JPH0690430B2 - Direct positive silver halide photographic light-sensitive material - Google Patents

Description

Detailed Description of the Invention [Industrial applications]

The present invention relates to a direct positive silver halide photographic light-sensitive material, and more particularly to a direct positive silver halide photographic light-sensitive material in which fogging is prevented even when stored under high temperature and high humidity.

[Prior art]

Conventionally, the method used for producing a positive image using a known direct positive type photosensitive material can be mainly classified into two types. One type is to obtain a positive image after development by using a fog-fogged silver halide emulsion and destroying fog nuclei (latent image) in the exposed area by utilizing solarization or Herschel effect. The other type is to obtain a positive image by using an internal latent image type silver halide emulsion which has not been fogged in advance and performing surface development after image exposure or after fog treatment or while performing fog treatment. Here, the fog treatment may be performed by exposing the entire surface, may use a fog agent, may use a strong developing solution, heat treatment, or the like, but usually a light or fog agent is used. The method used is adopted. The internal latent image type silver halide photographic emulsion means a silver halide photographic emulsion having a photosensitive nucleus mainly inside the silver halide grains and forming a latent image inside the grains upon exposure. This latter type of method is generally more sensitive than the former type of method and is suitable for applications requiring high strength, and in particular the invention relates to this latter type. Various techniques have been known so far in this technical field. For example, U.S. Patents 2,592,250 and 2,466,957
No., No. 2,497,875, No. 2,588,982, No. 3,761,266,
No. 3,761,276, No. 3,796,577 and British Patent 1,151,36
The main ones are those listed in No. 3 and so on. By using these known methods, a photographic light-sensitive material having a relatively high sensitivity as a direct positive type can be produced. For details of the mechanism of forming a direct positive image, see, for example, Photographic Science and Engineering, 20.
As described in Volume 158 (1976), it is considered as follows. That is, photoelectrons generated in the silver halide crystal grains by imagewise exposure are selectively captured inside the grains to form an internal latent image. Since this internal latent image acts as an effective trap center for electrons in the conduction band, in the exposed particles, the electrons injected in the subsequent development process are trapped inside and trap the latent image. Become. In this case, the latent image is not developed because it is entirely inside. On the other hand, in the particles that have not been image-exposed, the injected electrons are at least temporarily captured on the surface of the particles, which are developed by surface development to give a positive image. Photosensitive materials capable of forming positive images can be produced by using the above-mentioned known techniques, but further improvement of photographic performance is desired in order to apply these photosensitive materials to various photographic fields. For example, in such a direct positive silver halide photographic emulsion, there is a drawback that the fog (minimum density Dmin) in the image background portion is high, although relatively high sensitivity and density can be obtained. It is well known that a re-inversion negative image is formed in a high exposure amount area in addition to the positive image. The formation of this negative image is particularly remarkable when imagewise exposed to light having a high illuminance, for example, flash light, but also visible when exposed to normal tungsten light or sunlight. The degree of such a fog and a negative image varies depending on the type of silver halide emulsion, production conditions, storage state after production, development conditions, etc., but especially when stored over time at high temperature and high humidity. Remarkably, the quality of the white background of the image is seriously impaired. Further, in the recent photographic industry, it is well known that development and subsequent post-processing steps (desilvering, fixing, washing with water, etc.) are carried out at high temperatures to shorten the processing time and accelerate the processing. By the way, when the above-mentioned fog development is carried out at a high temperature, for example, at a temperature of 30 ° C. or higher, the fog and the negative image generated by the aging storage are further amplified, which is one of the problems in practical use of this type of emulsion. Has become. Conventionally, various antifoggants or development inhibitors have been known for the purpose of improving such an undesirable phenomenon. For example, benzotriazoles described in U.S. Pat.No. 2,497,917, heterocyclic thione compounds described in JP-B-45-12709, and tetrazole compounds described in U.S. Pat.No. 3,352,672 are used as inhibitors. Came. However, even when these compounds are used, they are insufficient for the suppression of fog and negative images that occur over time, a sufficient white background cannot be obtained, and a large amount of the inhibitor as suggested in the above patents is not obtained. The use of is not preferable because it significantly suppresses development and lowers the image density.

