic developing machine A uses a drying means using a heat roller.
Instead of this, it is preferable to employ a drying means using infrared radiation (for example, an infrared lamp).

Next, the operation of the present invention will be described with reference to the drawings. The processed amount information of the exposed photosensitive material is detected by the processed amount information means at the entrance of the automatic developing machine A. The processing agent supply control means issues a supply signal to the processing agent supply means when the accumulated area of the photosensitive material to be processed reaches a predetermined area in accordance with the processing amount information detected by the processing amount information detecting means. The processing agent supply means that has received the supply signal supplies the concentrated liquid or the tablets and dissolves them in the processing solution in the CM tank. The circulating means supplies the CM tank, the circulation pump, and the processing tank. On the other hand, the detected photosensitive material is sequentially conveyed by the roller conveying means through the developing tank 1A, the fixing tank 1B and the washing tank.
The developing tank 1A and the fixing tank 1B, which are processing tanks, respectively, may be provided with a processing agent supply means and supplied simultaneously.

In the present invention, the total processing time (Dry to
Dry) is preferably less than 45 seconds, more preferably 1
2 to 30 seconds.

In the present invention, the replenishment amounts of the developing solution and the fixing solution are preferably 200 ml / m ² or less for development processing. Since each replenishment amount cannot be processed only by taking out the processing liquid without replenishment, at least 30 ml / m ²
It is necessary to replenish, more preferably 30 to 1
60 ml / m ² , particularly preferably 30-100 ml / m
² .

The silver halide grains in the silver halide emulsion are preferably tabular silver halide grains. The tabular silver halide grain means a grain having two parallel main planes facing each other, and the aspect ratio is represented by a ratio of grain size to grain thickness. Here, the grain size means an average projected area diameter (hereinafter referred to as a grain size), and a diameter corresponding to a circle of a projected area of the tabular silver halide grains (a diameter of a circle having the same projected area as the silver halide grains). ), And the thickness means the distance between two parallel principal planes forming tabular silver halide grains.

The average aspect ratio of the tabular silver halide grains of the present invention is preferably 2 or more and less than 20, more preferably 3 or more and less than 15.

In the present invention, the emulsion layer containing tabular silver halide grains preferably comprises tabular silver halide grains having an aspect ratio of 2 or more in 50% or more of the total projected area, and more preferably 70% or more. , And more preferably 9
0% or more.

The tabular silver halide grains of the present invention are preferably silver chloroiodobromide or silver iodobromide, and the average silver iodide content is preferably 0 to less than 2 mol%,
1.0 mol% is more preferable.

The average grain size of the tabular silver halide grains of the present invention is preferably 0.15 to 5.0 μm,
The thickness is more preferably from 4 to 3.0 μm, most preferably from 0.4 to 2.0 μm.

The tabular silver halide grains of the present invention are preferably monodisperse emulsions having a narrow grain size distribution. Specifically, (standard deviation of grain size / average grain size) × 100 = broadness of grain size distribution (% When the breadth of distribution is defined by (), it is preferably 25% or less, and more preferably 20% or less.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method.

The above-mentioned emulsion is either a surface latent image type that forms a latent image on the grain surface, an internal latent image type that forms a latent image inside the grain, or a type that forms a latent image on the surface and inside. May be. These emulsions may use a cadmium salt, a lead salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof at the stage of physical ripening or grain preparation. The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method to remove soluble salts. As a preferred washing method, for example, a method using an aromatic hydrocarbon-based aldehyde resin containing a sulfo group described in JP-B-35-16086, or an aggregating polymer agent exemplified by G3 and G8 described in JP-A-63-158644 may be used. The method used is a particularly preferred desalting method. The chemical ripening method of the emulsion used in the light-sensitive material of the present invention is preferably gold sensitization, sulfur sensitization, reduction sensitization, increase with a chalcogen compound, or a combination thereof.

