JPH0310930B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an internal latent image type silver halide photographic emulsion, and more specifically, after image exposure, appropriate exposure is given to the entire surface during development processing, or development processing is carried out in the presence of a fogging agent, and then directly processed. In the method of forming a positive image, fogging of the exposed area (minimum density) that can be used appropriately and is undesirable;
The present invention relates to a photographic emulsion suitable for providing an internal latent image type silver halide photographic light-sensitive material which has high sensitivity and excellent stability, effectively suppressing negative images. Internal latent image type silver halide photosensitive materials are conventionally well-known photosensitive materials, such as the solarization of the photographic sensitivity curve seen in silver halide emulsions that are coupled by prior exposure to strong light for a short time. Development processing is performed by bleaching and destroying the fog nuclei in the exposed areas using the Herschel effect, etc. when a silver chloride emulsion exposed to weak diffused light is irradiated with strong infrared rays with a wavelength of 700 mμ to 800 mμ. Since it is generally easier to obtain high-sensitivity materials than photosensitive materials that obtain positive images using photosensitive materials, it has recently become a subject of much research. Although it cannot be said that a clear explanation has been given regarding the details of the direct positive image formation mechanism, for example, in ``The Theory of the Photographic Process'' by Mies and James, of the photographic
You can understand to some extent the process by which a positive image is formed by the ``desensitizing effect of an internal latent image'' as discussed on page 161 of the 3rd edition. In other words, fog nuclei are selectively generated only on the surface of the silver halide grains in unexposed areas due to the surface desensitization effect caused by the so-called internal latent image generated inside the silver halide grains by the first image exposure. It is thought that a photographic image is then formed in the unexposed area by developing the fog nuclei on the surface by normal development. In order to selectively fog in this manner, it is known to uniformly expose the entire surface or to use a hydrazine compound or a heterocyclic quaternary nitrogen salt compound as a fogging agent. Various techniques are known to date in this technical field. For example, US Pat. No. 2,592,250,
Same No. 2497917, Same No. 2497875, Same No. 2588982,
Same No. 3761266, Same No. 3796577, Same No. 3761276,
Specifications of 3352672, 3935014, and 3957488, JP-A-50-138820, JP-A-51-148419
No. 53-60222, No. 53-71829, No. 53-
No. 66727, No. 55-127549, No. 56-54437, No. 55
- It is described in each publication such as No. 21067. By using these known methods, it is possible to directly produce a positive-type photographic material with relatively high sensitivity. However, it has become clear that the above-mentioned representative known techniques still have deficiencies that need to be resolved for practical production. That is, if the time from preparing the silver halide emulsion to coating becomes longer,
As the sensitivity decreases, the minimum density (Dmin) increases and the reproduced density range narrows, and a negative image is formed in a high exposure area, resulting in a significant deterioration in image quality. This phenomenon occurs when an internal latent image type silver halide emulsion is prepared and then stored as a set for a long period of time at a low temperature (below 10°C) (hereinafter referred to as set storage), or when various additives are added to form a coating solution. This occurs when the coating is left at 35 to 45°C for more than 3 hours before coating (hereinafter referred to as coating liquid stagnation). When such development occurs, the coating performance of the silver halide emulsion changes each time, resulting in a serious quality defect in that a uniform and stable product cannot be obtained. That is, since high-sensitivity direct positive internal latent image emulsions are very often used for direct photography, if the sensitivity or minimum density changes, the resulting image quality will deteriorate, making them impractical. Furthermore, in some cases, the photosensitive material may have to be photographed again, which is a serious defect in that the reliability of the photosensitive material is lost. At first glance, the so-called continuous preparation coating method, in which the silver halide emulsion that has been emulsified and ripened and is ready to be coated after adding various additives, is stored as a set and prepared and coated continuously without stagnation of the coating solution, seems ideal at first glance. However, due to the large size of manufacturing equipment, the complexity of continuous injection control, and the lack of quality control in each process of silver halide emulsion, it is often impossible to confirm the design performance. If this occurs, it is often discovered after a large amount of it has been applied and dried, which poses a risk of causing great damage. On the other hand, if the set is stored and the coating solution is allowed to stagnate in each process, the process can be well controlled and there is an advantage that abnormalities can be detected before coating. Furthermore, the equipment can be simplified because it can perform batch processing. To this end, it is necessary to take technical measures to ensure that the performance does not change during process control tests to determine whether the design quality target performance is obtained during set storage and stagnation of the coating solution. However, the reality is that there are almost no known techniques from this standpoint regarding internal latent image type silver halide emulsions, and their performance from a practical standpoint cannot be said to be sufficient. Most of the known techniques are aimed at the storage stability of photosensitive materials after coating and drying. For example, JP-A-50-138820,
