JPH11258742A - Developer or developing solution for silver halide photographic sensitive material and developing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent a developer or a developing solution containing a reduction compound from being deteriorated due to air oxidation by incorporating water- soluble antioxidizing agent containing a component as an effective component extracted from a natural material. SOLUTION: This developer or this developing solution for a silver halide photographic sensitive material contains one or more kinds of water-soluble antioxidizing agent making a component extracted from natural materials as an effective component and at least one or more kinds of reduction compounds. The water-soluble antioxidizing agent making the component extracted from the natural materials as the effective component are substances extracted from seeds of a pumpkin, grapes and sunflowers and coffee beans, unripe apples, tea, and the other plants. The sunflower seeds belong to Compositae family, sunflower genus and they are mainly used for a raw material of sunflower oil for cakes and pet foods. Especially preferably compounds among the reduction compounds are ascorbic acids and or iso-ascorbic acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a developer or a developer for a silver halide photographic material and a method for developing a silver halide photographic material using the developer or the developer.

[0002]

2. Description of the Related Art Generally used black-and-white silver halide photographic materials (for X-ray, plate making, micro, and negative) are:
Conventionally, image formation has been suitably carried out after development with an alkaline developing solution in which dihydroxybenzenes are used as a developing agent and a metol or 3-pyrazolidone compound is used as an auxiliary developing solution, followed by fixing and washing steps.

However, in recent years, with increasing interest in environmental issues, dihydroxy compounds which have been conventionally used have been used in view of the use of compounds suspected of carcinogenicity and harmful compounds, and the use of compounds which are difficult to dispose of. In addition to raising the problem of developing solutions that use benzene as the developing agent, they are safer and more environmentally friendly due to their features such as being recyclable, easily decomposing waste easily and reducing the burden on the environment. Developers using reductone compounds typified by ascorbic acid (vitamin C), which are gentle on the environment, have been reviewed.

[0004] With respect to the developing agents and developing methods using a reductone compound as a developing agent, there have been 200 cases to date including JP-A-48-3623, JP-A-48-5431, and JP-A-48-20527. Although the disclosure has been made above, when a reductone compound is used as a developing agent, the development processing of the light-sensitive material, air oxidation, alkali decomposition, thermal decomposition and the like, the activity of the developer is easily reduced,
This was a major problem in practical use.

As a method for stabilizing against such unstable factors, use of a heterocyclic stabilizer such as 1-phenyl-5-mercaptotetrazole (JP-A-5-88306) and use of salicylic acid or the like (JP-A-5-88306). No. 5-210220), and the addition of a hydrazine derivative (JP-A-7-2873)
No. 64) is disclosed, but no stabilization method using a water-soluble antioxidant extracted from a natural product has been known at all.

As water-soluble antioxidants extracted from natural products, water-soluble antioxidants extracted from pumpkin seeds, grape seeds, sunflower seeds, coffee beans, immature apples and tea, etc. are well known. Food and drink, processed food,
It is used by adding a small amount to pharmaceuticals, quasi-drugs, tobacco, feed, cosmetics, and the like. However, it is used in an alkaline and air-exposed state like a photographic developer.
It has not been known that its antioxidant effect is effective even in a system under extremely severe conditions.

[0007]

An object of the present invention is to improve the stability of a developer or developer containing a reductone compound by preventing the developer or developer from deteriorating by air oxidation, and to substantially improve dihydroxybenzene. It is an object of the present invention to provide a safer and environmentally friendly developer or developer of a silver halide photographic light-sensitive material, which does not contain a system developing agent, and a developing method using the developer or the developer.

[0008]

Means for Solving the Problems The present inventors have found that the above-mentioned object is to provide a developer or a developer containing a reductone compound with a water-soluble antioxidant containing a component extracted from a natural product as an active ingredient. It has been found that the present invention is achieved by using a developer or a developer containing, and the present invention has been completed.

That is, the present invention relates to (1) a silver halide photographic light-sensitive material containing one or more water-soluble antioxidants containing as an active ingredient an ingredient extracted from a natural product and one or more reductone compounds. (2) The silver halide photographic light-sensitive material according to (1), wherein the water-soluble antioxidant comprises, as an active ingredient, a component extracted from sunflower seeds or oil cake thereof. Developer or developer,

(3) The developer or development of a silver halide photographic light-sensitive material according to (1) or (2), wherein the reductone compound is ascorbic acid and / or isoascorbic acid or a salt thereof. liquid,

(4) (a) a water-soluble antioxidant containing, as an active ingredient, a component extracted from sunflower seeds or its oil cake with water or hydrous alcohol; (b) a reductone compound or a salt thereof; c) an alkali agent, and (d) a photographic development inhibitor, and substantially free of a dihydroxybenzene-based developing agent, and a developer or a developer for a silver halide photographic light-sensitive material, and

(5) Development of a silver halide photographic light-sensitive material characterized by using the developer or developer of the silver halide photographic light-sensitive material according to any one of the above (1) to (4). Including the method.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble antioxidant containing, as an active ingredient, a component extracted from a natural product used in the present invention includes pumpkin seeds, grape seeds, sunflower seeds, coffee beans, unripe apples, tea and others. These are water-soluble antioxidants extracted from the above-mentioned plants, and any of them can be used as a water-soluble antioxidant of the present invention by adding one or more to a developer.

The sunflower seeds used in the present invention include sunflowers belonging to the family Asteraceae and the genus Sunflower "Japanese name; Hyuga, scientific name;
Helianthus a News
nnuus L .; )), Which is mainly used as a raw material for sunflower oil, for confectionery, and as feed for pets. In addition, the grain after oiling is usually used as feed for livestock, but this is also a suitable raw material for a water-soluble antioxidant.

A method for obtaining these water-soluble antioxidants is disclosed in Japanese Patent Application Laid-Open No. Hei 3-221587. Briefly, first, sunflower seeds are crushed by a crusher or the like until suitable particles are obtained. I do. As long as the shell has already been destroyed by oiled cake or the like, it may be used as it is. Then, about 10 times the amount of water or hydroalcohol is added to the solid content, and when extracting with water, the solid content is heated to 50 to 100 ° C. or treated at 120 ° C. and 1 atm using an autoclave.

When a hydroalcoholic is used, 2
0% to 80% alcohol solution, preferably 30% to 6%
The water-soluble antioxidant is extracted by heating and extracting from a room temperature to 70 ° C., preferably around 50 ° C. using a 5% alcohol solution. The extract can be concentrated under reduced pressure and dried to be powdered, or can be used as a water-soluble antioxidant in the form of a paste or aqueous ethanol solution. Similarly, water-soluble antioxidants from other natural plants can be obtained by pulverizing the material and extracting it with water or hydrous alcohol to obtain the water-soluble antioxidant used in the present invention.

These water-soluble antioxidants are easily soluble in water, and can be added to a developer by adding a necessary amount of the antioxidant to the developer at any time during the preparation of the developer. Preferably, immediately before adding the reductone compound to the alkaline aqueous solution.
The amount added to the developer is 0.05 g to 50 g, preferably 2 g to 20 g, as a dry powder per liter of the developer.
It is. When the amount added is less than 0.05 g, the antioxidant effect is not sufficient. On the other hand, when the amount used is more than 50 g, the effect is obtained but it is not economically suitable.

The amount of addition is 0.1 g to 50 g per liter for a concentrated type developer. When a solid developer is used, it may be used in an amount of 10 to 30% by weight based on the reductone compound as a developing agent.

The reductone compound used as a developing agent in the developer of the present invention is an enediol type (Endio)
l), enaminol type (Enaminel), endamine type (Endiamine), thiol enol type (Thiol-Enol) and enamine thiol type (
Enamine-Thiol) is generally known.
These compounds are disclosed in U.S. Pat. No. 2,688,549,
It is described in JP-A-62-237443. Methods for synthesizing these reductones are also well known, and are described in detail, for example, in "The Chemistry of Reducton", co-authored by Yuji Nomura and Hirohisa Omura (1969, Uchida Roizuruhoshinsha).

