JPH0731385B2 - Silver halide photographic light-sensitive material - Google Patents

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an internal latent image type silver halide photographic light-sensitive material (hereinafter referred to as light-sensitive material), and more specifically, it is formed on the entire surface after image exposure and during development. The present invention relates to a light-sensitive material suitable for directly forming a positive image by being subjected to appropriate exposure or development in the presence of a fogging agent, and having improved storage stability (hereinafter referred to as raw storage stability) of an unexposed light-sensitive material. .

BACKGROUND ART It is well known that internal latent image type light-sensitive materials are generally easier to obtain a high-sensitivity material than fog-destruction-type solar reversal type or Herschel effect reversal type direct positive light-sensitive materials. . Such an internal latent image type silver halide emulsion can be produced by a method of forming a silver halide grain and then converting it into a more sparingly soluble silver halide (conversion type), or after forming a silver halide grain and further forming a grain on the grain. A method of laminating silver halide on (a laminating type) is generally used.

Examples of these internal latent image type silver halide emulsions include:
A so-called conversion type silver halide emulsion according to the conversion method described in U.S. Pat.No. 2,592,250, or U.S. Pat.Nos. 3,206,316, 3,317,322 and 3,
367,778 and silver halide emulsions having internally chemically sensitized silver halide grains, or incorporating the polyvalent metal ions described in U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,531,291. A silver halide emulsion having silver halide grains, or US Pat.
No. 3,761,276, silver halide emulsions containing a doping agent, the surface of which is weakly chemically sensitized, or JP-A Nos. 50-8524, 50-38525 and 53-2408. So-called core-shell type silver halide emulsion by the above-mentioned lamination method described in JP-A-52-156
The silver halide emulsions described in Nos. 614, 55-127549 and 57-79940 are included.

For the mechanism of forming a positive image in a light-sensitive material using these internal latent image type silver halide emulsions, see, for example, Akira Sasai, "Direct positive image by core shell type internal latent image emulsion".
(Photograph Industry, December 1981, pp. 105-108). The same publication also mentions that a laminated emulsion can obtain higher sensitivity than a conversion emulsion. Laminated emulsions certainly have high sensitivity, but since the formation of a positive image in an internal latent image type emulsion is established under a delicate balance between internal photosensitive nuclei and surface photosensitive nuclei, its sensitivity, The tone, density, etc. vary greatly depending on the conditions (storage conditions) on which the light-sensitive material after coating and drying are placed, and there is a drawback that reproducibility and reliability are lacking for practical use.

Therefore, improvements have been attempted by adding mercapto compounds described in JP-A Nos. 50-138820 and 55-21067, and indazole compounds described in JP-A No. 56-54437. However, these compounds are not effective unless they are added to the silver halide emulsion in a large amount, and such a large amount causes serious adverse effects such as desensitization as a side effect and reduction in concentration due to development inhibition. However, it is hard to say that the addition of the compounds is an effective method.

On the other hand, in order to suppress desensitization or positively sensitize, optical sensitization for green and red light is performed with a sensitizing dye, and in order to increase sensitivity in the intrinsic sensitivity wavelength range, sensitization with a short wavelength sensitizing dye is performed. Although the feeling and the like were tried, it became clear that there was a defect that the raw storability was deteriorated.

Further, in the case of the conventional internal latent image type silver halide emulsion, when the time from the preparation of the silver halide emulsion to the coating becomes long, the maximum density fluctuates and the minimum density rises to narrow the effective density range. Not only does it lose its ground, but it also causes a change in sensitivity. This phenomenon occurs when, for example, an internal latent image type silver halide emulsion is prepared, and various additives are added to form a coating solution, which is left standing for 3 hours or more until coating at 35 to 45 ° C. (hereinafter referred to as coating solution stagnation). ) Occurs. When such a phenomenon occurs, the performance when the silver halide emulsion is coated changes each time, resulting in a serious quality defect that a uniform and stable product cannot be obtained. In other words, high-sensitivity direct-positive internal latent image emulsions are very often used for direct photography, so if the sensitivity or maximum and minimum densities change, the obtained image quality will not be constant and will be practical. I can't serve. Further, in some cases, the image is taken again, which is a serious defect that the reliability of the photosensitive material is lost.

