JPS60247237A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE:To obtain an internal latent image type photosensitive material having superior shelf stability, high sensitivity, high maximum density and low minimum density by forming an emulsion layer contg. core/shell type silver halide particles shelled in the presence of a tetrazaindene compound on a base. CONSTITUTION:At least one silver halide emulsion layer contg. core/shell type silver halide particles shelled in the presence of a tetrazaindene compound is formed on the base to obtain the internal latent image type photosensitive silver halide material. When the material is subjected to imagewise exposure and uniform exposure or development in the presence of a fogging agent, a direct positive image is formed. The development is preferably carried out by a surface developing process. The internal latent image type photosensitive material has superior shelf stability, high sensitivity, high maximum density and low minimum density.

Description

Detailed Description of the Invention ■ Background Technical Field of the Invention The present invention relates to an internal latent image type silver halide photographic light-sensitive material that directly forms a positive photographic image, and more particularly relates to an internal latent image type silver halide photographic light-sensitive material that has high sensitivity, maximum density, and low minimum density. The present invention relates to an internal latent image type silver halide photographic light-sensitive material which has an internal latent image type and has excellent storage stability over time.

PRIOR ART Various positive-working silver halide photographic materials have been known, but the photosensitive materials using internal latent image type halide emulsions that do not cause fogging on the surface are pre-fogged silver halide emulsions. Compared to photosensitive materials that produce positive images by destroying fog nuclei (latent images) in exposed areas using solarization or the Burschel effect, direct photosensitive materials that require high sensitivity generally have higher sensitivity. It is advantageously used in positive type silver halide photographic materials (hereinafter referred to as direct positive type photosensitive materials).

After image exposure, this internal latent image type direct positive photosensitive material
A positive image can be obtained directly by performing surface development after a fog treatment or while performing a capri treatment.

Various types of internal latent image type silver halide emulsions are known so far, such as conversion emulsions described in U.S. Pat. No. 2,592,250 and U.S. Pat. No. 3,206. , No. 313, Special Publication No. 43
-29405, US Patent No. 51-29012, US Patent No. 3,317,322, US Patent No. 3,447°927, US Patent No. 3,531,291, US Patent No. 3,703, 584
No. 3, 761, 266, No. 3, 761
, No. 267.

Metal ion doped emulsions or internally chemically sensitized core/shell emulsions described in JP-A No. 3,761,276, etc., JP-A-50-8524, JP-A-50-3852
To eliminate the emulsion in which silver chloride and silver bromide are deposited in a layered manner as described in Publication No. 5, and the core/shell type emulsion having a conversion emulsion as a core described in JP-A-55-127549. I can do it.

Among such internal latent image type silver halide emulsions, there are core/shell type direct positive silver halide emulsions in which a core whose internal sensitivity has been increased by metal ion doping, chemical sensitization, conversion, etc. is covered with a shell. has particularly excellent reversal performance.

However, there are still some problems in applying this type of emulsion to various applications in the photographic field, particularly applications requiring high sensitivity, to form positive images.

That is, in order to put this method into practical use, higher sensitivity, maximum density (Dmax), and lower minimum density (Dll) are required.
il), and is desired to have properties with good storage stability over time.

Until now, various studies and efforts have been made to solve the above problems. For example, JP-A-53-60222 proposes the use of very thin shells on core particles to obtain improved photographic performance (high sensitivity, high maximum density, low minimum density). There is. According to this method,
Although this method is very advantageous in terms of high maximum density and developability, on the other hand, by reducing the thickness of the shell, storage stability at high temperatures deteriorates and the minimum density tends to increase. Furthermore, preparation under strictly controlled conditions is required, which is extremely disadvantageous from a manufacturing standpoint.

Furthermore, in JP-A No. 57-52048, in order to obtain improved photographic performance in the same manner as described above, in the same layer as the layer containing the internal latent image type silver halide emulsion without capri,
Alternatively, a method of containing a silver halide emulsion in other constituent layers has been proposed. Although this method is advantageous in terms of photographic performance, it requires the preparation of a separate emulsion, and can be said to be disadvantageous in terms of production.

On the other hand, attempts to improve the storage stability of internal latent image type emulsions include, for example, JP-A-50-138820;
Mercapto compounds described in JP-A No. 5-21067, indazole compounds described in JP-A No. 56-54437, polyvinylpyrrolidones described in JP-A No. 57-138631, and red blood salts described in JP-A No. 53-66727. Examples include the use of compounds such as oxidizing agents. Another example is the use of polyvinylpyrrolidones during chemical ripening of the particle surface as described in JP-A-57-136641.

However, although these compounds cannot be effective unless used in large quantities in silver halide photosensitive materials, they also have the disadvantage of significant desensitization and a decrease in density due to development inhibition, so they are not very effective in practical use. It's hard to say.

■ Purpose of the invention The present invention has been made in view of the above problems.
The object of the present invention is to provide an internal latent image type direct positive silver halide photographic material which has excellent storage stability over time.