Mercabut compounds described in Publication No. 50-21067,
Typical examples include oxidizing agents such as the in-top dazole compounds described in Japanese Patent Publication No. 56-54437 and the red blood salt described in Japanese Publication No. 53-66727. However, although these stabilizers are not effective unless used in large quantities in silver halide emulsions, they also have serious disadvantages such as extensive desensitization and a decrease in density due to development inhibition, making them not very effective in practice. I can't say that there is. The present inventors have conducted intensive research to solve these problems, and as a result, it has become possible to obtain a more stable and superior internal latent image type silver halide photographic emulsion by the following method. A first object of the present invention is to provide an internal latent image type silver halide photographic emulsion with higher sensitivity. A second object of the present invention is to provide a silver halide photographic emulsion that can prevent changes in photographic performance during set storage or stagnation of the coating solution. A third object of the present invention is to provide an internal latent image type silver halide photographic emulsion with excellent developability and a high maximum density. The above objects are achieved by an internal latent image type silver halide photographic emulsion, which contains at least 15 wt % of gelatin oxidized with hydrogen peroxide or ozone, based on hydrophilic colloid. The oxidation treatment is preferably carried out using hydrogen peroxide or ozone, considering purification after treatment of gelatin, a decomposition by-product of oxides, or pollution prevention treatment of waste liquid. Since these decompose into water and oxygen, they are advantageous because they have little effect on photographic emulsions. Gelatin that can be used in the present invention is ossein gelatin, hydrogelatin (including pitgskin gelatin)
The raw material is subjected to oxidation treatment, and is not particularly limited by the treatment method of the raw material (for example, alkali treatment, acid treatment, enzyme treatment, etc.). For information on the general properties and manufacturing methods of gelatin, see The Theory of Photographic Processes, 4th edition (written by TH James, published by Macmillan).
1977) pp. 51-76, and The Science and.
Technology of Gelatin (AGWard, A.
Courts, Academic Press, 1977) 295~
It is detailed on page 365. This document describes purification methods using hydrogen peroxide, nitric acid, and ion exchange treatment to remove photographically harmful impurities contained in gelatin, and methods for bleaching gelatin coloring. However, it is said that none of the above methods is photographically satisfactory. Due to advances in negative-working silver halide photographic emulsion technology, in recent years there has been a demand for gelatin to be more inert, and gelatin that meets these demands will provide stable and consistent photographic materials. I'm getting used to it. However, even if extremely inert gelatin, which is said to be extremely stable in negative-working silver halide emulsions, is used, the set storage stability as described above cannot be achieved for positive-working internal latent image-type silver halide emulsions. The actual situation was that the coating liquid stagnation property was extremely insufficient, and it was far from being practical. The above-mentioned book by James, Ward et al. does not have any suggestion regarding the relationship between the internal latent image type silver halide emulsion and the oxidized gelatin used in the present invention, and even those skilled in the art would not have expected the effects of the present invention. It was a difficult thing to do. The oxidized gelatin used in the present invention may be oxidized at any step after extraction from raw materials. The method is shown as an example, but the gelatin of the present invention is not limited thereby. Gelatin A (hereinafter referred to as Gel-A) Ossein gelatin produced by an alkali treatment method (hereinafter referred to as Gel-A)
Dissolve 200g (referred to as Gel-O) in warm water of 3.0 (PH
= 6.13, 35°C), 6 ml of 10% hydrogen peroxide solution was added with stirring, and the mixture was aged at 40°C for 5 hours. Next, 1% sodium sulfite solution is added little by little to neutralize excess hydrogen peroxide. The neutralization point is confirmed by taking out a portion of the gelatin solution and performing an iodine reaction. Next, acetic acid was added to adjust the pH to 6.5, and the gelatin solution was passed through an ion exchange resin, concentrated and dried in a conventional manner to obtain 167 g of dry gelatin.