Furthermore, the so-called continuously prepared coating method, in which the silver halide emulsion, which has been emulsified and ripened and then coated with various additives, is continuously prepared and coated without stagnation of the coating solution, is seemingly ideal. However, it is not possible to confirm the design performance because the manufacturing equipment becomes huge and the relationship of continuous injection control becomes complicated, and the quality control of each step of the silver halide emulsion is not performed. If it occurs, it is often found after it has been coated and dried in a large amount, and there is a risk of causing great damage. On the other hand, if the coating liquid is stagnated in each process, the process control is thoroughly performed, and there is an advantage that an abnormality can be detected before the coating. In addition, the equipment can also be batch-processed so that it can be simplified. For that purpose, it is necessary to take a technical measure such that the performance does not change during the process control test whether or not the design quality target performance is obtained while the coating liquid is stagnant. However, in the actual situation, there is almost no known technique from such a viewpoint for the internal latent image type silver halide emulsion.

Furthermore, JP-A-53-66727 discloses a reduction of the minimum concentration and prevention of re-inversion by using a water-soluble oxidizing agent for silver halide grains produced under ammoniacal conditions.
According to this method, the minimum density and especially the re-inversion are significantly improved, but the disadvantage that the sensitivity is reduced by about 30% is also described. As a result of investigation by the present inventors, it was found that when a water-soluble oxidizing agent is added to a silver halide emulsion, the effect thereof increases as the amount increases, but it occurs even in an extremely small amount. It was found that this effect was particularly great when the surface layer of the core-shell type silver halide grains was not prepared under ammoniacal conditions, and also when the sensitizing dye was included.

II OBJECT OF THE INVENTION The present invention has been made to solve the above problems, and the first object of the present invention is to provide a light-sensitive material in which fluctuations in photographic performance due to changes in storage conditions are small. It is to provide a light-sensitive material suitable for a mold.

A second object of the present invention is to provide a light-sensitive material excellent in production stability with little variation in photographic performance such as sensitivity and density during production.

III. Specific Structure of the Invention The above object of the present invention is to provide a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer on a support. At least one of the light-sensitive silver halide emulsion layers contains an internal latent image type direct positive silver halide emulsion, and at least one of the non-light-sensitive hydrophilic colloid layers contains a water-soluble oxidizing agent. And a silver halide photographic light-sensitive material.

As the water-soluble oxidizing agent used in the present invention, any one having an oxidizing action can be used, and examples thereof include ferriciyanate, dichromate, ferric salt, cupric salt, and cerium cerium. Examples thereof include salts, permanganates, ketone peroxides, and the like. Specifically, potassium ferricinate, potassium dichromate, ethylenediaminetetraacetic acid sodium iron acetate, ethylenediaminetetraacetic acid ammonium ammonium, ceric sulfate, etc. As a preferable example. These water-soluble oxidizing agents may be used alone or in combination of two or more.

The amount of these water-soluble oxidizing agents used is appropriately in the range of 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol, preferably 2 × 10 ^{−5 to} 5 ×, per mol of silver halide coated. It is 10 ^-3 mol.
The optimum amount of the water-soluble oxidizing agent used varies depending on the type of the water-soluble oxidizing agent used and the pH of the coating liquid, so it may be appropriately changed depending on the layer to which the water-soluble oxidizing agent is added and the type of emulsion used.

In the water-soluble oxidizer used in the present invention, when the content in the light-sensitive material is low, the minimum concentration during raw storage increases and the effect is small, while when the content is high, the maximum concentration loss is too large. However, there is a drawback that the effective concentration range is narrowed.

The present invention can be applied to any of the known methods for producing a silver halide emulsion, such as the ammonia method, the neutral method and the acidic method, but the neutral method and the acidic method are preferable. This is because when the water-soluble oxidizing agent according to the present invention is added to a silver halide emulsion having a high color tone and a high development rate and having a high silver chloride content, fog tends to increase in the ammonia method. The tendency is small in the neutral method and the acidic method.

The pH of the coating solution for the light-sensitive emulsion and the non-light-sensitive emulsion is, in the light-sensitive emulsion, pH 4.0 to 7.0, preferably pH 5.0 to 6.5,
In the non-photosensitive emulsion, pH 4.0 to 7.5, preferably pH 5.
It is 0 to 7.0 and can be appropriately selected depending on the type and amount of the water-soluble oxidizing agent used. The lower the pH, the smaller the amount of the oxidizing agent added.