The emulsion of the light-sensitive material used in the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. A hydrazine compound can also be added, and a compound of Japanese Patent Application No. 5-134743 is preferable, and particularly a compound of the general formula (5) and a compound of the general formula (7) or (8) as a nucleation accelerator is preferable. A tetrazolium salt may be added, and those described in JP-A-2-250050 are particularly preferable. Other known additives include, for example, Research Disclosure No. 17
No. 643 (December 1978); 18716 (1
No. 997) and the same No. 308119 (1989
(December, 2000). The types of compounds and the locations described in these three research disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 III Hardener 26 X 651 Left 1004-5 X Surfactant Agents 26-27 XI 650 Right 1005-6 XI Antistatic Agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 003~4 IX support 28 XVII 1009 XVII

Examples of the support that can be used in the light-sensitive material of the present invention include the film containing SPS as a main component. The surface of the support may be provided with an undercoat layer, corona discharge, ultraviolet irradiation or the like in order to improve the adhesion of the coating layer. Further, a crossover cut layer or an antistatic layer may be provided. Emulsion layers may be present on both sides of the support, or only on one side. In the case of both sides, both sides may have the same performance or different performances.

[0065]

Embodiments of the present invention will be described below. The present invention is not limited to the examples described below. <Example 1> (Preparation of SPS support) << Polymerization example >> SPS pellets were prepared according to JP-A-3-131843. From the preparation of the catalyst to the polymerization reaction, all were carried out under a dry argon stream. Copper sulfate pentahydrate (CuSO ₄ .5H ₂ O) 1 in a glass container with an internal volume of 500 ml
Add 7.8 g (71 mmol) of purified benzene 200 ml and trimethylaluminum 24 ml,
The catalyst was adjusted by stirring for a period of time. This was placed under an argon gas flow. After filtering through a glass filter of No. 3, the filtrate was freeze-dried. This was taken out and placed in a 2-liter stainless steel container, and tributylaluminum and pentacyclopentadiethyl titanium methoxide were further mixed therein and heated to 90 ° C.

Into this, 1 liter of purified styrene was added, and further 70 ml of purified n-methylstyrene was added, and the polymerization reaction was continued at this temperature for 8 hours. After that, the mixture was cooled to room temperature, 1 liter of methylene chloride was added, and a methanol solution of sodium methylate was added with stirring to deactivate the catalyst. The content was gradually dropped into 20 liters of methanol, filtered through a glass filter, washed with methanol three times, and then dried.
Using 1,2,4-trichlorobenzene as a catalyst, 135
The weight average molecular weight of this polymer determined from the result of GPC measurement with standard polystyrene at 41 ° C was 415,000.
Met.

The melting point of this polymer is 13 at 245 ° C.
It was confirmed from the C-NMR measurement that the polymer obtained had a syndioctatic structure. This was pelletized with an extruder and then dried at 130 ° C.

(Preparation of SPS film) 330 in extruder
The SPS pellets obtained by the polymerization example were melt extruded at ℃. The molten polymer was extruded through a pipe into an extrusion die. Then, the SPS unstretched sheet having a film thickness of 1000 μm was obtained by extruding while being electrostatically applied to the casting drum cooled through the die slit and cooling.

The produced sheet was preheated at 115 ° C. and then stretched 3.3 times in the machine direction. After preheating at 100 ° C in a stenter, the film was stretched 3.3 times in the transverse direction at 130 ° C. Heat it at 225 ° C while relaxing it slightly in the lateral direction.
A 0 μm thick SPS film was obtained. The obtained SPS film was subjected to corona discharge for 23 w / m 2 and further sprayed with ion wind, and then the undercoating liquid 1 described below was provided so that the dry film thickness was 1 μm and dried at 140 ° C.

Undercoating liquid 1 Styrene-butadiene latex (No619 made by Japan Synthetic Rubber) 40 parts by weight Styrene-butadiene latex (made by No640 Japan Synthetic Rubber) 50 parts by weight Polystyrene matting agent (average particle size 3 μm) 5 parts by weight 2 , 4-dichloro-1,3,5-triazine sodium salt 3 parts by weight Sodium dodecylbenzene sulfonate 2 parts by weight After further corona discharge for 18 w / m 2 minutes, gelatin 80 parts by weight methyl cellulose 15 parts by weight dodecylbenzene Sodium sulfonate 3 parts by weight 2,4-dichloro-1,3,5-triazine sodium 2 parts by weight

A working liquid finished to 100 g with pure water was provided so as to have a dry film thickness of 0.1 μm, and further dried at 140 ° C. Next, this back surface was subjected to corona discharge for 23 w / m 2 and further sprayed with ion wind, and then the undercoating processing liquid 2 described below was provided so as to have a dry film thickness of 1 μm and dried at 140 ° C.