Among these, preferred reductone compounds for use in the present invention are compounds represented by the following general formula (I). General formula (I)

[0021]

Embedded image

Wherein R is a hydrogen atom or a hydroxyl group;
m is an integer of 1 to 4. Next, specific examples of preferred reductone compounds used in the present invention will be given. (Enediol type reductones)

[0023]

Embedded image

[0024]

Embedded image

(Other Reductones)

[0026]

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[0027] Among these preferred reductone compounds, a particularly preferred compound is ascorbic acid or isoascorbic acid. The reductone compound used in the present invention can be used in the form of an alkali metal salt such as a lithium salt, a sodium salt, and a potassium salt. These reductone compounds are generally used in an amount of 1 g to 200 g per liter of a developer,
Preferably, 5 g to 150 g is used. When a solid developer is used, it is preferably used in the range of 20 to 90% by weight in the developer.

The developer of the present invention has a pH of 9.0.
An alkali agent is added to set the above alkalinity. Examples of the alkali agent used for setting the pH include ordinary water-soluble inorganic alkali metal salts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, and potassium tertiary phosphate. For example, amine compounds such as various primary amines, secondary amines, and tertiary amines, or quaternary ammonium compounds can be used as the water-soluble organic alkali agent. These alkaline agents are used by adding in an amount necessary to set the pH of the developer to a predetermined preferable pH.

To the developer of the present invention, various inorganic and / or organic photographic development inhibitors are added for the purpose of preventing fog and / or pepper. Specifically, sodium bromide and potassium bromide are used as inorganic inhibitors, and 5-nitroindazole and 5-p are used as organic inhibitors.
-Nitrobenzoylaminoindazole, 1-methyl-
5-nitroindazole, 6-nitroindazole, 3
Indazole compounds such as -methyl-5-nitroindazole,

Benzimidazole compounds such as 5-nitrobenzimidazole and 2-isopropyl-5-nitrobenzimidazole, and benzotriazoles such as 5-nitrobenzotriazole, methylbenzotriazole, 5-methylbenzotriazole and 2-mercaptobenzotriazole Compound, 4-[(2-mercapto-
Mercapto compounds such as 1,3,4-thiadiazol-2-yl) thio] butanesulfonate and 5-amino-1,3,4-thiadiazol-2-thiol.

The amount of these photographic development inhibitors used is 0.01 g to 5 g per liter of developer in the case of inorganic inhibitors.
0 g, and in the case of an organic inhibitor, from 1 mg to 10 g per liter of developer. These photographic inhibitors may be used alone, or various inhibitors may be used in combination.
Various compounds other than the above-mentioned essential components can be added to the developer of the present invention for the purpose of maintaining and improving other properties as a developer.

In the developer or developer of the present invention, in addition to the above-mentioned main developing agent reductone compound, 3-pyrazolidones (for example, 1-phenyl-3-one) may be used as auxiliary developing agents.
Pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1
-Phenyl-4,4-dimethyl-3-pyrazolidone, 1
-Phenyl-4-methyl-4-hydroxymethyl-3-
Pyrazolidone, 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-
Phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxyphenyl-4,4-dimethyl-3-pyrazolidone,

1- (2-benzothiazolyl) -3-pyrazolidone, 3-acetoxy-1-phenyl-3-pyrazolidone, etc., 3-aminopyrazolines (for example, 1-
(P-hydroxyphenyl) -3-aminopyrazoline,
1- (p-methylaminophenyl) -3-aminopyrazoline, 1- (p-amino-m-methylphenyl) -3-
Aminopyrazoline, etc.), phenylenediamines (for example, 4-amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β- Hydroxyethylaniline,
3-methyl-4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline,

3-methyl-4-amino-N-ethyl-N
And aminophenols (for example, 4-aminophenol, 4-amino-3-methylphenol, 4- (N-methyl) aminophenol, 2,4-diaminophenol, N- ( 4-hydroxyphenyl) glycine, N- (2'-hydroxyethyl) -2-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-hydroxymethyl-4
-(N-methyl) aminophenol) and their hydrochlorides and sulfates. The amount of these auxiliary developing agents to be added is 0.2 g to 3 g / l of developer.
0 g, preferably O.D. 5 to 10 g.

The developer or developer of the present invention preferably contains a preservative. Sulfite can be used as a preservative. As the sulfite, sodium sulfite, potassium sulfite, lithium sulfite, ammonium sulfite,
Examples include sodium bisulfite, potassium bisulfite, and potassium metabisulfite. The addition amount of these sulfites is preferably 2 mol or less per liter of developer.

The developer of the present invention may contain, if necessary, a water-soluble acid (eg, acetic acid or boric acid), a pH buffer (eg, sodium borate, sodium metaborate, sodium tertiary phosphate) in addition to the above components. , Sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc.), organic solvents (eg, ethylene glycol, diethylene glycol, methyl cellosolve, diethanolamine, dimethylaminoethanol, diethylaminopropanediol, etc.), hardeners (eg, glutar) Aldehydes, bisulfite adducts, etc.),

Development accelerators (for example, various amine compounds,
Imidazole or a derivative thereof), various organic / inorganic chelating agents (eg, sodium tetrapolyphosphate, sodium hexametaphosphate, aminopolycarboxylic acids, organic phosphonic acids, organic phosphonocarboxylic acids, etc.), silver stain inhibitor, development unevenness prevention Agents, dissolution aids, color toning agents, surfactants, defoamers, water softeners and the like can be used as long as the effects of the present invention are not impaired.

The method for preparing a developer according to the present invention includes:
A slightly smaller amount of water than necessary is added to a container equipped with a stirrer prepared in advance, and then a necessary amount of the water-soluble antioxidant according to the present invention, a reductone compound or a salt thereof, an alkaline agent, a photographic developer, and other additives are added. Add and dissolve with stirring. At this time, it is effective to increase the solubility of the hardly soluble compound by heating or using the above-mentioned organic solvent.
After all the added compounds are dissolved, the pH is adjusted to a predetermined value using an alkaline aqueous solution such as an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution or an acidic aqueous solution such as a dilute sulfuric acid solution or a dilute acetic acid solution, and the total liquid volume is adjusted to a predetermined amount. After adjusting the liquid amount, the pH of the developer according to the present invention can be adjusted by confirming and adjusting the pH again.

The prepared developer is stored in a sealed air-tight airtight container, and can be opened and used when necessary. In preparing the developer of the present invention,
By using degassed water according to JP-A-6-273897, it is possible to prepare a developing solution whose storage stability is further increased at low cost.

It is preferable to concentrate the developing solution and dilute it at the time of use for the purpose of transport cost of the developing solution, packaging material cost, space saving and the like. It is effective to convert the contained salt component to potassium salt. The same refining method and concentration are applied to a replenishing developer used in an automatic developing machine or the like.

Further, as a developing agent for a silver halide photographic light-sensitive material, there is a solid developing agent instead of a liquid such as a developing solution. In the case of a solid developing agent, a solid material is selected as a necessary developing composition, and the raw materials are provided by uniformly mixing them into a powder or tablet, or by stacking them in layers to form a block and solidifying. can do. In the case of these solid developing agents such as tablets, powders and blocks, a developing solution can be easily obtained by dissolving a necessary amount of the developing agent in a predetermined amount of water in advance before the developing process. Regarding replenishment, it may be added to the developer as a solid, or may be dissolved in water in advance and added.

The developing conditions using the developing solution of the present invention are as follows:
The development processing temperature and the processing time are interrelated, and are determined in relation to the total processing time.
The range is from 5 ° C to 50 ° C, more preferably from 20 ° C to 40 ° C. The development time ranges from 5 seconds to 5 minutes, preferably from 7 seconds to 2 minutes. The amount of the replenisher is 500 ml or less, preferably 400 ml or less per square meter of the silver halide photographic material.

The silver halide photographic light-sensitive material to which the developer or the developer of the present invention and the developing method using the developer or the developer of the present invention are applied can be prepared by an appropriate method according to the purpose of use of the light-sensitive material, For example, using a device such as a camera, a light irradiation device, or an X-ray irradiation device, image exposure is performed using a light source such as natural light, a halogen lamp, a xenon lamp, a tungsten lamp, a laser beam, an electron beam, or an X-ray. Then development,
A final image (positive image or negative image) can be obtained through steps such as (bleaching), (stopping), fixing, washing, and drying.

