JPH061348B2 - Silver halide photographic light-sensitive material - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material, and more specifically, improvements have been made so that stable photographic performance can be maintained and exhibited from the time of production to the time of use. The present invention relates to a silver halide photographic light-sensitive material.

Conventional technology and its problems The demand for silver halide photographic light-sensitive materials is increasing more and more as an information recording material that can record information with high sensitivity and high density and can be easily used. The improvement in quality, simplification of handling, simplification of development processing and the like have been made, and it is becoming easier for users to use. In the case of silver halide photographic light-sensitive materials for printing, efforts have been made to shorten the development processing time, reduce the processing steps, simplify the development processing by introducing an automatic processor, etc. The productivity is being improved in response to the large-scale development processing of. For example, in the development processing of color photographic paper, the development processing time is shortened by adopting resin-coated paper as a support, and the development processing step is also reduced to a processing step of two baths of color development and bleach-fixing. I am trying to do. On the other hand, automatic processors have also been converted to space-saving and energy-saving types, and the productivity of the entire system in large-scale laboratories has greatly improved.

In this way, the productivity of large-scale laboratories is being improved in response to the increasing demand for silver halide photographic light-sensitive materials, while in recent years, so-called satellite laboratories, branch laboratories, and development laboratories and film retailers have become popular. Since small laboratories such as so-called in-store laboratories that perform development processing have emerged, and there is a tendency that photograph enthusiasts so-called Amatyuure photographers themselves enjoy the development processing, A development processing system different from the concentrated development processing by a large-scale laboratory is required, and accordingly, improvement of the silver halide photographic light-sensitive material itself is required.

A silver halide color photographic light-sensitive material for printing or the like, especially a color photographic paper, is required to have high sensitivity in order to produce a large amount of prints in a large-scale laboratory. Therefore, the silver halide contained is generally silver chlorobromide or silver chloroiodobromide having a high silver bromide content. However, silver halide having a high silver bromide content has a lower developing activity than silver halide having a high silver chloride content, and in order to develop sufficient photographic performance, a processing solution such as a color developing solution used in the development processing. It is necessary to activate the treatment by increasing the component concentration, pH, temperature, etc. Therefore, maintaining the composition of the processing solution is the most important control point, and during development processing by small laboratories and photography enthusiasts, a very complicated operation is forced to maintain the composition of the processing solution, and the development processing is stable. It loses its sexuality and wins.

Therefore, as one of the universal methods for improving the stability of development processing, it is possible to use silver halide having a high silver chloride content, which is excellent in development characteristics, in a silver halide photographic light-sensitive material. In this case, in order to maintain good stability of photographic performance such as sensitivity, gradation and fog (so-called raw storage stability) when the silver halide photographic light-sensitive material is stored in a state before exposure, cadmium has hitherto been used. It has been attempted to stabilize photographic performance by incorporating lead, etc. into silver halide, but since cadmium is harmful to the human body, it has been in a non-use direction in recent years. However, the use of a silver chloride-based silver halide containing no cadmium causes a serious inconvenience that the stability of photographic performance is impaired during the production of a silver halide photographic light-sensitive material. In particular, it is usual to store refrigerating a silver halide emulsion in which silver halide grains are dispersed in a hydrophilic binder such as gelatin, or to store a coating solution prepared by adding a coupler dispersion or the like to this silver halide emulsion. However, as a result of research, it was revealed that the storage stability of the photographic performance in each storage state, that is, the storage stability of the emulsion set and the stagnation of the coating solution is significantly impaired. It is extremely difficult to make the storage stability and the stagnation property of the coating liquid good.

II Object of the invention The object of the present invention is to have excellent emulsion set storability and coating solution stagnation property during production, as well as raw storability, and to show good development processing stability, which is stable from production to use. Another object of the present invention is to provide a silver halide photographic light-sensitive material capable of maintaining and exhibiting the above photographic performance.

The above object of the present invention is to obtain a Vogel by subjecting a support to oxidation treatment with at least one of silver halide grains having a surface layer portion substantially composed of silver chloride and a compound having an oxidizing action containing hydrogen peroxide and ozone. This is achieved by a silver halide photographic light-sensitive material having at least one silver halide emulsion layer containing gelatin having a reaction value of 20 or less.

