JP2520596B2 - Photographic material for direct positive - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a direct positive photographic light-sensitive material, and more particularly to a direct positive photographic light-sensitive material that gives stable photographic characteristics when subjected to running processing by an automatic processor. It is a thing.

(Prior Art) Conventionally, a silver halide inner core that has been doped with a metal ion, chemically sensitized, or both, and a halogenation that covers at least a photosensitive site of the inner core. Developed in the presence of an internal latent image type silver halide grain (hereinafter referred to as core / shell type grain) chemically sensitized, if necessary, consisting of an outer shell of silver and a fog-inhibiting agent. It is known that a reversal image can be obtained by a direct reversal method of the type in which the entire surface is exposed during development. More specifically, U.S. Pat.
No. 3,761,276 and the like.

Good reversal photographic characteristics can be obtained by using such core / shell type silver halide grains. However, such core / shell type silver halide emulsions are subject to fatigue during running processing by an automatic processor. There is a drawback that the photographic characteristics are greatly changed due to the fluctuation of the developer composition.

That is, in general, during the development processing step of a silver halide photographic light-sensitive material, a part of the components added to the light-sensitive material is eluted in a developing solution, or iodine which is a by-product of the development of silver halide is used. Ions, bromine ions, chlorine ions, etc. are eluted and accumulated in the developer. Further, a component of the developer composition that is easily adsorbed to the photosensitive material is carried out together with the photosensitive material when the photosensitive material is taken out of the developer after completion of the development, so that the concentration of the component in the developer gradually decreases with running. . Fluctuations in developer composition due to the accumulation of elution components from these light-sensitive materials and the reduction of developer components carried out along with the light-sensitive material affect the photographic characteristics of the silver halide photographic light-sensitive material to be developed, resulting in a finished quality. Was a cause of impairing the stabilization of the.

Such a problem is that in the case of an automatic developing machine of the type in which the developer replenisher is replenished and the tired developer overflows, the composition and amount of the replenisher should be set to the developer composition accompanying development of the photosensitive material. It can be solved to some extent by adjusting according to fluctuations. However, in such an automatic processor, when a new processing system is assembled by changing the type of photosensitive material to be developed and combining a new photosensitive material and an existing developing solution, the fluctuation of components in the developing solution due to fatigue There is a drawback that it may not be able to be adjusted.

Particularly in the case of direct positive photosensitive materials using core / shell type particles, the concentration of benzotriazoles in the developer greatly affects photographic characteristics such as maximum density (Dmax), sensitivity, fog, etc. Suppressing fluctuations in the concentration of benzotriazoles in the liquid is essential for obtaining stable photographic performance.

Further, in the case of a direct positive photosensitive material using core / shell type particles, the maximum concentration of benzotriazoles in the developing solution for each photosensitive material is the core / shell type particles coated on each photosensitive material. The particle size and the method of chemical sensitization, and the type and amount of the sensitizing dye, stabilizer, fog and the like used are largely dependent. Therefore, if the newly designed direct positive photosensitive material is combined with the existing developer,
In many cases, good photographic characteristics cannot be obtained. In particular, this development becomes remarkable in running processing using an automatic processor.

When benzotriazoles are added to the emulsion layer or the adjacent layer of the light-sensitive material in order to solve these drawbacks, there is a problem that the photographic characteristics are significantly affected. For example, there is a problem that the sensitivity of the light-sensitive material is lowered (especially, the sensitivity of the color sensitized region is lowered) and the life-time is deteriorated.

(Object of the Invention) An object of the present invention is to provide a photographic light-sensitive material for direct positive use, which does not have such a problem and has stable photographic characteristics in a running process.

Another object of the present invention is to provide a direct positive photographic light-sensitive material having stable photographic characteristics even when an existing developing solution is used.