[Object of the Invention]

The present invention has been made in view of the above circumstances, and its first object is to provide an internal latent image type direct positive silver halide photographic light-sensitive material capable of maintaining stable photographic characteristics even when it is stored under high temperature and high humidity over time. To provide the material. A second object of the present invention is to effectively suppress the fogging of the image background portion and the negative image appearing in the highly exposed portion, which occur during storage under high temperature and high humidity, and to obtain a good positive image without lowering the image density. Another object of the present invention is to provide an internal latent image type direct positive silver halide photographic light-sensitive material. A third object of the present invention is to provide an internal latent image type direct positive silver halide photographic light-sensitive material capable of rapidly forming a good direct positive image by high temperature development processing.

[Constitution of the invention]

The above object of the present invention is to have at least one silver halide emulsion layer containing an internal latent image type silver halide grain, and to provide a surface after fogging after image exposure and / or while performing fogging. A photographic light-sensitive material which directly obtains a positive image by development is contained in combination with at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. Achieved by General formula [I] In the formula, Z represents NR ', an oxygen atom, a sulfur atom or a selenium atom, and R'represents a hydrogen atom, an alkyl group or an aryl group. Q represents a hydrocarbon group necessary for forming a 5-membered heterocycle with Z and a nitrogen atom, and the heterocycle may be further condensed with a benzene ring or a naphthalene ring. Y represents a hydrogen atom or a substituent, and M represents a hydrogen atom, an alkali metal atom or an ammonium group. General formula (II) In the formula, R represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, an acyl group or a heterocyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. Hereinafter, the present invention will be described in detail. The compound represented by the general formula [I] is an imidazole (benzimidazole, naphthimidazole) having a mercapto group (including a salt) at the 2-position, imidazoline, oxazole (benzoxazole, naphthoxazole), thiazole (benzothiazole, naphthothiazole). ), Thiazoline or selenazole (benzoselenazole, naphthoselenazole). When Z is NR ', the alkyl group represented by R'is preferably an alkyl group having 1 to 8 carbon atoms (more preferably 1 to 6), for example, methyl group, ethyl group, isopropyl group, butyl group, t- Examples thereof include a butyl group and a hexyl group. These alkyl groups are hydroxy group, amino group, cyano group,
It may be substituted with an alkoxy group, an aryl group, a heterocyclic group or the like. Examples of the aryl group represented by R'include a phenyl group and a naphthyl group, and these aryl groups may be substituted with a halogen atom, an alkyl group, an alkoxy group or the like. The substituent represented by Y is not particularly limited as long as it is a group capable of substituting a benzene ring or a naphthalene ring of a heterocycle or a condensed heterocycle, but preferably a halogen atom, a hydroxyl group, a mercapto group (including a salt), a nitro group. , Amino groups, alkyl groups, alkoxy groups, aryl groups, carboxyl groups and salts thereof, sulfo groups and salts thereof, acyl groups, acylamino groups, carbamoyl groups, sulfamoyl groups, alkoxycarbonyl groups and the like. Examples of the alkali metal atom represented by M include sodium and potassium. Among the compounds represented by the general formula [I], benzimidazole and benzothiazole compounds are preferable. When the compound represented by the general formula [I] is a 2-mercaptoazole compound, it can have the following tautomeric structure, and any of these tautomers is included in the present invention. Typical examples of the compound represented by the general formula [I] (hereinafter referred to as the compound of the present invention) used in the present invention are shown below, but the present invention is not limited thereto. These compounds are known compounds, are readily available as commercial products, and are also available from Beileste Handbuch der Organischen Chemie.
ins handbuch der Organischen Chemie), 24, 119,
Ibid., 27 (2), 181 and 233 (1972), U.S. Pat. No. 2,730,528, Journal of the American Chemical Society (J. Am. Chem. Soc.), 49, 17
