JPS60237440A - Preparation of silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain a silver halide photosensitive material superior in sensitivity, raw storage stability, etc., by incorporating a water-soluble oxidizing agent in a coating fluid immediately before coating a support with a photosensitive silver halide emulsion layer and/or a nonphotosensitive emulsion layer. CONSTITUTION:The intended silver halide photosensitive material is obtained by incorporating a water-soluble oxidizing agent in a coating fluid immediately before coating the support with the photosensitive silver halide emulsion layer and/or the nonphotosensitive emulsion layer, and coating it. As the embodiable water-soluble oxidizing agent, potassium ferricyanate, potassium bichromate, etc. are used, preferably, in an amt. of 1X10<-5>-1X10<-3>mol. The obtained photosensitive material is subjected to proper uniform exposure during development, or developed in the presence of a fogging agent after imagewise exposure, and it is suitable for formation of a direct positive image.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to a method for producing an internal latent image type silver halide photographic light-sensitive material. Or a silver halide photographic light-sensitive material (hereinafter referred to as a photosensitive material) which is suitable for developing in the presence of a fogging agent to directly form a positive image and has improved shelf life as an unexposed light-sensitive material (hereinafter referred to as raw shelf life). (referred to as materials).

It is well known that internal latent image type photosensitive materials are generally more sensitive than fog-destructive solarization reversal type or Burschel effect reversal type direct positive photosensitive materials. The method of manufacturing such an internal latent image type silver halide emulsion includes a method of converting silver halide grains into more poorly soluble silver halide after forming them (conversion shop), or a method of converting silver halide grains to more poorly soluble silver halide, or a method of converting silver halide grains to a more poorly soluble silver halide emulsion, or a method of converting silver halide grains to a more poorly soluble silver halide emulsion, or a method of converting silver halide grains to more poorly soluble silver halide after forming silver halide grains, A method in which silver halide is laminated on the surface (laminated type) is generally used.

These internal latent image type silver halide emulsions include, for example:
So-called conversion silver halide emulsions by the conversion method described in U.S. Pat. No. 2,592,250, or U.S. Pat. Nos. 3,206,316 and 3,3
17,322 and 3,367,778, or the silver halide emulsions having internally chemically sensitized silver halide grains as described in U.S. Pat.
No. 7, No. 3,447,927 and No. 3,531,2
Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. No. 91, or silver halide containing dopants as described in US Pat. No. 3,761,276. Silver halide emulsion with weakly chemically sensitized grain surfaces, or JP-A-50-8524
The so-called core-shell type silver halide emulsions produced by the lamination method described in JP-A-52-156614, JP-A-55-127549-P and JP-A-57 The silver halide emulsion described in No. 79940 is included.

Regarding the mechanism of forming positive images in light-sensitive materials using these internal latent image type silver halide emulsions, see, for example, ``Direct positive images using core-shell type internal latent image emulsions'' by Akira Sasai.
Photo Industry (December 1981 issue, pages 105-108). The same author also states that higher sensitivity can be obtained with layered emulsions than with converted emulsions. Layered emulsions do have high sensitivity, but since the formation of positive images in internal latent image emulsions is achieved through a delicate balance between internal photosensitive nuclei and surface photosensitive nuclei, their sensitivity and gradation vary. The adjustment, density, etc. vary greatly depending on the conditions under which the photosensitive material is placed after coating and drying (storage conditions), and there is a drawback that it lacks reproducibility and reliability for practical use.

Therefore, JP-A-50-138820, JP-A-55-21
Mercapto compounds described in No. 067, JP-A-56-
Improvements have been attempted by adding indazole compounds as described in No. 54437. However, these compounds are not effective unless they are added in large amounts to silver halide emulsions, and the addition of such large amounts causes serious side effects such as decreased density due to desensitization and development inhibition. However, the addition of the above compounds cannot be said to be an effective method.

On the other hand, in order to suppress desensitization or actively increase sensitization, sensitizing dyes are used to optically sensitize green and red light, and to further increase the sensitivity in the specific wavelength range, sensitization using short wavelength sensitizing dyes, etc. was attempted, but it became clear that it had a defect in that it had a poor shelf life.

Furthermore, in the case of conventional internal latent image type silver halide emulsions, when the time from preparing the silver halide emulsion to coating increases, the maximum density fluctuates and the minimum density increases, narrowing the effective density range. Not only that, but also a change in sensitivity may occur.