III Detailed Description of the Invention The silver halide photographic light-sensitive material of the present invention comprises a support, silver halide grains whose surface layer portion is substantially composed of silver chloride (hereinafter, referred to as silver halide grains according to the present invention), and It has at least one silver halide emulsion layer containing gelatin having a Fogel reaction value of 20 or less (hereinafter, this gelatin is referred to as gelatin according to the present invention) (hereinafter referred to as silver halide emulsion layer according to the present invention). The silver halide emulsion layer including the silver halide emulsion layer according to the present invention and the non-photosensitive layer, which constitutes the silver halide photographic light-sensitive material of the present invention, such as an intermediate layer, a protective layer, a filter layer, and a backing layer There is no particular limitation on the number of layers and the order of layers. The silver halide photographic light-sensitive material of the present invention may be either a single-color silver halide photographic light-sensitive material or a multi-color silver halide photographic light-sensitive material. , A single layer or a plurality of layers, each of which is a blue light-sensitive silver halide emulsion layer containing a yellow coupler, a green light-sensitive silver halide emulsion layer containing a magenta coupler, and a red light-sensitive silver halide containing a cyan coupler. It includes a silver halide color photographic light-sensitive material having an emulsion layer.
Taking this silver halide color photographic light-sensitive material as an example, any one of these blue, green and red light-sensitive silver halide emulsion layers, or two or more layers are silver halide according to the present invention. Although it is referred to as an emulsion layer, in order to achieve the object of the present invention, it is preferable that all layers of the blue, green and red light-sensitive silver halide emulsion layers are silver halide emulsion layers according to the present invention. .

The silver halide grain according to the present invention may be either monodisperse or polydisperse, and may be a normal crystal or a twin crystal, and the ratio of (100) plane to (111) plane is arbitrary. Can be used. In addition, neutral method, acidic method, ammonia method, forward mixing method,
It may be produced by any method such as a reverse mixing method, a double jet method, a controlled double jet method, etc. Further, it is usually a so-called core / shell type in which silver halides having different compositions are laminated. It may be a silver halide grain. The shape of the silver halide grains according to the present invention may be any of a hexahedron, an octahedron and a tetradecahedron, or a combination of these shapes, as well as an irregular shape and a spherical shape. The size is appropriately selected according to the specific usage of the silver halide photographic light-sensitive material of the present invention, and is not particularly limited, but preferably, the particle size is relatively uniform. The silver halide grains have a grain size of 1 μm or less, more preferably 0.1 to 0.8 μm, and even more preferably 0.3 to 0.6 μm.

That at least the surface layer portion of the silver halide grain according to the present invention is substantially composed of silver chloride means that almost the entire surface layer portion of the silver halide grain according to the present invention is 90 mol% in terms of mole percentage.
It is meant to be composed of silver halide containing the above silver chloride. The amount of the surface layer portion is preferably 5% by weight or more based on the total amount of silver halide grains according to the present invention. If it is less than 5% by weight, the object of the present invention cannot be sufficiently achieved when the inside of the silver halide grain is composed of silver halide having low developing activity.
Further, when the silver chloride content in the surface layer portion is less than 90 mol%, the development progress is deteriorated and the development processing stability is deteriorated when the silver halide photographic light-sensitive material of the present invention is subjected to development processing. Not preferable. The surface layer portion of the silver halide grain according to the present invention may be any silver halide containing 90 mol% or more of silver chloride as described above, and usually bromide other than silver chloride is a component constituting silver halide. When silver and / or silver iodide is added, the silver halide in the surface layer portion is silver chloride, silver chlorobromide, silver chloroiodobromide, etc., or these silver halides have high illuminance and short-time exposure characteristics. A small amount of iridium salt, rhodium salt or the like is appropriately added for the purpose of improving and increasing the contrast. When the surface layer portion is silver chloroiodobromide, it is preferable that the content of silver iodide is 1 mol% or less in terms of mol percentage because the development processing stability is not impaired. Further, the silver halide composition of the portion other than the surface layer portion of the silver halide grain according to the present invention can be arbitrarily selected, and may be the same as or different from the silver halide composition of the surface layer portion, silver chloride, The composition may be any of silver chlorobromide, silver chloroiodobromide, silver bromide, silver iodobromide, and silver iodide. When the silver halide grain according to the present invention is a core / shell type silver halide grain, the entire shell can be regarded as the surface layer portion, and in this case as well, almost the entire shell is 90 mol% or more. It is necessary to contain silver chloride, and the amount of shell is preferably 5% by weight or more of the total amount of silver halide grains. As an embodiment of the silver halide grain according to the present invention, silver chloroiodobromide containing 90 mol% or more of silver chloride prepared by emulsification and mixing without containing cadmium or lead salt (containing silver iodide It is preferable that the amount is 1 mol% or less.), And silver halide converted from silver chloride to silver bromide, and further from silver bromide to silver iodide to a less soluble silver halide. Examples include so-called conversion core / shell type silver halide grains in which a silver halide containing 90 mol% or more of silver chloride is laminated as a shell on a core composed of grains.
Of course, it is not limited to these. This conversion core /
Shell-type silver halide grains are described in, for example, Japanese Patent Publication No. 55-4274.
It can also be prepared by the method described in No. 0 or the like, or JP-A-51-15423, 53-75921,
It is also possible to use the method for producing a silver halide photographic emulsion described in JP-A-56-78831 to change the silver halide in the surface layer portion to substantially consist of silver chloride.