The residual amount of hydrogen peroxide was 0.005% or less. Gelatin B (hereinafter referred to as Gel-B) Hydrogelatin produced by an alkali treatment method (hereinafter referred to as Gel-B)
Dissolve 200g (referred to as Gel-H) in warm water of 3.0 (PH
= 6.20, 35℃) and add sodium hydroxide to adjust the pH.
After adjusting the temperature to ≒8, 6 ml of 10% hydrogen peroxide solution was added with stirring, and the mixture was aged at 40°C for 2 hours. add acetic acid
After neutralizing the pH to 6.5, the gelatin solution was passed through an ion exchange resin and dried in a conventional manner to obtain 170 g of dry gelatin. The residual amount of hydrogen peroxide is 0.06%
It was hot. Gelatin C (hereinafter referred to as Gel-C) Pittskin gelatin produced by acid treatment (hereinafter referred to as Gel-C)
After dissolving 200g (referred to as Gel-P) in 3.0 warm water, Gel-P
- Treated in the same manner as A to obtain 170 g of dry gelatin. The residual amount of hydrogen peroxide was 0.005% or less. Gelatin D (hereinafter referred to as Gel-D) After dissolving 200 g of the above Gel-O in 4.0 ml of hot water, ozone was generated using an ozonizer model ON-11 manufactured by Yamato Scientific Co., Ltd., and the gas was poured into the gelatin solution using a silicon tube. It was introduced for 3 hours. The gelatin is then concentrated and dried by passing through an ion exchange resin.
Obtained 165g. The residual amount of ozone was less than 0.005%. The internal latent image type silver halide photographic emulsion according to the present invention can be coated on a support as at least one internal latent image type silver halide emulsion layer, thereby achieving the following:
A silver halide photographic material can be provided. The internal latent image type silver halide emulsion according to the present invention is
An emulsion having silver halide grains mainly forming a latent image inside the silver halide grains and having most of the photosensitive nuclei inside the grains, the emulsion comprising any silver halide, such as silver bromide, silver chloride, Silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. are included. Particularly preferably, the emulsion is prepared by exposing a portion of a sample coated on a transparent support to a light intensity scale for a defined period of time up to about 1 second and containing substantially no silver halide solvent. When developing only the surface image of the grain at 20°C for 4 minutes using surface developer A described below, another part of the same emulsion sample is exposed in the same way and the image inside the grain is developed. The maximum density is not greater than 1/5 of the maximum density obtained when developed with internal developer B at 20° C. for 4 minutes. More preferably, the maximum density obtained with surface developer A is not more than 1/10 of the maximum density obtained with internal developer B. [Surface developer A] Metol 2.5g L-ascorbic acid 10g NaBO _{2.4H 2} O 35g KBr 1g Add water 1 [Internal developer B] Metol 2.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate 1 Water salt 52.5g KBr 5.0g KI 0.5g Add water 1 Further, the internal latent image type silver halide emulsion according to the present invention includes those prepared by various methods.
For example, the convergence silver halide emulsions described in U.S. Pat. No. 2,592,250, or U.S. Pat.
Silver halide emulsions having internally chemically sensitized silver halide grains as described in U.S. Pat. No. 3,367,778 or U.S. Pat. A silver halide emulsion having silver halide grains incorporating polyvalent metal ions, or a U.S. patent
A silver halide emulsion in which the grain surface of silver halide grains containing a doping agent is weakly chemically sensitized as described in the specification of No. 3761276, or JP-A No. 50-8524
Silver halide emulsions comprising grains having a laminated structure as described in Japanese Patent Laid-Open No. 1983-156614 and Japanese Patent Application Laid-open No. 55-127549, and Special application 1984-
These include the silver halide emulsion described in No. 15680. Various photographic additives may optionally be added to the internal latent image type silver halide emulsion according to the present invention. For example, optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holoporacyanines, hemicyanines, and oxonols. These optical sensitizers include basic groups such as thiazoline and thiazole, or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, Those containing a nucleus such as thiobarbituric acid or pyrazolone are preferred, and such a nucleus can be substituted with alkyl, hydroxylalkyl, sulfoalkyl, carboxylalkyl, halogen, phenyl, cyano, or alkoxy, and can be fused with a carbocyclic or heterocyclic ring. It is optional to do so. The internal latent image type silver halide emulsion according to the present invention can be supersensitized. For information on the method of supersensitization, see, for example, ``Review of the mechanism of supersensitization.''
of Supersensitization) (Photographic Science
(PSE) Vol. 18, page 4418 (1974). In order to keep the surface sensitivity as low as possible, to give lower minimum density and more stable properties, the emulsion according to the invention contains stabilizers that are commonly used, such as compounds having an azaindene ring and heterocyclic compounds having a mercapto group. etc. can be contained. As a compound having an azaindene ring, 4-