The second object of the present invention is to achieve maximum density (Dmax) with high sensitivity.
) and a low minimum density (D-), an internal latent image type direct positive silver halide photographic light-sensitive material.

■Specific structure of the invention As a result of extensive research, the present inventors have found that the above object of the present invention is to provide core/shell type silver halide grains shelled in the presence of a tetrazaindene compound on a support. It has been found that this can be achieved by a silver halide photographic material having at least one silver halide emulsion layer containing the same.

The internal latent image type direct positive silver halide photographic material used in the present invention will be explained below.

The core/shell type silver halide grains used in the present invention are prepared by coating a silver halide grain serving as a core with silver halide serving as a shell, and further adding a tetrazaindene compound to the core during formation of the shell. It is characterized by:

The tetrazaindene compound used in the present invention is 6- Those represented by the following general formula exhibit particularly preferable effects.

In the general formula, river and bird each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a 5-membered ring or Represents a group of nonmetallic atoms necessary to form a 6-membered ring. Examples of the alkyl group which may have a substituent include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, a carboxymethyl group, a methoxymethyl group, a mercaptomethyl group, etc. Examples of suitable aryl groups include phenyl group, 1-naphthyl group, p-tolyl group, p-chlorophenyl group, and p-hydroxyphenyl group. k represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or a straight radical. The alkyl group and aryl group which may have substituents include Rt,
Items similar to those shown in ``t'' can be mentioned.

Specific examples of the tetrazaindene compounds effectively used in the present invention are shown below, but the tetrazaindene compounds of the present invention are not limited thereto.

Exemplary compound (1) 4-hydroxy-1,3,3a, 7-tetrazaindene (2) 4-hydroxy-6-methyl-1,3,3a,
7-tetrazaindene+314-methyl-6-hydroxy-1,3,3a,7
-Tetrazaindene (4) 4-hydroxy-6-butyl-1,3,3a,7
-Tetrazaindene (5) 4-hydroxy-5,6-cymethyl-1.3.
3m.

7-tetrazaindene (6) 2-ethyl-4-hydroxy-6-propyl-1
,3,3m,7-tetrazaindene(1)2-allyl-
4-hydroxy-1,3,3a, 7-tetrazaindene (8) 4-hydroxy-6-phenyl-1,3,3a,
7-tetrazaindene (9) 2-propyl-4-hydroxy-6-phenyl-
1,3,3a,7-tetrazaindene 1111 2-mercaptomethyl-4-hydroxy-6-methyl-1,3
,3a,7-tetrazaindene 1114-hydroxy-
5,6-)rimethylene-1゜3.351.7-tetrazaindene
It can be synthesized by referring to the description in Japanese Patent No. 2533 and the like.

The tetrazaindene compound according to the present invention may be present from the beginning to the end of shell formation.

Preferably, the amount of silver halide forming the shell is 50
It is preferable to add the amount equivalent to ~95% at the stage where a shell is formed.

Generally, during shell formation, a tetrazaindene compound solution is added to the reactor at other positions, such as a 9-silver nitrate aqueous solution and/or a halide salt aqueous solution, but if necessary, a second halogen It can also be added by being contained in a solution.

The amount of the tetrazaindene compound added cannot be determined unconditionally because it varies depending on the silver halide composition, mixing or physical ripening conditions, type of compound, etc., but it is usually IQ to 100OQ per mole of silver halide. , preferably 50
It is used in the range of Q to 500 Q.

If the amount of the tetrazaindene compound added is too small, the effect cannot be fully exhibited, and conversely, if the amount added is too large, development will be inhibited significantly and adverse effects such as poor color sensitization will occur. .

The silver halide core used in this invention can be prepared in a manner similar to conventional direct positive halide steel grain production. For example, it can be prepared by chemical sensitization, conversion to less soluble silver halide, or a combination of these methods. To chemically sensitize the core, chemical sensitization can be carried out by using known noble metal sensitizers, sulfur sensitizers, reduction sensitizers, etc., either alone or in combination. Furthermore, the internal sensitivity can also be adjusted by converting the core. Furthermore, sensitivity can also be increased by combining these.

The core prepared as described above is coated with silver halide to serve as a shell in the presence of the tetrazaindene compound, and, if necessary, chemical treatment such as chemical sensitization is performed.

The method of coating such a core with silver halide which becomes a shell includes forming a shell by the Ostwald ripening method;
For example, those disclosed in U.S. Patent No. 3,206,3 are directly deposited by a double jet addition method.
No. 13, No. 3,317,322, No. 3, 367
, No. 778, and the like can be referred to.

In order to fully exhibit the effects of the present invention, it is preferable to use the double-jet addition technique when preparing the shell part, and it is particularly preferable that the shell be produced under controlled conditions of PH, pAg, and temperature. .