It can be synthesized according to the method described on page 48 and the like. The compound represented by the general formula [II] is 1H-tetrazole having a substituent at the 5-position. The alkyl group represented by R preferably has 1 to 12 carbon atoms.
Examples of (more preferably 1 to 8) alkyl groups include a methyl group, an ethyl group, a butyl group, a hexyl group, and an octyl group. The cycloalkyl group represented by R is preferably a cycloalkyl group having 3 to 10 carbon atoms (more preferably 5 to 8), and examples thereof include a cyclopentyl group and a cyclohexyl group. The aryl group represented by R is preferably a phenyl group or a naphthyl group, and these aryl groups are a halogen atom, an amino group, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an acyl group, an acylamino group, a carboxyl group, an alkoxy group. It may be substituted with a carbonyl group or the like. The alkoxy group represented by R is preferably an alkoxy group having 1 to 12 carbon atoms (more preferably 1 to 8), and examples thereof include a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group and an octyloxy group. The amino group represented by R may be substituted and examples thereof include an ethylamino group, a dimethylamino group and a diethylamino group in addition to the amino group. Examples of the acyl group represented by R include an acetyl group and a benzoyl group.
The heterocyclic group represented by R has at least one hetero atom.
It contains one nitrogen atom, one oxygen atom or one sulfur atom, and examples thereof include a pyridyl group, a piperidinyl group, a morpholino group and a thiomorpholino group. Among the compounds represented by the general formula [II], 5-phenyl-tetrazole compounds are preferable. Typical examples of the compound represented by the general formula [II] (hereinafter referred to as the compound of the present invention) used in the present invention are shown below, but the present invention is not limited thereto. The above compound can be easily synthesized by a known method. For example, Journal of the American Chemical Society (J.Am.Chem.Soc.), 80, 3908 (1959) or Journal of Organic
Chemistry (J.Org.Chem.), 24, 1650 (1959)
And the like. The compound of the present invention is dissolved in water or an organic solvent having an affinity for water, for example, methanol, acetone or the like, or dissolved in a weak alkali or a weak acid to be added to a light-sensitive material component, or It is contained in the developing bath. The addition amount may be appropriately changed depending on the type of compound used and the layer to be added, and when it is added to a silver halide emulsion layer, it is generally 10 ^-8 to 10 per mol of silver halide.
^In the range of ^-2 mol, a more preferable amount is ^10-6 to ^10-3 mol. The compound of the present invention is added to any of the constituent layers provided in a usual light-sensitive material such as a silver halide emulsion layer of a light-sensitive material, a protective layer, an intermediate layer, a filter layer, an antihalation layer and an undercoat layer. However, a particularly preferable layer is a silver halide emulsion layer. In the case of a silver halide emulsion layer, it is added at an appropriate time after the ripening of the emulsion and before coating, and in the case of the other layers, it is added at a suitable time after adjusting the coating solution and before coating. The compound of the general formula [I] and the compound of the general formula [II] is added in a weight ratio of 1: 9 to 9: 1, preferably 1: 4 to 2: 1. The internal latent image type silver halide emulsion in the present invention is an emulsion having silver halide grains which form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains. Silver halides such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide and silver chloroiodobromide. Particularly preferably, the emulsion is exposed to a light intensity scale over a defined period of time of up to about 1 second on a portion of a sample coated on a transparent support, and only the surface image of the grains substantially free of silver halide emulsions. Surface developer A for developing