As the fixing agent used in the fixing step relating to the developing solution and the developing method of the present invention, those having a commonly used composition can be used. For example, the Photographic Society of Japan, “Basic Photographic Engineering, Silver Halide Photography”, p.
979 Corona), Akira Sasai, "Chemistry of Photography" 320
Pp. Et seq. (1982 Photo Kogyo Shuppansha) and Thomas (W. THOMAS, Jr.) ed., "SPSE Handbook of Photographic Science and Engineering (SPSE HANDBOOK OF PHOTOGRAP)"
HIC SCIENCE AND ENGINEERING), published by JOHNWILEY & SONS (1973) 5
See page 28 and the like.

As the fixing agent base, thiosulfates, thiocyanates, and organic sulfur compounds known to have an effect as a fixing agent can be used. Acid fixing agents (eg, acetic acid, citric acid, tartaric acid, malic acid, oxalic acid, succinic acid, maleic acid, glycolic acid, adipic acid, sulfuric acid, sulfurous acid, phosphoric acid, etc.), preservatives (eg, sodium sulfite) , Sodium bisulfite, etc.), buffers (eg, boric acid), hardeners (eg, alum, alum, aluminum sulfate, etc.), chelating agents, surfactants (eg, sulfates, anions such as sulfonates) System surfactant,

Nonionic surfactants such as polyethylene oxide, amphoteric surfactants, etc., wetting agents (for example,
An alkanolamine, an alkylene glycol or the like), a fixing accelerator (for example, a thiourea derivative, a thioether compound, an alcohol having a triple bond in a molecule, a mesoionic compound or the like), a dye elution accelerator or the like can be used. Further, as disclosed in JP-A-7-64250, by using degassed water as the water used for preparing the fixing solution, a fixing solution having good storage stability can be produced.

The photographic light-sensitive material that has been developed and fixed is
Then, it is washed or stabilized. In the water used for the washing or stabilizing treatment, a water-soluble surfactant, an antifoaming agent, a dye adsorbent, an ammonium compound, a bismuth, a metal compound such as aluminum or the like for suitably performing post-processing of the photographic light-sensitive material. A fluorescent whitening agent, a chelating agent, a film pH regulator, a hardening agent, a bactericide, a fungicide, an alkanolamine, and the like.

After exposure to the silver halide photographic material, the post-processing steps including the development processing method according to the present invention include developing,
It is convenient and preferable to use a roller transport type automatic developing machine capable of performing the fixing, washing and drying steps consistently. Roller transport type automatic developing machines are described in U.S. Pat. Nos. 3,025,779 and 3,545,971. When an exposed photographic photosensitive material is inserted from one end, the photographic photosensitive material is transported by a transport roller. The film is conveyed and successively goes through development, fixing, washing and drying steps, and at the same time, the processing in each step is performed, whereby a photographic photosensitive material having an image formed from the other end is obtained. In each step, the concentration and temperature of the processing solution used are controlled so that the processing can be sufficiently performed within the time when the photographic light-sensitive material passes through the steps.

The silver halide photographic light-sensitive material to which the developing solution and the processing method of the present invention are applied is used as a photographic light-sensitive material such as a film, a photographic paper and a dry plate. At least one silver halide gelatin emulsion is coated on the body, and a photosensitive layer having a thickness of about several μm to about 10 μm after drying is provided. The type, thickness, and shape of the support differ depending on the application. The nature of the emulsion is different, but it is adapted and used in any case.

The coating layer of the photographic light-sensitive material may have one to two or three silver halide photographic light-sensitive layers depending on the intended use, and may be a black-and-white photographic negative light-sensitive material, a black-and-white photographic positive light-sensitive material, a printing photographic light-sensitive material. Materials in which a silver halide photographic photosensitive layer is coated on the front and back of a support, such as materials, microphotographic photosensitive materials, ultra-high precision recording photosensitive materials, holographic photosensitive materials, etc., include black-and-white various radiation photosensitive materials. . These various silver halide photographic light-sensitive materials include not only a silver halide photographic emulsion layer but also other auxiliary layers such as a protective layer, an antistatic layer, a mat layer, a filter layer, an intermediate layer, an undercoat layer, a release layer, Various layers such as an anti-static layer may be provided.

The photosensitive layer of the silver halide photographic light-sensitive material is made of an emulsion in which silver halides such as silver bromide, silver chloride, silver chlorobromide and the like are dispersed in gelatin in the form of fine crystals. Various kinds of crystals such as halogen composition of silver halide crystals, crystal size, shape, size distribution, multilayer crystal, epitaxial crystal, and mixture of two or more types of crystals are adjusted and used according to the purpose of use. Can be

Emulsions used in silver halide photographic materials to which the developing solution and the developing method of the present invention are applied are roughly classified into negative emulsions and positive emulsions. The halogen composition of the negative-working silver halide emulsion is not particularly limited, and may be any composition such as silver chloride, silver chlorobromide, silver iodobromide, and silver iodobromochloride. It is desirable to use a silver bromide emulsion containing silver iodide of several mol% for a high-speed material and a silver chloride emulsion or a silver chlorobromide emulsion for a low-speed material.

With regard to the size of silver halide grains, high-sensitivity films and X-ray films have large grains, including grains having a size of 1 to several μm. About 0.4 μm or less for emulsions for photographic use, and 0.1 to 0.05 for emulsions for ultra-micro photography.
A particle size of the order of μm is preferred. Silver halide grains can have a relatively broad grain size distribution,
It can have a narrow grain size distribution, for example, a monodisperse emulsion in which the grain size occupying 90% of all grains is within + 40% of the average grain size can be achieved by sufficiently controlling the crystal adjustment. It is.

The silver halide grains may have a regular crystal form such as cubic or octahedral, or may have an irregular crystal form such as spherical, tabular, clam, or epitaxial crystal. Silver halide grains can be prepared using any known method. That is, any of an acidic method, a neutral method, an ammonia method, and the like may be used, and the reaction type of the soluble silver salt and the soluble halide salt is any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. You may.

As one of the simultaneous mixing methods, a method in which the silver ion concentration (pAg) in a liquid phase in which silver halide is formed is kept constant, that is, a pAg controlled double jet method (CDJ method) is used. Monodispersed silver halide grains having a uniform crystal form and a nearly uniform grain size can be obtained. Also, grains can be formed by using a silver halide solvent such as ammonia, thioether, and tetra-substituted thiourea. A cadmium salt, an iridium salt, a rhodium salt, a rhenium salt, a ruthenium salt and a complex salt thereof are coexistent with the silver halide emulsion in order to increase the contrast of the silver halide emulsion during silver halide grain formation or physical ripening. May be.

Emulsions usually remove soluble salts after precipitation or physical ripening.
A noodle washing method performed by gelatinizing gelatin may be used, and inorganic salts composed of polyvalent anions (eg, sodium sulfate, magnesium sulfate, etc.), anionic surfactants, anionic polymers (eg, polystyrene sulfonic acid, β A sedimentation method (flocculation) using a naphthalenesulfonic acid formalin condensate, an aromatic sulfonic acid formalin condensate, or a gelatin derivative (for example, an aliphatic acylated gelatin, an aromatic acylated gelatin, an aromatic carbamoylated gelatin, etc.) ) May be used.

The silver halide emulsion may or may not be chemically sensitized. As the method of chemical sensitization, known methods such as sulfur sensitization, reduction sensitization, noble metal sensitization, selenium sensitization, and tellurium sensitization can be used,
Used alone or in combination. As the sulfur sensitizer, various sulfur compounds such as thiosulfates, thioureas, thiazoles, rhodanines and the like can be used in addition to the sulfur compounds contained in gelatin. A specific example is
U.S. Pat. Nos. 1,574,944 and 2,278,9
No. 47, No. 2,410,689, No. 2,728,
No. 668, No. 3,501, 313, No. 3,65
No. 6,955.

As the reduction sensitizer, stannous salts, amines, formamidinesulfinic acid, silane compounds and the like can be used, and specific examples thereof are described in US Pat.
Nos. 487,850, 2,518,698, 2,983,609, 2,983,610, and 2,694,637. Among the noble metal sensitization methods, the gold sensitization method is a typical one and uses a gold compound, mainly a gold complex salt. Noble metals other than gold, for example, complex salts such as platinum, palladium, and iridium may be contained. A specific example is described in US Pat. No. 2,448,
060 and British Patent No. 618,061.