Undercoating liquid 2 Styrene-butadiene latex (No619 made by Japan synthetic rubber) 50 parts by weight Styrene-butadiene latex (No640 made by Japan synthetic rubber) 40 parts by weight Polystyrene matting agent (average particle size 3 μm) 5 parts by weight 2 , 4-dichloro-1,3,5-triazine sodium salt 3 parts by weight Sodium dodecylbenzene sulfonate 2 parts by weight After further corona discharge for 18 w / m 2 minutes, gelatin 20 parts by weight Methylcellulose 5 parts by weight Crystallinity Fine particles of tin oxide (antimony dope) 70 parts by weight Sodium dodecylbenzene sulfonate 3 parts by weight 2,4-dichloro-1,3,5-triazine sodium 2 parts by weight

A working liquid finished to 100 g with pure water was provided so as to have a dry film thickness of 0.1 μm, and further dried at 140 ° C. Furthermore, this undercoated support is 40 cm at 50 ° C.
It was wound on a radial core and heat-treated at this temperature for 3 days.

Example 2 A seed emulsion used in Examples and a method for preparing the emulsion will be shown. (Preparation of seed emulsion-1) A1 ossein gelatin 24.2 g water 9657 ml polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 6.78 ml potassium bromide 10.8 g 10% nitric acid 114 ml B1 2. 5N silver nitrate aqueous solution 2825 ml C1 potassium bromide 824 g potassium iodide 23.5 g Water is made up to 2825 ml. D1 1.75N potassium bromide aqueous solution Silver potential control amount below

Japanese Patent Publication Nos. 58-58288 and 5 at 35 ° C.
Solution A using a mixing stirrer described in JP-A-8-58289.
464.3 ml of each of the solution B1 and the solution C1 were added to the sample No. 1 by a simultaneous mixing method over 1.5 minutes to form nuclei. After that, it takes 60 minutes and the temperature of the solution A1 is adjusted to 60
After the temperature was raised to 0 ° C. and the pH was adjusted to 5.0 with 3% KOH, the solution B1 and the solution C1 were mixed again by the simultaneous mixing method.
Each was added at a flow rate of 55.4 ml / min for 42 minutes.

This temperature rise from 35 ° C. to 60 ° C. and solution B
The silver potentials (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during re-simultaneous mixing with 1 and C1 were controlled to be +8 mV and +16 mV, respectively, using the solution D1. After the addition was completed, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0. The hexagonal tabular grains have an average thickness of 0.06 μm and an average diameter. It was confirmed with an electron microscope that the (circle diameter conversion) was 0.59 μm. The variation coefficient of the thickness was 40%, and the variation coefficient of the distance between twin planes was 42%.

(Preparation of Emulsion Em-1) An emulsion Em-1 containing tabular grains having a core / shell structure was prepared by using the above seed emulsion 1 and the following four kinds of solutions. A2 Ocein gelatin 11.7 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous ethanol solution) 1.4 ml Seed emulsion 1 0.10 mol equivalent Make up to 550 ml with water. B2 Oscein gelatin 5.9 g Potassium bromide 6.2 g Potassium iodide 0.8 g Water to make 145 ml. C2 Silver nitrate 10.1 g Make up to 145 ml with water. D2 Oscein gelatin 6.1 g Potassium bromide 94 g Make up to 304 ml with water. E2 Silver nitrate 137 g Make up to 304 ml with water.

Solution A ₂ was stirred vigorously at 67 ° C. and solution B _{2 and} solution C ₂ were added by the double jet method in 58 minutes. Next, D ₂ liquid and E ₂ were added to the same liquid by the same double jet method for 48 minutes. During this time, the pH is 5.8.
The pAg was kept at 8.7. Seed emulsion 1 after addition
Desalination and precipitation were carried out in the same manner as in, and the pAg was 8.5 at 40 ° C.
A silver halide photographic emulsion having a pH of 5.85 and an average silver iodide content of 0.5 mol% was obtained. When the obtained emulsion Em-1 was observed with an electron microscope, 81% of the projected area had an average grain size of 0.96 μm, the breadth of the grain size distribution was 19%, and the average aspect ratio was about 4.5. It was a silver halide grain. The average twin plane distance (a) was 0.019 μm, and the coefficient of variation (a) was 28%.

(Emulsion sensitization) Obtained emulsion (Em-1)
Is heated to 60 ° C., and a predetermined amount of the following spectral sensitizing dye is added as a solid fine particle dispersion, and then a mixed solution of adenine, ammonium thiocyanate, chloroauric acid and sodium thiosulfate and triphenyl are added. Solid fine particle dispersion of phosphine selenide (average particle size 1.0μ
m) and 60 minutes later, a silver iodide fine grain emulsion is added.
Aging was performed for a total of 2 hours. At the end of aging, a predetermined amount of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene (hereinafter referred to as TAI) was added as a stabilizer.

