JPH0862789A - Development processing method for silver halide photographic sensitive material and developing solution regeneration method - Google Patents

Abstract

PURPOSE: To provide a processing method for the photosensitive material scarcely probable to cause problems, such as lowering of density, sensitivity, and contrast in the case of rapid processing in an automatic developing machine, and deterioration in linearity in a scanning process. CONSTITUTION: The photosensitive material has at least one silver halide emulsion layer on a substrate, and it is developed in the automatic developing machine by using a developing solution containing a developing agent comprising a transition metal complex salt but substantially not any of hydroquinones and the total processing time from the time of insertion of the forward end of the film into the automatic developing machine to the time of appearance of that from its drying zone (Dry to Dry) is <=60sec, and the regeneration method for the developing solution is contained in this invention.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a development processing method for silver halide photographic light-sensitive materials, and more particularly to a development processing method adapted for rapid development processing and a developer regenerating method thereof.

[0002]

2. Description of the Related Art A black and white silver halide photographic light-sensitive material, particularly a light-sensitive material for printing plate making, is generally photoprocessed by an automatic processor having four processes of developing, fixing, washing and drying after exposure. In the development, a developing solution containing an organic developing agent such as hydroquinone has been used.

On the other hand, when processing with an automatic processor,
Conventionally, the total processing time (Dry to
Dry) usually took 90 seconds or more, but in recent years, the development processing time has been shortened due to the increase in the number of printing points and the labor time, and the total processing time (Dry to Dry) is 60 seconds or less. It has become necessary to carry out rapid processing.

However, when the above-mentioned light-sensitive material is continuously processed by the automatic processor under such rapid processing conditions, problems such as lack of contrast and deterioration of linearity in the scanner process often occur.

Further, in recent years, there has been an urgent need to reduce the amount of developer waste liquid as interest in the environment has increased. As one of the means for reducing the amount of waste liquid, there is recycling of the developer. However, under the present circumstances, it is difficult to recycle the developer containing hydroquinone as the organic developing agent as described above.

[0006]

In order to solve the above problems, an object of the present invention is to reduce the density and sensitivity, soften the tone, and deteriorate the linearity in the scanner process even when the processing is rapidly performed by an automatic processor. It is an object of the present invention to provide a method of processing a silver halide light-sensitive material that is less likely to cause problems.
Another object of the present invention is to provide a method of regenerating a developer after processing a silver halide photographic light-sensitive material, and deterioration of photographic performance such as softening and deterioration of sensitivity even if development processing is performed with the regenerated solution. Another object of the present invention is to provide a method for developing and processing a silver halide photographic light-sensitive material that is less likely to occur.

[0007]

The above object of the present invention can be achieved by the following constitutions.

1) In a method for developing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support by an automatic processor, it contains substantially no hydroquinone and is a transition metal complex salt. The total processing time (Dry to Dry) from the time the film tip is inserted into the automatic processor to the time it comes out of the drying zone is 10 seconds or more 60
A method for developing and processing a silver halide photographic light-sensitive material, which comprises processing in seconds or less.

2) The silver halide photographic light-sensitive material is developed with the developer, the developer is regenerated by energizing, and then another silver halide photographic light-sensitive material is developed. Method for developing a silver halide photographic light-sensitive material.

3) The silver halide photographic light-sensitive material is
The silver / binder weight ratio of the silver halide emulsion layer forming an image is 0.7 or more and 1.3 or less, and the thickness of the protective layer coated on the silver halide emulsion layer is 0.6 μm or more and 2.0 or less.
3. The method for developing and processing a silver halide photographic light-sensitive material as described in 1 or 2 above, wherein the method is less than or equal to μm.

4) The silver halide photographic light-sensitive material is
1. The above-mentioned 1, 2 which is characterized in that it has at least one non-photosensitive hydrophilic colloid layer and at least one hydrophobic polymer layer on the surface opposite to the surface having the silver halide emulsion layer and the surface opposite the support. 4. The method for developing a silver halide photographic light-sensitive material as described in 3 above.

5) After developing the silver halide photographic light-sensitive material with a developing solution containing substantially no hydroquinones and containing a developing agent composed of a transition metal complex salt, the developing solution is regenerated by energizing. Characteristic developer regenerating method.

The present invention will be described in detail below.

Examples of the developing agent composed of a transition metal complex salt that can be used in the present invention include Ti, V, Cr, Mn and F.
It is a complex salt of a transition metal such as e, Co, Ni and Cu, preferably T
It is a complex salt of i, V, Cr and Fe. These may be in a form having a reducing power for use as a developing solution, for example, T
It is known to take the form of complex salts such as i ³⁺ , V ²⁺ , Cr ²⁺ , Fe ²⁺ . Specific ligands include aminopolycarboxylic acids such as ethylenediaminetetraacetic acid (EDTA) and diethylenetriaminepentaacetic acid (DTPA) and salts thereof, and phosphoric acids such as hexametapolyphosphoric acid and tetrapolyphosphoric acid and salts thereof. To be Among these, transition metal complex salts having a ligand such as EDTA and DTPA are particularly preferably used.