In the selenium sensitization method, an inorganic selenium compound or an organic selenium compound can be used as a selenium sensitizer, and specific examples are described in US Pat. No. 1,574,94.
No. 4, No. 1, 602, 592, No. 1, 623, 4
No. 99, No. 3,297,446, No. 3,297,
No. 447, No. 3,320,069, No. 3,40
Nos. 8,196, 3,408,197, 3,4
No. 42,653, No. 3,420,670, No. 3,
No. 591,385, JP-B No. 52-34491, 52
-34492, 53-295 and 57-2209
No. 0, JP-A-59-180536 and JP-A-59-1853.
No. 30, No. 59-181337, No. 59-18733
No. 8, No. 59-192241, No. 60-150046
No., No. 60-151637, No. 61-246738
And JP-A-5-11385.

Regarding tellurium sensitization method and tellurium sensitizer, US Pat. Nos. 1,623,499 and 3,320
No. 069, No. 3,772,031, No. 3,53
1,289, 3,655,394; British Patent 235,211; 1,121,496; 1,295,462; Canadian Patent 800,958.
JP-A-5-11386, JP-A-5-11387, JP-A-5-11388, JP-A-5-11390, and 5-113
Nos. 92, 5-11393, 5-19395, 5-45768, 5-45769, 5-457
No. 72, etc.

The negative working silver halide emulsion according to the present invention is desirably spectrally sensitized using one or more sensitizing dyes in order to impart photosensitivity to a desired photosensitive wavelength region. As the sensitizing dye, a cyanine dye, a merocyanine dye, a styryl dye, a hemicyanine dye, a holopolar cyanine dye, an oxonol dye, a hemioxonol dye, and the like can be used. Particularly useful dyes are cyanine dyes and merocyanine dyes. Any nucleus usually used for cyanine dyes as a basic heterocyclic nucleus of dyes can be applied. That is, pyrroline nucleus, oxazole nucleus, oxazoline nucleus, thiazole nucleus, thiazoline nucleus, pyrrole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, indole nucleus, benzoxazole nucleus, benzothiazole nucleus, benzoselenazole nucleus, benzimidazole A nucleus and a quinoline nucleus can be applied.

In the negative working silver halide emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Examples of known additives include development accelerators, development inhibitors, antifoggants, antifoggants, emulsion stabilizers, and “Basics of photographic engineering, silver salt photography”, edited by The Photographic Society of Japan, published by Corona, pp. 105 and 189. Ripening accelerator, physical ripening inhibitor, latent image regression inhibitor, covering power increasing agent, color tone agent, anti-irradiation dye, mordant, ultraviolet absorber, fluorescent whitening agent, gelatin plasticizer, antistatic agent, mat Agents, slip agents, anti-curling agents, adhesion improvers, thickeners, coating aids, antifoaming agents, preservatives,
Wetting agents, spreading agents, etc. and research / disclosure N
o. No. 17643 (December 1978) and the same No. 18
716 (November 1979), development accelerators, antifoggants, stabilizers, color stain inhibitors, image stabilizers, ultraviolet absorbers, filter dyes, brighteners, coating aids, surfactants, plasticizers , Sliding agent, antistatic agent, matting agent,
Binders and the like.

The binder contained in the silver halide photographic emulsion layer in the negative working silver halide photographic light-sensitive material according to the present invention preferably does not exceed 250 g per mol of silver halide. Gelatin is most preferred as the binder, but hydrophilic colloids other than gelatin can also be used. For example, albumin, casein, a graft polymer of gelatin and another polymer, polyvinyl alcohol,
A hydrophilic polymer such as polyacrylamide can be used.

The negative-working silver halide photographic light-sensitive material according to the present invention comprises a support on which at least one hydrophilic colloid layer containing a silver halide emulsion is coated. For example, a protective colloid layer, an antistatic layer, a mat layer, an intermediate layer, an undercoat layer, an antihalation layer, a filter layer, and the like may be provided. These hydrophilic colloid layers may contain an inorganic or organic hardener. Hardening agents include chromium salts (chromium alum, etc.), aldehydes (formaldehyde, glyoxal, etc.), N-methylol compounds (dimethylol urea,
Methylol dimethylhydantoin, active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, mucochloric acid, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-)
Triazines), epoxy and aziridine hardeners,
Pyridinium salt derivatives (JP-B-57-46539, JP-B-6-42036, etc.) and the like can be used.

When the silver halide photographic light-sensitive material according to the developer and the development processing method of the present invention is applied as a printing photographic light-sensitive material requiring a high contrast image having a gamma of 10 or more, the halogenated photographic light-sensitive material of the present invention is used. Known nucleating agents and nucleating accelerators can be added to the silver photographic light-sensitive material for use. Examples of known nucleating agents include, for example, those having a reduction potential of -0.1 as described in JP-A-6-043602 and EP-A-0518352A.
Heterocyclic compounds less than 6 volts and US Pat.
No. 8,977, No. 4,224,401, No. 4,2
No. 41,164, No. 4,243,734, No. 4,
Nos. 269,929, 4,272,614, 4,311,781, 4,323,643, 4,385,108, 4,650,746,
Nos. 4,686,167 and 4,927,734
No. 4,988,604,

Nos. 4,994,365 and 5,041,
No. 355, European Patent Nos. 253,665 and 3
No. 22,553, No. 333,435, No. 345
No. 025, No. 356,898 and JP-A-5
Nos. 6-106244, 61-267759, 61
No. 230145, No. 62-270953, No. 62-
No. 178246, No. 62-180361, No. 62-2
No. 75247, No. 63-223744, No. 63-23
No. 4244, No. 63-234245, No. 63-234
No. 246, No. 63-253357, No. 63-2652
No. 39, JP-A-2-77057 and JP-A-2-220042
Nos. 2-221953, 4-438 and 4-5
No. 652, No. 4-5653, No. 4-6548, No. 4
-6551, 4-9037, 4-15642
No. 4-16938,

Nos. 4-19645 and 4-196646
Nos. 4-196647, 4-19732, 4-
No. 21841, No. 4-29130, No. 4-34430
Nos. 4-34545, 4-51142, 4-
No. 51143, No. 4-56842, No. 4-56843
Nos. 4-56846, 4-56949, 4-
No. 60545, No. 4-62544, No. 4-67140
Nos. 4-67141, 4-70647, 4-
No. 76530, No. 4-76531, No. 4-76532
No., 4-76533, 4-76534, 4-
77732, 4-80741, 4-80748
Nos. 4-81841, 4-84134, 4-
96053, 4-98239, 4-98240
Nos. 4-106542, 4-114145, 4-114150, 4-119349, and 4-1
No. 22926, No. 4-130551, No. 4-1368
No. 38, No. 4-136839, No. 4-136840
issue,

Nos. 4-1366841 and 4-13684
No. 3, 4-161948, 4-163446,
4-163543, 4-166835, 4-1
Nos. 74424, 4-178644, 4-1863
No. 43, No. 4-190227, No. 4-194923
Nos. 4,194,928, 4,212,144, 4-212950, 4-212295, and 4-2
No. 16544, No. 4-218039, No. 4-2253
No. 46, No. 4-225347, No. 4-225348
Nos. 4-225349, 4-229589, 4-245243, 4-250444, and 4-2
No. 53051, No. 4-258951, No. 4-2644
No. 40, 4-264545, 4-265970
No. 4-2655971, 4-267248,

Nos. 4-273241 and 4-27554
No. 1, 4-278939, 4-280245,
4-283743, 4-285951, 4-
No. 291337, No. 4-298736, No. 4-311
No. 946, No. 4-316038, No. 4-316042
Nos. 4-331,054, 4-32023, 4-330432, 4-331951, 4-3
No. 38745, No. 4-365032, No. 5-1067
No. 5, 5-11384, 5-34853, 5
No. -34854, No. 5-45761, No. 5-4576
No. 2, 5-45763, 5-45764, 5
No. 45765, No. 5-45767, No. 5-6113
No. 9, No. 5-61140, No. 5-61141, No. 5
No. 61142, No. 5-61143, No. 5-6114
No. 4, No. 5-61145, No. 5-61146, No. 5
Nos. -61159, 5-66526, 5-8828
No. 8, 5-88290, 5-93977,

Nos. 5-93990 and 5-100371
Nos. 5-107667, 5-119422, 5-119426, 5-127285, and 5-1
No. 27286, No. 5-127287, No. 5-1343
No. 37, No. 5-134338, No. 5-134339
Nos. 5-134357, 5-142688, 5-142689, 5-150392, and 5-1
No. 58179, No. 5-165134, No. 5-1732
No. 81, No. 5- 197057, No. 5- 197091
Nos. 5-204075, 5-204076, 5-216151, 5-216181, and 5-2
No. 16182, No. 5-224330, No. 5-2326
No. 16, No. 5-241264, No. 5-249624
Nos. 5-257223, 5-257239, 5-257240, 5-265148, and 5-2
No. 65149, No. 5-273681, No. 5-2737
Various hydrazine compounds described in the specification such as No. 09 can be mentioned.