The above-mentioned additives and their addition amounts (per mol of AgX) are shown below. Spectral sensitizing dye (A) 120 mg Spectral sensitizing dye (B) 2.0 mg Adenine 15 mg Potassium thiocyanate 95 mg Chloroauric acid 2.5 mg Sodium thiosulfate 2.4 mg Triphenylphosphine selenide 0.4 mg Silver iodide fine particles 280 mg TAI 50mg

The solid fine particle dispersion of the spectral sensitizing dyes (A) and (B) was prepared by a method according to the method described in JP-A-5-297496. That is, a predetermined amount of the above spectral sensitizing dye was added to water whose temperature was previously adjusted to 27 ° C., and the mixture was stirred by high speed stirring (dissolver) at 500 rpm for 30 to 120 minutes. The solid fine particle dispersion of triphenylphosphine selenide was also obtained in the same manner as the solid fine particle dispersion of the sensitizing dye.
The spectral sensitizing dyes (A) and (B) are shown below.

Spectral sensitizing dye (A) 5,5'-dichloro-9-ethyl-3,3'-di- (sulfopropyl) -oxacarbocyanine sodium salt anhydrous Spectral sensitizing dye (B) 5,5 ′ -Di- (butoxycarbonyl) -1,1′-diethyl-3,3′-di (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride

(Preparation of Acid Polymer Solution) The acid polymer is
It was prepared by a method described in “Synthetic Polymer” edited by Shunsuke Murahashi, using a commercially available monomer as a starting material. On the way, the reaction conditions were changed to synthesize the copolymers having different copolymerization ratios. Table 1 shows a list of the obtained substances. The obtained acid polymer was dissolved in distilled water to prepare a 7.5% solution. The insoluble one was used after adding an appropriate amount of potassium hydroxide to completely dissolve it.

[0084]

[Table 1]

(Preparation of Sample) The following coating liquid was applied to the SPS support prepared in Example 1 and the undercoating-processed thickness 175.
Samples 1 to 12 were prepared by simultaneously applying a transverse light-shielding layer, an emulsion layer, and an emulsion protective layer in this order from both sides on both sides of a polyethylene terephthalate support (comparative support) having a thickness of .mu.m and drying.

First layer (transverse light shielding layer) Solid fine particle dispersion dye (AH) 50 mg / m ² gelatin 0.2 g / m ² sodium dodecylbenzenesulfonate 5 mg / m ² compound (I) 5 mg / m ² 2, 4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 5 mg / m ² colloidal silica (average particle size 0.014 μm) 10 mg / m ² latex (L) 0.2 g / m ² potassium polystyrene sulfonate 50 mg / M ²

Second Layer (Emulsion Layer) Emulsion (Em-1) The coated silver amount was adjusted to be 1.8 g / m ² .

Potassium tetrachloropalladium (2) ate 100 mg / m ² compound (G) 0.5 mg / m ² 2,6-bis (hydroxyamino) -4-diethylamino-1,3,5-triazine 5 mg / m ² t-butyl-catechol 130 mg / m ² polyvinylpyrrolidone (molecular weight 10,000) 35 mg / m ² trimethylolpropane 350 mg / m ² diethylene glycol 50 mg / m ² nitrophenyl-triphenyl-phosphonium chloride 20 mg / m ² 1,3- Ammonium dihydroxybenzene-4-sulfonate 500 mg / m ² 2-mercaptobenzimidazole-5-sodium sulfonate 5 mg / m ² Compound (H) 0.5 mg / m ² C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N _{(CH 2 COOH)} 2 50 mg / ^{m 2} Compound (M) 5 mg / ^{m 2} Compound (N) 5 mg / ^{m 2} Ludox AM (Dupont) 0.5 g / ^{m 2} Latex (L) 0.4 g / ^{m 2} Dextran (average molecular weight 50,000) 0.3 g / m ² sorbitol 0.1 g / m ² However, the amount of gelatin was adjusted so that the total amount on one side was the amount shown in Table 2.