This phenomenon can occur, for example, by preparing an internal latent image type silver halide emulsion and adding various additives to form a coating solution.
This occurs when the solution is left for more than 3 hours before being coated with O (hereinafter referred to as stagnation).

When such a phenomenon occurs, the coating performance of the silver halide emulsion changes from time to time, resulting in a serious quality defect in that a uniform and stable emulsion cannot be obtained. That is,
High-sensitivity direct positive internal latent image emulsions are very often used for direct photography, so if the sensitivity, maximum density, and minimum density fluctuate, the resulting image quality will not be constant, making them unusable for practical use. do not have. Furthermore, in some cases, the photosensitive material must be photographed again, which is a serious defect in that the reliability of the photosensitive material is lost.

Furthermore, the so-called continuous preparation coating method, in which the silver halide emulsion that has been emulsified and ripened and then coated after adding various additives, is continuously prepared and coated without causing the coating solution to stagnate, is ideal. However, due to the large size of the manufacturing equipment, the complexity of the continuous injection control relationship, and the lack of quality control in each step of the silver halide emulsion process, it is often impossible to confirm the design performance. If this occurs, it is often discovered after it has been applied and dried in large quantities, and this poses a risk of causing great damage. On the other hand, if the coating liquid is allowed to stagnate in each process, the process can be controlled well, and there is an advantage that abnormalities can be detected before coating. In addition, the equipment can be simplified because it can perform batch processing. To achieve this, 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 being obtained while the coating liquid is stagnant. The reality is that there are almost no known techniques from this perspective regarding silver halide emulsions.

Furthermore, Shokai No. 53-66727 discloses reducing the minimum concentration and preventing re-inversion by using a water-soluble oxidizing agent for silver halide grains produced under ammonia conditions. According to this method, the minimum density and especially the re-inversion are significantly improved, but the drawback is also stated that the sensitivity is reduced by about 30%. According to the investigation by the inventors,
It has been found that when a water-soluble oxidizing agent is added to a silver halide emulsion, the effect becomes greater as the amount increases, but it occurs even in very small amounts. It has been found that this effect is particularly large when the surface layer of the core-shell type silver halide grains is not prepared under ammonia conditions, and is also large when a sensitizing dye is included.

■ Purpose of the Invention The present invention has been made to solve the above-mentioned problems.The first purpose of the present invention is to provide a photosensitive material with high sensitivity and low density loss, and an internal image type material. It is an object of the present invention to provide a method for producing a photosensitive material suitable for.

A second object of the present invention is to provide a method for producing a highly sensitive light-sensitive material that has excellent performance even when a sensitizing dye is used.

■Specific Structure of the Invention The above-mentioned object of the present invention is a method for producing a silver halide photographic material, which comprises coating a support with at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive emulsion layer. When coating at least one of the photosensitive silver halide emulsion layer and/or the non-photosensitive emulsion layer, a water-soluble oxidizing agent is added to the coating solution immediately before coating, and -
This is achieved by a method for producing a silver halide photographic material that is coated.

The water-soluble oxidizing agent used in the present invention can be any one that has an oxidizing effect, but examples include ferricyanates, dichromates, ferric salts, cupric salts, and ferric salts. Examples include cerium salts, permanganates, ketone peroxides, etc. Specifically, potassium ferricyanate, potassium dichromate, sodium ethylenediaminetetraacetate, iron ammonia ethylenediaminetetraacetate, ceric sulfate etc. are mentioned as preferred examples. These water bath oxidizing agents may be used alone or in combination of two or more.

The amount of these water-soluble oxidizing agents used is suitably in the range of 1X10' to IX10-3 mol, preferably 2X10" to 5x10", per 1 mole of silver halide coated.
It is a mole. Further, since the optimum amount of the water-soluble oxidizing agent used varies depending on the type of water-soluble oxidizing agent used and the pH of the coating solution, it is preferable to change the amount appropriately depending on the layer to which the water-soluble oxidizing agent is added and the type of emulsion used.

Regarding the water-soluble oxidizing agent used in the present invention, when the content in the photosensitive material is small, the minimum concentration increases and the effect is small when stored raw, whereas when the content is large, the loss of maximum concentration is large. If the concentration is too high, the effective concentration range becomes narrow.

The present invention can be applied to any of the known methods for producing silver halide emulsions, such as the ammonia method, the neutral method, and the saturated method, but preferably the neutral method and the acid method. This is because when the water-soluble oxidizing agent according to the present invention is added to a silver halide emulsion with a high silver chloride content that has good color tone and fast development speed, fog tends to increase in the ammonia method. This is due to the fact that this tendency is small in the neutral method and acidic method.