For example, the pH value is 2.0 to 8.5, especially 3.0 to 8.5.
7.5 is preferable, and the pAg value is 6.0 to 10.0.
, particularly preferably 7.0 to 9.0. The temperature is preferably 40° to 85°, particularly 45° to 75°.

The silver halide composition of the shell may be silver chloride, silver bromide, silver chlorobromide, silver chloroiodobromide, or silver iodobromide, but any one of silver chloride, silver bromide, silver chlorobromide, and silver iodobromide can sufficiently exhibit the effects of the present invention and developability. In order to obtain a higher maximum concentration, the shell portion of the grain should be at least 80 mol% silver chloride, and the remainder should be silver bromide or silver bromide containing not more than 10 mol% silver iodide. The silver chloride content is preferably 100 mol %, and more preferably 100 mol % of silver chloride.

The molar ratio of silver halide used in the shell portion of the silver halide grains of the present invention to the silver halide in the core portion of the grain is usually about 1:4 to 8:1. In the present invention, a ratio of about 1=10 to 1:1 exhibits particularly preferable effects.

The average grain size of the core/shell type silver halide grains of the present invention is approximately 0.2 to 2 μm depending on the purpose, but preferably 0.3 to 1.5 μm. , the thickness of the shell portion at that time is 0.01 to 0.1
5μ straw is preferred.

Further, chemical sensitization can be applied to the surface of the shell using a known method as in the case of the core. That is, it can be prepared by using a sulfur sensitization method using a sulfur compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. alone or in combination.

Needless to say, the silver halide grains of the present invention thus obtained have characteristics as an internal latent image type emulsion.

The characteristics of an internal latent image type emulsion as used herein mean that this emulsion is coated on a transparent support and exposed to light on a light intensity scale for a predetermined period of about 1 second or less, so that the emulsion is substantially halogenated. The same emulsion sample was exposed in the same way when developed for 4 minutes at 20°0 using the surface developer (A) below, which does not contain a silver solvent and develops only the surface latent image of the grains. 2 with internal developer CB) below to develop a latent image of
It shows a maximum density not greater than the maximum density IA obtained when developed for 413 minutes at 0°0. More preferably, the maximum density obtained using the surface developer [A] is the same as that of the internal developer [A].
B] is not greater than 1/10 of the maximum density obtained in [B].

Surface developer [A] Internal developer CB) It is optional to add 14 kinds of photographic additives 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, oxonols, and hemicyanines. These optical sensitizers include oxonols, and these optical sensitizers have basic structures such as thiazoline and thiazole as nitrogen-containing heterocyclic nuclei, or rhodanine, thiohydantoin, oxazolidinedione, barbylic acid, thiobarbylic acid, and pyrazolone. Those containing a nucleus such as alkyl, hydroxyalkyl, sulfoalkyl, etc. are preferable.
It can be substituted with substituents such as carboxyalkyl, halogen, phenyl, cyano, and alkoxy, and may optionally be fused with a carbocyclic ring or a heterocyclic ring.

The internal latent image type silver halide emulsion according to the present invention can be supersensitized. For the method of supersensitization, see for example "
``Overview of the mechanism of supersensitization'' ``Review of supersensitization''
persensitization), [Photographic Science and Engineering J
(Photograp old C 5science and
Engineering) (PSE) Vol. 18. No. 4418 (1974).

The emulsion according to the present invention may further contain commonly used stabilizers such as compounds having an azaindene ring and heterocyclic compounds having a mercapto group.

As the compound having an azaindene ring, 4-hydroxy-6-methyl-1,3,3a,7-chitrazaindene is preferable. Examples of the nitrogen-containing heterocyclic compound having a mercapto group include a pyrazole ring, a 1,2.4-triazole ring, a 1,2.3- ) riazole ring, a 1.3.4-thiadiazole ring, and 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-) riazine ring, 1,2.4-) riazine ring, 1,3.5-) riazine ring, these moats are 2-
Three fused spheres 1 Examples include triazolotriazole ring, diazaindene ring, triazaindene ring, tetrazaindene ring, pentazaindene ring, etc. Also, phthalazinone ring, indazole ring, etc., 1-phenyl-5-mercaptotetrazole is preferred.

In addition, in the present invention, examples of lubricants used depending on the purpose include dihydroxyalkanes, and examples of film property improvers include combinations of alkyl acrylates or alkyl methacrylates with acrylic acid or methacrylic acid. Water-dispersible particulate polymeric substances obtained by emulsion polymerization such as polymers, styrene-maleic acid copolymers, styrene-maleic anhydride half-alkyl ester copolymers, etc. are suitable, and as coating aids, Examples include saponin, polyethylene glycol, lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers,
pH adjuster, antioxidant, antistatic agent, thickener, graininess improver, dye, mordant, brightener, development rate regulator,
It is optional to use matting agents, anti-radiation dyes, etc.