(Means for Achieving the Purpose) The above object of the present invention is to provide an inner nucleus of silver halide having one side on a support, which is doped with a metal ion, chemically sensitized, or both. And a direct positive photograph having at least one internal latent image type silver halide emulsion layer containing a core / shell type silver halide grain consisting of an outer shell covering at least a light-sensitive site of the inner core and a binder. A photographic light-sensitive material for direct positive use which is characterized in that at least one layer containing benzotriazoles is provided on the side of the support opposite to the silver halide emulsion layer.

 Hereinafter, the present invention will be described in detail.

The benzotriazoles used in the present invention are preferably compounds represented by the following general formula (I).

In the formula, X is a lower alkyl group (eg, methyl group, ethyl group, t-butyl group, etc.), lower alkoxy group (eg,
Methoxy group, ethoxy group, etc.), (Wherein R represents a lower alkyl group (eg, methyl group, ethyl group, butyl group, etc.)), nitro group or halogen atom (eg, chlorine atom, bromine atom, etc.), and n is
Represents 0, 1 or 2.

The substitution position of X is preferably the 5-position and / or the 6-position, and examples thereof include 5-methylbenzotriazole and 5-t-.
Butylbenzotriazole, 5-methoxybenzotriazole, 5-acetamidobenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 5,6-dimethylbenzotriazole, 5,6-dichlorobenzotriazole, 5,6-di Examples thereof include bromobenzotriazole.

In the above general formula (I), particularly preferably, n is 1
And X is a methyl group, or n is 0.
As a specific compound, 5-methylbenzotriazole,
Examples thereof include benzotriazole.

The coating amount of benzotriazoles used in the present invention is
1mg / m ² ~100mg / m ² is preferred. In another form, it is as follows.

That is, the coating amount of benzotriazoles is C: the concentration of benzotriazole in the replenishing solution [mg /] U: Replenishing amount of the developing solution when developing 1 m ² of the light-sensitive material [/ m ² ] X: Application of benzotriazole on the light-sensitive material When the amount is [mg / m ² ], in X = k × C × U, k is preferably in the range of 0.1 to 2, and more preferably in the range of 0.3 to 1. The optimum value of k tends to increase as the amount of silver coated on the light-sensitive material increases. Furthermore, the optimum value of X (the optimum value of the coating amount of benzotriazole in the light-sensitive material) also tends to increase as the coating amount of silver increases.

The benzotriazoles used in the present invention are dissolved in water or an appropriate organic solvent (for example, methyl alcohol, ethyl alcohol, propanol, methyl cellosolve, acetone, etc.) or a mixed solvent containing a plurality of these solvents, and are dissolved in the form of a solution. It is emulsified and dispersed in a hydrophilic colloid solution (eg gelatin solution). It is also possible to emulsify and disperse benzotriazoles in a water-soluble solvent and disperse this emulsion in a hydrophilic colloid solution.

The hydrophilic colloid solution containing benzotriazoles can be applied to the light-sensitive material by a known application method.

The benzotriazole content of the present invention may be combined with the antihalation layer and the curl adjusting layer. Further, the benzotriazole layer of the present invention may have at least one layer, and 2
It may be more than one layer.

A binder is typically used in the benzotriazole layer of the present invention. Specifically, the binder described below can be used.

The core / shell silver halide grains used in the present invention preferably have an average grain diameter of about 0.1 to 4 microns, more preferably about 0.2 to 2 microns. Further, two or more kinds of core / shell type silver halide grains having different average grain diameters may be used in the same layer or different layers.

The core / shell type silver halide grains constituting the emulsion of the direct positive photographic light-sensitive material of the present invention are the inner cores of silver halide which are first doped with metal ions, chemically sensitized, or both. Is prepared, and then the surface thereof is coated with an outer shell of silver halide and, if necessary, the outer shell is chemically sensitized. It is not necessary to coat the entire particle surface of the inner core with the outer shell, but it is sufficient to coat at least the photosensitive site of the inner core (the site that produces photolytic silver upon exposure). To dope the inner nucleus with a metal ion, for example, in the process of silver halide grain formation or physical ripening of the inner nucleus, cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt is used. A method of coexisting a metal ion source such as iron salt or its complex salt can be adopted.