The pH of the coating solution for the photosensitive emulsion and non-photosensitive emulsion is pH 4.0 to 7.0, preferably p
H5.0 to 6.5, pH 4 for non-photosensitive emulsions,
Q~765. The pH is preferably 5.0 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 oxidizing agent added.

Coating methods for 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 water-soluble oxidizing agent used in the present invention is added to a photosensitive silver halide emulsion layer and/or a non-photosensitive emulsion layer. Here, the non-photosensitive emulsion layer refers to an intermediate layer, an antihalation layer, a filter layer, a lower layer, a storage layer, etc.

When adding a water-soluble oxidizing agent to the silver halide emulsion layer, the photographic performance changes depending on the time it takes to mix the silver halide emulsion and the water-soluble oxidizing agent, apply it, and leave it for drying. It is preferable to carry out the process for as short a time as possible, preferably within a certain period of 4 minutes.

When adding a water-soluble oxidizing agent to a non-light-sensitive emulsion layer, the time of addition of the water-soluble oxidizing agent is not affected; It is preferable to apply it to

Specifically, just before coating, a water-soluble oxidizing agent liquid is pumped using a constant flow pump, added to a silver halide emulsion and/or a non-photosensitive emulsion, mixed using an in-line mixer, extrusion coating, and a slide hopper. This can be achieved by applying the coating onto a support by means such as coating or curtain flow coating, and then drying it.

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 emulsion using the conversion method described above or a core shell type emulsion using the lamination method described above. The internal latent image type silver halide used for is preferably one made of core-shell type grains, and in particular, the halide composition of the surface layer (shell) is 60 mol% or more of silver chloride, 1 mol% or less of iodide,
Furthermore, it is preferable that K be silver chloriobromoiodide which is K-plated with 75 mol % or more of silver chloride and 0.5 mol % or less of silver iodide without using an ammonia method.

The composition of the silver halide in the inner layer (core) is not particularly limited in the present invention, but silver chlorobromoiodide containing 30 mol% or less of silver chloride and 5 mol% or less of silver iodide is suitable. It is. Such silver halide can be produced by a conventional method for producing core-shell type silver halide. For example, JP-A-50-S524, JP-A-50-38525,
As described in No. 53-60222, No. 55-1524, and U.S. Patent No. 3,206,313, after forming silver chloride grains, adding bromide to convert into silver bromide grains,
Furthermore, there is a method in which a halide is laminated by adding silver nitrate, or a method in which silver iodobromide grains are prepared with a small amount of excess halogen, and then silver chloride and silver bromide are laminated in sequence.

Various photographic additives may optionally be added to the internal latent image type silver halide emulsion used in 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 thiazoline, thiazoline, and hemioxonol as part of their structure as a nitrogen-containing heterocyclic nucleus.
Those containing a basic group such as thiazole or a nucleus such as rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbital acid, pyrazolone, etc. are preferable, and such a nucleus is alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl. ,
Cyano and alkoxy can be substituted, and fusion with carbocycles or heterocycles 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 the mechanism of supersensitization J(I(viewof 5up)
ersensitization) (Photogr
aphic 5science and Engineer
ing) (PSE) Vol, 1B, 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 the compound having an azaindene ring, 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene is preferable. Examples of nitrogen-containing heterocyclic compounds having a mercapto group include pyrazole ring, 1,2.4-triazole ring, 1,2.3-triazole ring, 1°3.4-thiadiazole ring, and 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-) riazine ring, these rings are 2-
There are three fused rings, such as triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc., as well as phthalazinone ring, indazole ring, etc., and 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 meccrylic acid. Water-dispersible fine particulate polymeric substances obtained by emulsion polymerization such as polymers, styrene-maleic acid copolymers, and styrene-maleic anhydride half-alkyl ester copolymers are suitable, and as coating aids, for example, , saponin, polyethylene glycol,
Contains lauryl ether, etc. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers,
It is optional to use H adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed regulators, matting agents, anti-irradiation dyes, etc. be.

When the silver halide emulsion used in the present invention is used for color purposes, it is preferable to use a dye-forming coupler.

Yellow dye-forming couplers are of the benzoylacetanilide type, pivaloylacetanilide type, or those in which the carbon atom at the coupling position is substituted with a so-called split-off group that can be separated during coupling.
Equivalent type yellow couplers and the like are useful.