Hydroxy-6-methyl-1,3,3a,7-tetrazaindene is preferred. Examples of the nitrogen-containing heterocyclic compound having a mercapto group include 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, rings in which 2 to 3 of these rings are condensed, such as triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc. Although there are also phthalazinone rings and indazole rings, 1-phenyl-5-mercaptotetrazole is preferred. In addition, in the present invention, wetting agents used depending on the purpose include, for example, dihydroxyalkanes, and film property improvers include, for example, a combination of alkyl acrylate or alkyl methacrylate and acrylic acid or methacrylic acid. Polymers, water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc. are suitable; Examples include saponin, polyethylene glycol, lauryl ether, and the like.
Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, PH regulators, antioxidants, antistatic agents, thickeners, graininess improvers, dyes,
It is optional to use mordants, brighteners, development rate regulators, matting agents, anti-irradiation dyes, and the like. When the silver halide emulsion according to the present invention is used for color purposes, it is preferable to use a dye-forming coupler. Useful yellow dye-forming couplers include benzoylacetanilide type, piparoylacetanilide type, and two-equivalent type yellow couplers in which the carbon atom at the coupling position is substituted with a so-called split-off group that can be separated during coupling. As the magenta dye-forming coupler, a 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indazolone type, or a two-equivalent type magenta coupler having a split-off group is useful. As cyan dye-forming couplers, phenolic, naphthol, pyrazoquinazolone, or two-equivalent cyan couplers having a split-off group are useful. These dye-forming couplers can be selected arbitrarily;
Moreover, the usage method, usage amount, etc. are not particularly limited. The photographic emulsion according to the present invention is combined with a color image-providing substance for diffusion transfer that releases a diffusible dye in response to development of silver halide, and forms a desired transferred image on an image-receiving material after an appropriate development process. It can also be used to obtain Examples of such color image-providing materials for diffusion transfer include US Pat. No. 3,227,551;
No. 3227554, No. 3443939, No. 3443940, No. 3658824, No. 3698897, No. 3725062,
No. 3728113, No. 3751406, British Patent No.
No. 840781, No. 904364, No. 1038331, OLS No. 1930215, OLS No. 2214381,
Same No. 2228361, Same No. 2242762, Same No. 2317134,
Same No. 2402900, Same No. 2406626, Same No. 2406653,
Those described in the specification or publication of JP-A-49-114424 can be used. In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent color fading of dye images due to short-wavelength actinic rays. 326, same
It is advantageous to use 327 and 328 (both manufactured by Ciba Geigy) alone or in combination. In addition to the oxidized gelatin of the present invention, a silver halide photographic material produced using the photographic emulsion of the present invention may contain appropriate gelatin and derivatives thereof depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin. Furthermore, in the photographic light-sensitive material obtained by applying the present invention, the hydrophilic colloid layer may contain other hydrophilic binders in addition to the gelatin according to the present invention. In addition to the above-mentioned gelatins, suitable binders include colloidal albumin, agar, gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 10 to 20%, polyacrylamide, imidized polyacrylamide. , casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol-vinylaminoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins and monomers having vinyl groups. Polymer obtained by polymerization with
Contains polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and can be added to constituent layers of silver halide photographic light-sensitive materials such as emulsion layers, intermediate layers, protective layers, filter layers, backing layers, etc., depending on the purpose. Furthermore, the hydrophilic binder may contain appropriate plasticizers, lubricants, etc. depending on the purpose. Further, the constituent layers of the silver halide photographic light-sensitive material using the photographic emulsion according to the present invention can be hardened with any suitable hardener. These hardeners include chromium salts, zirconium salts, aldehyde-based hardeners such as formaldehyde and mucohalogen acids, halotriazine-based hardeners, polyepoxy compounds, ethyleneimine-based hardeners, vinyl sulfone-based hardeners, and acryloyl-based hardeners. Can be mentioned. Further, the silver halide photographic light-sensitive material using the photographic emulsion according to the present invention has various layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer on a support. It is manufactured by applying a photographic composition layer. The silver halide photographic emulsion according to the present invention can be effectively applied to various uses such as black and white general use, X-ray use, color use, false color use, printing use, infrared use, micro use, etc. Colloidal transfer method, U.S. Pat.