Examples of the coating method of the emulsion used in the present invention include dip coating, air doctor knife coating, extrusion coating, slide hopper coating, curtain flow coating and the like.

The silver halide emulsion used in the present invention is preferably an internal latent image type silver halide emulsion, and this emulsion may be either a conversion type by the conversion method or a core shell type by the laminating method. The internal latent image type silver halide used in the present invention is preferably made of core-shell type grains, and particularly, the halogenated composition of the surface layer (shell) is 60 mol% or more of silver chloride, 1 mol% or less of silver iodide, and Is preferably silver chlorobromoiodide made of 75 mol% or more of silver chloride and 0.5 mol% or less of silver iodide without using the ammonia method.

The composition of silver halide of the inner layer (core) is not particularly limited in the present invention, but silver chloride is 30 mol%
Silver chlorobromoiodide having a silver iodide content of 5 mol% or less is suitable. Such a silver halide can be prepared by a conventional method for producing a core-shell type silver halide. For example, JP-A-50-8524, 50-38525, 53-60222,
As described in U.S. Pat. No. 55-1524 and U.S. Pat. No. 3,206,313, a method of forming silver chloride grains, converting bromide to silver bromide grains to form silver bromide grains, and further laminating a halide by adding silver nitrate or an excess halogen. There is a method in which silver iodobromide grains are prepared in a state in which the amount is small, and silver chloride and silver bromide are sequentially laminated.

It is optional to add various photographic additives to the internal latent image type silver halide emulsion used in the present invention. For example, the optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxonols. And hemioxonol are included, and these optical sensitizers include a basic group such as thiazoline, thiazole or a rhodanine, thiohydantoin, oxazolidinedione, barbituric acid as a nitrogen-containing heterocyclic nucleus in a part of its structure. Those containing a nucleus such as thiobarbituric acid and pyrazolone are preferable, and such nucleus can be substituted with alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, alkoxy, and condensed with carbocycle or heterocycle. Doing is optional.

The internal latent image type silver halide emulsion according to the present invention can be supersensitized. Regarding the method of supersensitization, for example, "Review of Supersensitization Mechanism" (Review of Supersensitiza
tion) (Photographic Science and Engineering) (PS
E) Vol. 18, page 4418 (1974).

Emulsions according to the present invention include stabilizers usually used for suppressing surface sensitivity as low as possible and imparting a lower minimum density and more stable properties, for example, a compound having an azaindene ring and a heterocyclic compound having a mercapto group. Etc. can be contained.

The compound having an azaindene ring is preferably 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene. As the nitrogen-containing heterocyclic compound having a mercapto group, a pyrazole ring, a 1,2,4-triazole ring, a 1,2,3-triazole ring, a 1,3,4-thiadiazole ring, a 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, a ring in which two or three of these rings are condensed,
For example, triazolotriazole ring, diazaindene ring,
There are a triazaindene ring, a tetrazaindene ring, a pentazaindene ring and the like, a phthalazinone ring, an indazole ring and the like, and 1-phenyl-5-mercaptotetrazole is preferable.

In addition, in the present invention, examples of the wetting agent used according to the purpose include dihydroxyalkane and the like, and examples of the film physical property improving agent include, for example, a copolymer of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid. Polymers, styrene-maleic acid copolymers, water-dispersible particulate polymer substances obtained by emulsion polymerization of styrene maleic anhydride half alkyl ester copolymers, etc. are suitable, and as a coating aid , For example, saponin, polyethylene glycol,
Lauryl ether and the like are included. Other photographic additives include gelatin plasticizer, surfactant, UV absorber, pH
It is optional to use a regulator, an antioxidant, an antistatic agent, a thickener, a graininess improver, a dye, a moldant, a whitening agent, a development speed regulator, a matting agent, an anti-irradiation dye, or the like.

In the silver halide emulsion used in the present invention, a dye-forming coupler is preferably used when it is used for color.

As the yellow dye-forming coupler, a benzoylacetanilide type, a pivaloylacetanilide type, or a carbon atom at the coupling position is substituted with a so-called split-off group capable of leaving at the time of coupling 2
Equivalent yellow couplers and the like are useful.

As the magenta dye-forming coupler, a 5-pyrazolone type, a pyrazolotriazole type, a pyrazolinobenzimidazole type, an indazolone type, or a 2-equivalent type magenta coupler having a split off group is useful.