The metal ion is usually used in a ratio of 10 ^-8 mol or more with ^respect to 1 mol of silver halide. The silver halide in the inner nucleus may be chemically sensitized by using one or more of a noble metal sensitizer, a sulfur sensitizer and a reduction sensitizer instead of or in addition to the above-mentioned metal ion dope. In particular, the sensitivity increases when gold sensitization and sulfur sensitization are performed. A method of treating the silver halide of the inner nucleus and coating the grain surface of the silver halide constituting the inner nucleus with silver halide serving as an outer shell is known, for example, U.S. Pat.Nos. 3,206,316 and 3,317,322. No. 3,367,778 (excluding the fogging process on the particle surface), No. 3,761,
The method described in each specification of No. 276 can be advantageously applied.

The use ratio of the silver halide in the inner nucleus and the silver halide in the outer shell is arbitrary, but usually 1 to 1 mol of the former and 2 to 8 of the latter.
Use moles.

The silver halides of the inner core and the outer shell preferably have the same composition, but may have different compositions. In the present invention, as each silver halide, for example, a brominating agent, silver iodide, silver chloride, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide and the like can be used. Preferred silver halide emulsions are The most preferred emulsions consist of at least 50 mol% silver bromide and the silver bromoiodide emulsions, especially those containing less than about 10 mol% silver iodide.

Further, the core / shell type silver halide grains are cubic,
Those with regular crystals such as octahedron, but also irregular (irregula) such as spherical or plate-like
r), a composite form of these crystal forms, or a mixture of grains of various crystal forms.

The core / shell type silver halide grain surface prepared as described above may be chemically sensitized if necessary.

Chemical sensitization of the core / shell type silver halide grain surface is Gl
afkides "Chimie et Physique Photographique" (P
aul Montel, 1967), VL Zelikman et al "Maki
ng and Coating Photogra phic Emulsion "(The Focal
Press, 1964) or edited by H. Frieser “Die Grundlage
n der Photographischen Prozesse mit Silberhalogeni
den ”(Akademische Verlagsgesellschaft, 1968) and the like.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with silver ions or active gelatin, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or other noble metal compounds, etc. are used alone or in combination. . Of these, the combination of gold sensitization and sulfur sensitization gives the best results,
If necessary, a reduction sensitization method may be additionally used. As the sulfur sensitizer, thiosulfur salts, thioureas, thiazoles, rhodanines, other compounds can be used, specific examples thereof, U.S. Pat.No. 1,574,944,
2,410,689, 2,278,947, 2,728,668, 3,656,955. As the reduction sensitizer, primary tin salts, amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds and the like can be used, and specific examples thereof are U.S. Patents 2,487,850, 2,419,974, 2,518,698.
No. 2,2,983,609, 2,983,610, 2,694,637. For sensitizing precious metals, in addition to gold complex salts, platinum,
Complex salts of metals of Group VIII of the periodic table such as iridium and palladium can be used, and specific examples thereof are disclosed in US Pat. No. 2,399,08.
3, 2,448,060 and British Patent 618,061.

When carrying out such a chemical sensitization step, various conditions can be set arbitrarily, and generally pH 8 or less. pAg10
Hereinafter, it is preferable to carry out the treatment at a temperature of 40 ° C. or higher. However, in some cases, conditions outside this range may be set. It goes without saying that the surface / chemical sensitization of the core / shell silver halide grains is carried out to such an extent that the core / shell silver halide grains do not impair the characteristics of the internal latent image type. The term "characteristics as an internal latent image type" as used herein means that a silver halide emulsion is coated on a transparent support and exposed to light for a fixed time of 0.01 to 10 seconds to give a developer A (internal type developer) described below.
The maximum density measured by the usual photographic density measuring method when developed at 20 ° C. for 3 minutes was the same as that of the silver halide emulsion exposed in the same manner as the following developing solution B (surface type developing solution).
The maximum density obtained when developed at 20 ° C for 4 minutes in
Having at least 5 times greater concentration.