Specific examples of preferable ligands are shown below, but the ligands are not limited thereto.

(1) ethylenediaminetetraacetic acid (EDTA) (2) diethylenetriaminepentaacetic acid (DTPA) (3) triethylenetetraminehexaacetic acid (TTHA) (4) hydroxyethylethylenediaminetriacetic acid (HEDTA) (5) nitrilotriacetic acid ( NTA) (6) 1,2-diaminocyclohexanetetraacetic acid (7) 1,3-diamino-2-propanoltetraacetic acid (8) hexametapolyphosphoric acid (9) tetrapolyphosphoric acid -41899 are mentioned.

The complex according to the present invention can be formed in a developing solution by adding a transition metal salt and a ligand compound. The content of the compound according to the present invention in the developer is preferably 1 to 100 g per liter of the developer.

In the present invention, substantially hydroquinones (eg, hydroquinone, chlorohydroquinone,
Brom hydroquinone, methyl hydroquinone, hydroquinone monosulfonate, etc.) is not contained. The term "substantially free of" means a content of less than 0.01 mol per liter of the developing solution.

In the present invention, the developing agent comprising the transition metal complex salt according to the present invention and the developing agents of 3-pyrazolidones and aminophenols can be used in combination. When used in combination, the developing agents such as 3-pyrazolidones and aminophenols are usually preferably used in an amount of 0.01 to 1.0 mol per liter of the developing solution.

In the present invention, a sulfite, metabisulfite, sodium sulfite, potassium sulfite, ammonium sulfite, sodium metabisulfite and the like can be used as a preservative in the developing solution. Sulfite is 0.25 mol /
It is preferably 1 or more. It is particularly preferably 0.4 mol / l or more.

In the present invention, when processing with a developing solution containing a transition metal complex salt developing agent, it is preferable that the developing solution contains a compound represented by the following general formula (I) as a silver sludge inhibitor.

General formula (I) Z ₁ -SM _{1 In the} formula, Z ₁ represents an alkyl group, an aromatic group or a heterocyclic group, and a hydroxy group, -SO ₃ M ₂ , -COOM ₂ (here, M ₂ Represents a hydrogen atom, an alkali metal atom, a substituted or unsubstituted ammonium ion), a substituted or unsubstituted amino group, or a substituted or unsubstituted ammonio group.
Or a substituent having at least one selected from these. M ₁ represents a hydrogen atom, an alkali metal atom, or a substituted or unsubstituted amidino group (which may form a hydrohalide salt or a sulfonate salt).

The alkyl group represented by Z ₁ is preferably a straight chain, branched or cyclic group having 1 to 30 carbon atoms (more preferably 2 to 20 carbon atoms) and further having another substituent. Good. The aromatic group is preferably a monocyclic or condensed ring having 6 to 32 carbon atoms and may further have another substituent. The heterocyclic group is preferably a monocyclic ring or a condensed ring having 1 to 32 carbon atoms, and a 5- or 6-membered ring having at least one hetero atom (≤6) selected from nitrogen, oxygen and sulfur It may have a substituent. Z ₁ is preferably a heterocyclic group having 2 or more nitrogen atoms. More preferably, it is a heterocyclic group having at least one 6-membered ring having 2 or more nitrogen atoms.

When Z ₁ has an ammonio group as a substituent or a substituent of a substituent, it preferably has 20 carbon atoms.
Below, it has a substituted or unsubstituted alkyl group, a substituted or unsubstituted phenyl group, or a naphthyl group as a substituent.

Specific examples of the compound will be shown below, but the invention is not limited thereto.

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[0028]

[Chemical 3]

[0029]

[Chemical 4]

[0030]

[Chemical 5]

In the present invention, the compound of the general formula (I) is preferably used in an amount of 10 ^-6 to 10 ^-1 mol, and more preferably 10 ^-5 to 10 ^-2 mol, per liter of the developing solution.

