JP2007316374A - Silver halide photographic sensitive material and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material used in production and not changing its fogging value regardless of the kinds or production lots of gelatin, and its manufacturing method. <P>SOLUTION: The manufacturing method of this silver halide photographic sensitive material uses gelatin containing 15 mass% or less of alkali treated component gelatin having an isoionic point of 5.10 or larger. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

  In silver halide light-sensitive materials, gelatin has long been used as a dispersion medium for silver halide grains. Gelatin plays an important role not only in the formation of silver halide grains but also in the entire process from storage of the finally obtained photographic image.

  A general method for producing photographic gelatin is described in detail in, for example, “The Basics of Revised Photographic Engineering / Silver Salt Photo Edition” (Corona: 1998) edited by the Japan Photography Society.・ It can be obtained by extracting pork skin with warm water after alkali treatment or acid treatment. When viewed in terms of molecular weight, it has a fairly wide distribution centered on collagen having a molecular weight of about 100,000, which is called the α chain of collagen. It is also known that the distribution depends on raw materials, pretreatment, extraction conditions, and the like. From the chromatogram obtained by the gel filtration method, a component having a molecular weight of 300,000 or more (H component), a γ component of about 300,000, a β component of about 200,000, and low molecular components of about 5,000 to 10,000 are also present. Yes.

  Gelatin has a protective colloid action and an appropriate crystal growth action of silver halide grains in the process of forming silver halide grains. In the coating process, there are imparting a viscosity necessary for coating, gelling action, and in the drying process, moisture diffusion, silver halide holding action and the like. Even after becoming a light-sensitive material, it retains its photosensitivity and suppresses fogging during storage, and during exposure it has halogen acceptance and latent image regression prevention. There are retention, penetration of processing chemicals, image retention, image color tone, and the like, and during storage there is an image stabilization effect. Thus, gelatin is indispensable for photographic light-sensitive materials.

  In the process of studying production stabilization of silver halide photographic light-sensitive materials, the present inventor has a problem that the fog value of the light-sensitive material fluctuates when the type or lot of gelatin is changed, which is a major obstacle to production stabilization. I found out that Further examination of this problem revealed that the correlation between the fog value of the light-sensitive material and the isoionic point variation of the gelatin component is high. Here, the fog value refers to the minimum density of a film obtained by performing normal development processing.

The isoionic point (also referred to as isoelectric point) is the pH indicated when salt ions are completely removed from the gelatin solution. Patent Document 1 discloses a silver halide color photographic light-sensitive material which can obtain a color positive image excellent in sharpness and image storability by low replenishment rapid processing by using gelatin having an isoionic point of 5.2 or less. However, this patent document only mentions the stain improvement at the time of image storage and processing, and as in the present invention, the relationship between the isoionic point variation of the gelatin component and the fog value of the silver halide photographic material. Is not touched at all.
JP 7-319097 A

  Accordingly, an object of the present invention is to provide a silver halide photographic light-sensitive material and a silver halide photographic light-sensitive material in which the fog value of the light-sensitive material does not change even when the type or lot of gelatin is changed in the production of silver halide photographic light-sensitive materials. It is to provide a manufacturing method.

  The above object of the present invention is achieved by the following configurations.

  1. A silver halide photographic material comprising a gelatin containing an alkali-processed gelatin component having an isoionic point of 5.10 or more in a proportion of 15% by mass or less.

  2. 2. The silver halide photographic material as described in 1 above, wherein the gelatin is used for physical ripening or chemical ripening of a silver halide emulsion.

  3. In a method for producing a halogenated photographic light-sensitive material, a silver halide emulsion is formed by physical ripening or chemical ripening using gelatin, and then a coating solution containing the silver halide emulsion is coated on a support. A method for producing a silver halide photographic light-sensitive material, characterized in that the gelatin contains an alkali-processed gelatin component having an isoionic point of 5.10 or more in a proportion of 15% by mass or less.

  4). 4. The method for producing a silver halide photographic light-sensitive material as described in 3 above, wherein after the silver halide emulsion is formed, the silver halide emulsion is cooled and set.

  5. 5. The method for producing a silver halide photographic material as described in 3 or 4 above, wherein the silver halide emulsion has a pH of 5.5 or less.

  According to the present invention, in the production of a silver halide photographic light-sensitive material, there is provided a silver halide photographic light-sensitive material in which the fog value of the light-sensitive material does not change even if the type or lot of gelatin is changed, and a method for producing the silver halide photographic light-sensitive material Can be provided.

  The best mode for carrying out the present invention will be described in detail below, but the present invention is not limited thereto.

  The silver halide photographic light-sensitive material of the present invention is characterized by using gelatin containing an alkali-processed gelatin component having an isoionic point of 5.10 or more in a ratio of 15% by mass or less.

  As described above, the present inventor examined in detail the problem that the fog value of the light-sensitive material fluctuates when the type or lot of gelatin is changed in the process of studying the production stabilization of the silver halide photographic light-sensitive material. However, it has been found that the correlation between the fog value of the light-sensitive material and the variation of the isoionic point of the gelatin component is high. The fog value is, for example, a value obtained by measuring the blue density with a Konica Minolta densitometer PDA-65 (manufactured by Konica Minolta Co., Ltd.) as the minimum density of a film obtained by performing normal development processing.