No. 3,227,551 to Pearl et al., U.S. Pat. No. 3,227,552 to Whitemore, and U.S. Pat.
As described in each specification of No. 3415646, it can also be applied to color image transfer method, color diffusion transfer method, absorption transfer method, etc. Any support can be used to coat the photographic emulsion according to the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, and propylene film, which have been subbed as necessary. Film, cellulose acetate film, glass, baryta paper, polyolefin laminated paper such as polyethylene, etc. are included. The main process of directly creating a positive image in a photographic light-sensitive material using the photographic emulsion according to the present invention is to apply a fogging treatment to an uncoupled internal latent image type silver halide light-sensitive material after image exposure. Alternatively, surface development is performed while performing fogging treatment. Here, the fogging process can be performed by applying full-image exposure or using a fogging agent. In this case, full-image exposure is performed by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then uniformly exposing the entire image (full-surface exposure). The light source used here may be any light within the sensitive wavelength range of the photosensitive material, and high-intensity light such as flash light may be applied for a short time, or weak light may be applied for a long time. Further, the full-image exposure time can be varied over a wide range depending on the photosensitive material, development processing conditions, type of light source used, etc. so as to ultimately obtain the best positive image. Further, a wide variety of compounds can be used as the above-mentioned fogging agent, and this fogging agent only needs to be present in the development process, for example, in the internal latent image type silver halide photographic light-sensitive material such as the silver halide emulsion layer. Alternatively, it may be contained in a developing solution or a processing solution prior to development processing, but it is preferable to contain it in a silver halide photographic light-sensitive material. good). The amount used can vary widely depending on the purpose, and the preferred amount is 1 to 1,500 mg, particularly preferably 10 to 1,000 mg per mole of silver halide when added to a silver halide emulsion layer. It is. In addition, the preferred amount of addition when adding to processing solutions such as developing solutions is 0.01~
5g/, particularly preferably 0.08-0.15g/. Specific examples of such fogging agents include hydrazines described in US Pat. No. 2,563,785 and US Pat. No. 2,588,982, or US Pat.
Hydrazide or hydrazone compounds described in US Pat. No. 3227552; and heterocycles etc. described in US Pat. No. 3615615, US Pat. Quaternary nitrogen salt compounds; furthermore, U.S. Patent No. 4030925
The acylhydrazinophenylthioureas described in the specification of the present invention are included. It can also be used in combination with these fogging agents. For example, Research Disclosure No. 15162
The issue describes the use of a non-adsorption type fogging agent in combination with an adsorption type fogging agent. Specific examples of useful fogging agents include hydrazine hydrochloride, phenylhydrazine hydrochloride, 4-methylphenylhydrazine hydrochloride, 1-formyl-2-
(4-methylphenyl)hydrazine, 1-acetyl-2-phenylhydrazine, 1-acetyl-2
-(4-acetamidophenyl)hydrazine, 1
-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Hydrazine compounds such as 1-methylsulfonyl-2-(3-phenylsulfonamidophenyl)hydrazine and formaldehyde phenylhydrazine; 3-(2-formylethyl)-2-methylbenzothiazolium bromide , 3-(2-formylethyl)-2-propylbenzothiazolium bromide, 3-(2-acetylethyl)-2-benzylbenzoselenazolium bromide, 3-(2
-acetylethyl)-2-benzyl-5-phenyl-benzoxazolium bromide, 2-methyl-3-[3-(phenylhydrazono)propyl]
Benzothiazolium bromide, 2-methyl-3
-[3-(p-Tolylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-
[3-(p-sulfophenylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-[3-(p-sulfofenylhydrazono)
benzothiazolimioded, 1,2-
dihydro-3-methyl-4-phenylpyrido[2,1-b]benzothiazolium bromide,
1,2-dihydro-3-methyl-4-phenylpyrido[2,1-b]-5-phenylbenzoxazolium bromide, 4,4-ethylenebis(1,2-dihydro-3-methylpyrido[2, 1
-b]benzothiazolium bromide], 1,2
-N-substituted quaternary cycloammonium salt such as dihydro-3-methyl-4-phenylpyrido[2,1-b]benzoselenazolium bromide; 5-
[1-Ethylnaphtho(1,2-b)thiazoline-
2-ylideneethylidene]-1-(2-phenylcarbazoyl)methyl-3-(4-sulfamoylphenyl)2-thiohydantoin, 5-(3-ethyl-2-benzothiazolinylidene) 3-[4-
(2-formylhydrazino)phenyl]rhodanine, 1-[4-(2-formylhydrazino)phenyl]3-phenylthiourea, 1,3-bis[4-(2-formylhydrazino)phenyl] ) phenyl]thiourea, etc. The internal latent image type silver halide photographic light-sensitive material using gelatin according to the present invention directly forms a positive image by exposing the entire surface to light after imagewise exposure or by developing it in the presence of a fogging agent. Any development processing method may be adopted as the development processing method for the silver halide photographic light-sensitive material, and preferably a surface development processing method is employed. This surface development processing method means processing with a developer substantially free of silver halide solvent. Common silver halide developers that can be used in the above developer include polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, and phenylenediamines. etc. or a mixture thereof. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, N,N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N-(β-methanesulfonamidoethyl)aniline, Examples include 4-amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline. These developers can also be included in the emulsion in advance and allowed to act on the silver halide during immersion in a high pH aqueous solution. The developer solution may further contain specific antifoggants and development inhibitors. These developer additives may be optionally incorporated into the layers of the silver halide photographic light-sensitive material. Generally useful antifoggants include benzotriazoles such as 5-methylbenzotriazole; benzothiazoles; heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole; aromatic and aliphatic Includes mercapto compounds. The developer may also contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound. The present invention will be explained below with reference to Examples, but the embodiments are not limited thereto. The sensitometric conditions used in the present invention are as follows. [Exposure conditions] Using a KS-7 sensitometer (manufactured by Konishiroku Photo Industry Co., Ltd.), exposure was carried out through a wedge with a density difference of 0.10. [Development processing] Development 30°C for 3 minutes However, 15 seconds after the start of development, the entire surface is uniformly exposed to light of 5 lux for 5 seconds. Bleach-fixing 30℃ 2 minutes Washing 20-30℃ 2 minutes Drying Room temperature 30 minutes [Composition of the solution used] Developer solution 4-amino-3-methyl-N-ethyl-N-
(β-Methanesulfonamidoethyl) aniline sulfate 5g Sodium sulfite (anhydrous) 2g Sodium carbonate (monohydrate) 15g Potassium bromide 1g 5-methylbenzotriazole 0.05g Benzyl alcohol 10g Add water to make 1.0 (Adjust the pH to 10.2 with potassium hydroxide.) Bleach-fix solution Ethylenediaminetetraacetic acid ferric ammonium dihydrate 50g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Potassium sulfite (50% aqueous solution) 40ml Bisthiourea 0.1 g Add water to make 0.1. (However, the pH was adjusted to 6.5 with potassium carbonate or acetic acid.) [Measurement] Transmission or reflection density was measured using a Sakura photodensitometer PDA-65. The zero point was set to the surface of the support before coating with the emulsion, when nothing was added in the case of transmission, and with respect to the surface of the support before coating with the emulsion in the case of reflection. [Characteristic Values] (1) Sensitivity (S): The reciprocal of the exposure amount indicating a density point of 0.8 was determined and shown as the relative sensitivity with respect to the reference sample for each example. (2) Rate of change (%): Percentage of sensitivity for each day. (3) Minimum density (Dmin): Minimum density of highlighted area. (4) Maximum density (Dmax): Maximum density in the shadow area. Example 1 A potassium bromide aqueous solution and a silver nitrate aqueous solution each having a 1.0 molar concentration were prepared, and while controlling the PAg to 10.5 to 10.8 and the temperature to 65°C, a 4.0 molar aqueous solution containing a small amount of potassium iodide and 40 g of ossein gelatin was prepared. Inject 1200 ml into each container over 15 minutes using the simultaneous mixing method. Next, physical aging was performed for 60 minutes,
Precipitation was washed with water to remove excess salt. Furthermore, 800 ml of a 1.0 molar potassium bromide aqueous solution and a silver nitrate aqueous solution were each added in 10 minutes using the simultaneous mixing method.
It was further aged at 55°C for 10 minutes. The precipitation was then washed with water to remove excess salt. The amount of ossein gelatin remaining after washing the precipitate with water was about 12 g. Silver iodobromide emulsion with silver iodide content of 0.9 mol% and average grain size of 0.8μ
Obtained 600ml. Mix and disperse well, then divide into 12 equal parts.
After adding gelatin for setting (listed in Tables 1 and 2) to make a final volume of 260 ml, add a trace amount of phenol and 4-hydroxy-6-methyl-1,3,3a,
Add 40 ml of 7-tetrazaindene 0.5%, store it in a cool, dark place at 5±2°C in a porcelain beaker with a lid, and after a certain number of days, collect in 1/6 portions.
8 ml of sensitizing dye (), 40 ml of yellow coupler solution () or () below, and hardener () below.
Add 0.12 g and 0.3 g of hardener () to make a coated silver amount of 2.0 on the subbed polyester film.
It was coated at a concentration of g/m ² and dried. Using this sample, sensitometry was performed by the development process described above. The results are shown in Tables 1 and 2. Sensitizing dye () Dissolve the above in methanol to make 0.05%. Yellow coupler liquid () α-[4-(1-benzyl-2-phenyl-
3,5-dioxo-1,2,4-triazolidinyl)]-α-pivalyl-2-chloro-5-
[γ-(2,4-di-tert-amylphenoxy)butyramide]acetanilide 3g 2,5-di-tert-octylhydroquinone
0.03g 2,5-di-tert-butylhydroquinone
0.03g of the above, 2.5ml of ethyl acetate, dibutyl phthalate
Dissolve in 1.5 ml, mix in 2 g of ossein gelatin solution containing 0.3 g of sodium dodecylbenzenesulfonate, disperse by ultrasonication, and make a final volume of 40 ml. Yellow coupler solution (2) Prepared in the same manner as yellow coupler solution (2) except that gelatin was replaced with Gel-A described above.