As the magenta dye-forming coupler, 5-pyrazolone type, pyrazolotriazole type, pyrazolinobenzimidazole type, indasilone type, or two-mass type magenta coupler having a split-off group is useful.

As the cyan dye-forming coupler, phenolic, naphthol, virazoquinazolone, or 2-equivalent type cyan couplers having a split-off group are useful.

These dye-forming couplers can be selected arbitrarily, and there are no particular limitations on the method or amount of use.

The photographic emulsion according to the present invention is combined with a dye-providing substance for diffusion transfer that releases a diffusible dye in response to development of silver halide to obtain a desired transferred image on an image-receiving material after an appropriate development process. It can also be used for. As such a dye-providing substance for diffusion transfer, for example, U.S. Pat.
No. 7,551, No. 3,227.554, No. 3,443
, No. 939, No. 3,443,940, No. 3,658,
No. 824, No. 3,698,897, No. 3,725,0
No. 62, No. 3,728,113, No. 3,751,40
6, British Patent No. 840, 781, British Patent No. 904, 3
No. 64, No. 1.038, No. 331, West German Patent Publication (O
LS) No. 1, 930.

No. 215, No. 2,214,381, No. 2,228,3
No. 61.

Described in No. 2,242,762, No. 2,317,134, No. 2,402.9OO Rock - Former No. 12.406-626 Heat - No. 2.406.653, JP-A-49-114424, etc. You can use the one given.

In addition, it is useful to use ultraviolet absorbers such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds to prevent fading of dye images due to short-wavelength actinic rays.
, 320, 326, 327. It is advantageous to use 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. This suitable gelatin conductor is
Examples include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

Furthermore, in the photosensitive material of the present invention, the hydrophilic colloid layer may contain other hydrophilic binders in addition to gelatin. Suitable binders include, in addition to the gelatins mentioned above, 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-vinylamine acetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated-proteins with vinyl groups. Polymers obtained by polymerization with monomers include polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneamine, etc., and are useful for photographic constituent layers such as emulsion layers, intermediate layers, retention layers, filter layers, and backing layers. The above-mentioned hydrophilic binder may further contain an appropriate lubricant, lubricant, etc. depending on the purpose.

Further, the photographic constituent layers of the light-sensitive material of the present invention can be hardened with any suitable hardening agent. Examples of these hardeners include chromium salts, zirconium salts, aldehyde-based hardeners such as formaldehyde and mucohalogen acids, halo)-riazine-based hardeners, polyepoxy compounds, ethyleneimine-based hardeners, vinyl sulfone-based hardeners, and acryloyl-based hardeners. It will be done.

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 release retention layer, a subbing layer, a backing layer, and an antihalation layer on a support. be done.

The present invention can be effectively applied to photosensitive materials for various uses such as black and white general use, X-ray use, color use, false color use, printing use, infrared use, and micro use. U.S. Patent No. 3,087,817, 3
, 185,567 and 2,983.606, Weyertz et al., U.S. Pat. No. 3,253.915, Whitemore et al., U.S. Pat. , 551, Whitemore, U.S. Pat. No. 3,227,552, and Rand, U.S. Pat.
It can also be applied to color image transfer methods, color diffusion transfer methods, absorption transfer methods, etc., as described in No. 3,415,646.

Any support can be used in the present invention, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, polypropylene film, cellulose acetate film, glass, etc. , baryta paper, polyolefin laminated paper such as polyethylene, etc.