  In the present invention, the gelatin component is defined as a unit of gelatin having a certain characteristic for assembling a product by combining single or a plurality of extraction units of gelatin which are usually extracted a plurality of times in batch units.

  Gelatin is generally assembled by mixing a number of gelatin components in order to control various physical and chemical properties. Therefore, the isoionic point of the finally assembled gelatin approximates the weighted average value of the isoionic points of each gelatin component. According to the inventor's study, the weighted average value of the isoionic points and the fog value of the light-sensitive material have a weak correlation. Rather, a certain range of isoionic points within the isoionic points of the individual gelatin components are determined. As soon as the present invention has been made, the surprising fact that the fog value of the light-sensitive material is remarkably stabilized when the gelatin having the composition is contained within a certain range or less is achieved.

  In the silver halide photographic light-sensitive material of the present invention, it is necessary to use gelatin containing an alkali-processed component gelatin having an isoionic point of 5.10 or more at a ratio of 15% by mass or less. The mixing ratio is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably not included.

  Therefore, in order to obtain the effect of the present invention, an alkali-processed gelatin component having an isoionic point of 5.10 or more can be used within the scope of the present invention, but an alkali-processed gelatin having less than 5.10 as much as possible. It is preferable to use components. Further, the gelatin to be used is preferably a gelatin having an isoionic point of 4.5 to less than 5.10 in view of availability.

  The isoionic point can be measured by the Paggy method (photographic seratin test method 9th edition (2002 edition)).

  The gelatin used in the silver halide photographic light-sensitive material of the present invention is alkali-processed gelatin, and the alkali used is not particularly limited, but lime processing is preferable. The production process of alkali-treated gelatin is generally decalcified with acid such as beef bone and pork skin (referred to as ossein in the case of beef bone), alkali treatment of demineralized raw material (lime pickled), water washing, extraction, filtration, ion It is gelatinized through steps such as exchange, concentration, sterilization, solidification, and drying.

  Details of the gelatin production method are described in Arthur Weiss, The Macromolecular Chemistry of Gelasen (Academic Press, 1964).

  Lime pickling treatment promotes solubilization of gelatin by infiltrating the raw material with an alkali solubilizing chemical such as lime. Specifically, for example, by introducing a fine raw material into a saturated lime liquid and holding it for a certain period while stirring and changing the solution as needed, gelatin solubilization is promoted and the raw material is purified. According to the inventor's knowledge, a gelatin component in which the isoionic point is controlled can be obtained by controlling the period of lime pickling, the temperature, the number of times of lime liquid change, and the like.

  The fine raw material subjected to the lime pickling treatment is neutralized and washed with water, and then gelatin is extracted. Specific treatment conditions for neutralization and water washing may be the same as those in the case of normal lime pickling, but a relatively short time treatment is sufficient as in the case of lime picking described above. Specifically, the excess lime content is removed from the fine raw material that has been pickled, and the pH is adjusted to near neutral.

  In the gelatin extraction step, a normal extraction apparatus and extraction conditions can be employed. Specifically, any of a batch method and a continuous extraction method using a column can be employed. The continuous extraction method may be any of an upflow method, a downflow method, and a countercurrent method.

  Further, the gelatin may be deionized by ion exchange or the like using at least one of cation exchange resin and anion exchange resin.

  The gelatin containing an alkali-treated gelatin component having an isoionic point of 5.10 or more according to the present invention at a ratio of 15% by mass or less comprises several to several tens of gelatin components whose isoionic points have been measured in advance. The seeds are mixed and manufactured. About mixing, it is preferable to mix using mixers, such as a Nauta.

  The gelatin according to the present invention is preferably used for physical ripening and chemical ripening of a silver halide photographic light-sensitive material, but the amount used varies depending on the type of the silver halide photographic light-sensitive material and is not particularly limited. .

(Silver halide photographic material)
In the following, the silver halide photographic light-sensitive material of the present invention will be described in detail. However, the gelatin according to the present invention is not limited to the following constitution, and the silver halide photographic light-sensitive material for X-rays and the silver halide color photographic light-sensitive material are used. It can also be applied to materials.

  The halogen composition of the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention is not particularly limited, but the silver chloride content is 60 mol% in consideration of the reduction in the replenishing amount of the processing solution and the rapid processability. It is preferable to use a silver halide emulsion having the above silver chloride, silver chlorobromide or silver chloroiodobromide composition.

  The average grain size of silver halide is preferably 1.2 μm or less, particularly preferably 0.8 to 0.1 μm. The shape of the silver halide grains is not limited, and may be any of flat, spherical, cubic, tetradecahedral, regular octahedral and other shapes. A narrow grain size distribution is preferable, and a so-called monodispersed emulsion in which 90%, preferably 95% of the total number of grains falls within a grain size region of ± 40% of the average grain size is particularly preferred.

  In order to achieve the effects of the present invention remarkably, it is preferable that at least one silver halide emulsion layer is a tabular grain having an aspect ratio of 2 or more of 50% or more of the total projected area of all grains. In particular, as the proportion of tabular grains increases from 60% to 70% and further to 80%, more favorable results are obtained. The aspect ratio represents the ratio of the diameter of a circle having the same area as the projected area of tabular grains and the distance between two parallel planes.