Third Layer (Protective Layer) Latex (L) 0.2 g / m ² Compound (K) 15 mg / m ² TAI 50 mg / m ² Polymethylmethacrylate (matting agent: average particle size 5.0 μm) 50 mg / m ² Colloidal silica (average particle size 0.014 μm) 10 mg / m ² Formaldehyde 20 mg / m ² Compound (P) 20 mg / m ² 2,4-Dichloro-6-hydroxy-1,3,5-triazine sodium salt 10 mg / m ² Bis-vinylsulfonylmethyl ether 36 mg / m ² polyacrylamide (average molecular weight 10,000) 0.1 g / m ² dextran (average molecular weight 50,000) 0.1 g / m ² polysiloxane (SI) 20 mg / m ² compound ( I) 12mg / ^{m 2} compound (J) 2mg / ^{m 2} compound ^{(S-1) 7mg / m} 2 compound (O 50 mg / ^{m 2} Compound ^{(S-2) 5mg / m} 2 Compound ^{(F-1) 3mg / m} 2 Compound ^{(F-2) 2mg / m} 2 Compound ^{(F-3) 1mg / m} 2 , however, the amount of gelatin is one-sided The total amount was adjusted so as to be the amount shown in Table 2.

[0090]

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[0091]

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[0092]

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The coating amount of the material was for one side, and the coated silver amount was adjusted to be 1.3 g / m ² for one side.

<< Evaluation >> (Measurement of Sensitivity) Samples 1 to 12 applied by dry coating were heated at a temperature of 23 ° C.
After storing at 55% RH for 3 days, it was divided into 4 parts, and one of them was sandwiched with an X-ray photographic intensifying screen KO-250 for sensitivity measurement, and was irradiated with X-rays through a penetrometer type B, and then, as shown in FIG. The automatic developing machine A shown in Fig. 6 and the automatic developing machine B different from the automatic developing machine A except that the drying process of the automatic developing machine A is changed to a drying means by infrared radiation.
Was treated with a developing solution and a fixing solution having the following composition. The sensitivity was expressed as a relative value with the reciprocal of the exposure energy amount required for the sample 1 to give a density of fog +1.0 as 100.

(Measurement of Fog) Two of the above remaining samples were used, and one of them was stored under the above conditions for a further 5 days. The other one is stored at high humidity as a substitute test at a temperature of 50 ° C and 8
Stored at 0% RH for 5 days. These samples were treated with a developing solution and a fixing solution having the following compositions without being exposed, and then fog was measured to evaluate the storage stability. The fog value indicates the net fog density after subtracting the film base density.

(Evaluation of Roller Mark) The remaining one of the above-obtained samples was uniformly exposed to a blackening density of 1.0 (10 × 12 inches) per four-section size, and then Processed. However, the developing rack used at this time and the transfer rack from developing to fixing were intentionally fatigued. That is, the rollers in each rack are fatigued, so about 1
Unevenness of about 0 μm was formed on the entire surface. Due to the pressure caused by this unevenness in the processed sample, many fine spot-like density unevenness occurred in the sample with poor pressure resistance. This level was visually judged by the following ranks.

Evaluation Criteria 5: No Spots Occurred 4: Slight Spots Occurred but Not a Practical Problem Level 3: Permissible Limit Level where Small Spots Occur but Not Normally in Rack 2: Spots It occurs, and it sometimes occurs even in normal racks. 1: There are many spots, and it always occurs in normal racks.

[0098] Note) Drying temperature is the temperature of the drying fan. The surface temperature of the heat roller is 70 ℃ and the temperature of the infrared heater is 2
00 ° C.

(Developer Formulation) Part A (for 12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethyleneetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-phenyl- 5-Mercaptotetrazole 0.2 g Hydroquinone 340 g Water is added to make 5000 ml.

Part B (for 12 liter finish) glacial acetic acid 170 g triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0.4 g

<Starter> Glacial acetic acid 120 g Potassium bromide 225 g Water is added to make 1000 ml.

(Fixing Solution Formulation) Part A (for 18 liter finish) Ammonium thiosulfate (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate / trihydrate 450 g Glacial acetic acid 17.3 g Sodium citrate 50 g Gluconic acid 70 g 1- (N , N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g

Part B (for 18 liter finish) Aluminum Sulfate 800 g

The developer was prepared by adding Part to about 5 liters of water.
A and Part B were added at the same time, water was added while stirring and dissolving to make 12 liters, and the pH was adjusted to 10.40 with glacial acetic acid. This was used as a developing solution, and the developing replenisher used was the same as the developing solution. 20 ml / l of the starter was added to the developer replenisher to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part to 5 liters of water.
Add A and Part B at the same time, add water while stirring and dissolve to make 18 liters, and add sulfuric acid and NaOH to p.
The H was adjusted to 4.4. This was used as a fixing solution, and the fixing replenishing solution was the same as the fixing solution. Table 2 shows the results.