When the silver halide emulsion according to 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 2 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 magenta dye-forming couplers, 5-pyrazolone type, pyrazolotriazole type, pyrazoli7penzimidazole type, indasilone type, or two-equivalent type magenta 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 can be used in combination with a dye-providing material for diffusion transfer which releases a diffusible dye in response to the development of silver halide, and after a suitable development process, the desired transfer can be achieved on an image-receiving material. It can also be used to obtain images. Examples of such dye-providing substances for diffusion transfer include, for example, U.S. Pat. No. 3,227,551;
No. 4, No. 3,443,939, No. 3.443,9
No. 40, No. 3,658,824, No. 3゜698
．． No. 897, No. 3,725,062, No. 3,72
8.113, British Patent No. 3,751,406, British Patent No. 840.781, British Patent No. 904, 364, British Patent No. 1,
038゜331, West German Patent Publication (OLS) No. 1,93
No. 0,215, No. 2,214,381, No. 2,2
No. 28,361, No. 2, 242, 762, No. 2,317,134, No. 2,402,900, No. 2, 406, 626, No. 2 406, 65
No. 3, JP-A No. 49-114424, and those described in the specifications and publications can be used.

In addition, it is useful to use ultraviolet absorbers, such as thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds, in order to prevent dye images from fading due to short-wavelength actinic rays.
0, 320, 326°, 327. It is advantageous to use 328 (all manufactured by Ciba Geigy) alone or in combination.

When the silver halide photographic material of the present invention is a multicolor element, the layers necessary for the photographic element can be arranged in various orders as known in the art, but are preferably arranged on a support. In order, a cyan dye image-forming unit containing a cyan dye-forming coupler and having a red-sensitive silver halide emulsion layer; a magenta dye image-forming unit containing a magenta dye-forming coupler and having a green-sensitive silver halide emulsion layer; It contains a yellow dye-forming coupler as a structural unit and supports a yellow dye image-forming structural unit having a blue-sensitive silver halide emulsion layer. A great effect can be obtained by adding the tetrazaindene compound according to the present invention to at least the blue-sensitive silver halide emulsion layer, which is the outermost layer of the layer structure. More preferably, it is added to all three layers.

The silver halide photographic material according to the present invention may contain appropriate gelatin and derivatives thereof depending on the purpose. Suitable gelatin derivatives include, for example:
Examples include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

Additionally, other hydrophilic binders can be included in the hydrophilic colloid layer. In addition to the gelatins mentioned above, suitable binders include colloidal albumin, agar,
Gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 10-20% K, polyacrylamide,
Vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups, such as imidized polyacrylamide, casein, vinyl alcohol-vinylaminoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, proteins or saturated acylated proteins and vinyl Polymers obtained by polymerization with monomers having groups, polyvinylpyridine, polyvinyl 21-amine, polyaminoethyl methacrylate, polyethyleneamine, etc., are included, and they can be used as emulsion layers or intermediate layers, protective layers,
It can be added to the constituent layers of a silver halide photographic light-sensitive material such as a filter layer and a backing layer depending on the purpose, and the hydrophilic binder may further contain a suitable plasticizer, lubricant, etc. depending on the purpose. I can do it.

Further, the constituent layers of the silver halide photographic light-sensitive material according to the present invention can be hardened with any suitable hardening agent. These hardeners include chromium salts, zirconium salts, aldehydes such as formaldehyde and mucohalogen acids,
Examples include halotriazine hardeners, polyepoxy compounds, ethyleneimine hardeners, vinyl sulfone hardeners, and acryloyl hardeners.

In addition, the silver halide photographic light-sensitive material according to the present invention has various photographic constituent layers coated on the support, such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer. set up and produced.

The silver halide photographic material 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, mark 22-use, infrared use, and micro use. and the colloidal transfer method, Rogers, U.S. Pat. No. 3,087,817;
No. 67 and No. 2,983,606; U.S. Pat. No. 3,253,915 to Weyarts et al.; U.S. Pat. Whitemore et al., U.S. Pat. No. 3,227,552, and Rand, U.S. Pat. No. 3.
It can also be applied to the color image transfer method, color diffusion transfer method, absorption transfer method, etc. described in the specifications of No. 415,644, No. 3,415,645, and No. 3.415,646. .

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 polypropylene film, which have been subbed as necessary. , cellulose acetate film, glass, baryta paper, polyolefin laminated paper such as polyethylene, etc. Among these, opaque supports using plastics, such as polyethylene terephthalate films using white pigments, polyolefin laminated paper, etc., contain pigments such as ultramarine to improve the appearance of white background, but such pigments This deteriorates the photographic performance over time and is also a cause of spot failures and the like. The emulsion of the present invention exhibits its effects even on an opaque support containing such a pigment.

In the photographic light-sensitive material according to the present invention, the main step of directly forming a positive image is to perform a fogging treatment on an internal latent image type silver halide light-sensitive material whose surface is not coupled, or after performing a fogging treatment after imagewise exposure. It consists of performing surface development while processing. The fogging process can be performed by exposing the entire surface to light or using a fogging agent. In this case, the entire surface exposure is preferably 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 to light.