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

These dye-forming couplers can be arbitrarily selected, and the usage method, usage amount and the like are not particularly limited.

The photographic emulsion according to the present invention is combined with a diffusion transfer dye-providing substance capable of releasing a diffusible dye in response to the development of silver halide to obtain a desired transferred image on the image-receiving material after suitable development processing. It can also be used for Examples of such a dye transfer material for diffusion transfer include U.S. Pat. No. 3,227,55.
No. 1, 3,227,554, 3,443,939, 3,443,940,
3,658,824, 3,698,897, 3,725,062, 3,7
28,113, 3,751,406, British Patents 840,781, 90
4,364, 1,038,331, West German Patent Publication (OLS) 1,93
0,215, 2,214,381, 2,228,361, 2,242,762
No., No. 2,317,134, No. 2,402,900, No. 2,406,626,
Those described in JP-A No. 2,406,653 and JP-A-49-114424 can be used.

Further, it is useful to use an ultraviolet absorber, for example, thiazolidone, benzotriazole, acrylonitrile, or a benzophenone compound in order to prevent fading of the dye image due to short-wavelength actinic rays, and particularly, tinuvin PS, 120, 3
It is advantageous to use 20, 20, 326, 327 and 328 (all manufactured by Ciba Geigy) alone or in combination.

The light-sensitive material according to the present invention may contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. As this suitable gelatin derivative,
For example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin and the like can be mentioned.

In the light-sensitive material of the present invention, the hydrophilic colloid layer may contain other hydrophilic binder in addition to gelatin. Examples of suitable binders include colloidal albumin, agar, arabic gum, dextran, alginic acid, and acetyl, in addition to the above gelatins.
Cellulose derivatives such as cellulose acetate hydrolyzed to 10 to 20%, polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups such as vinyl alcohol-vinyl aminoacetate copolymer or cyanoacetyl groups , Polyvinyl alcohol, polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerizing proteins or saturated acylated proteins with monomers having vinyl groups, polyvinyl pyridine, polyvinyl amine, polyaminoethyl methacrylate, polyethylene amine, etc. Layers or intermediate layers, protective layers,
It can be added to a photographic constituent layer such as a filter layer or a backing layer depending on the purpose, and the hydrophilic binder can contain a proper plasticizer, lubricant or the like depending on the purpose.

The photographic constituent layers of the light-sensitive material of the present invention can be hardened with any suitable hardener. Examples of these hardeners include chromium salts, zirconium salts, aldehyde-based hardeners such as formaldehyde and mucohalogenic acid, halotriazine-based, polyepoxy compounds, ethyleneimine-based, vinyl sulfone-based and acryloyl-based hardeners. .

Further, the light-sensitive material of the present invention is produced by coating various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, an undercoat layer, a backcoat layer and an antihalation layer on a support. It

INDUSTRIAL APPLICABILITY The present invention can be effectively applied to light-sensitive materials for various purposes such as general black and white, X-ray, color, false color, printing, infrared, micro, and also colloid transfer method, logic sheet. U.S. Patent Nos. 3,087,817 and 3,185,567
No. 2,983,606, U.S. Pat.
3,253,915, US Patent 3,227,550 to Whitemore et al.
U.S. Pat. No. 3,227,551 to Pearl et al., U.S. Pat. No. 3,227,552 to Whitemore and U.S. Pat. No. 3,4 to Rand.
No. 15,644, No. 3,415,645 and No. 3,415,646, a color image transfer method, a color diffusion transfer method,
It can also be applied to the absorption transfer method and the like.

As the support used in the present invention, any support may be used, but as a typical support, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, a cellulose acetate film, and a glass, which have been subjected to an undercoating if necessary. , Baryta paper, polyolefin laminated paper such as polyethylene, and the like.