The gelatin according to the present invention is gelatin having a Fogel reaction value of 20 or less. Here, the Fogel reaction value means
"Photographic gelatin test method Paggy method" 5th edition, published by Joint Council of Photographic gelatin test method, October 1982, 21
Refers to the Fogel reaction value that can be measured by the method specified in detail on the page and the like. The gelatin according to the present invention can be obtained, for example, by subjecting ossein gelatin, hide gelatin (including pigskin gelatin) and the like to oxidation treatment to bring the Fogel reaction value to 20 or less. The oxidation treatment can be easily carried out by bringing the ossein gelatin, the hide gelatin and the like into contact with a compound having an oxidizing action such as hydrogen peroxide, ozone, persulfuric acid and nitric acid. As the compound having an oxidizing action, hydrogen peroxide or ozone is preferably used in consideration of a decomposition by-product of an oxide, a purification treatment after treating gelatin, or a pollution prevention treatment of waste liquid, and these are decomposed. Because it becomes water and oxygen,
This is advantageous because it has little effect on the silver halide emulsion. The gelatin such as ossein gelatin and hide gelatin used in the present invention may be processed and purified by any extraction treatment method such as alkali treatment, acid treatment and enzyme treatment.

For general properties and manufacturing methods of gelatin, see The Theory of Photographic Process, 4th Edition [THJames, Macmillan, 1977], pages 51-76. And The Science and Technology of Gelatin [AGWard, A.Courts]
, Academic Press Press, 1977] 295-365. Among them, in order to remove photographically harmful impurities contained in gelatin, a purification method by hydrogen peroxide, nitric acid, an ion exchange treatment, a method of bleaching coloring of gelatin and the like are described. However, even in these methods, there is no photographically satisfactory gelatin. With the progress of silver halide photographic emulsion technology, it has been required in recent years to make gelatin more inactive, and gelatin in response to the demand has led to the provision of photographic materials that are stable and have little variation. Is coming. However, even if an inert gelatin which is said to be extremely stable in a silver halide emulsion is used, the above-mentioned silver halide grains according to the present invention whose surface layer portion is substantially silver chloride are not described above. The storage stability of the emulsion set and the stagnation property of the coating solution are extremely insufficient, and the actual situation is that they are far from practical use. The above-mentioned book by James and Ward et al. Does not suggest what kind of effect is exerted in the combination of the silver halide grains according to the present invention and the gelatin according to the present invention. It was unpredictable. Generally, photographic gelatin has a fogel reaction value of 5
It is about 0 to 70, and even in gelatin called inactive form, the Fogel reaction value is in the range of 30 to 40, and it can be clearly distinguished from the gelatin according to the present invention. The higher the Fogel reaction value, the worse the storage stability. Therefore, the lower the value, the better. In the present invention, the Fogel reaction value of 2
By using gelatin of 0 or less, the effect of the present invention is remarkably improved and it can be put to practical use.

The molecular weight of gelatin according to the present invention is 50,000 to 3,000,000.
And the amount of free sulfur contained is
It is preferably 20 μg or less per 1 g of gelatin.

When an oxidative treatment is used to obtain gelatin according to the present invention, this oxidative treatment may be performed during or after any treatment step after the gelatin is extracted from the raw material, but it is preferable to perform it before drying. . It is also possible to carry out after the drying, at the time of dissolution before adding to the silver halide emulsion.

The method for producing gelatin according to the present invention is exemplified below,
It is not limited to these.

Gelatin A (hereinafter referred to as Gel-A) 1 kg of an inactive ossein gelatin (hereinafter referred to as Gel-O) prepared by the alkali treatment method is dissolved in 15 warm water to prepare 1
Add 25 ml of 0% hydrogen peroxide while stirring and add 40 ° C.
And reacted for 5 hours. Then, 1% sodium sulfite aqueous solution is added little by little to neutralize excess hydrogen peroxide.
The neutralization point was confirmed by taking out a part of the gelatin solution and performing an iodine reaction. Pass this gelatin solution through an ion exchange resin,
It was concentrated by a conventional method and dried to obtain 840 g of dried gelatin.

Gelatin B (hereinafter referred to as Gel-B) Hyde gelatin by the alkali treatment method (hereinafter referred to as Gel-H)
1 kg was dissolved in 15 warm water, pH was adjusted to about 8 by adding sodium hydroxide aqueous solution, 25 ml of 10% hydrogen peroxide solution was added with stirring, and the mixture was reacted at 40 ° C. for 2 hours. Next, acetic acid was added to the reaction solution to adjust the pH to about 6.5, the gelatin solution was passed through an ion exchange resin, concentrated by a usual method, and dried to obtain 850 g of dried gelatin.