In the light-sensitive material of the present invention, the main process of directly creating a positive image is to subject the uncoupled internal latent image type light-sensitive material to image exposure and then subjecting it to fogging treatment or surface development while subjecting it to capri-treatment. It consists of doing the following. The capri processing can be performed by exposing the entire surface to light or using a fogging agent. In this case, the entire surface exposure is carried out by immersing or moistening the image-exposed photosensitive material in a developer or other aqueous solution, and then uniformly exposing the entire surface. The light source used here may be any light within the wavelength range to which the photosensitive material is sensitive, and high-intensity light such as flash light may be applied for a short period of time, or weak light may be applied for a long period of time. Further, the total 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 it is sufficient that the fogging agent is present during the development process. Although it may be contained in a liquid or a processing liquid prior to development processing, it is preferably contained in the light-sensitive material of the present invention (particularly preferably in the silver halide emulsion layer). The amount used can vary widely depending on the purpose, and the preferred amount is 1 to 150,019 per mole of silver halide, particularly preferably 1 when added to a silver halide emulsion layer.
0 to i o o o mg. In addition, the preferable amount of addition when added to a processing solution such as a developer is 0.01 to 51
1/l, particularly preferably 0.08-0.15 g/l. Specific examples of such fogging agents include the hydrazines described in U.S. Pat. No. 2,563,785, U.S. Pat.
, 227,552; and U.S. Pat. No. 3,615°615;
3,718,470, 3,719,494, 3,734, 738" and 3,759,90
The heterocyclic quaternary nitrogen salt compounds described in No. 1, etc. further include acylhydrazinophenylthioureas described in US Pat. No. 4,030,925. It can also be used in combination with these fogging agents. For example, Research Disclosure
ure) No. 15162 describes the use in combination with a non-adsorption type fogging agent, which can also be applied 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-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1
- Hydrazine compounds such as 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-
Benzoxacillium bromide, 2-methyl-3-[
3-(phenylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-(3-(p-)lylhydrazono)propyl]benzothiazolium bromide, 2-methyl-3-[3-'(p -sulfophenylhydrazono)propyl]benzothiazolium bromide,
2-Methyl-3-(3-(p-sulfophenylhydrazono)pentyl]benzothiazolium iodite, 1.
2-dihydro-3-methyl-4-phenylpyrido (2,
1-b] Benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyride [2,1-b
) -5-phenylbenzoxacilium bromide, 4,4-ethylenebis(1,2-dihydro-3-methylpyrido[2,1-b)benzothiazolium bromide), 1,2-dihydro-3-methyl -4-Phenylpyrido (2,1-b) N-substituted quaternary cycloammonium salt such as benzoselenazolium bromide: 5-(1-
Ethylnaphtho(1,2-b)thiazolin-2-ylideneethylidene)-1-(2-phenylcarbazoyl)methyl-3-(4-sulfamoylphenyl)-2-thiohydantoin, 5-(3-ethyl -2-penzothiazolinylidene) -3-C4'-(2-formylhydrazino)phenyl]rhodanine, 1-[4-(2-formylhydrazino)phenyl]3-phenylthiourea, 1, 3
-bis(4-(2-formylhydrazino)phenylcothiourea) and the like.

After imagewise exposure, the light-sensitive material of the present invention directly forms a positive image by exposing the entire surface to light or developing it in the presence of a fogging agent. Any development method can be used for developing the light-sensitive material. A surface development treatment method is preferred. 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, phenylenediamines, etc. or a mixture thereof.

Specifically, hydroquinone, aminephenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, NLN-diethyl-p-phenylenediamine, diethylamine-〇-toluidine, 4-amino-3-methyl-N-ethyl-N-
(β-methanesulfonamidoethyl)aniline, 4-
Examples include amino-3-methyl-N-ethyl-N-(β-hydroxyethyl)aniline. These developers may 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 anti-capri agents and development inhibitors. These developer additives may be optionally incorporated into the constituent layers of the light-sensitive material of the present invention. Typically useful antifoggants include benzotriazoles such as 5-methylbenzotriazole:
Benzothiazoles: Heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole: Aromatic and aliphatic mercapto compounds, etc. are included. The developer may also contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound.

(2) Specific Examples of the Invention The present invention will be explained in more detail with reference to Examples below, but the embodiments of the present invention are not limited thereto.

Example 1 A 1.5% inert gelatin solution was maintained at 50'O, and the following solutions A and B were simultaneously injected over 5 minutes while stirring.

After 10 minutes, the following solution C was added by injection over a period of 3 minutes, and the mixture was aged for 30 minutes. Excess water-soluble salts were removed by precipitation washing method, and then hypo(Na2S20..5H,0)3 II? After aging for 25 minutes, the following solution and solution E were simultaneously injected over a period of 2 minutes. After 10 minutes, excess water-soluble salts were removed again by the precipitation washing method.

<Liquid A><LiquidB><LiquidC> Liquid B> Liquid E> Then, the following sensitizing dye (1) -11, CD-2] and dibutyl phthalate were added to this layered silver halide emulsion. A liquid containing protected dispersed 2,5-dioctylhydroquinone and the following cyan coupler [CC-1:], 4-hydroxy-6-methyl-1,3,3a,7-
Citrazainden, gelatin, coating aid below (S-1)
Appropriate amounts of each were added, and the emulsion was coated on subbed polyethylene laminate paper so that the pi-t of the coating solution was 5.8 and the coated silver amount was 0,89/qn,'. Furthermore, add colloidal silica to the gelatin aqueous solution and the following coating aid [
8-2] and the following hardening agent CI-1-11 (added immediately before coating) using a gelatin solution containing gelatin amount of 0.911.
/L", and a protective layer was provided.