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 overall 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 developing solution or a processing solution prior to development processing, it is preferably contained in a silver halide photographic light-sensitive material (among these, it is preferably contained in an emulsion layer containing silver halide grains according to the present invention). ). The amount used can vary widely depending on the purpose, and the preferable amount is 1 to 1 per mole of silver halide when added to a silver halide emulsion layer.
1500119. Particularly preferably 10 to 100011g
It is. Further, when added to a processing solution such as a developer, the preferred amount is 0.01 to 5-511/l, particularly preferably 0.08 to 0.15 F/J.
It is. Such fogging agents include, for example, U.S. Pat.
, 563,785, hydrazines described in U.S. Pat. No. 2,588, 982, U.S. Pat.
27,552, and U.S. Pat. No. 3,615,65.
No. 1, No. 3,718,470, No. 3,719,4
94, No. 3, 734, 738 and No. 3,
Included are the heterocyclic quaternary nitrogen salt compounds described in US Pat.

Further, these fogging agents can also be used in combination. For example, Research Disclosure (Re5
Disclosure) No. 15162 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-phenyl Hydrazine, 1-acetyl-2-(4-acetamidophenyl)hydrazine, 1-methylsulfonyl-2-phenylhydrazine, 1-benzoyl-2-phenylhydrazine, 1-methylsulfonyl-2-(3-
Hydrazine compounds such as 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-benzoxacilium 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)benzylcobenzothiazolium iodite, 1,2-dihydro-3-methyl-4-phenylpyrido[2,1-b]benzothiazolium bromide.
1,2-dihydro-3-methyl-4-phenylpyrido [
: 2.1-b]-5-phenylbenzoxacilium bromide, 4,4-ethylenebis(1,2-dihydro-3-methylpyrido[2,1-b)benzothiazolium bromide, 1.2- N-substituted quaternary cycloammonium salts such as dihydro-3-methyl-4-phenylpyrid (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-penzothiazolinidene)-3-(4-(2-formylhydrazino)phenyl]rhodanine, 1-[4-(2-formylhydrazino)phenyl ]3-Phenylthiourine X, 1.3-
Examples include bis(4-(2-formylhydrazino)phenylcothiourea).

The internal latent image type silver halide photographic light-sensitive material 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 that does not substantially contain a silver halide solvent.

Common copper halide developers that can be used in the above developer include polyhydroxybenzenes such as hydroquinone, amine phenols, 3-pyrazolidones, ascorbic acid and its derivatives, reductones, phenylene diamines, etc. or a mixture thereof. Specifically, hydroquinone, aminophenol, N
-Methylaminephenol, 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-0-toluidine, 4-amino-3-methyl-N-ethyl-N-(-1methanesulfonamidoethyl)aniline, 4-amino-3-methyl-N-ethyl-N-(-1hydroxyethyl) Examples include 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 antifoggants and development inhibitors. These developer additives may be optionally incorporated into the layers of the silver halide photographic light-sensitive material. Typically useful antifoggants include, for example:
Included are benzotriazoles such as 5-methylbenzotriazole; benzothiazoles; heterocyclic thiones such as 1-phenyl-5-mercaptotetrazole; aromatic and aliphatic mercapto compounds, and the like.

Further, the developer can also contain a development accelerator such as a polyalkylene oxide derivative or a quaternary ammonium salt compound.

- (Equipment) - ■ Specific Examples of the Present Invention The present invention will be explained below with reference to Examples, but the embodiments are not limited to these.

The sensitometric conditions used in the present invention are as follows.

[Exposure Conditions] Using a KS-7 sensitometer (manufactured by Konishiroku Photo Industry ■), exposure was carried out through a wedge with a density difference of 0.10.

[Development processing]

[Composition of the solution used] Developer solution bleach-fix solution [Measurement] Sakura Photodensitometer PDA-65 [manufactured by Konishiroku Photo Industry ■]
The transmission or reflection density was measured using

The zero point was determined when nothing was added in the case of transmission, and the reflection density of the support surface before emulsion coating was determined in the case of reflection.

[Characteristic value]

1) Maximum density (1) nax); Maximum density of shadow areas 2) Minimum density (Dmin); Minimum density of highlight areas 3) Sensitivity; Inverse of the exposure amount that gives a density of (maximum density + minimum density)/2 The numerical values were calculated and shown as relative sensitivity to the comparative sample for each example.

Example 1 A conversion core emulsion was prepared as follows.

175 mA' of a 2 molar aqueous solution of silver nitrate and 175 Tnl of a 2.1 molar aqueous solution of potassium chloride were simultaneously added over 15 minutes to a solution containing 10 p of gelatin while controlling the temperature at 60°C, and after physical ripening for 10 minutes, the odor was removed. Potassium chloride 2
200 ml of a molar aqueous solution was added, and physical ripening was further performed for 10 minutes. Next, after removing the water-soluble halide by precipitation and washing with water, 10.9 g of gelatin was added and water was added to give a total volume of 500 m.