Further, the above-mentioned silver halide photographic light-sensitive material can contain at least one of an amine compound, a hydrazine compound and a quaternary onium salt compound as a nucleation promoting compound. Specific examples include JP-A-53-77616, JP-A-53-137133, JP-A-54-37732, JP-A-60-14959, and JP-A-60-59959.
140340, JP-A-2-8833, 4-438
No., 4-5652, 4-5653, 4-65
No. 48, No. 4-114150, No. 4-212144
No. 4,122,926, etc., an amine compound described as a development accelerator or an accelerator for nucleation infectious development,

JP-A-2-170155 and 5-9397
7, amine compounds as "inclusion boosters" described in U.S. Pat. No. 4,975,354, and the like; JP-A-2-327402, pp. 117-118; -127286, 5-13
No. 4337, No. 5-134357, No. 5-19705
No. 7, No. 5-232616, amine compounds used for improving photographic performance such as photographic light-sensitive materials with little black spots, photographic light-sensitive materials with little fog,
Hydrazine compounds, quaternary onium salt compounds and the like can be mentioned.

The nucleating agent compound and the nucleation promoting compound described above include:
All are suitable water-soluble solvents, for example, alcohols (methanol, ethanol, propanol, fluorinated alcohol), ketones (acetone, methyl ethyl ketone), dimethylformamide, dimethyl sulfoxide,
It can be dissolved in methylcellosolve or the like and added to a silver halide photographic material. Also, by an already well-known emulsification dispersion method, an oil such as dibutyl phthalate, tricresyl phosphate, glyceryl triacetate or diethyl phthalate, and an auxiliary solvent such as ethyl acetate or cyclohexanone are dissolved and mechanically emulsified and dispersed. Objects can also be created and used. Alternatively, the powder of the additive substance can be dispersed in water using a ball mill, a colloid mill, or ultrasonic waves by a method known as a solid dispersion method.

The positive-working silver halide photographic light-sensitive material to which the developing solution and the developing method of the present invention are applied is used for a positive film for printing plate making and for copying various photographs. In recent years, reproduced photographs such as X-ray CT (computer tomography), MRI (magnetic resonance imaging), and CR (computer radiography) have been attracting attention. There is no particular limitation on the positive-working silver halide emulsion that can be used in the positive-working silver halide photographic light-sensitive material, and there are no directly fogged silver halide emulsions for direct positive or pre-fogged internal latent images. A silver halide emulsion can be used.

The silver halide grains of the pre-fogged direct positive silver halide emulsion according to the present invention include silver chloride, silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide and the like. And these emulsions can be prepared in various ways, for example, as described in US Pat. No. 1,186,717.
A method for incorporating a soluble metal salt of the genus
184,013, a monodisperse preparation method described in U.S. Pat. No. 3,501,305;
627, a method for preparing regular grain emulsions as described in U.S. Pat. No. 3,501,306, and a method for preparing heterodisperse emulsions as described in U.S. Pat. No. 3,367,785; UK Patent Nos. 1,22
No. 9,865, No. 1,186,718 and the like can be applied to the method for preparing a coated grain (covered grain) emulsion.

The pre-fogged direct positive silver halide emulsion according to the present invention needs to be fogged by any suitable method to the silver halide emulsion prepared by the above method. Suitable methods for imparting fog include, for example, uniform exposure to light over the entire surface, or a suitable reducing agent or more electrically positive than silver as described in GB 723,019. It can be chemically fogged using a metal compound. In order to obtain a direct positive image having high sensitivity, the method described in JP-B-46-40,900 for giving fog with a combination of a reducing agent and a gold compound is effective.
A combination of a metal compound which is more positive than silver and at least one compound of thiosulfate, thiocyanate and hydrocyanic acid described in JP-A-49-22118, and By giving fog by a method in which the above combination is further combined with a reducing agent, a positive image with higher sensitivity, higher contrast and better omission can be obtained.

Representative reducing agents useful for preparing such emulsions include, for example, formalin, hydrazine, polyamines (such as triethylenetetramine and tetraethylenepentamine), formamidinesulfinic acid, tetra (hydroxymethyl) Examples of useful metal compounds that include phosphonium chloride, amine borane, borohydride compounds, stannous chloride, tin (II) chloride, and are more positive than silver are gold, rhodium, Soluble salts of platinum, palladium, iridium and the like, for example, potassium chloroaurate, chloroauric acid, palladium ammonium chloride, iridium sodium chloride and the like are included.

The degree of fogging of the previously fogged silver halide emulsion for direct positive use can be varied in a wide range. The degree of fogging depends on the silver halide composition and grain size of the silver halide emulsion used, the type and concentration of the fogging agent used, the pH, pAg, temperature and temperature of the emulsion at the time of fogging. Related to time, etc. For details, see U.S. Patent Nos. 3,023,102 and 3,367,77.
No. 8, No. 3,361,564, No. 3,501,3
No. 05, No. 3,501, 306, No. 3,501,
Nos. 307 and 3,637,392 and British Patent No. 70
7, 704 and the like.

In the pre-fogged direct positive silver halide emulsion according to the present invention, an electron acceptor known as an electron acceptor can be used. That is, a polyvalent cation may be doped into the silver halide crystal as an inorganic desensitizer, or an electron acceptor may be used as an organic desensitizer. Soluble rhodium salts, soluble iridium salts and the like can be used as the inorganic desensitizer. These compounds may be added during the preparation of the silver halide crystal to make the inorganic desensitizer contained in the silver halide crystal. These compounds are preferably added in an amount of 1 × 10 ^-8 to 1 × 10 ^-2 mol per mol of silver halide. As the organic desensitizer, those described in the aforementioned patent can be used.

The pre-fogged silver halide photographic emulsion for direct positive use according to the present invention may contain a known sensitizing dye such as a cyanine dye or a rhodanine dye in addition to the electron acceptor.

Other photographic additives can be added to the pre-fogged direct positive silver halide photographic emulsion according to the present invention. As a stabilizer, for example, Japanese Patent Publication No. 49-1
No. 6,053, JP-A-49-12,651, JP-A-48
Compounds described in -66,828 and the like are preferable,
Alternatively, a water-soluble inorganic salt such as a triazole, an azaindene, a benzothiazolium compound, a mercapto compound, or cadmium, cobalt, nickel, manganese, or zinc may be contained.

As hardening agents, for example, aldehydes such as formalin, glyoxal, mucochloric acid, etc., s-triazines, epoxies, aziridines, vinylsulfonic acid, etc., and as development accelerators, for example, JP-B-42-2
No. 5,203, No. 43-10, No. 245, No. 43-1
No. 3,822, No. 43-17,926, No. 46-2
Nos. 1,186, 49-8, 102, 49-8, 3
Polyalkylene oxides selected from those described in No. 32 and the like and derivatives thereof can also be contained.
In addition, if necessary, ultraviolet absorbers, preservatives, matting agents,
An antistatic agent and the like can be contained.

The pre-fogged silver halide photographic emulsion for direct positive use according to the present invention contains, as protective colloids, natural substances such as gelatin, gelatin derivatives, albumin, agar, gum arabic, and alginic acid, as well as polyvinyl ether and polyvinyl acrylate. , Polyvinylpyrrolidone, cellulose esters partially hydrolyzed cellulose acetate, and hydrophilic polymers such as poly (N-hydroxyalkyl) β-alanine derivatives grafted with ethylene oxide described in JP-B-49-20,530.

A dispersion-polymerized vinyl compound may be contained as a binder for the emulsion. For example, Japanese Patent Application No. 45-55,
No. 956, a polymer latex of an unsaturated ethylenic monomer emulsion-polymerized in the presence of an activator, and a polymer having a hydroxyl group by using a cerium salt 2 described in JP-B-49-20,964. A polymer latex in which the compound is grafted with an unsaturated ethylenic monomer may be contained, and the inclusion of such a polymer latex is preferred from the viewpoint of improving the physical properties of the film.