In the light-sensitive material of the present invention, the main step for directly producing a positive image is to perform surface development of an uncoupled inner latent image-type light-sensitive material after image-exposure fogging or after fogging. Consists of doing. The fog treatment can be performed by exposing the entire surface or using a fog agent. In this case, the whole surface exposure is carried out by immersing or moistening the imagewise exposed light-sensitive material in a developing solution or other aqueous solution, and then uniformly exposing the whole surface. The light source used here may be any light as long as it is within the light-sensitive wavelength range of the light-sensitive material, and high illuminance light such as flash light may be applied for a short time, or weak light may be applied for a long time. Also, the total exposure time depends on the photosensitive material, development processing conditions, type of light source used, etc.
It can be varied over a wide range to obtain the final positive image. In addition, a wide variety of compounds can be used as the above-mentioned fogging agent, and it is sufficient that this fogging agent is present during development processing, for example, in the internal latent image type light-sensitive material of the present invention such as a silver halide emulsion layer or in the development. Although it may be contained in the solution or a processing solution prior to the development processing, it is preferably contained in the light-sensitive material of the present invention (among these, particularly in the silver halide emulsion layer). The amount used can be varied over a wide range according to the purpose, and when it is added to the silver halide emulsion layer, it is preferably from 1 to 1500 mg, and particularly preferably from 10 to 10 mg per mol of silver halide.
It is 00 mg. Further, when added to a processing solution such as a developing solution, a preferable addition amount is 0.01 to 5 g / l, particularly preferably 0.08 to 0.
It is 15 g / l. Specific examples of the fogging agent, for example, U.S. Pat.Nos. 2,563,785 and 2,588,982, hydrazines, or hydrazides described in U.S. Pat.No. 3,227,552, or hydrazone compounds: U.S. Pat. No. 3,718,470, No. 3,719,494,
Heterocyclic quaternary nitrogen salt compounds described in U.S. Pat. Nos. 3,734,738 and 3,759,901; and acylhydrazinophenyl thioureas described in U.S. Pat. No. 4,030,925. Further, they can be used in combination with these fog agents. For example, Research D
isclosure) No. 15162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, which is also applicable to the present invention.

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-methylsulphonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine,
Hydrazine compounds such as 1-methylsulphonyl-2- (3-phenylsulphonamidophenyl) hydrazine and formaldehydephenylhydrazine; 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 -Sulfophenyl hydrazono) propyl] benzothiazolium bromide,
2-Methyl-3- [3- (p-sulfofenylhydrazono) pentyl] benzothiazolium iodide, 1,2
-Dihydro-3-methyl-4-phenyl chloride [2,1-
b] Benzothiazolium bromide, 1,2-dihydro-3
-Methyl-4-phenyl pyrido [2,1-b] -5-phenyl benzoxazolium bromide, 4,4-ethylenebis (1,2-dihydro-3-methyl pyrido [2,1-b] benzothiazo Lithium bromide), 1,2-dihydro-3-methyl-4-phenylbilide [2,1-b] benzoselenazolium bromide and other N-substituted quaternary cycloammonium salts; 5- [1-ethylnaphtho (1, 2-b) Thiazoline-2-
Ilidene ethylidene] -1- (2-phenylcarbazoyl) methyl-3- (4-sulfamoylphenyl) -2
-Thiohydantoin, 5- (3-ethyl-2-benzothiazolinylidene) -3- [4- (2-formylhydrazino) phenyl] rhodamine, 1- [4- (2-formylhydra Dino) phenyl] 3-phenylthiourea, 1,
3-bis [4- (2-formylhydrazino) phenyl] thiourea and the like can be mentioned.

The light-sensitive material of the present invention is subjected to imagewise exposure and then exposed to the entire surface or is subjected to development treatment in the presence of a fogging agent to directly form a positive image. Is used, and the surface development processing method is preferable. This surface development processing method means processing with a developing solution which does not substantially contain a silver halide solvent.

Usual silver halide developers that can be used in the above developing solution include polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones and phenylenediamines. Etc. or mixtures 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-Methanesulphonamidoethyl) aniline, 4-
Amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline and the like can be mentioned. These developing agents may be contained in the emulsion in advance so that they act on the silver halide during the immersion in the high pH aqueous solution.

The developer may further contain a specific antifoggant and development inhibitor. These developer additives may be optionally incorporated in the constituent layers of the light-sensitive material of the present invention. Usually, useful antifoggants include benzotriazoles such as 5-methylbenzotriazole;
Benzothiazoles; heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole; aromatic and aliphatic methylcapto compounds and the like. Further, the developer may contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound.

IV Specific Examples of the Invention Hereinafter, the present invention will be described in more detail with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example 1 A 1.5% inactive gelatin solution was kept at 50 ° C., and the following solutions A and B were simultaneously injected with stirring for 5 minutes. After 10 minutes, the following solution C was added by pouring over 3 minutes, followed by aging for 30 minutes. After removing excess water-soluble salt by a precipitation water washing method, 3 mg of hypo (Na ₂ S ₂ O ₃ .5H ₂ O) was added, and after aging for 25 minutes, the following solution D and solution E were simultaneously injected over 2 minutes. After 10 minutes, the excess water-soluble salt was removed again by the precipitation washing method.