A core/shell emulsion was prepared as follows using the conversion emulsion grains prepared as described above as a core.

Add 100 d of a 2 molar aqueous solution of silver nitrate and 100 ml of a 2.1 molar aqueous solution of potassium chloride at 60°C to 500 ml of the core emulsion.
1 was simultaneously added for 5 minutes to precipitate a silver chloride shell, the precipitate was washed with water, and an aqueous gelatin solution was added to give a total amount of 500 d (emulsion 1-A).

Similarly, a 2 molar aqueous solution of silver nitrate (100,117I) and potassium chloride (2.1
Molar aqueous solution 100mA! An emulsion was prepared by precipitating a silver chloride shell by simultaneously adding 5 min.

However, when silver nitrate equivalent to 80 parts of the silver chloride shell amount is added, the solution of exemplified compound (1) is 50T per mole of silver.
n9 was added to the emulsion in a rush (emulsion 1-B).
).

Emulsion 1-C, Emulsion 1-D, and Emulsion 1-E were prepared in the same manner as Emulsion 1-B. However, Example 34 - The amount of water compound (1) added was 100 m/mole of silver, respectively.
1p, 2001n9,500■.

To each of the five emulsions prepared as above, 71v of the following sensitizing dye (D-1) was added per 0.1 mole of silver, and a magenta coupler solution (M-1) with the following composition and a hardening agent were added. (I-I-1) was added and coated on polyethylene laminate paper so that the coated silver amount was 0.4.9/- and dried.

(D-1) SO, Na (M-1) The above two compounds were dissolved in ethyl acetate and dioctyl phthalate, and protected and dispersed in sodium dodecylbenzenesulfonate and gelatin solution.

(H-1) (H-2) αχ■2c) 12 In addition, a gelatin solution containing hardeners (H-1), (H-2) and a spreading agent is added to the upper layer so that the amount of gelatin is II/I. A protective layer was applied and dried.

These samples were aged at 35° C. and 301 RH for 3 days to prepare test samples (conditions 1). Thermo-treated samples are
The pre-aged test sample was further heated at 50°C and 104RH.
Heat treatment was performed for 5 days under the following conditions (condition 2).

The obtained sample was exposed to wedge light through a yellow filter, and then subjected to the development process described above. The obtained sensitometry results are shown in Table 1.

Table 1 37- As is clear from the results in Table 1, the samples of the present invention to which exemplified compound (1) was added are superior to the comparative samples in terms of photographic performance, particularly in terms of sensitivity and minimum density. In particular, the performance after thermo-processing, ie, under the condition of 1 forced deterioration, decrease in sensitivity and increase in minimum density are significantly suppressed, which is very effective. However, when a large amount of Exemplary Compound (1) is added, the maximum concentration tends to decrease and desensitization tends to occur.
In order to use the present invention more advantageously in practice, it is also necessary to consider the amount added.

Example 2 An internal latent image type direct positive silver halide emulsion was prepared by the following method.

While controlling the emulsification and ripening temperature to 60°C, a 2 molar silver nitrate aqueous solution 200-, 0.9 molar potassium bromide and 1.6 molar potassium chloride were added to an aqueous solution containing gelatin 10Ii. Aqueous solution 400
tnl was added by co-injection over 20 min, followed by an additional 10 min.
Physical aging was performed for 1 minute.

Next, water-soluble halides were removed by precipitation and washing with water, and then an aqueous solution containing gelatin 1011 was added, the temperature was raised to 60°C, Hypo 2 was added, and the mixture was aged for 15 minutes. Furthermore, 100 m of a 2 molar aqueous solution of silver nitrate was added to this core emulsion at 60°C.
After coating the silver chloride shell by simultaneously adding 100 - of a 2.1 molar aqueous solution of potassium chloride and potassium chloride over 5 minutes, the precipitate was washed with water, and a gelatin solution was added to give a total amount of 5001 n.
(Emulsion 2-A).

In the method for preparing Emulsion 2-A, 200 .mu.m of exemplified compound (1) was added per mole of silver before coating the silver chloride shell (Emulsion 2-B).

In the method for producing Emulsion 2-A, when a silver nitrate solution equivalent to 20% of the silver chloride shell was added, a solution containing Exemplified Compound (1) was added at a lattice of 200 m9 per mole of silver (Emulsion 2-C). .

In the same manner as Emulsion 2-C, a solution containing Exemplified Compound (1) was added during the formation of the silver chloride shell to form Emulsion 2-C and Emulsion 2-C.
E was prepared. However, the exemplified compound (I) was added at a position after silver nitrate equivalent to 50% of the silver chloride shell was added and after silver nitrate equivalent to 80% of the silver chloride shell was added.