Further, from the viewpoint of emulsion technology, Japanese Patent Publication No.
No. 23, 44-9, 499, a developer is protected and contained, or liquid paraffin or stearyl acetoglyceride is protected and contained for improving film physical properties. An absorbent or the like can be protected and contained.

The pre-fogged direct-positive halogenated photographic emulsion obtained as described above can be used in any suitable photographic support such as glass, wood, metal, film (eg, cellulose acetate, cellulose acetate butyrate, cellulose night). Rate, polyester, polyamide, polystyrene, etc.) paper, baryta coated paper, polyolefin coated paper, etc.

The pre-fogged internal latent image type silver halide emulsion according to the present invention contains silver halide in which the surface of the silver halide grains is not pre-fogged and the latent image is mainly formed inside the grains. More specifically, a silver halide emulsion is coated on a transparent support in a fixed amount (0.5 to 3 g / m ² ), and the coated silver halide emulsion is coated for a fixed time of 0.01 to 10 seconds. When exposed in the following developer A (inner type developer) at 20 ° C. for 6 minutes,
The maximum density measured by the usual photographic density measurement method is
A silver halide emulsion coated in the same amount as described above and exposed in the same manner was developed at a temperature of 18 ° C. for 5 minutes in the following developer B (surface type developer) at a density at least 5 times larger than the maximum density obtained. Preferably, more preferably 10
It has twice the concentration.

(Internal developing solution A) Methol 2 g Sodium sulfite (anhydrous) 90 g Hydroquinone 8 g Sodium carbonate (monohydrate) 52.5 g KBr 5 g KI 0.5 g Water was added. 1 liter

(Surface developer B) Methol 2.5 g L-ascorbic acid 10 g NaBO ₂ .4H ₂ O 35 g KBr 1 g Water was added to add 1 liter

Specific examples of the internal latent image type emulsion include, for example, a converter described in US Pat. No. 2,592,250.
John-type silver halide emulsion, U.S. Pat.No. 3,761,276,
3,850,637, 3,923,513, 4,035,185, 4,3
Nos. 95,478, 4,504,570, JP-A-52-156614, 55-1
No. 27549, No. 53-50222, No. 56-22681, No. 59-208540
Nos. 60-107641, 61-3137, 62-215272, Research Disclosure No.23510 (Jan. 1983)
Patents disclosed on page 236, further disclosed in U.S. Pat. No. 4,789,510 having a silver chloride shell, JP-A-63-10160 and JP-A-63-47766 relating to silver chlorobromide core-shell emulsions,
JP-A-63-191145 concerning emulsion doped with metal ions
And JP-A-1-52146, and JP-A-1-52146 relating to a core / shell type silver halide emulsion.

The core / shell silver halide molar ratio of the internal latent image type core-shell silver halide emulsion is 20/1 or less.
/ 100 or more is particularly preferred. The internal latent image type silver halide grains not previously fogged according to the present invention contain Mn, C
u, Zn, Cd, Pd, may be incorporated by selecting at least one from the group consisting of metals belonging to Bi or periodic table group VIII, addition amount per mol of silver halide 10 ^-9
To ^10-2 mol is preferred.

Of the above metals, the use of lead, iridium, bismuth and rhodium is particularly preferred. When these metals are mixed with a silver ion solution and a halogen aqueous solution to form silver halide grains, the metal ions can coexist in the form of an aqueous solution or an organic solvent solution and can be incorporated in the grains. Alternatively, after forming the grains, the metal ions may be added in the form of an aqueous solution or an organic solvent solution, and then covered with silver halide. Methods for incorporating these metals are described in U.S. Pat. Nos. 3,761,276 and 4,395,478 and JP-A-59-216136.

The shape of the silver halide grains used in the core-shell silver halide emulsion which is not previously fogged and which is an internal latent image type according to the present invention has a regular shape such as cubic, octahedral, dodecahedral, and tetradecahedral. Irregular crystal forms such as crystals and spheres, and the lengths described in JP-A Nos. 1-131547 and 1-158429 /
Particles having a tabular shape having a thickness ratio value of 5 or more, particularly 8 or more,
An emulsion occupying 50% or more of the total projected area of the grains may be used. In addition, those having a composite form of these various crystal forms,
Emulsions composed of a mixture thereof may also be used.

The silver halide composition includes silver chloride and silver bromide mixed silver halide. The silver halide preferably used in the present invention does not contain silver iodide or contains 3 mol% or less of silver iodide. (Iodo) silver bromide, (iodo) silver chloride or (iodo) silver bromide. The average grain size of the silver halide grains is preferably 1.5 μm or less and 0.1 μm or more, and particularly preferably 1.2 μm or less and 0.2 μm or more.

The particle size distribution may be narrow or wide, but may be within ± 40%, preferably ± 30% of the average particle size in terms of the number or weight of the particles in order to improve graininess and sharpness. Most preferably, a so-called "monodisperse" silver halide emulsion having a narrow grain size distribution such that 90% or more, particularly 95% or more of all grains fall within ± 20% is used.

In order to satisfy the target gradation of the light-sensitive material, two or more kinds of monodispersed silver halide emulsions having different grain sizes or substantially the same size in an emulsion layer having substantially the same color sensitivity. Can be mixed in the same layer or multi-layer coated in another layer. Further, two or more kinds of polydispersed halogenated emulsions or a combination of a monodispersed emulsion and a polydispersed emulsion can be mixed or layered.

The internal latent image type core-shell silver halide emulsion according to the present invention, which has not been previously fogged, can be chemically sensitized with sulfur or selenium sensitization, reduction sensitization, noble metal sensitization or the like alone or in combination inside or on the surface. can do. As a chemical sensitization method for core particles, Japanese Patent Application No. 1-17488,
The method described in JP-A-1-17487 can be used. JP1
In the presence of a mercapto compound as described in -197742,
Also, thiosulfinic acid, sulfinic acid and sulfite may be added as described in JP-A-1-254946, JP-A-2-699738, and JP-A-1-95394. Detailed examples are, for example,
No.17643-III, published in December 1978
See patents on page 3 and others.

The internal latent image type core-shell silver halide emulsion of the present invention is spectrally sensitized with a photographic sensitizing dye according to a conventional method well known in the art. Particularly useful dyes are dyes belonging to cyanine dyes, merocyanine dyes and complex merocyanine dyes, and these dyes can be used alone or in combination. Further, the above dyes and supersensitizers may be used in combination. Specific examples are described in Patents described in Research Disclosure No. 17643-IV (published in December 1978), pp. 23-24.

The silver halide photographic material using the internal latent image type silver halide emulsion which has not been previously fogged according to the present invention is further provided with a bleaching accelerator described in JP-A-4-274232, 62-215272 No. No. 6,098,098, compounds releasing a photographically useful group described in
No. 63-237985, 63-2403
A dye for preventing irradiation and halation described in No. 93 can be added and used.

In addition, various photographic additives known in the art include Research Disclosure No. 17643 (1.
No. 18716 (November 1979)
Moon) Development accelerators, antifoggants described on pages 647 to 651,
Stabilizers, image stabilizers, ultraviolet absorbers, brighteners, coating aids, surfactants, plasticizers, slip agents, antistatic agents, matting agents, binders, hardeners, etc. can be used. it can.

The fogging of the internal latent image type silver halide emulsion not fogged in advance according to the present invention is carried out by the "light fogging method" and / or the "chemical fogging method". The entire surface exposure in the “light fogging method”, that is, fog exposure is performed after imagewise exposure, after development processing, or during development processing. The imagewise exposed photographic light-sensitive material is immersed in a developing solution or a pre-bath of the developing solution, or is exposed before being taken out of these solutions and dried, but is most preferably exposed in the developing solution.

As a light source for fog exposure, Japanese Patent Application Laid-Open No.
Light sources having high color rendering properties (close to white as possible) described in JP-A-350 and JP-A-58-70223 are preferred. Light illuminance is 0.0
1 to 2000 lux, preferably 0.05 to 5 lux is suitable. A photographic light-sensitive material using a higher-sensitivity emulsion preferably has a lower illuminance. The adjustment of the illuminance may be performed by changing the luminous intensity of the light source, or by changing the sensitivity between various light sources, the distance between the photographic material and the light source, or the angle between the photographic material and the light source. Further, the illuminance of the fog light can be continuously or stepwise increased from low illuminance to high illuminance.