Gelatin C (hereinafter Gel-C) Pickskin gelatin by acid treatment (hereinafter Gel-P
1 kg was dissolved in 15 warm water and treated by the same method as for obtaining Gel-A to obtain 850 g of dried gelatin.
Got

Gelatin D (hereinafter referred to as Gel-D) 200 g of Gel-O was dissolved in 4 warm water, ozone was generated by using Ozonizer ON-11 type manufactured by Yamato Scientific Co., Ltd., and the gas was passed through a silicon tube into a gelatin solution. It was introduced for 2 hours. Then, this gelatin solution was passed through an ion exchange resin, concentrated and dried to obtain 900 g of dried gelatin.

The Fogel reaction value of the thus-obtained gelatin according to the present invention and the gelatin used as the raw material was measured by the above-mentioned Paggy method. The results are shown in Table 1.

The gelatin according to the present invention can be contained in the silver halide emulsion layer according to the present invention in combination with other known hydrophilic binders. Examples of the hydrophilic binder used in the present invention include gelatin such as the aforementioned ossein gelatin and hide gelatin, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanol gelatin and esterified gelatin, and the like, colloidal gelatin. Albumin, agar, gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate having an acetyl group and hydrolyzed to 10 to 20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol-vinyl aminoacetate copolymer. Such as vinyl alcohol polymer having urethane carboxylic acid group or cyanoacetyl group, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, protein or Polymers obtained by polymerization of a monomer having a saturated acylated protein and a vinyl group, polyvinyl pyridine, polyvinyl amine, poly aminoethyl methacrylate and polyethylene amine. The amount of the gelatin according to the present invention is 15% by weight or more, and further 25% by weight or more based on the total amount of the hydrophilic binder including the gelatin according to the present invention contained in the silver halide emulsion layer according to the present invention. The effect of the present invention is more sufficiently obtained as the amount of gelatin according to the present invention increases.

The timing of adding the gelatin according to the present invention to the silver halide grains according to the present invention is not particularly limited, and it is already present at the time of forming the silver halide grains according to the present invention, or when the silver halide grains are dispersed. It is added as a gelatin for dispersion, or a silver halide emulsion is prepared and stored in a set, and then added as an additional gelatin.When preparing a coating solution, a coupler, a surfactant or various photographic additives are added for dispersing the coupler. In any case, it may be added together with the agent. It is preferably added during the formation of the silver halide grains according to the present invention or during the dispersion of the silver halide grains as a gelatin for dispersion, and more preferably with the silver halide grains according to the present invention. It is particularly advantageous for achieving the object of the present invention to add it as a dispersing gelatin which can remain in the silver halide emulsion layer according to the present invention while keeping contact with it.

The content of the silver halide grains according to the present invention and the hydrophilic binder containing gelatin according to the present invention in the silver halide emulsion layer according to the present invention is determined by the color sensitivity and photosensitivity of the silver halide emulsion layer according to the present invention. It should be appropriately selected as known in the art according to the characteristics such as. In the present invention, it is preferable to use 15 parts by weight or more, further 25 parts by weight or more of the gelatin according to the present invention to 100 parts by weight of the silver halide according to the present invention, and the silver halide emulsion layer according to the present invention. The amount of the hydrophilic binder containing gelatin according to the present invention contained in the above is preferably 100 to 1000 parts by weight with respect to 100 parts by weight of the silver halide grains according to the present invention.

It is optional to add various photographic additives to the silver halide emulsion layer according to the present invention and the other silver halide emulsion layers constituting the silver halide photographic light-sensitive material of the present invention.
For example, the optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, styryls, holopolar cyanines, hemicyanines, oxonols and hemioxonols. , These optical sensitizers have a basic group such as thiazoline, thiazole or the like as a nitrogen-containing heterocyclic nucleus, or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, thiobarbituric acid, pyrazolone, etc. Those containing a nucleus are preferable, and these nuclei are substituted with an alkyl group, a hydroxyalkyl group, a sulfoalkyl group, a carboxyalkyl group, a halogen atom, a phenyl group, a cyano group, an alkoxy group, or condensed with a carbocycle or a heterocycle. May be. Further, the silver halide emulsion layer and the other silver halide emulsion layers according to the present invention may contain a stabilizer usually used, for example, a compound also having an azaindene ring, a heterocyclic compound having a mercapto group and the like. it can. The compound having an azaindene ring is preferably 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. As the heterocyclic compound having a mercapto group, a pyrazole ring, 1,2,4-triazole ring, 1,2,3-triazole ring, 1,3,4-thiadiazole ring, 1,2,3-thiadiazole ring, 1, 2,4-thiadiazole ring, 1,2,5-thiadiazole ring, 1,2,3,4-tetrazole ring, pyridazine ring, 1,2,3-triazine ring, 1,2,4-triazine ring, 1, 3,5-triazine ring, these rings are 2-3
There are compounds having an individually condensed ring such as a triazolotriazole ring, a diazaindene ring, a triazaindene ring, a tetrazaindene ring, a pentazaindene ring, and a phthalazinone ring, an indazole ring, and the like. 1-phenyl-5 -Mercaptotetrazole is preferred.