  Of these tabular grains, tabular grains having a (100) plane having 50 mol% or more of silver chloride as the main plane are preferably used. These are U.S. Pat. Nos. 5,264,337 and 5,314,798. No. 5, 320,958 and the like, and the desired tabular grains can be easily obtained.

  Tabular grains can be epitaxially grown or shelled with silver halides having different compositions at specific surface sites. In order to control the photosensitive nuclei, transition lines can be provided on the surface or inside of the tabular grains. In order to provide transition lines, silver iodide fine grains can be present during chemical sensitization or by adding iodine ions. The preparation of the particles can be appropriately selected from an acidic method, a neutral method, an ammonia method, and the like. When doping a metal, it is particularly preferable to form particles under an acidic pH of 1-5.

  In order to control grain growth during the formation of tabular grains, for example, ammonia, a thioether, a thiourea compound, a thione compound, or the like can be used as a silver halide solvent.

Zinc, lead, thallium, iridium, rhodium, ruthenium, osmium, palladium, platinum, and other metal salts can coexist during physical aging and chemical aging. In order to obtain high illuminance characteristics, iridium is preferably doped in the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver.

In the present invention, rhodium, ruthenium, osmium and / or rhenium is preferably doped in the range of 10 ⁻⁹ mol to 10 ⁻³ mol per mol of silver halide in order to obtain a hard emulsion.

  When a metal compound is added to the particle, the metal is coordinated with halogen, carbonyl, nitrosyl, thionitrosyl, amine, cyan, thiocyan, ammonia, tellurocyan, selenocyan, dipyridyl, tripyridyl, phenanthroline or a combination of these compounds. Can be made. The oxidation state of the metal can be arbitrarily selected from the maximum oxidation level to the minimum oxidation level. Preferred ligands include hexadentate ligands described in JP-A-2-2082, JP-A-2-20853, JP-A-2-20854, JP-A-2-20855, etc. There are sodium salts, potassium salts, cesium salts or primary, secondary and tertiary amine salts. Moreover, a transition metal complex salt can be formed in the form of an aco complex.

Examples of these include, for example, K ₃ [RuCl ₆ ], (NH ₄ ) ₃ [RuCl ₆ ], K ₂ [Ru (NO) Cl ₄ (SCN)], K ₂ [RuCl ₅ (H ₂ O)] and the like. It can be expressed as The Ru part can be replaced with Rh, Os, Re, Ir, Pd and Pt.

  Rhodium, ruthenium, osmium and / or rhenium compounds are preferably added during the formation of silver halide grains. As addition positions, there are a method in which the particles are uniformly distributed in the particles, and a method in which a core / shell structure is used so that a large amount is localized in the core portion or the shell portion.

Better results are often obtained when there are many in the shell. Further, in addition to localizing in a discontinuous layer configuration, a method of increasing the abundance as the particle continuously becomes outside may be used. The addition amount can be appropriately selected in the range of 10 ⁻⁹ to 10 ⁻³ mol per mol of silver halide.

  The silver halide emulsion and its preparation method are described in detail in the literature described or cited in Research Disclosure (RD) 17643, pages 22-23 (December 1978).

  The silver halide emulsion may or may not be chemically sensitized, but is preferably. As chemical sensitization methods, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization and noble metal sensitization methods are known, and any of these methods may be used alone or in combination. As the sulfur sensitizer, known sulfur sensitizers can be used. Preferred sulfur sensitizers include various sulfur compounds such as thiosulfates, thioureas, in addition to sulfur compounds contained in gelatin. Rhodanines, polysulfide compounds and the like can be used.

  The photosensitive material used in the present invention can contain various compounds for the purpose of preventing fogging during the production process, storage or photographic processing of the photosensitive material, or stabilizing the photographic performance. That is, azoles such as 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 oxazolinethiones; azaindenes, eg triazaines Dens, tetrazaindenes (especially 4-hydroxy-1,3,3a, 7-tetrazaindene), pentazaindenes, etc .; Phosphate, benzene sulfinic acid, can be added to many compounds known as antifoggants or stabilizers such as benzenesulfonic acid amide.

  As the binder or protective colloid of the photographic emulsion according to the present invention, the gelatin according to the present invention is preferably used in an optimal amount for an optimal process. It is particularly preferable to use it during physical ripening or chemical sensitization. Further, gelatin is preferably added at the initial stage of physical ripening or chemical ripening.

  A silver halide emulsion is formed by physical ripening or chemical ripening using gelatin containing an alkali-treated gelatin component having an isoionic point of 5.10 or more according to the present invention in a ratio of 15% by mass or less, In producing a halogenated photographic light-sensitive material by coating a coating solution containing the silver halide emulsion on a support, the silver halide emulsion is preferably cooled and set after the silver halide emulsion is formed. . The cooling set can be carried out by transferring the silver halide emulsion to a suitable light-shielding pot and placing it in a refrigerator at 5 to 10 ° C. while shielding the light. By using the gelatin according to the present invention, good characteristics can be maintained without fogging even when the silver halide emulsion is stored for a long period of time.

  Moreover, it is a more preferable aspect that the pH of the silver halide emulsion is 5.5 or less in order to enhance the effect of suppressing fogging during storage of the present invention.