Then, in the laminated silver halide emulsion, the following sensitizing dyes [D-1], [D-2], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, and the following cyan coupler [CC-1] A liquid containing 4-hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene, gelatin,
Add the appropriate amount of the following coating aid [S-1] to adjust the pH of the coating solution.
As 5.8, the emulsion was coated on a polyethylene-laminated paper having an undercoat so that the coated silver amount was 0.8 g / m ² . Further, a gelatin solution containing colloidal silica, the following coating aid [S-2] and the following hardener [H-1] (added immediately before coating), and the water-soluble oxidizing agent shown in Table 1 was added to a gelatin amount of 0.9. A protective layer was provided so as to have g / m ² . The coating solution for the protective layer was adjusted to pH 5.8 in the same manner as the coating solution for the emulsion layer.

Sensitizing dye [D-1] Sensitizing dye [D-2] Cyan coupler [CC-1] Coating aid [S-1] Coating aid [S-2] Hardener [H-1] After subjecting each sample to wet exposure, the following development processing was performed and the photographic performance was examined by sensitometry. The results are shown in Table 1.

[Development processing]

Image 33 ° C 3 minutes Bleach-fix 30 ° C 1 minute 30 seconds Water wash 30 ° C 1 minute 30 seconds Dry 50 ° C 2 minutes [Treatment solution composition] [Note] (1) Sensitivity (S): The reciprocal of the exposure amount showing the density point of 0.8 was obtained and shown as the relative sensitivity to the reference sample.

(2) Minimum density (Fog): The minimum density of the highlight part.

(3) Maximum density (D): Maximum density of the shadow portion.

(4) Fresh: After coating and drying, it was left at 30 ° C. for 5 days.

(5) Thermo treatment: 5 fresh samples were used to check the raw preservation property.
It was left at 0 ° C. for 5 days.

(6) Below S (%): S (thermo treatment) / S (Fresh) x 1
00 (7) D below (ΔD): D (thermo processing) -D (Fres
h) (8) (ΔF) under Fog: Fog (thermo treatment) -Fog (Fr
As is clear from the results of Table 1, in Samples 2 to 7 (invention), both the sensitivity (S) and the minimum density (Fog) after the thermo treatment have small changes as compared with Sample 1 (comparison), It has excellent storability.

Example 2 In the laminated silver halide emulsion used in Example 1, the following sensitizing dye [D-3], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, the following antioxidant [AO], Liquids containing magenta coupler [MC-1], 2-mercaptobenzthiazole, gelatin, and coating aid [S-2] used in Example 1 were added in appropriate amounts, and pH was adjusted with acetic acid or potassium hydroxide as shown in Table 2. In addition, the hardener [H-1] used in Example 1 was added immediately before coating so that the coated silver amount was 0.4 g / m ² and then the protective layer having the following composition was used. Was coated on polyethylene laminated paper by a slide hopper method so that the amount of gelatin would be 1.0 g / m ^2, and dried. As the protective layer, a gelatin solution containing the coating aid [S-2] and the following hardener [H-3] (added immediately before coating) was added as a water-soluble oxidizing agent to ferric acid as shown in Table 2. Potassium (hereinafter referred to as red blood potassium) and ethylenediaminetetraacetic acid iron sodium salt (hereinafter,
EDTA-Fe Na) was added.

Sensitometry was performed on each of the above samples in the same manner as in Example 1. The results are shown in Table 2.

Sensitizing dye [D-3] Antioxidant [AO] Magenta coupler (MC-1) Hardener [H-3] As is clear from Table 2, the sample compared to sample 11 (comparison)
The samples of the present invention in the pH range of 13 to 15 and 18, 19 have sensitivity (S), maximum concentration (D), minimum concentration (Fog) after thermotreatment.
Fluctuation is small. When the pH is low (Samples 12 and 17), the maximum concentration (D) and the minimum concentration (Fog) vary greatly, and when the pH is high (Sample 16), the sensitivity (S) and minimum concentration (Fog) The fluctuation of is large. It can be seen that both the water-soluble oxidizer potassium red blood and EDTA-Fe Na have little fluctuation after the thermo treatment.