The photographic material is preferably immersed in a developing solution or a solution in a prebath thereof, and the light is preferably irradiated after the solution has sufficiently penetrated the emulsion layer of the photographic material. The time from the permeation of the liquid to the light fogging exposure is generally 2 seconds to 2 minutes, preferably 5 seconds to 1 minute, more preferably 10 seconds to 30 seconds. The exposure time for fogging is generally from 0.001 second to 2 minutes, preferably from 0.1 second to 1 minute, more preferably from 1 second to 40 seconds.

The nucleating agent used for fogging the internal latent image type silver halide emulsion which has not been previously fogged according to the present invention by the "chemical fogging method" is either in the photographic material or in the photographic material. It can be contained in the processing solution. Here, the "nucleating agent" is a substance which acts upon surface development of an internal latent image type silver halide emulsion which has not been previously fogged and which directly functions to form a positive image.

When a nucleating agent is contained in a photographic light-sensitive material, it is preferably added to an internal latent image type silver halide emulsion layer. It may be added to other layers such as an intermediate layer, an undercoat layer and a back layer, as long as it adsorbs to silver halide. When the nucleating agent is added to the processing solution, it may be contained in a developing solution or a low pH pre-bath as described in JP-A-58-178350. Further, two or more nucleating agents may be used in combination.

Examples of the nucleating agent which can be used in a silver halide photographic light-sensitive material using an internal latent image type silver halide emulsion not fogged in advance according to the present invention include, for example, "Research Disclosure". − ”Magazine, No. 22534 (1983
January) 50-54 pages, same magazine, No.15162 (November 1976) 76-77
And quaternary heterocyclic compounds and hydrazine compounds described on page 346-352 of the same magazine, No. 23510 (November 1983).

Examples of the quaternary heterocyclic nucleating agent include, for example, US Pat. Nos. 3,615,615, 3,719,494, 3,734,738,
3,759,901, 3,854,956, 4,094,683, 4,3
No. 06,016, UK Patent No. 1,283,835, JP-B-49-38164
No. 52-19452, No. 52-47326, JP-A-52-69613,
No. 52-3426, No. 55-138742, No. 60-11837 and `` Research Disclosure '', No. 23213 (August 1983, 2
67 to 270). Further active quaternary salt compounds, JP-A-63-121042, 63-30
No. 1942, JP-A No. 1-191132, No. 2-79038, No. 2-101450
No. can be used.

Examples of hydrazine nucleating agents having a silver halide adsorbing group include, for example, US Pat. No. 4,030,925.
Nos. 4,080,207, 4,031,127, 3,718,470,
4,269,929, 4,276,364, 4,278,748, 4,3
No.85,108, No.4,459,347, UK Patent No. 2,011,391B,
JP-A Nos. 54-74729, 55-163533, 55-74536, 6
Nos. 0-179734 and 63-231441. Other hydrazine nucleating agents, for example,
U.S. Pat.Nos. 4,560,638, 4,478,928, 2,563,785
And No. 2,588,982, and JP-A-57-86829.

Further, as a highly active hydrazine compound
Are JP 63-231441, JP 234244, JP 234245, JP 2
Use those described in 34246, 204256, etc.
Can be. Quaternary heterocyclic compounds originated as nucleating agents
This is preferable in that the light effect is large. Quaternary heterocyclic compounds and
A hydrazine compound may be used in combination. Processing solution for nucleating agent
When added to the developer, the developer or JP-A-58-178350
It may be contained in a low pH prebath as described.
When adding a nucleating agent to the processing solution, the amount used is 1 liter.
10 per Torr^-8-10^-1Mole is preferred, more preferred
H10^-7-10 ^-3Is a mole.

Although the nucleating agent may be contained in the hydrophilic colloid layer adjacent to the silver halide emulsion layer, it is preferably contained in the silver halide emulsion layer. The addition amount may vary over a wide range because it varies depending on the characteristics of the silver halide emulsion actually used, the chemical structure of the nucleating agent, and the development conditions, but 1 × 10 5 per mol of silver in the silver halide emulsion. A range of from ^-8 to 1 x ^10-2 moles is practically useful, preferably from 1 x ^10-7 to 1 x ^10-3 mole per mole of silver.

When a nucleating agent is used, it is preferable to use a nucleating agent for promoting the action of the nucleating agent. A nucleating agent has no function as a nucleating agent, but is necessary to promote the action of the nucleating agent to increase the maximum density of a direct positive image and / or to obtain a certain direct positive image. A substance that functions to speed up the development time. Examples of such a nucleation accelerator include tetrazaindenes, triazaindenes and pentazaindenes having at least one mercapto group optionally substituted with an alkali metal atom or an ammonium group, and JP 63-106
No. 656, pp. 5-16, JP-A-63-2266
Nos. 52 and 63-8740.

The nucleation accelerator can be contained in the light-sensitive material or the processing solution. In the light-sensitive material, the internal latent image type silver halide emulsion and other hydrophilic colloid layers (intermediate layer and protective layer) can be used. And the like).
Particularly preferred is a layer in or adjacent to a silver halide emulsion. The addition amount of the nucleation accelerator is preferably 10 ^-6 to 10 ^-1 mol per mol of silver halide, more preferably 1 to 10 ^-1 mol.
0 ^-5 to 10 ^-2 mol. In addition, a nucleation accelerator is treated with a processing solution,
That is, when it is added to the developing solution or its pre-bath, the amount is preferably 10 ^-8 to 10 ^-2 mol, more preferably 10 ^-7 to 10 ^-4 mol, per liter of the processing solution. Also, two or more nucleation accelerators can be used in combination.

[0113]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which, however, are not intended to limit the scope of the invention.

Reference Example Sunflower seed extract 400 g of sunflower seeds was ground in a coffee mill, and 2 liters of tap water was added thereto.
Performed at 0 ° C. for 30 minutes. After filtration with a Buchner funnel, 2 L of tap water was further added to the remaining residue, and autoclave extraction was performed again under the same conditions, followed by filtration with a Buchner funnel. The obtained filtrate was combined with the previous filtrate, and concentrated under reduced pressure using an evaporator. After concentrating to about 200 ml,
Lyophilization gave 38.6 g of a powdered water-soluble antioxidant.

Example 1 An aqueous solution of silver nitrate and 1.5 × 10 ^-7 per mol of silver were placed in an aqueous solution of gelatin maintained at 40 ° C.
A mixed aqueous solution of potassium bromide and sodium chloride containing molar sodium rhodium (III) chloride (molar ratio B
r: Cl = 30: 70) at the same time over a period of 75 minutes while maintaining a pAg of 7.2 to give a mean particle size of 0.3.
28 μm cubic monodisperse silver chlorobromide emulsion (AgCl 7
0 mol%).

After the soluble salts were removed by a conventional method, 5 × 10 ^-5 mol of sodium thiosulfate was added per mol of silver halide, followed by chemical ripening at 52.2 ° C. for 120 minutes. This emulsion contains 80 g of gelatin per mole of silver halide. The emulsion thus prepared was added to 8 × 10 ^-3 mol of 6-hydroxy-4-methyl-mol per mol of silver halide.
1,3,3a, 7-tetrazaindene and 3.5 × 10
^{After addition of -4} moles of 3,3'-dimethylthiazolinocarbocyanine methyl sulphate, 40 per 100 cm ² on polyethylene terephthalate (PET) base
It was applied so that the amount of silver became mg.

The emulsion layer was protected by a gelatin protective layer containing formalin and dimethylol urea as hardeners to prepare a film sample 1. Next, a developer 1 (present invention) and a developer 2 (comparative example) having the compositions shown in Table 1 were prepared.

[0118]

[Table 1]

The developer 1 and the developer 2 were separately placed in a 1-liter beaker, and allowed to stand in a cool and dark place for 7 days.
After 7 days, the reduced water was replenished to 1 liter each to obtain developer samples 1 'and 2'. Using the previously prepared film sample 1, the developer properties of developer 1, developer 2, developer 1 'and developer 2' were examined. That is, the film sample 1 was prepared using an LB-200 filter.
After exposing for 5 seconds through a step wedge with a step of 0.15 using a 666K tungsten light source, 35% of developer 1, developer 2, developer 1 'and developer 2' were used.
Developed at 30 ° C. for 30 seconds, stopped, fixed, washed with water and dried. Table 2 shows the results.