  Other hydrophilic colloids can also be used, such as gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, cellulose sulfates, etc. Sugar derivatives such as sodium alginate, starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. And various synthetic hydrophilic polymer materials.

  The silver halide emulsion of the present invention may contain a dispersion of a water-insoluble or hardly soluble synthetic polymer for the purpose of improving dimensional stability. For example, alkyl (meth) acrylate, alkoxy acrylic (meth) acrylate, glycidyl (meth) acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic acid, A polymer having a combination of methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate, sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like as monomer components can be used.

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

  The support used in the present invention may be either permeable or non-permeable, but for the purposes of the present invention, a permeable plastic support is preferred. As the plastic support, a support made of a polyethylene compound (for example, polyethylene terephthalate, polyethylene naphthalate, etc.), a triacetate compound (for example, triacetate cellulose, etc.), a polystyrene compound, or the like is used.

  The thickness of the support is preferably 50 to 250 μm, particularly preferably 70 to 200 μm.

  Furthermore, it is preferable to perform a heat treatment after film formation in order to improve curling and curling of the support. Most preferred is after film formation and after emulsion coating, but may be after emulsion coating. The heat treatment conditions are preferably 45 ° C. or more and the glass transition temperature or less and between 1 second and 10 days. It is preferable to make it within 1 hour from the viewpoint of productivity.

In the present invention, the following compounds are preferably contained in the constituent layers of the silver halide photographic material.
(1) Solid-dispersed fine particles of dye The compound described in JP-A-7-5629 (page 3), pages [0017] to (16) [0042] (2) Compound having an acid group JP-A-62-237445 Compound (3) Acidic polymer described on page 292 (8), lower left column, line 11 to page 309 (25), lower right column, line 3, JP-A-6-186659, page (10) [0036] to (17) [ [0062] Compound (4) Sensitizing dye described in JP-A-5-224330 (3), pages [0017] to (13) [0040] Compounds described in JP-A-6-194971 (page 11) [0042] Compound described on page (22) [0094] Compound described on JP-A-6-242533 (page 2) [0015]-page 8 (0034) JP-A-6-337492 (page 3) [0012] ~ (34) pages Compound described in [0056] Compound (5) supersensitizer described in JP-A-6-337494 (4), pages [0013] to (14) [0039] JP-A-6-347938, page (3) [0011] to (16) page [0066] compound (6) redox compound compound described in JP-A-4-245243, pages 235 (7) to 250 (22) (7) SPS support A support described in Japanese Patent No. 54551.

  In the light-sensitive material of the present invention, the above-mentioned additives and other known additives are, for example, (RD) 17643 (December 1978), 18716 (November 1979) and 308119 (December 1989). Compounds described in (Month). The following table shows the types of compounds and their locations shown in these three research disclosures.

  The silver halide photographic light-sensitive material of the present invention is preferably subjected to photographic processing after exposure by an automatic processor having at least 4 processes of development, fixing, washing (or stabilizing bath) and drying. A known developing agent can be used as the developer used.

  Specifically, dihydroxybenzenes (for example, hydroquinone, hydroquinone monosulfonate, etc.), 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4) , 4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.), aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc.), ascorbic acids (ascorbic acid, sodium ascorbate, erythorbic acid, etc.) and metal complex salts (EDTA iron salt, DTPA) Iron salt, DTPA nickel salt, etc.) alone or It can be used in conjunction seen.

  Among them, it is preferable to use a developer containing ascorbic acid and its derivatives. Ascorbic acid and its derivatives are known as developing agents. For example, U.S. Pat. Nos. 2,688,548, 2,688,549, 3,022,168, 3,512,981, Those described in US Pat. Nos. 4,975,354 and 5,326,816 can be used.

  In the present invention, ascorbic acid and derivatives thereof and 3-pyrazolidones (for example, 1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone) 1-phenyl-4-ethyl-3-pyrazolidone, 1-phenyl-5-methyl-3-pyrazolidone, etc.) and aminophenols (for example, o-aminophenol, p-aminophenol, N-methyl-o-aminophenol) N-methyl-p-aminophenol, 2,4-diaminophenol, etc.) and dihydroxybenzenes substituted with a hydrophilic group (for example, hydroquinone monosulfonate, hydroquinone monosulfonate sodium salt, potassium 2,5-hydroquinone disulfonate) (Salt etc.) Theft is more preferable.

  When used in combination, 3-pyrazolidones, aminophenols, and dihydroxybenzenes substituted with a hydrophilic group are usually used in an amount of 0.01 to 0.2 mol per liter of developer. Is preferred. The concentration of ascorbic acids is preferably 0.2 to 1 mol per liter of the developer. Most preferably, it is 0.4-0.6 mol. In particular, a combination of ascorbic acid and its derivatives and 3-pyrazolidones, and a combination of ascorbic acid and its derivatives, 3-pyrazolidones and dihydroxybenzenes substituted with a hydrophilic group are preferably used.

When ascorbic acids are used as the developing agent, the pH of the developer is preferably 10.2 or less and 8.0 or more, more preferably less than 10.0 and 9.0 or more. It is preferable to add an agent (sodium hydroxide, potassium hydroxide, etc.) and a pH buffer (for example, carbonate, phosphate, borate, boric acid, acetic acid, oxalic acid, alkanolamine, etc.). The pH buffer is preferably a carbonate, and the amount added is preferably 0.5 mol or more and 2.5 mol or less, more preferably 0.75 mol or more and 1.5 mol or less per liter.