When developed at 20 ° C. for 4 minutes, another part of the same emulsion sample is similarly exposed and the image inside the grain is developed. The maximum concentration is not more than 1/5 of the maximum concentration obtained in. Preferably, the maximum densities obtained with surface developer A are no greater than 1/10 of the maximum densities obtained with internal developer B. Surface developer A Metol 2.5 g L-ascorbic acid 10 g Sodium metaborate (tetrahydrate) 35 g Potassium bromide 1 g Water was added 1 Internal developer B Metol 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate ( Monohydrate) 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water is added 1. The internal latent image type silver halide emulsion used in the present invention includes those prepared by various methods. For example, a conversion type silver halide emulsion described in U.S. Pat.No. 2,592,250, or U.S. Pat.No. 3,206,316,
Silver halide emulsions having internally chemically sensitized silver halide grains described in U.S. Pat. Nos. 3,317,322 and 3,367,778, or multivalent compounds described in U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,531,291. A silver halide emulsion having silver halide grains containing metal ions incorporated therein, or a silver halide emulsion in which the grain surface of a silver halide grain containing a dopant described in US Pat. No. 3,761,276 is weakly chemically sensitized. Emulsion or JP-A-50-8524
No. 50-38525 and No. 53-2408, and silver halide emulsions composed of grains having a laminated structure described in JP-A-52-156614 and JP-A-55-127549. Silver halide emulsion. In the light-sensitive material of the present invention, in addition to the fog inhibitor represented by the general formula [I] or [II] according to the present invention, a known fog inhibitor or stabilizer can be used in combination. Examples of the compound that can be used in combination include 1-phenyl-5-mercaptotetrazole and 4-hydroxy-6-methyl-
Mention may be made of 1,3,3a, 7-tetrazaindene. The silver halide emulsion according to the present invention can be optically sensitized with a commonly used sensitizing dye. A combination of sensitizing dyes used for supersensitization such as an internal latent image type silver halide emulsion and a negative type silver halide emulsion is also useful for the silver halide emulsion of the present invention. For sensitizing dyes, see Research Disclosure (R,
(Abbreviated as D) No. 15162 and No. 17643 can be referred to. The photographic light-sensitive material of the present invention is image-exposed (photographed) by an ordinary method
After that, a positive image can be easily obtained directly by developing the surface. That is, the main step of directly producing a positive image is a process of generating a fog nucleus by a chemical action or an optical action after the imagewise exposure of the previously unfogged internal latent image type light-sensitive material of the present invention, that is, The surface development is performed after the fog treatment and / or while the fog treatment is performed. The fog treatment can be performed by exposing the entire surface or by using a compound that generates a fog nucleus, that is, a fog agent. In the present invention, the whole surface exposure is carried out by immersing or moistening the imagewise exposed light-sensitive material in a developing solution or other aqueous solution, and then uniformly exposing the whole surface. The light source used here may be any light within the photosensitive wavelength range of the photographic light-sensitive material, and high-illuminance light such as flash light can be applied for a short time or weak light can be applied for a long time. . Also, the total exposure time depends on the photographic light-sensitive material, the development processing conditions, the type of light source used, etc.
It can be varied over a wide range to obtain the final positive image. A wide variety of compounds can be used as the fog agent used in the present invention, and the fog agent only needs to be present during the development processing, for example, in the internal latent image type light-sensitive material such as a silver halide emulsion layer or in the development. It may be contained in the solution or the processing solution prior to the development processing, but it is preferably contained in the light-sensitive material (among these, particularly in the silver halide emulsion layer). The amount used can be varied over a wide range according to the purpose, but the preferable addition amount is 1 to 1500 mg, particularly preferably 10 mg per mol of silver halide when added to the silver halide emulsion layer. ~ 1000 mg
Is. When it is added to a processing solution such as a developing solution, the addition amount is preferably 0.01 to 5 g / l, particularly preferably 0.05 to 1 g / l. Examples of the fogging agent used in the present invention include U.S. Pat.
563,785, 2,588,982 hydrazines, or hydrazide or hydrazone compounds described in US Pat. No. 3,227,552; US Pat. No. 3,615,