Example 3 A 1.5% inactive gelatin solution was maintained at 60 ° C., and the following solutions A ′ and B ′ were added at the same time with stirring and the mixture was injected over 15 minutes. After 15 minutes, the C'solution was injected over 2 minutes, and after 1 minute, hypo was added in an amount of 3 mg / Ag 1 mol, followed by aging for 40 minutes. When sampled and analyzed for composition, it was silver chlorobromoiodide consisting of 3.1 mol% AgCl, 96.5 mol% AgBr, and 0.4 mol% AgI. Excess water-soluble salt was removed by precipitation water washing method, and gelatin-containing dispersion was added.
And

On the other hand, after removing excess water-soluble salt by the precipitation washing method,
Liquid D'and liquid E'were added to form a surface layer of 97 mol% AgCl and 3 mol% AgBr, excess water-soluble salts were removed by a precipitation washing method, and a dispersion gelatin was added. This was designated as Em-2.

Also, instead of the E'solution, add G solution and D'solution,
After embedding a surface layer of 80 mol% of Cl and 20 mol% of AgBr, excess water-soluble salt was removed by a precipitation washing method, and gelatin for dispersion was added to prepare a solution, which was designated as Em-3.

A liquid containing the following sensitizing dye [D-4], a yellow coupler [YC-1] protected and dispersed in dibutyl phthalate in the above Em-1,2,3, 2-mercaptobenzthiazole,
Add appropriate amounts of gelatin and the following coating aid [S-3],
After adjusting the pH of the coating solution to 6.0, the hardener [H-1] used in Example 1 was further added to make the coated silver amount 0.55 g / m ² on synthetic paper (polypropylene type, princely oil type). Synthetic paper YUPO FPG-
200) on top. Further, a coating aid [S-3] and a hardening agent [H-3] used in Example 2 (added just before coating).
After adjusting the gelatin solution to pH6.0 containing gelatin amount 1.0 g / m ²
A protective layer was provided so that (Samples 21, 24, 27). In addition,
As a sample of the present invention, 1 × 10 ⁻⁴ mol of red blood potassium was added to 1 mol of silver halide coated on the above protective layer (Samples 22, 25, 28), 2 × 10 ⁻³ mol A considerable amount of ED
A sample to which TA-Fe Na was added (samples 23 and 26) and a sample to which 1 × 10 ⁻⁴ mol of potassium dichromate was added (sample 29) were prepared.

Sensitizing dye [D-4] Yellow coupler [YC-1] Coating aid [S-3] Each sample was subjected to the following development processing and sensitometry. The results are shown in Table 3.

[Development processing]

Immersion (Developer) 35 ° C for 8 seconds Exposure-1 lux for 10 seconds Development (Developer) 35 ° C for 2 minutes 30 seconds Bleach-fixing (bleach-fixing solution) 30 ° C for 1 minute Washing 30 ° C for 1 minute Drying 50 ° C for 1 minute As is clear from Table 3, the effect of the water-soluble oxidizing agent is
It can be seen that -1 is more effective than Em-2,3 which is a laminated emulsion. That is, in Em-1, Fresh red potassium, E
The gamma (G) and maximum intensity (D) of the sample to which DTA-Fe Na was added are low, and the maximum concentration (D) changes greatly with the thermo treatment. On the other hand, in Em-2 and 3, changes in gamma (G) and maximum density (D) are small in Fresh, and changes in gamma (G) and minimum density (Fog) are small in thermoprocessing. Further, when potassium dichromate was used, the same effect as that obtained when potassium red blood was used was obtained.

Example 4 A multilayer color light-sensitive material was prepared by the following method.

Red-sensitive emulsion layer (first layer) A 2.0% inactive gelatin solution was kept at 50 ° C., and the following solution A ″ and solution B ″ were added at the same time with stirring and the mixture was injected over 3 minutes.
After 10 minutes, the following C ″ solution was added by pouring over 3 minutes. After aging for 40 minutes, excess water-soluble salt was removed by a precipitation water washing method, then D ″ solution and E ″ solution were added, and 100 ml% AgCl chloride was added. Silver was laminated on the surface, excess water-soluble salt was removed again by the precipitation washing method, and a small amount of gelatin was added to disperse the salt.