In addition, in the silver halide photographic light-sensitive material of the present invention,
The wetting agent used according to the purpose includes, for example, dihydroxyalkane, and the film physical property improving agent further includes, for example, a copolymer of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid, styrene-maleic acid. A water-dispersible particulate polymer substance obtained by emulsion polymerization such as a copolymer or a styrene maleic anhydride half alkyl ester copolymer is suitable. Other photographic additives include gelatin plasticizers, surfactants, UV absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, moldants, brighteners, development speeds. The use of regulators, matting agents, anti-irradiation dyes and the like is optional.

When the silver halide photographic light-sensitive material of the present invention is used for color, it is preferable to use a coupler.

Examples of the yellow coupler used in the present invention include benzoylacetanilide type, pivaloylacetanilide type,
Alternatively, a 2-equivalent type yellow coupler in which the carbon atom at the coupling position is substituted with a so-called split-off group which can be released during coupling is useful.

As the magenta coupler, 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type,
2 with indazolone or split-off group
Equivalent magenta couplers are useful.

As the cyan coupler, a phenol type, naphthol type, pyrazoquinazolone type, or 2-equivalent type cyan coupler having a split off group is useful.

Any of these couplers can be selected, and the method of use, the amount used, etc. are not particularly limited, but usually 0.1 to 0.4 mol of the coupler is used per 1 mol of the silver halide according to the present invention. It is preferably used in proportion.

The silver halide photographic light-sensitive material of the invention is combined with a color image-providing substance for diffusion transfer so as to release a diffusible dye in response to the development of silver halide, and the desired transfer is carried out on the image-receiving material during an appropriate development process. It can also be used to obtain an image. Examples of such diffusion transfer color image donors include, for example, U.S. Pat.
227,551, 3,227,554, 3,443,939, 3,443,9
No. 40, No. 3,658,824, No. 3,698,897, No. 3,725,062
No. 3,728,113, No. 3,751,406, British Patent No. 840,78
No. 1, 904,364, 1,038,331, West German patent publication (OL
S) No. 1,930,215, No. 2,214,381, No. 2,228,361, No.
2,242,762, 2,317,134, 2,402,900, 2,40
Those described in JP-A No. 6,606, JP-A-2,406,653 and JP-A-49-114424 can be used.

Further, in the case of forming a dye image, an ultraviolet absorber for preventing browning due to short wavelength actinic rays of the dye image,
For example, it is useful to use thiazolidone, benzotriazole, acrylonitrile, benzophenone compounds and the like. Chinupin PS, 120, 320, 326, 3
Single use or combined use of 27 and 328 (both manufactured by Ciba-Geigy) is advantageous.

Each constituent layer of the silver halide photographic light-sensitive material of the present invention can be hardened with an optional hardener. As the hardener, it is possible to use a hardener such as a chromium salt, a zirconium salt, an aldehyde-based compound such as formaldehyde or mucohalogen acid, a halotriazine-based compound, a polyepoxy compound, an ethyleneimine-based compound, a vinyl sulfone-based compound, or an acryloyl-based compound. it can.

The silver halide photographic light-sensitive material of the present invention comprises a support, a silver halide emulsion layer containing the silver halide emulsion layer of the present invention, a filter layer, an intermediate layer, a protective layer, an undercoat layer and a backing layer. , Various photographic constituent layers such as a non-photosensitive layer such as an anti-halation layer are coated.

The silver halide photographic light-sensitive material of the present invention is a black and white general-purpose X,
It can be effectively used for various purposes such as ray, color, pseudo color, printing, infrared, and micro, and also colloid transfer method, Rogers US Pat. No. 3,087,81
7, 3,185,567 and 2,983,606, U.S. Pat.No. 3,253,915 to Weyerts et al., U.S. Pat.No. 3,227,550 to Whitemore et al., U.S. Pat.
51, Whitemore U.S. Pat.No. 3,227,552, and Rand U.S. Pat.Nos. 3,415,644, 3,415,645 and 3,415,646, color image transfer processes, color diffusion transfer processes, absorption transfer processes. It can also be applied as a silver halide photographic light-sensitive material. In particular, each dye image formed from a silver halide emulsion, a coating solution, a red-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer and a blue-sensitive silver halide emulsion layer in a silver halide photographic light-sensitive material before exposure. It is useful as a silver halide photographic light-sensitive material for color, in which it is important that the color balance is not upset.