For comparison, an emulsion was prepared by adding 200 μm of exemplified compound (1) per mole of silver after the formation of a shell (emulsion 2-F).

The following sensitizing dye (D-2) was added at 13.5 μm per 0.1 mole of silver to each of the six emulsions prepared as described above, and a yellow coupler solution (Y-1) having the following composition and Add hardener (H-1) and coat on polyethylene laminate paper so that the coating silver amount is 0.5 g/rrl.
Dry.

(D-2) (Y-1) A solution in which the above two compounds are dissolved in ethyl acetate, dioctyl phthalate, and dibutyl phthalate, mixed with a gelatin solution containing sodium dodecylbenzenesulfonate, and dispersed by an ultrasonic dispersion method.

Furthermore, a gelatin solution containing hardeners () T-1) and (H-2) and a spreading agent was applied to the upper layer so that the amount of gelatin was 1 g/- and dried.

These samples were aged and thermotreated under the same conditions as in Example 1.

The obtained sample was exposed to wedge light and then subjected to the development treatment described above, and the results of sensitometry are shown in Table 2.

41- Table 2 As is clear from the results in Table 2, compared to the 42- system of emulsions prepared without the addition of tetrazaindene compounds and emulsions prepared by adding them after shell formation, It can be seen that the emulsion system prepared in the presence of a tetrazaindene compound has excellent photographic performance and performance under forced deterioration conditions.

Furthermore, even with the same amount added, it is more effective when added at the time of shell formation than when added in advance before shell formation, and it is especially effective when added after silver nitrate injection of 50 times or more of the shell formation amount. It is.

Example 3 An internal latent image type silver halide emulsion was prepared by the following method.

200 ml each of a 2 molar silver nitrate aqueous solution and a potassium bromide aqueous solution were added into a solution containing gelatin ION by a controlled simultaneous mixing method for 20 minutes while controlling the temperature to 60°C to obtain monodisperse silver bromide crystals. Ta. To the core emulsion thus prepared were added 1.21n9 of hypo and 1.81n9 of potassium chloroaurate(m) per mole of silver, and the emulsion was chemically ripened at 60°C.

Next, this chemically ripened core emulsion was further added with a 2 molar silver nitrate aqueous solution at 100 mA! and 100 mA' of a 2 molar potassium bromide aqueous solution were simultaneously added at 60° C. to prepare a core/shell emulsion. After shell formation, 0.6 ■ hypo and 0.9 ■ gold chloride (r
n) Potassium acid was added and chemical ripening was performed at 60°C (
Emulsion 3-A).

In the method for producing Emulsion 3-A, when a silver nitrate solution equivalent to 80% of the silver bromide shell was added, the following compound was added in a rush.

Emulsion 3-B: 200% of exemplified compound (1) per mole of silver
Tn9 addition.

Emulsion 3-C: 200% of exemplified compound (4) per mole of silver
■Addition.

Emulsion 3-D: Exemplary compound (9) at 200% per mole of silver
■Addition.

Emulsion 3-E: mercaptobenzothiazole was added in an amount of 40 m9 per 1 mole of mercaptobenzothiazole.

Emulsion 3-F: 40 µm of phenylmercaptotetrazole was added per mole of silver.

A sensitizing dye (D-
1) was added at 81n9 per 0.1 mole of silver, the coupler dispersion (M-1) and hardener (H-1) of Example 1 were added, and the amount of silver coated on the subbed polyester film was 2.9n9. 0
Apply so that it becomes 11/rrl.

Dry.

Further, in the upper layer, a gelatin solution containing hardeners (H-1), (H-2) and a spreading agent is added in an amount of gelatin of 11! A protective layer was applied so as to have a ratio of /- and dried.

These samples were aged and thermotreated under the same conditions as in Example 1.

The obtained sample was subjected to wedge exposure through a yellow filter, and then subjected to the following development treatment. The results are shown in Table-3.

[Development processing]

45- [Composition of the solution used] Developer bleach-fix solution 46- ((However, adjusted to I)H6.9 with potassium carbonate or acetic acid.)Table 3 As is clear from the results in Table 3, Even if the tetrazaindene compound of the present invention forms a shell in the presence of a different type of stabilizer, it cannot improve the minimum concentration and performance fluctuation under forced deterioration conditions, and it also affects the maximum concentration. On the other hand, the photosensitive material in which a shell is formed in the presence of the compound of the present invention exhibits a remarkable effect on performance under conditions such as 1 forced deterioration.

Example 4 □ A conversion core emulsion was prepared by the method shown in Example 1. A core/shell emulsion was prepared as follows using the obtained conversion type core emulsion grains as a core.