In the developer of the present invention, if necessary, an alkaline agent (sodium hydroxide, potassium hydroxide, etc.),
pH buffers (eg carbonates, phosphates, borates,
Boric acid, acetic acid, citric acid, alkanolamine, etc.),
Dissolution aids (eg polyethylene glycols, their esters, alkanolamines, etc.), sensitizers (eg nonionic surfactants containing polyoxyethylenes,
Quaternary ammonium compounds, etc., surfactants, defoamers,
Antifoggants (eg, halogens such as potassium bromide, sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazoles, thiazoles, etc.), chelating agents (eg ethylenediaminetetraacetic acid or its alkali) Metal salts, nitrilotriacetates, polyphosphates, etc., development accelerators (eg US Pat. No. 2,304,025,
The compounds described in JP-B-47-45541), hardeners (eg glutaraldehyde or bisulfite adduct thereof), antifoaming agents and the like can be added. The pH of the developer is preferably adjusted to less than 11.0.

As the fixer used in the automatic processor of the present invention, those having a generally used composition can be used. The fixing solution is generally an aqueous solution containing a fixing agent and others, and the pH is usually 3.8 to 5.8. Examples of the fixing agent include thiosulfates such as sodium thiosulfate, potassium thiosulfate and ammonium thiosulfate, thiocyanates such as sodium thiocyanate, potassium thiocyanate and ammonium thiocyanate, and organic sulfur compounds capable of forming a soluble stable silver complex salt. A known fixing agent can be used.

A water-soluble aluminum salt acting as a hardening agent, for example, aluminum chloride, aluminum sulfate, potassium alum or the like can be added to the fixing solution. If desired, the fixer may contain a compound such as a preservative (eg, sulfite or bisulfite), a pH buffer (eg, acetic acid), a pH adjusting agent (eg, sulfuric acid), a chelating agent having a water softening ability, or the like. Can be included.

In the development processing of the present invention, the development temperature is
It can be set to a normal temperature range of 20-30 ° C,
It can also be set to a high temperature treatment range of 30 to 40 ° C.

In the present invention, the total processing time (Dry to Dry) from the insertion of the leading edge of the film into the automatic processor until the leading edge of the film comes out of the drying zone is 10 to 60 seconds. The total processing time referred to here includes all process times required for processing a black and white silver halide photographic light-sensitive material, and specifically includes, for example, development, fixing, bleaching, washing with water, stabilization processing and drying necessary for processing. Time including all process time, that is, Dry to D
It's ry time. If the total processing time is less than 10 seconds, satisfactory photographic performance cannot be obtained due to desensitization and softening. More preferably, the total processing time (Dry to Dry) is 20 to 48 seconds.

The black-and-white light-sensitive material according to the present invention is processed by using an automatic developing machine. At that time, the black-and-white light-sensitive material is processed while replenishing a certain amount of developing solution proportional to the area of the light-sensitive material. The development replenishment rate is 300 m / m ² to reduce the amount of waste liquid.
l or less. It is preferably 75 to 200 ml per 1 m ² .

In the automatic processor, a heat conductor having a temperature of 90 ° C. or higher (for example, a heat roller of 90 ° C. to 130 ° C.) or 150
Radiant materials above ℃ (for example, tungsten, carbon, nichrome, zirconium oxide / yttrium oxide / thorium oxide mixture, silicon carbide, etc. can be used to generate heat and radiate heat directly, or to generate heat energy from resistance heating elements such as copper, stainless steel, nickel, etc. Those that emit infrared radiation by transmitting heat to a radiator such as ceramic) and those that have a drying zone are included.

In the present invention, the developing solution having deteriorated developing ability is regenerated by energizing. Specifically, a cathode is put in the deteriorated developer and an anode is put in the electrolyte solution so that the deteriorated developer tank and the electrolyte solution tank are in contact with each other through an anion exchange membrane, and both electrodes are energized for regeneration. It is also possible to process the light-sensitive material according to the present invention while energizing.

The cathode used in the present invention may be an electric conductor or a semiconductor. For example, stainless steel or the like is preferably used, and stainless wool is particularly preferable in order to increase the surface area and increase the efficiency. An insoluble electric conductor is used as the anode. For example, carbon, gold, platinum, titanium and the like are preferable, and platinum plating of titanium is particularly preferable.
As the anion exchange membrane used in the present invention, a commercially available one can be used.

The regenerated developer is returned to the developing tank of the automatic developing machine and is used again for development. At that time, various additives added to the developer, for example, a pH buffer agent, a preservative, which can be added to the developer as described above,
A development inhibitor, a silver sludge inhibitor, etc. can be additionally added. Further, as another embodiment, there is a method of processing the light-sensitive material of the present invention while energizing a developing solution, and in that case, an additive which can be added to the developing solution as described above can be additionally added.

The image forming silver halide emulsion layer in the present invention refers to a photosensitive silver halide emulsion layer according to the present invention described later. The silver / binder weight ratio referred to in the present invention refers to a value obtained by dividing the weight of silver per unit area by the weight of the binder, and the binder means a solid content other than the silver halide grains contained in the emulsion, Specifically, it represents the total solid content of gelatin, latex, and other various additives contained in the emulsion layer. The silver / binder weight ratio is 0.7 or more and 1.3 or less, and particularly preferably 0.8 to 1.2.