  If necessary, dissolution aids (eg, polyethylene glycols, esters thereof, alkanolamines, etc.), sensitizers (eg, nonionic surfactants containing polyoxyethylenes, quaternary ammonium compounds, etc.), surfactants, Antifoaming agents, antifoggants (for example, halides such as potassium bromide and sodium bromide, nitrobenzindazole, nitrobenzimidazole, benzotriazole, benzothiazole, tetrazole, thiazoles, etc.), chelating agents (for example, ethylenediamine Acetic acid or alkali metal salts thereof, nitrilotriacetate, polyphosphate, etc.), development accelerators (eg, compounds described in US Pat. No. 2,304,025, JP-B 47-45541), hardeners (eg, Glutaraldehyde or its bisulfite adduct), or antifoam And the like may be added.

  The pH of the developer is preferably adjusted to 7.5 or more and less than 10.5. When used as an ascorbic acid developing agent, the pH of the developer is preferably 10.2 or less and 8.0 or more, and more preferably less than 10.0 and 9.0 or more.

  As the fixing solution, a commonly used composition can be used. The fixer generally has a pH of usually 3-8. Fixing agents include organic thiosulfates such as sodium thiosulfate, potassium thiosulfate, and ammonium thiosulfate, and thiocyanates such as sodium thiocyanate, potassium thiocyanate, and ammonium thiocyanate, as well as soluble stable silver complex salts. Any compound known as a fixing agent can be used.

  In the present invention, a water-soluble aluminum salt that acts as a hardener, such as aluminum chloride, aluminum sulfate, potassium alum, aldehyde compounds (for example, glutaraldehyde, glutaraldehyde sulfite adduct, etc.), etc., may be added to the fixing solution. it can.

  If desired, the fixing solution may be a compound such as a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, citric acid), a pH adjuster (eg, sulfuric acid), or a chelating agent capable of softening water. Can be included.

  In the present invention, the ammonium ion concentration in the fixing solution is preferably 0.1 mol or less per liter of the fixing solution. The ammonium ion concentration is preferably in the range of 0 to 0.05 mol per liter of the fixing solution. As a fixing agent, sodium thiosulfate may be used instead of ammonium thiosulfate, or ammonium thiosulfate and sodium thiosulfate may be used in combination.

  In the present invention, the acetate ion concentration in the fixing solution is preferably less than 0.33 mol / liter. The type of acetate ion is arbitrary, and the present invention can be applied to any compound that dissociates acetate ion in the fixing solution. However, acetic acid and lithium, potassium, sodium, and ammonium salts of acetic acid are preferably used. Salts and ammonium salts are preferred. The acetate ion concentration is more preferably 0.22 mol or less, and particularly preferably 0.13 mol or less, per liter of the fixing solution, whereby the amount of acetic acid gas generated can be greatly reduced. Most preferred is substantially free of acetate ions.

  The fixer includes salts such as citric acid, isocitric acid, tartaric acid, malic acid, and succinic acid, and optical isomers thereof. These acid salts may be lithium salt, potassium salt, sodium salt, ammonium salt, lithium hydrogen tartrate, potassium hydrogen, sodium hydrogen, ammonium hydrogen, ammonium potassium tartrate, sodium potassium tartrate, etc. Of these, citric acid, isocitric acid, malic acid, succinic acid, and salts thereof are more preferable. Most preferred are malic acid and its salts.

  The silver halide photographic light-sensitive material of the present invention can be processed using a developing / fixing replenisher prepared from a solid processing agent.

  The solid processing agent referred to here is a solid processing agent such as a powder processing agent, a tablet, a pill, or a granule, and is subjected to moisture-proof processing if necessary.

Further, in order to reduce the amount of waste liquid, the present invention is preferably processed while fixing a fixed amount in proportion to the area of the photosensitive material. The fixing replenishment amount is 300 ml or less per 1 m ² . Preferably, the amount is 30 to 250 ml per 1 m ² .

In order to reduce the amount of waste liquid, the development replenishment amount is preferably 250 ml or less per 1 m ² , more preferably 30 to 200 ml per 1 m ² . Here, the fixing replenishment amount and the development replenishment amount indicate the replenishment amount.

The washing water in the washing process is desired to be washed with a small amount of washing water, which is called a stabilizing solution, from a washing method using running tap water due to problems with waste liquid treatment and piping work when installing an automatic processor. In the present invention, the effect of the present invention is great when the replenishing amount of washing water is 500 ml / m ² or less. In particular, the effect of the present invention is remarkable when it is 50 ml / m ² or more and 300 ml / m ² or less.