No. 615, No. 3,718,479, No. 3,719,494, No. 3,734,738, and No. 3,759,901, etc., heterocyclic quaternary nitrogen salt compounds ;: Further, acylhydrazinophenylthioureas described in U.S. Pat. , A compound having an adsorption group on the surface of silver halide. Further, these fog agents may be used in combination. For example, RD No.1
No. 5162 describes that a non-adsorption type fogging agent is used in combination with an adsorption type fogging agent, and this combination technique is also effective in 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
-Methylsulfonyl-2- (3-phenylsulfonamidophenyl) hydrazine, hydrazine compounds such as formaldehydephenylhydrazine; 3- (2-formylethyl) -2-methylbenzothiazolium bromide, 3-
(2-Formylethyl) -2-propylbenzothiazolium bromide, 3- (2-acetylethyl) -2-benzylbenzoselenazolium bromide, 3- (2-acetylethyl) -2-benzyl-5-phenyl Benzoxazolium bromide, 2-methyl-3- [3- (phenylhydrazino) propyl] benzothiazolium bromide,
2-Methyl-3- [3- (p-tolylhydrazino) propyl] benzothiazolium bromide, 2-methyl-3-
[3- (p-sulfophenylhydrazino) propyl] benzothiazolium bromide, 2-methyl-3- [3-
(P-Sulfophenylhydrazino) pentyl] benzothiazolium iodide, 1,2-dihydro-3-methyl-4
-Phenylpyrido [2,1-b] benzothiazolium bromide, 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] -5-phenylbenzoxazolium bromide, 4,4'- Ethylene bis (1,2-dihydro-3-methylpyrido [2,1-b] benzothiazolium bromide), 1,2-dihydro-3-methyl-4-phenylpyrido [2,1-b] benzoselenazolium N- such as bromide
Substituted quaternary cycloammonium salt; 5- [1-ethylnaphtho (1,2-b) thiazoline-2-ylideneethylidene]
-1- (2-phenylcarbazoyl) methyl-3- (4
-Sulfamoylphenyl) -2-thiohydantoin,
5- (3-ethyl-2-benzothiazolinylidene) -3
-[4- (2-Formylhydrazino) phenyl] rhodamine, 1- [4- (2-formylhydrazino) phenyl] -3-phenylthiourea, 1,3-bis [4- (2-
Formylhydrazino) phenyl] thiourea and the like. The internal latent image type photosensitive material used in the present invention, after image exposure,
A positive image is directly formed by exposing the entire surface or performing surface development treatment in the presence of a fog agent. This surface image processing method means processing with a developing solution which does not substantially contain a silver halide solvent. Examples of the developer that can be used in the surface developer used for developing the light-sensitive material of the present invention include ordinary silver halide developers such as polyhydroxybenzenes such as hydroquinone, aminophenols, 3-pyrazolidones and ascorbine. Acids and their derivatives, reductones, phenylenediamines, etc. or mixtures thereof are included. Specifically, hydroquinone, aminophenol, N-methylaminophenol, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidone, ascorbic acid, N, N-diethyl-p-phenylenediamine, diethylamino-o-toluidine, 4-amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) aniline, 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline and the like can be mentioned. These developers may be contained in the light-sensitive material in advance and immersed in a high pH aqueous solution so as to act on the silver halide. The developer used in the present invention may further contain a specific antifoggant and development inhibitor, or these developer additives may be optionally incorporated in the layer film of the light-sensitive material. is there. To the silver halide emulsion according to the present invention, various photographic additives such as a wetting agent, a film physical property improving agent and a coating aid can be added depending on the purpose. Examples of the wetting agent include dihydroxyalkane and the like, and further examples of the film physical property improving agent include, for example, a copolymer of alkyl acrylate or alkyl methacrylate with acrylic acid or methacrylic acid, styrene-maleic acid copolymer, styrene. -A water-dispersible particulate polymer substance obtained by emulsion polymerization of a maleic anhydride half alkyl ester copolymer or the like is suitable, and as a coating aid, for example, saponin,
Polyethylene glycol lauryl ether and the like are included. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, moldants, brighteners, development speeds. It is also possible to use regulators and matting agents. The silver halide emulsion prepared as described above is coated on a support through an undercoat layer, an antihalation layer, a filter layer, etc., if necessary, to obtain the internal latent image type light-sensitive material of the present invention. It is useful to use the light-sensitive material used in the present invention for color, and in this case, it is preferable to include cyan, magenta and yellow dye-forming couplers in the silver halide photographic emulsion. As the coupler, those usually used can be used. Further, in order to prevent fading of the dye image due to the actinic rays having a short wavelength, it is useful to use an ultraviolet absorber, for example, thiazolidone, benzotriazole, acrylonitrile, or a benzophenone-based compound, and particularly, tinuvin PS, 32