The protective layer coated on the silver halide emulsion layer forming an image is a hydrophilic colloid layer having substantially no photosensitivity and is used for the purpose of protecting the photosensitive emulsion layer. Usually, it is provided on the outermost surface. The light-sensitive material according to the present invention may have a single emulsion layer or protective layer, or 2
It may be a multi-layer composed of more than one layer. In the case of multiple layers, an intermediate layer or the like may be provided between them. When there are two or more emulsion layers, the protective layer means the thickness from the uppermost emulsion layer. An emulsion layer which is a non-photosensitive layer and does not substantially contribute to image formation can be coated for various purposes.

The method of 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, grapia coating method, or US Pat.
Extrusion coating method using a hopper described in 681,294, or U.S. Patents 2,761,418 and 3,508,947
No. 2,761,791, the multilayer simultaneous coating method can be used.

The back layer of the present invention may be one layer or may be composed of two or more layers. When the back layer is composed of two or more layers, it is necessary to provide the hydrophobic polymer layer of the present invention on at least one of the back layers.

The appropriate value of the total hydrophilic colloid amount of the back layer / the total hydrophilic colloid amount of the emulsion surface (weight ratio) varies depending on the total hydrophilic colloid amount of the silver halide photographic light-sensitive material, the coated silver amount and the support thickness. However, a larger value is preferable in terms of curling. Therefore, the total amount of the hydrophilic colloid in the back layer of the present invention is 0.1 times or more (the total amount of the hydrophilic colloids in the emulsion surface) of the total amount of the hydrophilic colloids in the surface (A side) on which the silver halide emulsion layer is coated. The weight ratio is preferably 0.32 or more.

Gelatin is most preferably used as the hydrophilic colloid used as the binder of the back layer of the present invention. 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.

Examples of hydrophilic colloids other than gelatin include colloidal albumin, proteins such as casein, agar, sodium alginate, sugar derivatives such as starch derivatives, carboxymethyl cellulose and hydroxymethyl cellulose.

Next, the hydrophobic polymer layer (hereinafter referred to as polymer layer) on the back surface of the present invention will be described. The polymer layer is a layer using a hydrophobic polymer as a binder. 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, and cellulose resins such as cellulose triacetate. , Water-insoluble polymer such as silicone resin, or
These derivatives can be mentioned. 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. Particularly preferred binders are copolymers of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid (acrylic acid or methacrylic acid is preferably 5 mol% or less), styrene-butadiene copolymer, styrene-butadiene-acrylic acid copolymer (acrylic acid is 5 mol% or less), styrene-butadiene-divinylbenzene-methacrylic acid copolymer (methacrylic acid is preferably 5 mol% or less), vinyl acetate-ethylene-acrylic acid copolymer (acrylic acid is 5 mol% or less), vinylidene chloride -Acrylonitrile-
Examples thereof include methyl methacrylate-ethyl acrylate-acrylic acid copolymer (acrylic acid 5 mol% or less), ethyl acrylate-glycidyl methacrylate-acrylic acid copolymer and the like. These may be used alone or 2
You may use it in combination of 2 or more types.

In the polymer layer of the present invention, a photographic additive such as a matting agent, a surfactant, a dye, a slipping agent, a cross-linking agent, a thickener, a UV absorber, and inorganic fine particles such as colloidal silica may be added, if necessary. May be added. For these additives, Research Disclosure Vol. 176, Item 17646 (197)
You can refer to the description in December 8).

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 hindered, 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 in the range of 0.05 to 10 μm, 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 the solvent of the binder of the polymer layer and applied in a solvent system, or may be applied in an aqueous system using an aqueous dispersion of the binder polymer.

The halogen composition of the silver halide in the silver halide emulsion layer according to the present invention is not particularly limited, but is preferably silver chloride, silver chlorobromide containing 60 mol% or more of silver chloride or 60.
Silver chloroiodobromide containing silver chloride in an amount of more than mol%.

The average grain size of silver halide is preferably 0.7 μm or less, and more preferably 0.5 to 0.1 μm. The average particle size is a term that is commonly used and easily understood by experts in the field of photographic science. The particle size means a particle diameter when the particles are spherical or particles which can be approximated to a sphere. When the particle is a cube, it is converted into a sphere, and the diameter of the sphere is taken as the particle size. For more information on determining the average particle size, see Mies, James: The Theory of the
Photographic process (CEMees & T.H.James
Author: The theory of the photographic process), No. 3
Edition, pp. 36-43 (1966 (published by McMillan "Mcmillan")).