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【table】

【table】

[Table] Sensitivity (S) is the relative sensitivity when the sensitivity after one day of sample No. 1 or No. 9 is set as 100, and Dmin is the minimum transmitted density when the polyester film is referenced. The density was measured by transmitting blue light using the Sakura photoelectric densitometer. According to Table 1, samples 1 to 5 in which oxidized gelatin-A was used as the gelatin for setting showed a small decrease in sensitivity (S) even when the setting was stored for a long time, and the minimum concentration (Dmin) The increase is also small. Furthermore, there was no difference in performance even when gelatin-A was used to disperse the yellow coupler during coating (i.e., samples 1 and 6, samples 3 and 7, and 5 and 8), and even when oxidized gelatin was added during coating, the performance remained unchanged. Since the photographic performance did not improve, it is clear that the gelatin during set storage has a large influence on the photographic performance. Table 2 shows the effects of changing the type of gelatin during set preservation. It is understood that among all gelatins, those using oxidized Gel-B, C, and D show little change in sensitivity and minimum concentration. Example 2 After thoroughly mixing the precipitated and water-washed emulsion used in Example 1, the emulsion was divided into 12 equal parts, and hydrogen peroxide solution was added as shown in Table 3 below, and the emulsion was set and stored. I made a comparison with The emulsion was prepared in the same manner as in Example 1 except that yellow coupler liquid (2) was used. Note that 0.2 ml of hydrogen peroxide solution (5%) is the same ratio as added to gelatin A or B, and is more than 10 times larger than the remaining amount.

[Development processing]

Development 33°C 3 minutes Bleach-fixing 30°C 1 minute Washing 20-30°C 2 minutes Drying Room temperature 30 minutes [Composition of the solution used] Developer solution 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamide ester) aniline sulfate. 5g Sodium sulfite (anhydrous) 1g Sodium carbonate (monohydrate) 20g Hydroxylamine sulfate 1.5g Potassium bromide 1g 5-methyl-benzotriazole 0.05g Benzyl alcohol 10g Phenylhydrazine hydrochloride 1.5g Add water to make 1.0 (However, the pH was adjusted to 13.0 with sodium hydroxide.) Bleach-fix solution Ferric ammonium ethylenediaminetetraacetate (trihydrate) 50g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Potassium sulfite (50% aqueous solution) Add 30ml water to make 1.0. (However, the pH was adjusted to 6.9 with potassium carbonate or acetic acid.)

【table】

[Table] As is clear from Table 4, it will be understood that according to the present invention, even if the emulsion is changed, the change in sensitivity and minimum density during set storage is small, and an emulsion with high sensitivity can be obtained. . Example 4 Using the emulsion used in Example 3, 2 mg of the following sensitizing dye (), cyan coupler solution (), hardener (), 4-hydroxy-6-methyl- Add 0.02 g of 1,3,3a,7-tetrazaindene (however, add the hardener () just before coating) so that the amount of coated silver is 0.6/ ^m2 .
It was applied to polyethylene laminated paper and dried. Cyan coupler solution (2,4-dichloro-3-methyl-6-[α-
2,4-di-tert-(amylphenoxy)butyramide]phenol 3g 2,5-di-tert-octylhydroquinone
0.05g Both of the above were dissolved in 5ml of ethyl acetate and 3ml of dioctyl phthalate, and the solution was protected and dispersed by ultrasonic waves in a gelatin solution containing 0.2g of sodium dodecylbenzenesulfonate and 3g of ossein gelatin. Table 5 shows the changes in photographic performance and the number of days the set was stored.

【table】

[Table] As is clear from Table 5, it is well understood that even if the number of days of set storage increases, the rate of change in sensitivity is small, the increase in Dmin is also small, and the change in performance is small. It is also clear that samples using the oxidized gelatin according to the present invention have higher sensitivity. Example 5 Ossein gelatin and Gel- used in Example 3
An emulsion was prepared using ossein gelatin or Gel-A as a coupler or additional gelatin for coating, respectively, to the emulsion using A for setting, and various additives were added in the same manner as in Example 3 to form a coating solution. did. Differences in sensitivity (S) and minimum density (Dmin) were investigated by comparing a dried sample coated at 40°C within 30 minutes and a sample coated and dried after stagnating at 40°C for 10 hours. In addition, the amount of coated silver was 5mg/
It was coated on 0.15 mm photographic polyethylene laminate paper so that it was dm ² . The results are shown in Table 6.