0, 326, 327, 328 (all manufactured by Ciba Geigy)
The single use or the combined use of is advantageous. Any support may be used as the support of the light-sensitive material used in the present invention, but as a typical support, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, or a cellulose film, which has been subjected to undercoating if necessary. Examples thereof include acetate film, glass, baryta paper, and polyethylene laminated paper. The light-sensitive material used in the present invention may contain, in addition to gelatin as a protective colloid or a binder, a suitable gelatin derivative depending on the purpose. Examples of suitable gelatin derivatives include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin and the like. Further, in the present invention, other hydrophilic binder can be included depending on the purpose, 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, urethane carboxylic acid such as vinyl alcohol-vinyl aminoacetate copolymer. Vinyl alcohol polymer containing acid group or cyanoacetyl group, polyvinyl alcohol, polyvinyl pyrrolidone, hydrolyzed polyvinyl acetate, polymer obtained by polymerization of protein or saturated acylated protein and monomer having vinyl group, polyvinyl viridine, polyvinyl amine , Polyaminoethylmethacrylate, polyethyleneimine, etc. are added according to the purpose in the photosensitive material constituting layers such as emulsion layer or intermediate layer, protective layer, filter layer, backing layer, etc. Further, the hydrophilic binder may contain an appropriate plasticizer, lubricant or the like depending on the purpose. Further, the constituent layers of the light-sensitive material used in the present invention can be cured with any suitable hardener. Examples of these hardeners include chromium salts, zirconium salts, aldehyde compounds such as formaldehyde and mucohalogen acid, halotriazine compounds, polyepoxy compounds, ethyleneimine compounds,
Examples thereof include vinyl sulfone-based and acryloyl-based hardeners. The light-sensitive material used in the present invention has at least one photosensitive emulsion layer containing the internal latent image type silver halide grains according to the present invention on a support, a filter layer, an intermediate layer, a protective layer, It is possible to install a large number of various photographic constituent layers such as an undercoat layer, a backcoat layer, an antihalation layer and the like. When the photographic light-sensitive material of the present invention is used for full color, at least one red-sensitive silver halide emulsion layer, green-sensitive silver halide emulsion layer and blue-sensitive silver halide emulsion layer are coated on a support. To be done. At this time, at least one light-sensitive silver halide emulsion layer may contain the internal latent image-type silver halide grains according to the present invention, but all the light-sensitive silver halide emulsion layers include the internal latent image-type silver halide grains according to the present invention. It preferably contains latent image type silver halide grains. Further, each light-sensitive silver halide emulsion layer may be the same color-sensitive layer or may be divided into two or more layers having different sensitivities. In this case, at least one layer having different sensitivities should be the same. The color-sensitive layer may contain the internal latent image type silver halide grains according to the present invention, but it is preferable that all the emulsion layers contain the internal latent image type silver halide grains according to the present invention. The light-sensitive material used in the present invention can be effectively applied to various uses such as general black and white, X ray, color, pseudo color, printing, infrared, micro, and silver dye bleaching. , Also colloidal transfer method, Rogers US patent
3,087,817, 3,185,567 and 2,983,606, U.S. Pat.No. 3,253,915 by Weyerts et al., U.S. Pat.No. 3,227,550 by Whitemore et al., U.S. Pat.
7,551, Whitemore U.S. Patent 3,227,552 and Rand U.S. Patents 3,415,644, 3,415,645 and 3,
Color image transfer method as described in No. 415,646,
It can also be applied to a color diffusion transfer method, an absorption transfer method and the like.