The shape of the silver halide grains is not limited,
Any shape such as a flat plate shape, a spherical shape, a cubic shape, a 14-sided shape, a regular octahedron shape or the like may be used. Also, it is preferable that the particle size distribution is narrow, especially 90% of the total number of particles within the particle size range of ± 40% of the average particle size.
%, Desirably 95%, so-called monodispersed emulsions are preferred.

As the method for reacting the soluble silver salt and the soluble halogen salt in the present invention, any of a one-sided mixing method, a simultaneous mixing method, a combination thereof and the like may be used.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one type of simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is formed, that is, a so-called controlled double jet method can be used. A silver halide emulsion having a uniform grain size can be obtained.

The silver halide grains used in the silver halide emulsion are cadmium salt, zinc salt, lead salt, thallium salt, iridium salt, rhodium salt, or at least one of them during the grain forming process or the growing process. It is preferable to add a complex salt containing the element.

For details of the silver halide emulsion and its preparation method, see Research Disclosure (Resear).
ch Disclosure) No. 176, 17643, pages 22-23 (December 1978)
It is described in the literature described or cited.

The silver halide emulsion may or may not be chemically sensitized. As chemical sensitization methods, sulfur sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these may be used alone or in combination. The preferred chemical sensitization method is sulfur sensitization, and as the sulfur sensitizer, various sulfur compounds other than the sulfur compound contained in gelatin, such as thiosulfates, thioureas, rhodanins, and polysulfide compounds, are used. Can be used.

Among the noble metal sensitizing methods, the gold sensitizing method is a typical one, and a gold compound, mainly a gold complex salt is used. Noble metals other than gold, for example, platinum, palladium, rhodium and other complex salts may be contained.

Examples of the reduction sensitizer include stannous salt, amines,
Formamidine sulfinic acid, a silane compound, etc. can be used.

The silver halide emulsion can be spectrally sensitized to a desired wavelength with a sensitizing dye. Sensitizing dyes that can be used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these Nuclei of aromatic hydrocarbon ring fused to the nuclei of indolenin, benzindolenine, indole, benzoxazole, naphthoxazole, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole , Quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms. As a nucleus having a ketomethylene structure in the merocyanine dye or the composite merocyanine dye,
5-6 such as pyrazolin-5-one nucleus, thiohydantoin nucleus, 2-thiooxazolidine-2,4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbituric acid nucleus
A member ring can be applied. Specifically, those described in Research Disclosure Vol. 176, RD-17643 (December, 1978), pages 2-3, US Pat. Nos. 4,425,425 and 4,425,426 can be used. The sensitizing dye may be dissolved using ultrasonic vibration described in US Pat. No. 3,485,634. In addition, as a method of dissolving or dispersing the sensitizing dye of the present invention in an emulsion, U.S. Patent Nos. 3,482,981, 3,585,195 and 3,469,98 are cited.
7, 3,425,835, 3,342,605, British Patent 1,271,3
No. 29, No. 1,038,029, No. 1,121,174, U.S. Pat.
The methods described in No. 101 and No. 3,658,546 can be used. These sensitizing dyes may be used alone or in combination, and the combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Research Disclosure is a combination of dyes that exhibit useful supersensitization and substances that exhibit supersensitization.
Volume 176, 17643 (issued December 1978), page 23, IV, section J.

The light-sensitive material used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, azoles, for example, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-
Phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, such as triazaindenes, tetrazaindenes (especially 4-hydroxy-substituted-1,3, 3a, 7-Tetrazaindenes), pentazaindenes, etc .; many compounds known as antifoggants or stabilizers such as benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, etc. may be added. it can.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methyloldimethylhydantoin etc.), dioxane derivative (2,3-dihydroxydioxane etc.), active vinyl compound (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-
Methylenebis- [β- (vinylsulfonyl) propionamide] etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine etc.), mucohalogen acids (mucochloric acid, phenoxymucochloric acid etc.) isoxazole , Dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin and the like can be used alone or in combination.

The photosensitive emulsion layer and / or the non-photosensitive hydrophilic colloid layer of the present invention may be used for various purposes such as a coating aid, antistatic property, slipperiness improvement, emulsion dispersion, adhesion prevention and photographic property improvement. Known surfactants may be used.

Gelatin is advantageously used as the binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol. , Polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid,
A wide variety of synthetic hydrophilic polymeric substances such as polyacrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used.

Examples of gelatin include lime-processed gelatin,
Acid-treated gelatin may be used, gelatin hydrolyzate,
Gelatin enzymatic degradation products can also be used.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxyacryl (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide,
Vinyl ester (eg vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination,
Alternatively, it is possible to use a polymer having a monomer component of a combination of these with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrenesulfonic acid, or the like. it can.