Such core / shell type silver halide grains of the present invention are dispersed in a binder as is well known.

As the binder, gelatin is advantageously used, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein:
It is possible to use cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, cellulose sulfates and the like, sugar derivatives such as sodium alginate and starch derivatives.

As gelatin, lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan.No.16, p.30 (1966)
Oxygenated gelatin as described in may be used,
Also, a hydrolyzate or an oxygen hydrolyzate of gelatin can be used. Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds. What is used is used. Specific examples thereof are U.S. Patents 2,614,928 and 3,132,945.
No. 3,186,846, No. 3,312,553, British Patent 861,414
No. 1, No. 1,033,189, No. 1,005,784, Japanese Patent Publication No. 42-26845
No. etc.

As the gelatin-grafted polymer, a single (homo) or copolymer of a vinyl monomer such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile and styrene is grafted onto gelatin. Can be used. In particular,
Graft polymers with polymers having a certain degree of compatibility with gelatin, for example, polymers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, and hydroxyalkyl methacrylate are preferred. Examples of these are described in U.S. Pat. Nos. 2,763,625, 2,831,767, and 2,956,884.

The internal latent image type silver halide photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like.
Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes and complex merocyanine dyes. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; Nucleus fused with an aromatic hydrocarbon ring, i.e., indolenine nucleus, benzoindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole A nucleus and a quinoline nucleus can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
2,4-dione nucleus, thiazolidine-2,4-dione nucleus,
A 5- to 6-membered heterocyclic nucleus such as a rhodanine nucleus and a thiobarbituric acid nucleus can be applied.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. For example, aminostilbene compounds substituted with a titanium-containing heterosensitive group (for example, those described in U.S. Pat.Nos. 2,933,390 and 3,635,781), aromatic organic acid formaldehyde condensates (for example, those described in U.S. Pat. It may contain a cadmium salt, an azaindene compound or the like. US Patents 3,615,613, 3,615,641, 3,617,295,
The combination described in U.S. Pat. No. 3,635,721 is particularly useful.

To prepare a direct positive photographic light-sensitive material using an internal latent image type silver halide photographic emulsion, the photographic emulsion is coated on a support together with other photographic layers if necessary. In this case, two or more types of internal latent image type silver halide grains having different sizes may be mixed and coated on the same layer, or two or more types of different grain may be divided into two or more different layers. May be applied.

Although the coating amount is arbitrary, it is usually coated so that the total amount of silver per square foot of the support is about 40 mg to 800 mg.

Support is Research Disclosure vol.176 (1978, XII)
Those described in RD-17643 [XVII] can be used.

The internal latent image type silver halide photographic emulsion of the present invention has, for example, a polyalkylene oxide or a derivative thereof such as an ether, an ester or an amine, a thioether compound, a thiomorpholine or a quaternary compound for the purpose of increasing sensitivity, increasing contrast or promoting development. It may contain an ammonium salt compound, a urethane derivative, a urea derivative, an imidazole derivative, 3-pyrazolidones and the like. For example, U.S. Patent 2,400,532
No. 2,423,549, 2,716,062, 3,617,280,
Those described in No. 3,772,021 and No. 3,808,003 can be used.

The internal latent image type silver halide photographic emulsion of the present invention may contain an antifoggant (Antifoggant) and a stabilizer (Stabilizer). As a compound, Reseach Disclosure vol.176
(1978, XII) RD-17643 [VI] can be used.