As a water-soluble oxidizing agent, blush potash was added to the emulsion in an amount of 3 x 10' mol per mol of silver halide, and the time from addition to coating was varied.The coating solution for the protective layer was also the same as the coating solution for the emulsion layer. The pH was adjusted to 5.8. A comparative sample was prepared in the same manner except that the water-soluble oxidizing agent was not added.

Sensitizing dye CD-1) Sensitizing dye (D-2) Cyan coupler (CC-1) Coating aid [8-1) ShiH8 Coating aid [:S-2] C,H.

CH2-COO-CH, -CH-(CH,)s -CH
8CH-COO-CH, -CH-(CH,), -CH
51 So, Na C, H.

Hardener (H-1'll) After each sample was exposed to wedge light, the following development treatment was performed, and the photographic performance was examined by sensitometry. The results are shown in Table 1.

[Development processing]

Development 33'0 3 minutes Bleach-fix 30'0 1 minute 30 seconds Washing 30'0 1 minute 30 seconds Dry 50'0 2 minutes [Processing solution composition] <Developer> Bleach-fix solution> Below is the margin No. 1 mark (1) Sensitivity (S): The reciprocal of the exposure amount that indicates the density point 0.8 is calculated and expressed as the relative sensitivity to the reference sample. (2) Minimum density (Fog): The minimum density of the highlight area.

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

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

(5) Thermo treatment: To evaluate storage stability over time,
The sh samples were left at 50°C for 15 days (or 10 days).

(6) Below S (%): S (Thermo treatment or change in conditions) / S (Standard) X 100 (7) Below D (△D): D (Thermo treatment or change in conditions) - D (Standard) (8) Below Fog (ΔF): FOg (thermal treatment or change in conditions) - Fog (Standard) As is clear from the results in Table 1, sample 1 does not require water-soluble oxidizing agents. For samples 4 to 4, there is almost no change in Fresh even if the emulsion is left to stand, but sensitivity (S) decreases and maximum density (D) and minimum density (POG) increase due to thermoprocessing. On the other hand, in samples 5 to 8 containing water-soluble oxidizing agents,
A decrease in maximum concentration (D) is observed in samples where the time from addition to application is long (15 minutes or more). Further, after the thermo-treatment, the maximum density (1)) increased and the sensitivity (8) decreased more than in Samples 5 and 6, which were coated in a short time. Therefore, by applying the water-soluble oxidizing agent in a short time after adding it, the sensitivity is high, and even after thermo-treatment, the maximum concentration and
It can be seen that a photosensitive material with little variation in minimum density can be obtained.

Example 2 The following sensitizing dye CD-3), 2,5-dioctylhydroquinone protected and dispersed with cyphthyl phthalate, and the following antioxidant [ AO], magenta coupler (MC-
1), 2-mercaptobenzthiazole, gelatin, and the coating aid [:5-2) used in Example 1 above, were added in appropriate amounts, and immediately (3 minutes before coating), the solution containing As shown in the hardening agent (H-1) used and water-soluble oxidizing agents, blush potash, sodium ferric ethylenediaminetetraacetate (hereinafter referred to as EDTA-FeNa), potassium dichromate, and potassium permanganate were determined as shown in Table 2. Add by flow pump and after mixing, coated silver amount o, 43g7.
Further, a protective layer of the following composition was coated on a polyethylene laminate paper using a slide hopper coating method so that the amount of gelatin was 1.0 g Art, and then dried.

The gelatin solution for the protective layer is a 3% seratin solution containing the coating aid (S-2) described above and the hardening agent (H-3) described below.

For each sample above, perform the following development treatment,
Sensitometry was performed. The results are shown in Table 2.

Sensitizing dye (D-3) Antioxidant (AO) Magenta coupler (MC-1) CA ShiB Hardener [:1-f-3) [Development processing] Immersion (developer) at 35℃ for 8 seconds Dew light 10 seconds at 1 lux Development (developer) 35"C2 minutes 30 seconds Bleach-fixing (bleach-fixing solution) 30℃ 1 minute Water wash 30℃ 1 public Tumble drying at 50℃ for 1 minute [Bleach-fix solution composition] 1. Hit Table 2 [Tears] Symbols are in accordance with Table 1.