Various other additives are used in the light-sensitive material used in the present invention. Examples thereof include desensitizers, plasticizers, slip agents, development accelerators, oils and dyes.

Regarding these additives and the above-mentioned additives, specifically, those described in Research Disclosure No. 176 (supra), pages 22 to 31 can be used.

In the light-sensitive material of the present invention, the photographic emulsion layer and other layers are coated on one side or both sides of a flexible support usually used for light-sensitive materials. Useful as the flexible support are films made of synthetic polymers such as cellulose acetate, cellulose acetate butyrate, polystyrene and polyethylene terephthalate.

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EXAMPLES Next, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.

Example 1 8 W / (m
After corona discharge with energy of ² · min), an antistatic liquid having the following composition was applied at a rate of 30 m / min using a roll-fit coating pan and an air knife so as to have the following coating amount.

(Preparation of Support Having Conductive Layer) After corona discharge to 100 μm-thick polyethylene terephthalate subjected to undercoating treatment, an antistatic liquid having the following constitution was applied at 70 m / min at the following coating amount. It was applied at high speed using a roll-fit coating pan and air knife.

Water-soluble conductive polymer P-6 0.6 g / m ² Hydrophobic polymer particles L-1 0.4 g / m ² Polyethylene oxide compound Ao-1 0.06 g / m ² Hardener E-8 0.2 g / m ² This was dried at 90 ° C. for 2 minutes and heat-treated at 140 ° C. for 90 seconds. A substrate was prepared by coating this conductive layer on one side.

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[Chemical 6]

(Preparation of silver halide emulsion) Silver chloroiodobromide (62 mol% of silver chloride, 0.5 mol% of silver iodide) was prepared by the simultaneous mixing method.
Others were silver bromide) emulsions.

In the mixing step from the formation of 5% of the final reaching average particle size to the reaching of the final reaching average particle size, hexabromorhodiate potassium salt and potassium hexachloroiridate were respectively added in an amount of 8 × per mol of silver. 10 ⁻⁸ mol and 8 × 10 ⁻⁷ mol were added.

The obtained emulsion was desalted by a conventional flocculation method using a modified gelatin treated with phenyl isocyanate and then dispersed in gelatin to be used as an antifungal agent [A] or [B] below. And [C] are added and the average particle size is 0.30
An emulsion consisting of cubic monodisperse grains of 10 μm (coefficient of variation 10%) was obtained.

[0081]

[Chemical 7]

To this emulsion was added citric acid and sodium chloride and
After adding 1-phenyl-5-mercaptotetrazole, chloroauric acid and sodium thiosulfate were added and chemically aged at 60 ° C to reach maximum sensitivity, then 4-hydroxy-6-methyl-1,3,3
After ripening was stopped by adding 1 g of a, 7-tetrazaindene per 1 mol of silver, 600 mg of potassium bromide and 150 mg of a sensitizing dye having the following structure SD-1 were added per 1 mol of silver halide.

(Preparation of emulsion coating solution) In this emulsion, 4 g of hydroquinone per mol of silver halide, 15 g of polymer latex P-1 having the following structure, 150 mg of inhibitor ST-1 and 2 g of styrene-maleic acid polymer were used. , 1N sodium hydroxide solution, 1.5 g of the following structure S-1 and saponin as a coating aid and 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt as a hardener were added. .

(Preparation of Emulsion Protective Layer Coating Solution) For every 1 m ² , an aqueous solution containing 1.1 g of gelatin was added with 1 mg of formalin adduct of sodium bisulfite and 5.5 mg of 1-phenyl-4-hydroxymethyl-3-pyrazolidone. 15 mg each of monodispersed silica having an average particle size of 3 μm and an average particle size of 8 μm was added with the following structure S-2 as a coating aid and citric acid, and formalin was added as a hardening agent. Further, a fluorinated surfactant FA-33 was added so that the coating amount was 3 × 10 ^-6 mol / m ² .

(Preparation of coating solution for backing layer) An aqueous solution containing 2.3 g of gelatin per 1 m ² was added with 100 mg of the water-soluble dye compound III-1, 25 mg of III-3 and 100 mg of III-3.
Polymer latex P-1 350 mg, styrene-maleic acid polymer 60 mg, colloidal silica 150 mg, [A],
55 mg of a mixture of [B] and [C], sodium dodecylbenzenesulfonate as a coating aid, glyoxal as a hardener and E-2 were added and stirred.

[0086]

Embedded image

[0087]

[Chemical 9]

(Preparation of Backing Layer Protective Layer Coating Solution) 1
7 mg of S-2 was added to an aqueous solution containing 0.7 g of gelatin per m ² .
A dispersion of monodisperse polymethylmethacrylate having an average particle size of 5.5 μm, a mixture of [A], [B] and [C], styrene-
The maleic acid polymer was added and stirred, and then glyoxal and sodium salt of 2,4-dichloro-6-hydroxy-1,3,5-triazine were added as a hardener.