[Table] As is clear from Table 6, sample No. 31 containing only ossein gelatin showed a large decrease in sensitivity after 10 hours.
Dmin has increased dramatically. On the other hand, oxidation treatment
It can be seen that the change in the sample using Gel-A is small. This small change makes it possible to produce a stable photosensitive material with little change in performance during coating. Furthermore, similar results were obtained even when the additives (sensitizing dyes, couplers, etc.) used in Example 4 were used. Example 6 Using the emulsion used in Example 3, a comparison was made between the sample of the present invention and the case where a stabilizer was added. The stabilizers used for comparison were the following compounds. As [S-7], 4-hydroxy-6-methyl-1,3,3a,7-tetrazaindene was used. After dissolving the emulsion used in Example 3, 2 mg of the sensitizing dye () was added while keeping the emulsion at 55°C, and after 5 minutes, 40°C
After cooling to ℃, add the above-mentioned stabilizers [S-1] to [S-7], then add cyan coupler solution () and hardener, and coat so that the coated silver amount is 0.5 g/m ² and dried. The results are shown in Table 7.

【table】

[Table] As is clear from Table 7, stabilizers [S-1] ~
Samples 42 to 55 using [S-7] show a decrease in sensitivity, whereas sample 56 of the present invention exhibits high sensitivity. In addition, when a large amount of stabilizer is used, some products show a rate of change at stagnation (10 hours) close to that of the present invention, but a decrease in Dmax with respect to development time and an increase in Dmin are observed, indicating that it is not sufficient. It is understood that No. 56 of the present invention is the only one that can satisfy both sensitivity, Dmin, and Dmax. Comparative Example (Comparison with Example 3) A surface latent image type emulsion was prepared by the following method.
While stirring the aqueous solution containing ossein gelatin at 60°C, add 705 ml of a 2.0 molar silver nitrate aqueous solution,
A mixed solution of 600 ml of a 2.0 molar potassium bromide aqueous solution, 5.4 ml of 0.5 molar potassium iodide and 200 ml of 2.2 molar sodium chloride were added simultaneously over 25 minutes. After aging for 10 minutes after the end of addition, 10
After dividing into equal parts, lower the temperature of each emulsion to 40℃,
Magnesium sulfate was added to precipitate the silver halide grains, and water-soluble salts were removed by decantation. Set gelatin was added as an aqueous solution as described in Table 8 below and thoroughly mixed and dispersed. In each emulsion obtained, per mole of silver halide,
3.0 mg of sodium thiosulfate and 2.0 mg of chloroauric acid were added, and the mixture was aged at 60°C for 75 minutes. Each emulsion thus obtained was further divided into four equal parts, set and stored in a dark place at 10±1°C, and coated after a certain period of time. Dissolve the set-preserved emulsion,
While keeping at 40℃, add sensitizing dye () 5 mg, yellow coupler solution () 40 ml, hardener () 0.2 g,
4-hydroxy-6-methyl-1,3,3a,7
- Add 0.02g of tetrazaindene, and the amount of coated silver is
It was applied to an undercoated polyester film at a weight of 1.7 g/m ² and dried. Sensitometry was performed on this sample by the following development treatment. The results are shown in Table 8. [Development processing] Development 33℃
3 minutes Bleach-fixing 30℃ 1 minute Washing with water 20-30℃ 2 minutes Drying at room temperature 30 minutes [Composition of the solution used] Developer solution amino-3-methyl-N-ethyl-N-(β
-Methanesulfonamidoethyl) Aniline sulfate 5g Sodium sulfite (anhydrous) 1g Sodium carbonate (monohydrate) 20g Hydroxylamine sulfate 1.5g Potassium bromide 1g Benzyl alcohol 10g Add water to make 1.0. (However, the pH was adjusted to 10.2 with sodium hydroxide.) The bleach-fix solution described in Example 3 was used.

【table】

[Table] As is clear from the results in Table 8, in the case of surface latent image type negative emulsions, the same effect as internal latent image type emulsions is not obtained, and the effect of the present invention is It can be seen that this is noticeable in the case of positive emulsions.

Claims (1)

[Claims] 1 Gelatin oxidized with hydrogen peroxide or ozone is applied to hydrophilic colloid at least
An internal latent image type silver halide photographic emulsion characterized by containing 15 wt%.