【The invention's effect】

The direct positive silver halide photographic light-sensitive material of the present invention has a high temperature,
It can be stably stored with time even under high humidity, and it is possible to almost completely prevent fog in the image background area and generation of a negative image in the highly exposed area.

【Example】

Hereinafter, the present invention will be specifically described with reference to examples, but the embodiments of the present invention are not limited thereto. Example 1 A halide conversion type internal latent image type silver chloroiodobromide emulsion was prepared according to the method described in US Pat. No. 2,592,250. That is, to 300 ml of an aqueous gelatin solution containing 5 g of potassium chloride, 300 ml of a 1 mol aqueous solution of silver nitrate and 300 ml of a 1 mol aqueous solution of potassium chloride were gradually added simultaneously at 50 ° C. and mixed. After physical ripening for 10 minutes, 300 ml of a 1 mol aqueous solution of potassium bromide and 30 ml of a 0.1 mol aqueous solution of potassium iodide were added and mixed. Then, after physical ripening for 10 minutes, 300 ml of 1 molar aqueous solution of potassium bromide and 0.1 molar aqueous solution of potassium iodide 30
A mixed solution of ml was added and mixed. After physical ripening for 10 minutes, it was washed with water to prepare an internal latent image type silver chloroiodobromide emulsion.
The following green-sensitive sensitizing dyes were added to the obtained silver chloroiodobromide emulsion for spectral sensitization. Then, as a coupler solution, 1- (2,4,6-trichlorophenyl) -3- (2-
Chloro-5-octadecylsuccinimidoanilino)-
5-pyrazolone 40 g, 2,5-di-t-octylhydroquinone 1 g, dioctyl phthalate 75 g, and ethyl acetate 30 g were mixed and dissolved, and the mixture was emulsified and dispersed in a gelatin solution and added to an emulsion (per 0.3 mol of silver halide). did. Green-sensitive sensitizing dye: Then 4-hydroxy-6-methyl 1,3,3 as a stabilizer
An emulsion was prepared by adding an appropriate amount of a, 7-tetrazaindene. The obtained emulsion was divided into equal portions, and the compound of the present invention (single use and combined use of [I] or [II]) and the comparative compound were added, and a hardener was added to perform resin coating as shown in Table 1 below. Fifteen types of direct positive photographic materials (Samples 1 to 15) were prepared by coating on a paper support so that the amount of silver was 6 mg / 100 cm ^2, and drying. Comparative compound (a) ... Compound described in US Pat. No. 2,497,917 One set of the obtained samples was placed in a refrigerator set at 5 ° C (condition-
In 1), the other 2 sets were left under high temperature and high humidity of 65 ° C relative humidity 50% (condition-2) and 50 ° C relative humidity 80% (condition-3) for 5 days respectively, and then these 3 sets 20CM in the usual way
After performing S wedge exposure,
Development was carried out at 0 ° C for 2 minutes. 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline sulfate 5.5 g sodium sulfite (anhydrous) 2 g sodium carbonate (monohydrate) 18 g sodium bromide 1.2 g benzyl alcohol 10 ml water 1 (adjusted to pH 10.2 with potassium hydroxide) However, the entire surface was uniformly exposed to light of 1 lux for 10 seconds from the start of development for 10 seconds. Then, bleach-fixing, washing with water and drying were carried out by a conventional method. The maximum density (Dmax) and the minimum density (Dmin) of the magenta positive image obtained by each development process were measured. The results are shown in Table-1. In the table, NS represents the relative sensitivity of the negative image (represented by the reciprocal of the exposure amount at the minimum density + 0.1 density on the characteristic curve of the negative image), and the sensitivity under condition -1 of Sample 1 was expressed as 100. . The larger the value is, the larger the negative image is generated. From the results in Table-1, when stored under high temperature and high humidity,
Fog and negative images are remarkably generated (Sample 1), and when the comparative compound is added, the fog and negative images are not sufficiently suppressed, and when added in large amounts, a good positive image cannot be obtained because the density is lowered. I understand. On the other hand, by using the compounds [I] and [II] of the present invention in combination, a fog and a negative image are suppressed by a synergistic effect which cannot be expected from the single use of each, and a good positive image with a high maximum density is obtained. It turns out that it forms. Example 2 The method for forming a positive image using the compound of the present invention can also be applied to the diffusion transfer method. Internal latent image type core / shell emulsions were prepared by the method described in US Pat. No. 3,761,276. That is, a 1 mol silver nitrate aqueous solution and a potassium bromide aqueous solution are mixed by a simultaneous mixing method to obtain 50