  In such washing water, for the purpose of stabilizing the image, inorganic and organic acids and salts thereof, or alkali agents for adjusting the film surface pH (the film surface pH after treatment is 3 to 8) and Its salts (eg borate, metaborate, borax, phosphate, carbonate, potassium hydroxide, sodium hydroxide, aqueous ammonia, monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, citric acid, oxalic acid, malic acid , Acetic acid, etc.), aldehydes (for example, formalin, glyoxal, glutaraldehyde, etc.), chelating agents (for example, ethylenediaminetetraacetic acid or its alkali metal salts, nitrilotriacetic acid salts, polyphosphates, etc.), anti-bacterial agents ( For example, phenol, 4-chlorophenol, cresol, o-phenylphenol, chlorophene, dichlorophene, formaldehyde, -Hydroxybenzoic acid ester, 2- (4-thiazoline) -benzimidazole, benzisothiazolin-3-one, dodecyl-benzyl-methylammonium chloride, N- (fluorodichloromethylthio) phthalimide, 2,4,4'-trichloro -2'-hydroxydiphenyl ether, etc.), a color tone adjusting agent and / or a residual color improving agent (for example, a nitrogen-containing heterocyclic compound having a mercapto group as a substituent; specifically, 2-mercapto-5-sulfonic acid sodium-benz Imidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzthiazole, 2-mercapto-5-propyl-1,3,4-triazole, 2-mercaptohypoxanthine and the like). The flush water according to the present invention preferably contains a bactericidal agent.

  Any bactericides may be used as long as they do not adversely affect photographic performance. Specifically, thiazolylbenzimidazole compounds, isothiazolone compounds, chlorophenol compounds, bromophenol compounds, thiocyanic acid and isothionic acid compounds, acids Azide compounds, diazine and triazine compounds, thiourea compounds, alkylguanidine compounds, quaternary ammonium salts, organotin and organozinc compounds, cyclohexylphenol compounds, imidazole and benzimidazole compounds, sulfamide compounds, chlorinated isocyanuric compounds There are various antibacterial and antifungal agents such as active halogen compounds such as sodium acid, chelating agents, sulfite compounds, and antibiotics represented by penicillin.

  In the present invention, the washing tank is preferably a multistage countercurrent system divided into two or more tanks as disclosed in JP-A-9-218493.

  The temperature of the development, fixing, washing and / or stabilizing bath is preferably between 10 and 45 ° C., and each of them may be temperature adjusted separately.

  According to the present invention, the total processing time (Dry to Dry) from when the film tip is inserted into the automatic processor until it comes out of the drying zone is 10 to 60 seconds when processing using an automatic processor due to the demand for shortening the development time. It is preferable that The total processing time mentioned here includes the total processing time required for processing the black and white photosensitive material, specifically, for example, development, fixing, bleaching, washing with water, stabilization processing, drying, etc. required for processing. This time includes all process 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 is 15 to 50 seconds. Further, in order to stably run a large amount of light-sensitive material of 100 m ² or more, the development time is preferably 2 to 18 seconds.

  The effect of the present invention is remarkable when the drying time is shorter than 15 seconds. Furthermore, the effect was remarkable when it dried with the drying time of less than 10 seconds.

In the present invention, an automatic processor having the method and mechanism described below can be preferably used.
(1) Deodorizing device: JP-A-64-37560, page 544 (2), upper left column to 545 (3) Page, upper left column (2) Waste liquid treatment method: JP-A-2-64638, page 388 (2), lower left column to 391 (5) Lower left column on page (3) Rinse bath between developer bath and fixing bath: JP-A-4-313749, page (18), "0054" to page (21), page "0065"
(4) Water replenishment method: JP-A-1-281446, page 250 (2), lower left column to lower right column (5) Method of detecting the outside air temperature and humidity to control the drying air of the automatic processor: JP-A-1-315745 496 (2), lower right column to 501 (7) lower right column, and JP-A-2-108051, page 588 (2), lower left column to 589 (3), lower left column, page (6) Kaihei 6-27623 (4) Page "0012" to (7) "0071"

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

[Preparation of silver halide photographic light-sensitive material 1]
(Preparation of silver halide emulsion)
Add B solution of silver nitrate aqueous solution and C solution of water-soluble halide solution containing sodium chloride and potassium bromide to solution A at pH 3.0, 46 ° C, constant flow rate in 5 minutes by simultaneous mixing method, and further 3 minutes Thereafter, a silver nitrate aqueous solution D and a water-soluble halide solution E were added thereto at a constant flow rate for 40 minutes to obtain 0.23 μm silver chlorobromide (AgCl / AgBr = 65/35 mol%) cubic crystals. It was. At this time, the silver potential (EAg) was 120 mV at the end of mixing. Subsequently, unnecessary salts were removed by ultrafiltration, 15 g of ossein gelatin A was added per mole of silver, the pH was adjusted to 5.45, and the mixture was dispersed at 55 ° C. for 30 minutes. The silver potential of the obtained emulsion was 200 mV (40 ° C.).