As the support used in the silver halide photographic light-sensitive material of the present invention, any support can be used, and typical supports include a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, which is optionally undercoated. Examples thereof include polypropylene film, cellulose acetate film, glass plate, baryta paper, and paper coated with a resin such as polyolefin such as polyethylene. The support may be transparent or white opaque.

IV. Specific Use of the Invention The silver halide photographic light-sensitive material of the present invention thus constituted can be developed, for example, after imagewise exposure, by a known method usually used as a development processing.

When the silver halide photographic light-sensitive material of the present invention is a silver halide black-and-white photographic light-sensitive material for general black-and-white use, a black-and-white developer which can be used for development processing is preferably polyhydroxybenzenes such as hydroquinone, aminophenol. , 3-pyrazolidones, ascorbic acid and derivatives thereof, etc. as black-and-white developing agents. Specific compounds of these black and white developing agents include hydroquinone, aminophenol, N-methylaminophenol,
1-phenyl-3-pyrazolidone, 1-phenyl-4,4
Examples thereof include dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone and ascorbic acid.

When the silver halide photographic light-sensitive material of the present invention is a silver halide color photographic light-sensitive material for color or the like, a color developing agent that can be contained in a color developing solution that can be used in the development processing is preferably an aromatic compound. It contains a primary amine color developing agent as a main component, and typical examples thereof include N, N-diethyl-p-phenylenediamine, diethylamino-O-toluidine, 4-amino-3-methyl. -N-ethyl-N- (β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-
Examples thereof include N- (β-hydroxyethyl) aniline.

The black and white and color developing solutions may further contain a specific antifoggant and development inhibitor. These developer additives may be optionally incorporated in the layer film of the silver halide photographic light-sensitive material. Generally, useful antifoggants include, for example, benzotriazoles such as 5-methylbenzotriazole; benzothiazoles; heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole; aromatic and aliphatic A mercapto compound and the like are included. Further, the developing solution may contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound.

Thus, after or before black-and-white development or color development, the silver halide photographic light-sensitive material of the present invention has a bleaching, fixing, bleach-fixing, washing, stabilizing, hardening, neutralizing, reversing, stopping, rinsing and A usual processing step selected from drying and the like is performed. In some cases, black-and-white development and color development can be combined and processed.

V. Specific Effect of the Invention The silver halide photographic light-sensitive material of the present invention is a silver halide emulsion containing silver chloride as a main component, without using cadmium, lead, etc., which have been conventionally added to the silver halide emulsion. A silver halide excellent in storage stability, coating solution retention and raw storage stability, and capable of improving the decrease in development activity when using a silver halide emulsion containing silver bromide as a main component, and having excellent development characteristics. It can be a photographic light-sensitive material.

As described above, according to the silver halide photographic light-sensitive material of the present invention, stable photographic performance can be maintained and exhibited from the time of production to the time of use, and a good image can be obtained even in a development process by a small laboratory or an amateur photographer. It can be said that the improvement was made in response to the increase in demand for silver halide photographic light-sensitive materials.

VI Specific Examples of the Invention The present invention is described in more detail below by showing specific examples, but the embodiments of the present invention are not limited thereto.

Example 1 Solution B and solution C, which were kept at 65 ° C. and each had the following composition, were mixed by injecting solution B and solution C over 10 minutes, and aged for 45 minutes. Then, after cooling and removing excess salt by a precipitation washing method, pure water was added to make 600 ml, pH was adjusted to 4 with acetic acid, and the temperature was raised to 60 ° C. Then, a solution D and a solution E having the following compositions were injected and mixed by a simultaneous mixing method over 3 minutes, and after aging for 20 minutes,
Hypo 15 ml, 4-hydroxy-6-methyl-1,3,3a, 7
-Add tetrazaindene and ripen for another 75 minutes to contain silver halide grains having an average particle size of 0.4μ, a core / shell ratio of 10/3 by weight, and a silver chloride content of shell of 94.5 mol%. A silver halide emulsion was obtained. To the silver halide emulsion thus obtained, 43.3 g of the gelatin shown in Table 1 was added as dispersed gelatin, and the mixture was cooled.
It was stored in a low temperature set aside so that the amount of gelatin was about 3 mol (10 g of gelatin).