As is clear from Table 2, the maximum density (D) is slightly lowered by adding a water-soluble oxidizing agent, but the increase due to thermoprocessing is also small and can be controlled by adjusting the amount of silver coated. In addition, in the sample to which a water-soluble oxidizing agent was added, the decrease in sensitivity (S) was small even after thermo-treatment, and the minimum concentration (lI'
og) is also small, indicating that it has excellent storage stability.

Example 3 A 15% inert gelatin solution was kept at 62°C, and while stirring, solutions '' and 'B' were simultaneously added to the following and injected over a period of 15 minutes. The 15-minute Kobono solution was injected over 2 minutes, and 1 Kobono Hypo was added in an amount equivalent to 3 m9AJ11 moles, and the mixture was further aged for 40 minutes. After sunblinking and analyzing the composition, AJ
iCll 3.1 mol%, A7Br 96.5 mol%
, A, 9IO was silver chlorobromoiodide consisting of 14 mol %.

Excess water-soluble salts were removed by precipitation and water washing. Further D
' solution and E' solution were added, kg (J) 97 mol%,
A: After laminating a surface layer containing 3 mol % of 1ilBr, excess water-soluble salts were removed by a precipitation washing method, and gelatin for dispersion was added, which was designated as Toy-1. On the other hand, the B s k'
Add D1G solution instead of A
After laminating a surface layer consisting of 10 mol% of gCl and 90 mol% of AgBr, it was neutralized with acetic acid (PH''-: 6.0), excess water-soluble salts were removed by a precipitation washing method, and gelatin for dispersion was added. The added product was designated as Em-2.

<Liquid A> Hexachloroiridate(I) salt 2X10″I<B
'Liquid'<C'liquid><D'liquid><E/liquid>G'liquid> Ammonia water (28%) 35 Fresh The following sensitizing dye CD-43 was added to Em-1 and 2 above, and protected in dibutyl phthalate. Appropriate amounts of a liquid containing the following dispersed yellow coupler (YC-1), 2-mercaptobenzthiazole, gelatin, and the following coating aid (S--3) were added, and the pH of the coating liquid was adjusted to 6.0. Add hardener (H-1) and coated silver amount Em-1 is 0.5
5 g/rt, Em-2 is 0.7 μ synthetic paper (polypropylene, egg oil synthetic paper, Yupoli”
PG-200). A sample to which no sensitizing dye (D-4) was added was also prepared.

Furthermore, coating aid (S-3) and hardening agent [H-3] (
After adjusting the pH of the gelatin solution (added immediately before coating) to 6.0, a protective layer was provided so that the amount of gelatin was 1.0μ. As a sample of the present invention, a water-soluble oxidizing agent, red blush potash, was added to the above emulsion immediately before coating (3 minutes) in an amount equivalent to 5×10' molar amount per 1 mole of silver halide.

Sensitizing dye CD-4) Yellow coupler [YC-1] C/ Coating aid (8-3) CH2-COOCH2 (CF2 CF2) 2HCH
-COOCH2(CF2CF2)2H03Na Each of the above samples was treated in the same manner as in Example 2, and sensitome l-IJ- was performed. The results are shown in Table 3.

Table 3 Note: (1) Samples 21 to 24 were converted into relative values with S in 21 set as 100.

(2) Samples 25 to 28 were converted into relative values with S in 25 set as 100.

(3) Other symbols shall conform to Table 1.

As is clear from Table 3, the core-shell emulsion Em-1 having a surface layer useful in the present invention is affected by the sensitivity (S), maximum density CD), minimum density (
Fog), the change was small in all cases, and high sensitivity (excellent sensitization) was exhibited. On the other hand, it can be seen that in emulsion Em-2 whose surface was laminated under ammonia conditions, when a sensitizing dye was added (sample 28), the sensitivity decreased more in thermoprocessing than sample 24 of 8m71.

The effect of the water-soluble oxidizing agent was observed in both Em-1 and Em-2, and especially in Em-), it was found that desensitization was small even when a sensitizing dye was added.

Example 4 A multilayer color photosensitive material was prepared by the following method.

Red-sensitive emulsion layer (first layer) A 20% inert gelatin solution was kept at 50°C, and the following solutions A'' and B'' were added simultaneously with stirring, and poured over a period of 3 minutes. After a 10-minute break, the liquid was injected and added over a period of 3 minutes. 4
After aging for 0 minutes, excess water-soluble salts were removed by precipitation washing method, and then liquid D'' and liquid L were added to give AgCA 100 mol%.
of silver chloride was laminated on the surface. Excess water-soluble salts were removed again by the precipitation washing method, and a small amount of gelatin was added and dispersed.