Liquid A ossein gelatin A (alkali treatment) 50g
Nitric acid (5%) 6.5ml
Ion exchange water 5000ml
Sodium chloride 2.3g
B liquid silver nitrate 47.9g
Nitric acid (5%) 7.9ml
455 ml of ion exchange water
C liquid ion exchange water 500ml
Potassium bromide 13g
Sodium chloride 11.8g
Oise gelatin A (alkali treatment) 13g
D liquid silver nitrate 1150g
Nitric acid (5%) 38ml
Ion exchange water 1520ml
Liquid E: Ossein gelatin A (alkali treatment) 43g
311 g of potassium bromide
285g of sodium chloride
Na ₃ [IrCl ₆ ] 2.2 mg
Na [RhCl ₅ (H ₂ O)] 0.33 mg
To the resulting emulsion, 1 × 10 ⁻³ mole of stabilizer 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene and 8.5 × 10 ⁻⁴ potassium bromide per mole of silver. Mole, stabilizer 1-phenyl-5-mercaptoterazole was added to 1.5 × 10 ⁻³ mol, and adjusted to pH 5.6 and EAg 123 mV. After the dispersed sublimed sulfur into fine particles, was 100 minutes chemical ripening at 2 × 10 ^-5 mol and to 62 ℃ 1.5 × 10 ^-5 mol per mol of chloroauric acid as a sulfur atom, a stabilizer 4- Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added at 3 × 10 ⁻³ mol. Thereafter, 3 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole and 1.5 × 10 ⁻³ mol of potassium iodide were added. After the temperature was lowered to 40 ° C., 2 × 10 ⁻⁴ moles of sensitizing dyes (S-1, S-2) were added to each silver mole to prepare a chemically ripened silver halide emulsion, and the pH was adjusted to 5. After adjusting to 4, it moved to the light-shielding pot and set by cooling in a 5 degreeC refrigerator.

  Ossein gelatin A uses 6 types of gelatin components, and the isoionic point measurement of each component is measured by the Paggy method (the ceratin test method for photography 9th edition (2002 edition)), as shown in Table 2. It was assembled and mixed so that it would be a cumulative percentage. Incidentally, ossein gelatin A has a content ratio of gelatin components having an isoionic point exceeding 5.10 of 15% or less.

(Support, subbing layer)
After a biaxially stretched polyethylene terephthalate support (thickness: 100 μm) was corona discharged at 30 W / (m ² · min), an undercoat layer having the following composition was coated on both sides and dried at 100 ° C. for 1 minute.

2-hydroxyethyl methacrylate / butyl acrylate / t-butyl acrylate / styrene copolymer (25/30/25/20 mass ratio)
0.5g / m ²
Surfactant A 3.6 mg / m ²
Hexamethylene-1,6-bis (ethylene urea) 10 mg / m ²
(Antistatic layer)
After applying a corona discharge of 10 W / (m ² · min) on both sides of the polyethylene terephthalate support with the undercoat layer on both sides, roll-fit an antistatic layer having the following composition on one side at a speed of 70 m / min. It applied using the coating pan and the air knife, dried at 90 degreeC for 2 minutes, and heat-processed at 140 degreeC for 90 second, and provided the antistatic layer.

Water-soluble conductive polymer B 0.6g / m ²
Hydrophobic polymer particles C 0.4 g / m ²
Polyethylene oxide compound (Mw 600) 0.1 g / m ²
Curing agent E 0.01g / m ²
On the undercoat layer of the undercoated support, the following first emulsion layer (containing the above-mentioned silver halide emulsion) and second layer were simultaneously coated from the support side, and set to cool.

  Thereafter, on the opposite antistatic layer, the following backing layer was applied at a coating speed of 200 m / min, cooled at -1 ° C. and dried on both sides simultaneously to obtain a silver halide photographic light-sensitive material 1. .

First layer (emulsion layer): coating solution pH 5.2
Gelatin 1.92 g / m ²
Silver halide emulsion prepared above 3.4 g / m ² as the amount of silver
Hydrazine derivative H-34 0.015 g / m ²
Hydrazine derivative H-39 0.020 g / m ²
Benzyladenine 0.02 g / m ²
Colloidal silica / vinyl acetate / vinyl pivalate suspension polymer (ratio of 75 / 12.5 / 12.5% by mass) 1.4 g / m ²
Sodium polystyrene sulfonate (average molecular weight 500,000)
0.015 g / m ²
Composite latex PL10 0.5g / m ²
Polymer latex L1 (particle size 0.10 μm) 0.5 g / m ²
Second layer (emulsion protective layer)
Gelatin 0.90 g / m ²
Matting agent (monodispersed polymethyl methacrylate with an average particle size of 3 μm)
0.045 g / m ²
Nucleation promoter Na-21 0.01 g / m ²
Bactericidal agent Z 0.005 g / m ²
Hardener D7 0.07 g / m ²
Surfactant a 50 mg / m ²
Sliding agent R21 75mg / m ²
(Backing layer)
Gelatin 3.2 g / m ²
Dye f1 0.03 g / m ²
Dye f2 0.1 g / m ²
Colloidal silica / vinyl acetate / vinyl pivalate suspension polymer (ratio of 75 / 12.5 / 12.5% by mass) 0.7 g / m ²
Sodium polystyrene sulfonate 0.010 g / m ²
Sodium dihexyl sulfosuccinate 0.020 g / m ²
Matting agent (monodispersed polymethyl methacrylate with an average particle size of 3 μm)
0.045 g / m ²
Hardener h1 0.05g / m ²
Hardener h2 0.07g / m ²
The compounds used are as follows.

[Preparation of silver halide photographic light-sensitive materials 2 to 10]
Silver halide photographic light-sensitive materials 2 to 10 were prepared in the same manner except that the gelatins shown in Table 2 were used in place of gelatin A of silver halide photographic light-sensitive material 1.

  The silver halide photographic light-sensitive material 8 was subjected to physical aging and chemical ripening using ossein gelatin D, and then coated without cooling setting to produce a silver halide photographic light-sensitive material.