Core emulsion 500+nA! pH 6.2, temperature 1160℃
, 1) Adjusted to #7.5. While controlling to maintain these conditions, a 2 molar aqueous solution of silver nitrate was
and a 2.1 molar aqueous potassium chloride solution were simultaneously added over 5 minutes to precipitate a silver chloride shell. This solution was precipitated and washed with water, and a gelatin solution was added to make the total volume 5001 (emulsion 4-
A).

An emulsion was prepared by precipitating a silver chloride shell in the same manner as Emulsion 4-A. However, when silver nitrate equivalent to 80 parts of the silver chloride shell amount is added, the solution of exemplified compound (1) is
150 μm per mole was added to the emulsion (emulsion 4-B).

A large excess of potassium chloride solution was added in advance to 500 d of the core emulsion, and a 2 mol silver nitrate aqueous solution was heated at 60° C. at 100 mA.
' was added by a forward mixing method for 5 minutes to precipitate a silver chloride shell. This solution was precipitated and washed with water, and a gelatin solution was added to make the total amount 500-(emulsion 4-C).

An emulsion was prepared by precipitating a chlorinated steel shell in the same manner as Emulsion 4-C. However, when silver nitrate equivalent to 80 parts of the silver chloride shell amount is added, the solution of exemplified compound (1) is
It was added into the emulsion in an amount of 150Tn9 per mole (emulsion 4-D).

To each of the four emulsions prepared as described above, 7 μm of sensitizing dye (D-1) was added per 0.1 mole of silver, magenta coupler solution (M-1) and hardener (H-1) were added in the same manner. ) was added, and the amount of silver coated on polyethylene laminated paper was 0.41.
49- Furthermore, as a protective layer, a gelatin solution containing hardeners (H-1), (H-2) and a spreading agent was applied in an amount of gelatin of 11 I/m. Dry.

The obtained sample was aged and thermotreated under the same conditions as in Example 1. These samples were exposed to wedge light through a yellow filter, and then developed. The obtained sensitometry results are shown in Table 4.

Table 4 50- As is clear from the results in Table 4, samples 4-B and 4- were prepared using emulsions containing the tetrazaindene compound of the present invention.
It can be seen that D has excellent photographic performance and performance after thermoprocessing. In addition, the sample (4-B) prepared under controlled conditions during shell formation was particularly good.
It can be seen that the addition of tetrazaindene compounds is also particularly effective when shell formation occurs under controlled conditions.

Example 5 A core/shell emulsion was prepared according to the method of Example 1.

However, the amounts of silver nitrate, potassium chloride, and potassium bromide were adjusted so that the composition of silver halide in the shell and its proportion to the total silver halide were as shown in Table 5 below.

Margin Table 5 Below: To each emulsion shown in Table 5 above, the sensitizing dye and yellow coupler liquid used in Example 2 were added, and a hardener was added, and the amount of silver coated on polyethylene laminated paper was 0.511.
It was coated and dried so that it became 7-.

Further, a gelatin solution containing hardeners (H-1) and (H-2) and a spreading agent was applied to the upper layer so that the amount of gelatin was 19/-, and dried.

These samples were aged and thermotreated under the same conditions as in Example 1.

Table 6 shows the results of sensitometry obtained by performing the above-mentioned development treatment after wedge exposure of the obtained sample.

Table 6 53- Table 6 (Continued) As is clear from the results in Table 6, the present invention is superior in terms of photographic performance, especially in the minimum density value and in the small variation after thermo-processing. It can be seen that the sample to which such a tetrazaindene compound was added was superior in terms of 54-.

Furthermore, it can be seen that the greater the silver chloride content in the silver halide composition of the shell, the better the effect can be exhibited, and the more the shelling ratio is less than 50%, the better the effect can be exhibited.

Example 6 Using emulsions 1-A, 1-B, and 1-D prepared in Example 1, a coating solution was prepared under the same conditions as in Example 1, and a coating solution was prepared containing a pigment as a support. Hardeners (H-1) and (H-2) were coated on polyethylene laminate paper (referred to as X) and polyethylene laminate paper (referred to as Y) obtained by removing only the pigment from support X, and hardeners (H-1) and (H-2) were applied as protective layers. A gelatin solution containing a spreading agent was applied so that the amount of gelatin was 11/m' and dried.

The obtained sample was aged and thermotreated under the same conditions as in Example 1, then exposed and developed in the same manner as in Example 1. The minimum concentration at that time and the occurrence of spots were observed. The results are shown in Table-7.

The results of the occurrence of bochi are based on the following criteria.

○: Not occurred at all.

△...Small spot-like spots occur.

×...Large spot-like spots occur.

Table 7 As is clear from the results in Table 7, it can be seen that the samples of the present invention, especially those containing pigments, can significantly improve minimum density and spot failure after aging when applied to reflective supports.

Patent applicant Konishiroku Photo Industry Co., Ltd.

Claims (1)

[Claims] A silver halide photographic light-sensitive material having, on a support, at least one silver halide emulsion layer containing core/shell type silver halide grains shelled in the presence of a tetrazaindene compound.