[0106]

[Table 2]

From the results shown in Table 2, it can be seen that the samples according to the present invention have high sensitivity, excellent storability and excellent roller mark resistance.

Example 3 Samples 1 to 6, 8, 10, and 12 prepared in Example 2 were irradiated with X-rays, and then the automatic developing machine A shown in FIG. Was processed in the same manner as in Example 2. Each sample was treated under the following conditions until it reached running equilibrium to prepare running equilibrium solutions 1 and 2.

[0109] The replenishment conditions for the developing equilibrium solutions 1 and 2 are shown as replenishment conditions for the developing solution per one-quarter size sheet (10 × 12 inches). In parentheses, the converted amount per m ² is shown.

Replenishment Conditions Running Equilibrium Solution 1 Running Equilibrium Solution 2 Development Replenishment Amount 14.0 ml 7.0 ml (180 ml / m ² ) (90 ml / m ² ) Fixing Replenishment Amount 14.0 ml 70. ml (180 ml / m ² ) (90 ml / m ² )

Each of the above samples was treated under the above conditions using Running Equilibration Solution 1 (Condition 1) and (Condition 2), and the sensitivity, roller mark, developed silver color tone and reflection spot unevenness were evaluated. The sensitivity and the evaluation of the roller mark are the same as in Example 2.

(Evaluation of color tone of developed silver) The prepared sample was exposed to light so that the transmission density after development was 1.2, and then developed using the automatic developing machine. The obtained developed sample was observed on a Schaukasten, and the silver tone due to transmitted light was visually evaluated. Evaluation A: Pure black B: Reddish black C: Yellowish black D: Yellowish black

(Evaluation of reflection spot unevenness) The sample exposed to a density of 1.0 was developed by the above method, the glossiness of the sample surface was observed, and the occurrence of spot unevenness was visually evaluated by the following. . A: Almost no occurrence B: Some occurrence but no problem C: Many problems D: D

[0114]

[Table 3]

From the results of Table 3, the samples according to the present invention were treated with the equilibrium solution which had been subjected to the running treatment with a low replenishment amount,
It can be seen that the developed silver color tone is excellent without occurrence of roller marks and uneven reflection spots.

[Brief description of the drawings]

FIG. 1 is a schematic view of an automatic processor A used in an example.

Claims (6)

[Claims] 1. At least 50% or more of the components of the support are made of a styrene polymer having a syndioctatic structure, and a hydrophilic colloid layer containing at least one silver halide emulsion layer is provided on the support. In the silver halide photographic light-sensitive material, a polymer containing 15 mol% or more of a monomer having at least one kind of acid residue selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group and salts thereof in the hydrophilic colloid layer. A silver halide photographic light-sensitive material comprising: 2. At least 50% or more of the components of the support are made of a styrene polymer having a syndioctatic structure, and a hydrophilic colloid layer containing at least one silver halide emulsion layer is provided on the support. In a silver halide photographic light-sensitive material, at least one of the hydrophilic colloid layers contains a monomer having at least one kind of acid residue selected from a carboxyl group, a phosphoric acid group, a sulfonic acid group and salts thereof. A method of processing a silver halide photographic light-sensitive material, which comprises processing a silver halide photographic light-sensitive material containing a polymer in an amount of at least mol% in a processing step including a developing step, a fixing step and a drying step. 3. The method of processing a silver halide photographic light-sensitive material according to claim 2, wherein the drying step is a heat roller drying method. 4. The method of processing a silver halide photographic light-sensitive material according to claim 2, wherein the drying step is a drying method by infrared radiation. 5. The method for processing a silver halide photographic light-sensitive material according to claim 2, 3 or 4, wherein the total processing time (Dry
to Dry) is less than 45 seconds, a method for processing a silver halide photographic light-sensitive material. 6. The method for processing a silver halide photographic light-sensitive material according to claim 2, 3 or 4, wherein the total processing time (Dry) is
to Dry) is less than 45 seconds, and the replenishing amount of the developing solution in the developing process and the replenishing amount of the fixing solution in the fixing process are each 200 ml / m ² or less. Processing method.