  These samples were subjected to wedge exposure and then developed under the following processing conditions to evaluate each characteristic.

(Processing conditions)
(Process) (Temperature) (Time)
Current image 38 ° C 15 seconds Settling 37 ° C 15 seconds Washing water Normal temperature 15 seconds Squeeze / Dry 50 ° C 15 seconds Total 60 seconds The formulation of each treatment solution is as follows.

Developer HQ (per liter of working solution)
224ml of pure water
Diethylenetriaminepentaacetic acid ・ 5sodium 1.0g
Potassium sulfite 12.54g
Sodium sulfite 42.58g
Potassium bromide 4g
8g borate
55g potassium carbonate
Diethylene glycol 40g
5-methylbenzotriazole 0.21 g
1-Phenyl-4-methyl-4-hydroxylmethyl-3-pyrazolidone (Dimaison S) 0.85 g
Hydroquinone 20g
Potassium hydroxide 18g
Dissolved in accordance with the recipe and finished to a total volume of 400 ml. In use, it is mixed with 600 ml of pure water to make 1 liter. The pH of the working solution was adjusted to 10.4.

Fixing solution (starting solution: per liter of working solution)
200g sodium thiosulfate
Sodium sulfite 22g
Sodium gluconate 5g
Trisodium citrate dihydrate 12g
Citric acid 12g
The pH of the working solution was adjusted to 5.4 with sulfuric acid and finished to 1 liter.

Fixing solution (replenisher: 2x concentrated solution)
200g sodium thiosulfate
Sodium sulfite 22g
Sodium gluconate 5g
Trisodium citrate dihydrate 12g
Citric acid 12g
The pH of the working solution was adjusted to 5.2 with sulfuric acid and finished to 500 ml.
Flushing water A solution obtained by adding 8.8 ml of the following purification agent to 1 liter of tap water was placed in a washing tank to obtain washing water.

(Preparation of purification agent)
800g of pure water
0.1g salicylic acid
171 g of 35 mass% hydrogen peroxide solution
Pluronic F-68 3.1g
Hokusite F-150 15g
Diethylenetriaminepentaacetic acid ・ 5sodium 10g
Finish to 1 liter with pure water.

(Replenishment amount of processing solution)
The development / fixing replenisher of the above formulation, the cleaning agent, and the tap water for dilution were replenished directly to the developing tank, the fixing tank, and the washing tank, respectively, under the following three conditions.

(Replenishment amount condition 1)
Developer replenishment amount Working solution: 150 ml / m ²
Fixing agent replenishment amount Concentrate: 125 ml / m ²
Dilution water: 125 ml / m ²
Flushing water replenishment amount Tap water: 2.3 l / m ²
Cleaner: 20 ml / m ²
(Replenishment amount condition 2)
Developer replenishment amount Working solution: 75 ml / m ²
Fixer replenishment amount Concentrate: 65 ml / m ²
Dilution water: 65 ml / m ²
Flushing water replenishment amount Tap water: 1 liter / m ²
Cleaning agent: 10ml / m ²
(Replenishment amount condition 3)
Developer replenishment amount Working solution: 40 ml / m ²
Fixing agent replenishment amount Concentrate: 35 ml / m ²
Dilution water: 35 ml / m ²
Flushing water replenishment amount Tap water: 1 liter / m ²
Cleaner: 10 ml / m ²
Development processing was performed under the above-described development processing conditions.

  The following evaluation was performed using each developed film sample.

<Evaluation of fog value>
The fog value was obtained by measuring the blue density of the minimum density of the developed film sample with a Konica Minolta densitometer PDA-65 (manufactured by Konica Minolta Co., Ltd.). The results are shown in Table 2.

  As is apparent from Table 2, the silver halide photographic light-sensitive materials 1 to 8 of the present invention use the gelatins A to G of the present invention, so that the silver halide photographic light-sensitive materials using the gelatins of Comparative Examples 1 and 2 are used. It is clear that the fog value is greatly improved with respect to 9,10. Further, the pH of the chemically ripened emulsion is set to 5.5 or less (compared to the silver halide photographic light-sensitive materials 2 and 3), and the chemically ripened emulsion is cooled and set (the silver halide photographic light-sensitive materials 4 and 8 are It was also found that the fog value is further improved by comparison).

Claims (5)

A silver halide photographic material comprising a gelatin containing an alkali-processed gelatin component having an isoionic point of 5.10 or more in a proportion of 15% by mass or less. 2. The silver halide photographic material according to claim 1, wherein the gelatin is used for physical ripening or chemical ripening of a silver halide emulsion. In a method for producing a halogenated photographic light-sensitive material, a silver halide emulsion is formed by physical ripening or chemical ripening using gelatin, and then a coating solution containing the silver halide emulsion is coated on a support. A method for producing a silver halide photographic light-sensitive material, characterized in that the gelatin contains an alkali-processed gelatin component having an isoionic point of 5.10 or more in a proportion of 15% by mass or less. 4. The method for producing a silver halide photographic material according to claim 3, wherein after the silver halide emulsion is formed, the silver halide emulsion is cooled and set. 5. The method for producing a silver halide photographic light-sensitive material according to claim 3, wherein the silver halide emulsion has a pH of 5.5 or less.