<Liquid A><LiquidB''><Liquidd><LiquidD'><LiquidB> After that, the following sensitizing dye CD-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 CCC-2),
4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene, 1-phenyl-5-mercaptotetrazole, further gelatin, and the coating aid (S-1)
An appropriate amount of was added to coat the coating so that the amount of silver coated was 0.4 l.

First intermediate layer (second layer) 2,5-dioctylhydroquinone dispersed in dioctyl phthalate and the ultraviolet absorber Tinuvin 328 (
Prepare a gelatin solution containing a coating aid (S-1) (manufactured by Ciba Geigy), and apply a coating amount of Tinuvin 328 to 0.15 gi.
It was applied so that it was m.

Green-sensitive emulsion layer (third layer) Silver halide grains were prepared in the same manner as the red-sensitive emulsion. Add to this the sensitizing dye CD-5) 1. CD-3) in place of CD-2), a liquid containing 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate and the following magenta coupler (MC-2), 4-hydroxy-6
-Methyl-1,3,3a, 7-tetrazaindene, 1
- Add appropriate amounts of phenyl-5-mercaptotetrazole, gelatin, and coating aid [S-2], and coated silver amount is 0.4.
It was applied to a total length of 717 m.

2nd intermediate layer (4th layer) The same formulation as the 1st intermediate layer with a coating amount of Tinuvin 328 of 0.2
I got it.

Yellow Filter Single Layer (5th Layer) Yellow filter made by oxidation under an alkaline weak reducing agent (weak reducing agent removed by Tardel water washing method after neutralization) Yellow colloidal silver and 2,5- dispersed in dioctyl phthalate.
A dioctyl hydroquinone solution, a coating aid (S-2), and a hardener Cl-1-1,1 (added immediately before coating) were added, and coating was carried out so that the coated silver i was 0.15 ji/rrt.

Third intermediate layer (6th layer) Tinuvin 328 coating amount 0, 1' with the same formulation as the first intermediate layer
It was applied at a rate of 5 fl/m.

Blue-sensitive emulsion layer (State 71) Using Em-2 used in Example 3, sensitizing dye [D-4]
, a liquid containing the yellow coupler ('YC-1) dispersed with dioctyl phthalate, 2-mercaptobenzothiazole, 4-hydroxy-6-methyl-1,3,3a
, 7-chitrazaindene, gelatin, coating aid [S-3
] and a hardener [:1(-3) (added immediately before coating) in a coated silver amount of 0.5,! il/7L''.

Fourth intermediate layer (eighth layer) Same as the first intermediate layer, the coating amount of Tinuvin 328 was 0.3 bar. However, a hardener [H-3J] was added immediately before coating.

Protective layer (9th layer) Colloidal silicone strength, coating aid (S-3J1 hardener [:H
-2) and [:H-3) (added immediately before coating) was used to apply gelatin at a coating amount of 1.09/lrt.

Nine layers, from the red-sensitive emulsion layer to the protective layer, were coated on a surface-treated polyethylene laminated paper from the support side using a simultaneous coating method and dried.

The water-soluble oxidizing agent was prepared as shown in Table 4.

In addition, the PH of the photosensitive emulsion layer is 5.8, and the PH of the non-photosensitive layer is 5.8.
was adjusted to 6.1.

The water-soluble oxidizing agent was added and mixed in the amount shown in Table 4 to the photosensitive layer (layer 1.3.7) immediately before coating (3 minutes before coating).

Sensitome l-IJ- was carried out in the same manner as in Example 2. The results are shown in Table 4.

Sensitizing dye (D-5) Cyan coupler (CC-2) Mazenk coupler (MC-2) 11β I3 As is clear from Table 4 in the margin below, the sample to which the water-soluble oxidizing agent of the present invention was added (32. 33 and 34), the changes in sensitivity (S), gamma (G), maximum density (D), and minimum density (Fog) after thermoprocessing are small, confirming the effect of the present invention. can.

Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] A method for producing a silver halide photographic material comprising coating at least one light-sensitive silver halide emulsion layer and at least one non-light-sensitive emulsion layer on a support, wherein the light-sensitive silver halide emulsion layer and Production of a silver halide photographic light-sensitive material, characterized in that, when coating at least one of the non-light-sensitive emulsion layers, a water-soluble oxidizing agent is added to the coating solution immediately before coating. Method.