(Preparation of sample) 15 on one side of the polyethylene terephthalate film support having the above-mentioned antistatic layer.
After corona discharge with an energy of W / (m ² · min), the backing layer coating solution and the backing layer protective film layer coating solution prepared as described above were applied to the side having the antistatic layer. Further, one side on the support was subjected to corona discharge with an energy of 15 W / (m ² · min), and then an emulsion layer and an emulsion protective film layer were coated. The emulsion layer had a silver content of 4.0 mg / m ² , a gelatin content of 1.7 g / m ² ,
The emulsion protective layer is coated so that the amount of gelatin is 1.0 g / m ² ,
Dried.

The obtained sample was brought into close contact with a step wedge and exposed at a wavelength of 670 nm as a substitute characteristic of a red semiconductor laser beam, and then an automatic developing machine for rapid processing (GR- 26SR Konica Corporation) was processed under the following conditions.

(Developer composition) Amount per 1 liter of used solution Developer A Developer B Developer C Developer D Developer E Ammonia water (25%)-50 ml 50 ml 50 ml 50 ml Diethylenetriamine 5 acetic acid-5 sodium salt 0.05 Mol ----- diethylenetriamine pentaacetic acid --- 0.15 mol 0.15 mol EDTA-0.15 mol 0.15 mol 0.15 mol 0.15 mol sodium sulfite 50 g 20 g 20 g 20 g 20 g boric acid 8 g 8 g 8 g 8 g 8 g potassium bromide 5 g 15 g 15 g 15 g 15 g potassium carbonate 40 g 40 g 40g 40g 40g Silver sludge inhibitor-I-7 I-10 I-35 I-41-60mg 60mg 60mg 60mg Diethylene glycol 40g 40g 40g 40g 40g Benztriazole 0.2g 0.2g 0.2g 0.2g 0.2g Hydroquinone 21.0g --- _{FeSO 4 (NH 4) 2 SO} 4 · 6H 2 O - 0.15 mol 0.15 mol 0.15 mol 0.15 mol 1-phenyl-4-methyl-4-hydroxymethyl -3-Pyrazolidone 0.9g 0.9g 0.9g 0.9g 0.9g pH10.4pH7.0pH7.0pH7.0pH7.0 Comparison with the present invention The present invention The present invention The present invention (fixer composition) used Amount of liquid per liter Ammonium thiosulfate (70% aqueous solution) 200 ml / liter Sodium sulfite 22 g / liter Boric acid 9.8 g / liter Sodium acetate trihydrate 34 g / liter Acetic acid (90% aqueous solution) 14.5 g / liter Tartaric acid 3.0 g / 25 ml of aluminum sulphate (27% aqueous solution) / liter The pH of the working solution was 4.9.

(Development processing conditions) (Process) (Temperature) (Time) Development 38 ° C 12 seconds Fixing 35 ° C 10 seconds Washing 40 ° C 10 seconds Drying 50 ° C 12 seconds Total 44 seconds (Evaluation of sensitivity, gamma and maximum density) The developed sample thus obtained was measured with PDA-65 (Konica Digital Densitometer). The sensitivities in the table are expressed as relative sensitivities when the sensitivity of Sample 1-1 at a concentration of 3.0 is 100. Further, gamma is represented by tangents of densities of 0.1 and 3.0, and if the gamma value in the table is less than 6, it cannot be used, and if it is 6 or more and less than 9, it is still insufficient. It is shown that a gamma value of 9 or more gives a super-high contrast image for the first time and is a sufficiently practical photosensitive material. The highest concentration is
If it is less than 3.5, it cannot be used, and if it is 4 or more, it becomes fully practical.

The evaluation results are shown in Table 1.

[0094]

[Table 1]

From Table 1, according to the method of the present invention, Dry to
It can be seen that the sensitivity is higher than that of the comparison even in the processing of Dry 60 seconds or less, the gamma and the maximum density are sufficient, and the levels are usable.

Example 2 In Example 1, the sample was treated with 100 m ² while replenishing the developing solution with 150 ml per 1 m ² of the sample. Put the following cathode in the deteriorated developer that occurs at that time, put the following anode in the electrolyte solution,
The deterioration developer tank and the electrolyte solution tank should be in contact with each other through the following anion exchange membrane, and both electrodes should be 6V under the condition of 0.1A / dm ² at 2V.
Played by energizing for a time.

Cathode: Stainless wool Anode: Platinum plating of titanium Electrolyte solution: KCl 10% solution Anion exchange membrane: Selemion AWV / ASR manufactured by Asahi Glass No precipitation occurred even after regeneration by applying electricity. The regenerated developer was put into the developing tank again and developed in the same manner as in Example 1, and the results are shown in Table 2.