Then, the above sensitizing dye [D-5] was added to the above silver halide emulsion.
And a liquid containing the sensitizing dye [D-2], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate and the following cyan coupler [CC-2], 4-hydroxy-6-methyl-1,3,3a , 7-Tetrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, and an appropriate amount of the above-mentioned coating aid [S-1] were added, and the coating silver amount was 0.4 g / m ^2.
Was applied so that

First intermediate layer (second layer) A gelatin solution containing 2,5-dioctylhydroquinone dispersed in dioctyl phthalate, an ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a coating aid [S-1] is prepared, Tinuvin 328 was applied at a coating amount of 0.15 g / m ² .

Green light-sensitive emulsion layer (third layer) Silver halide grains were prepared in the same manner as the red light-sensitive emulsion. Instead of the sensitizing dyes [D-5] and [D-2], [D-
3], 2,5-protected and dispersed with dibutyl phthalate
A liquid containing dioctylhydroquinone and the following magenta coupler [MC-2], 4-hydroxy-6-methyl-1,3,
3a, 7-Tetrazaindene, 1-phenyl-5-mercaptotetrazole, gelatin, coating aid [S-2]
Was added in an appropriate amount, and coating was performed so that the coated silver amount was 0.4 g / m ² .

Second intermediate layer (fourth layer) With the same formulation as the first intermediate layer, the coating amount of Tinuvin 328 was 0.2 g / m ² .

Yellow filter layer (fifth layer) Yellow colloidal silver and 2,5-dioctylhydroquinone dispersed in yellow colloidal silver and dioctyl phthalate, which is made by oxidizing under alkaline weak reducing agent (weak reducing agent is removed by Neudel washing method after neutralization) Liquid, coating aid [S-2] and hardener [H-1] (added just before coating) to give a coated silver amount of 0.15 g
It was applied so as to be / m ² .

Third intermediate layer (sixth layer) The same formulation as the first intermediate layer was applied so that the coating amount of TINUVIN 328 would be 0.15 g / m ² .

Blue-sensitive emulsion layer (seventh layer) A liquid containing Em-2 used in Example 3 and containing the sensitizing dye [D-4] and the yellow coupler [YC-1] dispersed with dioctyl phthalate. -Mercaptobenzothiazole,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, gelatin, coating aid [S-3] and hardener [H-3]
A liquid containing (added immediately before coating) was coated so that the coated silver amount was 0.5 g / m ² .

Fourth Intermediate Layer (Eighth Layer) The same as the first intermediate layer, it was applied so that the coating amount of Tinuvin 328 would be 0.3 g / m ² . However, the hardener [H-3] was added immediately before coating.

Protective layer (9th layer) A gelatin solution containing colloidal silica, coating aid [S-3], hardener [H-2] and [H-3] (added immediately before coating) was used, and a gelatin coating amount of 1.0 It was applied so as to be g / m ² .

Nine layers from the red photosensitive emulsion layer to the protective layer were coated on the surface-treated polyethylene laminated paper by the simultaneous coating method and dried. The water-soluble oxidizing agent was added as shown in Table 4. In addition, the pH of the coating solution for the first to ninth layers
Was adjusted to 5.8.

Sensitometry was performed in the same manner as in Example 3. The results are shown in Table 4.

Sensitizing dye [D-5] Cyan coupler (CC-2) Magenta coupler (MC-2) As is clear from Table 4, by adding potassium red blood as a water-soluble oxidant, sensitivity (S), gamma (G),
It can be seen that the fluctuation after the thermo treatment is small in both the maximum density (D) and the minimum density (Fog). Also,
Even if the added layer is changed, the effect of the present invention can be recognized.

For each sample (Samples 31 to 34), the same result was obtained when the sensitometry was performed by the same treatment as in Example 1.

 ─────────────────────────────────────────────────── --Continued from the front page (56) References JP-A-47-13280 (JP, A) JP-A-49-120628 (JP, A) JP-A-54-103017 (JP, A) JP-A-57- 105738 (JP, A) JP 60-222843 (JP, A) JP 60-136736 (JP, A) JP 60-41037 (JP, A)

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material having on a support at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive hydrophilic colloid layer.
At least one of the light-sensitive silver halide emulsion layers contains an internal latent image type direct positive silver halide emulsion, and at least one of the non-light-sensitive hydrophilic colloid layers contains a water-soluble oxidizing agent. A silver halide photographic light-sensitive material characterized by the above.