[Solution A]

[Solution B] 500 ml of 1 molar silver nitrate solution [Solution C] [Solution D] 150 ml of 1 molar silver nitrate solution [Solution E] Thus, the silver halide emulsion stored at low temperature for 1, 15, 30 and 50 days was redissolved, and a coupler solution having the following formulation, a hardener H-1 and 13 g of Gel-O as additional gelatin were added. In addition, a coating solution is prepared, and this coating solution is coated on polyethylene laminated paper with a silver amount of 0.4 g /
m ² (2.0 g / m ² as the amount of gelatin) is coated, and further gelatin is coated on the coated silver halide emulsion layer so that the coating amount is 1.0 g / m ^2, and then After drying, five types of monochromatic silver halide photographic light-sensitive materials were prepared. (Sample Nos. 1 to 5 in Table 1) [Coupler liquid] 2,4-dichloro-3-methyl-6- [α-2,4-di-tert
-(Amylphenoxy) butyramide] phenol 2 g
And 0.02 g of 2,5-di-octylhydroquinone were dissolved in 2 ml of ethyl acetate and 1 ml of dioctyl phthalate,
Sodium dodecylbenzene sulfonate 0.1g and Gel
The mixture was mixed with a gelatin solution containing -O2g and protected and dispersed by an ultrasonic method.

[Hardener H-1] Thus, the samples prepared by using the silver halide emulsion stored at low temperature for 1 day, 15 days, 30 days and 50 days were exposed under the following conditions and then developed in the following processing steps.

[Exposure conditions]

Using a KS-7 type sensitometer (manufactured by Konishi Roku Photo Industry Co., Ltd.),
Exposure is performed through a wedge with a density difference of 0.10.

[Processing step of development processing]

Temperature Time Color development 30 ± 0.5 ℃ 2 minutes Bleach fixing 25 ± 2 ℃ 1 minute 30 seconds Water wash 25 ± 5 ℃ 2 minutes Dry 80 ℃ or less 1 minute 30 seconds [Composition of solution used for development] ( Color developer) (Bleaching fixer) Photographic performance, i.e. sensitivity, of the sample thus developed
(S), gradation (γ) and fog (Fog) were measured in the following manner. The results are shown in Table 2.

[Measurement procedure]

Sensitivity (S): The amount of exposure that gives a fog (Fog) + density of 1.0 was determined, and the reciprocal of this was taken and expressed as a relative value when the reference sample was 100.

Gradation (γ): Fog (Fog) + density 0.25 and Fog (Fog) +
It was expressed by the slope (tan θ) of a straight line connecting the concentrations of 1.5.

Fog: Density of unexposed area after development Note that the density is Sakura photoelectric densitometer PDA-65 (manufactured by Konishi Roku Photo Industry Co., Ltd.)
Was measured using. Here, the reference densities (zero points) of the reflection density and the transmission density are the same as those of the color developing solution of each sample, but the color developing agent 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) -aniline sulfate Was taken as the concentration when treated.

From Table 2, Samples 1 to 3 having the silver halide grain according to the present invention and the silver halide emulsion layer containing the gelatin according to the present invention, even when the silver halide emulsion was stored at a low temperature set for a long period of time, It can be seen that there is little decrease in γ and increase in Fog, and S, γ and Fog are stable.

Example 2 After preparing the same silver halide emulsion as in Sample Nos. 1 and 4 of Example 1, the ratio of Gel-A and / or Gel-O shown in Table 3 was further added to this emulsion as additional gelatin. Further, the same coupler solution and hardening agent as those in the case of sample numbers 1 and 4 were added to prepare a coating solution, and the time until the coating solution was coated on polyethylene laminated paper (coating solution leaving time) was 0.5, 5. 10 and 20 hours (the temperature of the coating solution was 40 ± 0.5 ° C., the pH was 6.1), and after coating the silver halide emulsion layer, the coating amount of gelatin was 1.
Multi-layer coating was carried out so as to obtain 0 g / m ² to prepare a monochromatic silver halide photographic light-sensitive material. (Samples 6 to 14 in Table 3) S and Fog values of these samples 6 to 14 were measured in the same manner as in Example 1, and the results are shown in Table 3. Next, sample 6
The values of S, γ and Fog in the case of forced aging by leaving Nos. 14 to 50 ° C. for 0 days, 2 days and 5 days were measured in the same manner as in Example 1, and the results are shown in Table 3. In addition, the S value in the forced aging test is a relative value when the S value on day 0 is 100, and the γ and Fog values are the measured values on day 0 and the values on day 0 for 2 and 5 days. Expressed as a difference.

From Table 3, in the case of the silver halide photographic light-sensitive material of the present invention, the stagnation property of the coating solution of the silver halide emulsion layer and the raw storability are excellent, and moreover, in the hydrophilic binder contained in the silver halide emulsion layer. It can be seen that the higher the ratio of gelatin according to the present invention, the better the stagnation of these coating solutions and the raw preservation life.