[0098]

[Table 2]

From Table 2, it can be seen that according to the method of the present invention, even when the regenerant is used, the sensitivity is not lowered and the softening is small, and the maximum concentration is sufficient and is at a usable level.

Example 3 In Example 1, the thickness of the emulsion protective layer and the silver of the emulsion layer /
It was prepared by changing the amount of silver and the amount of gelatin so that the binder ratio becomes a value as shown in Table 3. The thickness of the protective layer is
SEM photographs were taken at 6000 times and measured. The amount of gelatin in the backing layer was 0.6 g / m ² and the amount of gelatin in the backing protective layer was 0.4 g / m ^2, and a polymer layer having the following formulation was simultaneously coated on the lower layer of the backing layer.

(Polymer Layer) Methylmethacrylate: Acrylic acid = 97: 3 1.0 g / m ² Glyoxal (Hardener) 6.0 mg / m ² Samples were prepared in the same manner as in Example 1 except for the amount of silver and the amount of gelatin. Was produced.

[0102]

[Table 3]

The obtained sample was exposed in the same manner as in Example 1 and treated with the developer B. The gamma and the maximum concentration were evaluated in the same manner as in Example 1, and the sensitivity was 100 times that of Sample 3-1.
Is expressed as relative sensitivity. The dryness, fog and linearity were evaluated as follows. The measurement results are shown in Table 4.

(Evaluation of Drying Property) The samples immediately after the treatment were brought into close contact with each other, and the degree of sticking of the samples at that time was ranked.
The highest rank was 5, which did not stick at all, and the rank was lowered to 4, 3, 2, 1 according to the degree of sticking. Ranks 1 and 2 are practically unusable levels.

(Evaluation of Fog) The density of the unexposed portion of the processed sample was measured, and the sample having no fog was given the highest rank of 5, and the rank was lowered to 4, 3, 2, 1 according to the occurrence of fog. . Ranks 1 and 2 are practically unusable levels.

(Evaluation of linearity) SG-747 manufactured by Dainippon Screening Co., Ltd. was used to output 95% and 5% nets,
The net% after treatment was measured. The closer to 95% and 5%, the higher the linearity.

[0107]

[Table 4]

From Table 4, the silver halide photographic light-sensitive material of the present invention has a high sensitivity and good levels of gamma, maximum density, fog and drying property, and can be sufficiently used. Further, it can be seen that the linearity is also very good as compared with the comparison.

[0109]

According to the present invention, there is provided a method of processing a silver halide light-sensitive material which is less likely to cause problems such as a decrease in density and sensitivity, softening, and deterioration of linearity in a scanner process even when processed rapidly by an automatic processor. It was or,
Method of regenerating a developing solution after processing a silver halide photographic light-sensitive material and development of a silver halide photographic light-sensitive material in which deterioration of photographic performance such as softening and deterioration of sensitivity hardly occurs even if development processing is performed with the regenerated liquid A treatment method was obtained.

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Claims (5)

[Claims] 1. A process for developing a silver halide photographic light-sensitive material having at least one silver halide emulsion layer on a support by an automatic processor, which is substantially free of hydroquinones and contains a transition metal complex salt. The total processing time (Dry to Dry) from the time the film tip is inserted into the automatic processor to the time it comes out of the drying zone is 10 seconds or more 60 A method for developing and processing a silver halide photographic light-sensitive material, which comprises processing in seconds or less. 2. A silver halide photographic light-sensitive material is developed with the developing solution, and then the developing solution is regenerated by energizing it to develop another silver halide photographic light-sensitive material. A method for developing a silver halide photographic light-sensitive material as described above. 3. The silver halide photographic light-sensitive material, wherein the silver / binder weight ratio of the silver halide emulsion layer forming an image is 0.7 or more and 1.3 or less, and the silver halide emulsion layer is coated on the silver halide emulsion layer. The method of developing a silver halide photographic light-sensitive material according to claim 1 or 2, wherein the protective layer has a thickness of 0.6 µm or more and 2.0 µm or less. 4. The silver halide photographic light-sensitive material is provided with at least one non-photosensitive hydrophilic colloid layer and at least one hydrophobic layer on the surface opposite to the surface having the silver halide emulsion layer and the support. 4. The method for developing and processing a silver halide photographic light-sensitive material according to claim 1, which has a photosensitive polymer layer. 5. Substantially free of hydroquinones,
A method for regenerating a developing solution, which comprises regenerating the developing solution by energizing the silver halide photographic light-sensitive material after development processing with a developing solution containing a developing agent composed of a transition metal complex salt.