The mixture was added and mixed at 0 ° C. to obtain 0.3 μm tetradecahedral silver bromide crystal grains (core grains). This silver bromide emulsion was chemically sensitized with sodium thiosulfate and chloroauric acid, and then an aqueous solution of silver nitrate and an aqueous solution of potassium bromide were simultaneously added, and the core grains were coated with silver bromide to give an octahedron of 0.45 μm. Particles (core / shell particles) were obtained. Further, this emulsion was chemically sensitized with sodium thiosulfate and chloroauric acid to prepare an internal latent image type emulsion. A photosensitive sheet was prepared by sequentially coating the following layers on an opaque film support made of polyethylene terephthalate (Sample 16). Layer (1) A gelatin layer containing the following magenta dye image-forming compound. Layer (2) Gelatin intermediate layer. Layer (3) Green-sensitive internal latent image type silver bromide emulsion spectrally sensitized by adding a dye to the aforementioned internal latent image type emulsion, the following fog agent and scavenger 2-octadecylhydroquinone-5-potassium sulfonate Containing layers. Layer (4) Gelatin protective layer. In addition, 14 kinds of photosensitive sheets were prepared in the same manner except that the compound ([I] or [II} alone or in combination) and the comparative compound of the present invention were added to the layer (3) of Sample 16 as shown in Table 2. Were prepared (Samples 17 to 30). Comparative compound (b): Compound described in JP-B-45-12709 A dye image receiving sheet was then prepared by sequentially coating the following layers on an opaque paper support. Layer (1) Styrene and N, N-dimethyl-N-benzyl-N
An image receiving layer composed of a copolymer of p- (methacryloylaminophenyl) methylammonium chloride and divinylbenzene, gelatin and 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidinone. Layer (2) A gelatin intermediate layer containing an ultraviolet absorber. Layer (3) Gelatin protective layer. Each of the obtained photosensitive sheets was subjected to Condition-1 and Condition-2 of Example 1.
After being left to stand for 3 days, the wafer was exposed to a wedge, immersed in an activator solution having the following composition for 15 seconds, and then passed through a pair of pressure rollers and laminated on the image-receiving sheet (lamination). Activator solution Potassium hydroxide 56.2g 5-Methylbenzotriazole 7.2g 11-Aminoundecanoic acid 2.0g Potassium bromide 2.0g Water is added 1 Treatment is performed in an atmosphere of 30 ° C, and after 4 minutes, a photosensitive sheet and an image receiving sheet are prepared. Was peeled off. The results of the magenta dye transfer image (positive) obtained on the image receiving sheet are shown in Table 2. However,
NS is shown as a relative value when sample 16 (condition-1) is expressed as 100. From the results shown in Table 2, it can be seen that the inclusion of the compound of the present invention in combination suppresses the generation of fog and negative image even under the severe storage condition even in the diffusion transfer method, and obtains a good positive image. .

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Claims (1)

[Claims] 1. A surface development treatment comprising at least one silver halide emulsion layer containing internal latent image type silver halide grains, which is subjected to fog treatment after image exposure and / or while undergoing fog treatment. In the photographic light-sensitive material for directly obtaining a positive image, the photographic light-sensitive material is a combination of at least one compound represented by the following general formula [I] and at least one compound represented by the following general formula [II]. A direct positive silver halide photographic light-sensitive material, characterized in that General formula [I] [In the formula, Z represents NR ', an oxygen atom, a sulfur atom or a selenium atom, and R'represents a hydrogen atom, an alkyl group or an aryl group. Q represents a hydrocarbon group necessary for forming a 5-membered heterocycle with Z and a nitrogen atom, and the heterocycle may be further condensed with a benzene ring or a naphthalene ring. Y represents a hydrogen atom or a substituent, and M represents a hydrogen atom, an alkali metal atom or an ammonium group. ] General formula [II] [In the formula, R represents an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an amino group, an acyl group or a heterocyclic group containing at least one nitrogen atom, oxygen atom or sulfur atom as a hetero atom. ]