[0120]

[Table 2]

The measured pH values in Table 2 are the measured pH values of each developer immediately before the development processing. The iAA% is a numerical value obtained by quantifying the amount of isoascorbic acid contained in each developer by liquid chromatography and expressing the content in the developer 1 according to the present invention as 100, as a relative value. The sensitivity of photographic performance is a relative value of the reciprocal of the exposure amount at which a density of 3.0 excluding fog can be obtained, and the sensitivity when developed with developer 1 (invention) at 35 ° C. for 30 seconds is shown as 100. is there. Toe gamma is the average gradient between 0.1 and 0.5 of the blackening density excluding fog, gamma is the average gradient between 0.5 and 3.0 of the blackening density excluding fog, and fog is the density of the unexposed area. Is shown.

From Table 2, it can be seen that the developer 1 containing the extracted water-soluble antioxidant and reductones according to the present invention exhibited the properties of the developer after being exposed to air for 7 days. In comparison with the developer 2 of the example, it can be seen that the photographic properties are clearly maintained.

Example 2 An aqueous silver nitrate solution and 1.5 × 10 ⁻⁷ per mol of silver were placed in an aqueous gelatin solution kept at 40 ° C.
A mixed aqueous solution of potassium bromide and sodium chloride containing molar sodium rhodium (III) chloride (molar ratio B
r: Cl = 35: 65) at the same time over a period of 70 minutes while maintaining a pAg of 7.2 to give an average particle size of 0.3.
26 μm cubic monodisperse silver chlorobromide emulsion (AgCl 6
5 mol%).

After the soluble salts were removed by a conventional method, 5 × 10 ^-5 mol of sodium thiosulfate was added per mol of silver halide, and the mixture was chemically ripened at 52.2 ° C. for 120 minutes. This emulsion contains 80 g of gelatin per mole of silver halide. The emulsion thus prepared was added to 8 × 10 ^-3 mol of 6-hydroxy-4-methyl-mol per mol of silver halide.
After adding 1,3,3a, 7-tetrazaindene and 0.004 mol of N-ethylquinolinium iodide, the mixture was coated on a polyethylene terephthalate (PET) base to a silver amount of 40 mg per 100 cm ^2. did. The emulsion layer was protected by a gelatin protective layer containing formalin and dimethylol urea as hardeners to prepare a film sample 2. Next, a developer 3 (present invention) and a developer 4 (comparative example) having the compositions shown in Table 3 were prepared.

[0125]

[Table 3]

The developing solution 3 and the developing solution 4 were separately placed in a 1-liter beaker, and left in a cool and dark place for 5 days.
After 5 days, the reduced water was replenished to 1 liter each to obtain a developer 3 'and a developer 4'. Using the prepared film sample 2, a developer 3, a developer 4, and a developer 3 '
And the developing characteristics of the developing solution 4 'were examined. That is, using a LB-200 filter for film sample 2, 2666K
Exposure for 5 seconds through a step wedge with a step of 0.15 with a tungsten light source of 35%, and then developing solution 35, developing solution 4, developing solution 3 'and developing solution 4'
Developed at 45 ° C. for 45 seconds, stopped, fixed, washed with water and dried. Table 4 shows the results.

[0127]

[Table 4]

The measured pH values in Table 4 are the measured pH values of each developer immediately before the development processing. The AA% is a numerical value obtained by quantifying the amount of ascorbic acid contained in each developer by liquid chromatography, and expressing the content in the developer 3 according to the present invention as 100, as a relative value. The sensitivity of the photographic performance is a relative value of the reciprocal of the exposure amount with which a density of 3.0 excluding fog can be obtained.
The sensitivity in the case of development processing at 45 ° C. for 45 seconds is shown as 100. Toe gamma is the average gradient between 0.1 and 0.5 of the blackening density excluding fog, gamma is the average gradient between 0.5 and 3.0 of the blackening density excluding fog, and fog is the density of the unexposed area. Is shown.

From Table 4, it can be seen that the developer 3 containing the extracted water-soluble antioxidant and reductones according to the present invention exhibited the characteristics of the developer after exposure to air for 5 days. As compared with No. 4, it can be seen that the photographic properties are clearly high and good photographic characteristics are maintained.

(Example 3) Powdery isoascorbic acid 2
6.7 g, powdered methol 7.5 g, powdered 5-nitroindazole 30 mg, powdered polyethylene oxide # 4000 15 g, and powdered extracted water-soluble antioxidant 5 g
Was uniformly mixed and placed in a container to obtain a solid layer first layer. 1.5 g of powdered potassium bromide was uniformly spread on the first layer of the solid layer to form a second layer of the solid layer. Next, 1.9 g of flaky potassium hydroxide and powdered potassium metaborate
After the mixture obtained by uniformly mixing 4/3 water salt was spread over the second layer, the solid layers were fixed by applying light pressure from above so that the solid layers did not mix with each other. After the container containing the solid developer 1 was sealed, the container was left in a cool and dark place for 3 months.

As a comparative example, a solid developer 2 was prepared in exactly the same manner except that the powdered water-soluble antioxidant was not contained in the first layer of the solid layer.
It was left in a cool dark place for months. A fresh solid developer 1 was dissolved in 1 liter of water to obtain a developer 5. The solid developer 1 after 3 months was dissolved in 1 liter of water to obtain a developer 5 ′. Further, the developer 5 'was placed in a 1-liter beaker, left as it was in a cool and dark place for 7 days, and then the lost water was replenished to make 1 liter of the developer to be a developer 5 ".

As a comparative example, the same operation was performed for the solid developer 2 to prepare a fresh developer 6, a developer 6 'after 3 months, and a developer 6 "in which the developer 6' was left for 7 days. With respect to the developer properties of the six types of developer 5, developer 5 ', developer 5 ", developer 6, developer 6' and developer 6" prepared above, a commercially available X-ray film was used. That is, using "Kodak T-mat / RA film" (manufactured by Eastman Kodak Co., Ltd.),
An X-ray exposure was performed for 0.05 seconds from both sides using a ray irradiation device, and then a developing treatment was performed at 35 ° C. for 20 seconds with each developer, followed by fixing, washing, and drying to obtain an evaluation sample. Table 5 shows the results.

[0133]

[Table 5]

In Table 5, the sensitivity is the reciprocal of the exposure amount that gives a density of 1.0 excluding fog, and is expressed as 100 when the developing solution 5 is developed at 35 ° C. for 20 seconds. is there. The gradation is 0. Blackening density excluding fog.
Shows the average slope between 25 and 2.0. As is clear from Table 5, the solid developer containing the water-soluble antioxidant according to the present invention has a better air oxidation resistance than the developer of the comparative example in terms of the stability of the developer even when stored for a long period of time. Demonstrated stability.

[0135]

According to the present invention, a developer containing a reductone compound is prevented from deteriorating due to air oxidation to improve the stability, and is substantially free of a dihydroxybenzene-based developing agent and is safer and environmentally friendly. , A developing solution for a silver halide photographic light-sensitive material, and a developing method using the developing solution.

Claims (5)

[Claims] 1. A developer or developer for a silver halide photographic light-sensitive material, comprising one or more water-soluble antioxidants containing a component extracted from a natural product as an active ingredient and one or more reductone compounds. 2. The silver halide photographic light-sensitive material developer according to claim 1, wherein the water-soluble antioxidant contains, as an active ingredient, a component extracted from sunflower seeds or its oil cake. Developer. 3. The developer or developer of a silver halide photographic light-sensitive material according to claim 1, wherein the reductone compound is ascorbic acid and / or isoascorbic acid or a salt thereof. 4. A water-soluble antioxidant comprising, as an active ingredient, (a) a sunflower seed or an oily cake thereof extracted with water or a hydrous alcohol; (b) a reductone compound or a salt thereof; A developer or a developer for a silver halide photographic light-sensitive material, which contains an alkali agent and (d) a photographic development inhibitor and is substantially free of a dihydroxybenzene-based developing agent. 5. A method for developing a silver halide photographic light-sensitive material, comprising using the developer or developer for the silver halide photographic light-sensitive material according to claim 1.