Example 3 2 × 10 ^-6 mol iridium salt, 0.1 g adenine, 0.1 g
While maintaining 640 ml of 1 M NH ₄ Cl solution (adjusted to pH 6.0) containing KCNS and 40 g of gelatin Gel-A at 60 ° C., 1200 ml of 0.5 M AgNO ₃ solution was added over 3 minutes. It was After 10 minutes, 600 ml of a 1 molar NH ₄ Br aqueous solution and 30 ml of a 0.1 molar KI aqueous solution were added, and the mixture was aged for 40 minutes. Then, 600 ml of a 0.5 molar AgNO ₃ aqueous solution was added to stack a shell mainly composed of silver chloride to form a conversion core / shell type silver halide grain. (The conversion of the core was 96 mol% silver bromide by X-ray diffractometry, the shell composition was 92 mol% silver chloride, and the core / shell ratio was 2/1 by weight). Then, after removing excess salt by a precipitation washing method, hypo and 4-hydroxy-6 were used.
-Methyl-1,3,3a, 7-tetrazaindene was added for chemical sensitization, and this solution was divided into 3 parts to obtain gel-dispersed gelatin.
64.8 g of A, Gel-C or Gel-H was added to each. Note that about 70% of the gelatin used during emulsification is removed by washing with precipitation water. On the other hand, an emulsion was prepared in the same manner as described above, except that 200 ml or 400 ml of a 0.5 mol NH ₄ Br solution was added when laminating shells as a comparative emulsion, and then a 0.5 mol AgNO ₃ solution was added. . In this case, the shell composition was 41 mol% silver chloride and 74 mol% silver chloride, respectively.
The silver halide emulsion thus obtained is then treated after 1 or 30 days with further 4-hydroxy-6-methyl-1,3,3.
a, 7-Tetrazaindene, mercaptobenzotriazole, styrene-maleic anhydride polymer, the following magenta coupler solution, the following hardener H-2 and an additional gelatin in an appropriate amount to make a coating solution, and a coating silver amount of 1.5 g / m ² , The amount of gelatin coated is 4.0 g / m ² and coated on an undercoated polyester film, and the amount of gelatin coated on this coating layer is 1.0 g.
A gelatin protective layer was applied so as to be / m ² and dried.
(Samples 15 to 23 in Table 4) [Magenta coupler liquid] And the color tingling inhibitor 2.5-di-tert-octylhydroquinone in tricresyl phosphate, dioctyl phthalate and ethyl acetate to dissolve the alkanol XC
Protected dispersion in Gel-O containing (Dyupon).

[Hardener H-2] Samples 15 to 23 thus obtained were exposed to light and developed in the same manner as in Example 1, and then stored in emulsion set for 1 day and 30 days, respectively, S, γ and Fog.
The values and S, γ and Fog values in the case of forced aging of a sample stored for one day in emulsion set were measured in the same manner as in Example 1, and the results are shown in Table 4.

In Table 4, in both cases of set storage and forced aging, the S value is the actual measured value for the S value of one day of set storage, and otherwise the S value of one day of set storage is 100. The relative values, γ and Fog values were represented by the measured values when the set was stored for 1 day, and the other values were represented by the difference from the measured values.

From Table 4, in the case of the silver halide photographic light-sensitive materials of the present invention of sample numbers 15 to 17, the composition of gelatin according to the present invention is 3
Sample Nos. 15 and 16 in which the composition of gelatin according to the present invention is 75% by weight are superior in emulsion set storage stability and raw storage stability as compared with Sample No. 17 in which the halogen content of the present invention is less. The improvement effect of the combination of silver halide grains and gelatin according to the present invention is clearly shown. Further, in Sample Nos. 18 to 23 using the silver halide grains having a low silver chloride content of shell, such an improving effect was not found, and the combination of the silver halide grains according to the present invention and the gelatin according to the present invention was not found. First, the storage stability and raw storage stability of the emulsion set are improved.

Next, sample Nos. 15, 18 and 21 produced as described above
Each sample was developed in the same manner as in Example 1 except that the color development temperature was changed as shown in Table 5, and the S and γ values in each process were measured in the same manner as in Example 1. ,
The results are shown in Table 5 based on the case of 30.0 ° C.

In the table, the (change amount) of S is expressed as a relative value when the value at 30.0 ° C. is set to 100, and the (change value) of γ is expressed as a difference from the value at 30.0 ° C.

From Table 5, it can be seen that the silver halide photographic light-sensitive material of the present invention has little variation in S and γ values even when the temperature for color development changes, and has excellent development processing stability.

Claims (1)

[Claims] 1. A Vogel reaction value by subjecting a support to an oxidation treatment with at least one of silver halide grains having a surface layer portion substantially composed of silver chloride and hydrogen peroxide and a compound having an oxidizing action containing ozone. Has at least one silver halide emulsion layer containing 20 or less gelatin, and a silver halide photographic light-sensitive material.