The internal latent image type silver halide photographic emulsion of the present invention may contain a developing agent. As a developing agent, Reseach Disclosure v
Those described in the section of ol.176 (1978, XII) RD-17643 [XX] can be used.

The internal latent image type silver halide photographic emulsion of the present invention can be dispersed in a colloid which can be hardened by various organic or inorganic hardeners. As a hardener, Reseach Disclosure vo
Those described in the section of l.176 (1978, XII) RD-17643 [X] can be used.

The internal latent image type silver halide photographic emulsion of the present invention may contain a coating aid. As a coating aid, Reseach Disclosure v
Those described in the section of ol.176 (1978, XII) RD-17643 [XI] can be used.

The internal latent image type silver halide photographic emulsion of the present invention can contain a so-called color coupler. As a color coupler, Reseach Disclo sure vol.176 (1978, XII)
Those described in the section of RD-17643 [VII] can be used.

The internal latent image type silver halide photographic emulsion of the present invention also comprises an antistatic agent, a plasticizer, a matting agent, a lubricant, an ultraviolet absorber,
It may contain a fluorescent whitening agent, an air antifoggant and the like.

The light-sensitive material produced by using the internal latent image type silver halide photographic emulsion of the present invention may contain a dye in the photographic emulsion layer or other hydrophilic colloid layer as a filter dye or for various purposes such as prevention of irradiation. . As such a dye, Reseach Disclosure vol.176 (19
78, XII) RD-17643 [VII] is used.

The internal latent image type silver halide photographic emulsion of the present invention produces a reversal image by developing in the presence of a fog-inhibiting agent (nucleating agent) or under whole exposure. As the fog-reducing agent that can be used, U.S. Patent Nos. 2,588,982, and 2,
Hydrazines described in 563,785; hydrazides and hydrazones described in 3,227,552; British Patent 1,28
3,855, Japanese Patent Publication No. 49-38164, U.S. Patent No. 3,615,615,
No. 3,719,494, No. 3,734,738, No. 4,094,683, No. 4,1
Quaternary salt compounds described in 15,122, US Pat. No. 3,718,
Nucleating as described in No. 470
Sensitizing dyes having a substituent in the dye molecule; US Pat. No. 4,030,
Representative examples are the acylhydrazinophenylthiourea compounds described in JP-A Nos. 925 and 4,031,127, and the acylhydrazinophenyl urea compounds described in JP-A-57-86829. Other examples include compounds described in U.S. Pat. No. 4,139,387, JP-A-54-133126 and JP-A-54-74729.

The amount of the fog-providing agent used here is preferably an amount which gives a sufficient maximum density when the internal latent image type silver halide emulsion of the present invention is developed with a surface developing solution. The fogging agent is preferably added to the photographic emulsion layer or an adjacent layer.

There is also a method of exposing the entire surface during processing without using a fogging agent.

The light-sensitive material of the present invention can be used as a black and white direct positive photographic light-sensitive material having a single layer or multiple layers, a multi-layered reversal color photographic light-sensitive material, a multi-layered color diffusion transfer light-sensitive material.

For developing the light-sensitive material of the present invention, various known developing agents can be used. That is, polyhydroxybenzenes such as hydroquinone, 2-chlorohydroquinone, 2-methylhydroquinone, catechol, pyrogallol, etc .; aminophenols such as p-aminophenol, N-methyl-p-aminophenol, 2,4-diaminophenol, etc. 3-pyrazolidones, for example 1-phenyl-3-pyrazolidones, 1-phenyl-4,4'-dimethyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 5, 5-Dimethyl-1-phenyl-3-pyrazolidone and the like; ascorbic acids and the like can be used alone or in combination. Further, the developing solution described in Japanese Patent Application No. 56-154116 can also be used. To obtain a dye image in the presence of a dye-forming coupler, an aromatic primary amine developing agent,
Preferably, a p-phenylenediamine type developing agent can be used. Specific examples thereof include 4-amino-3-methyl-N, N-diethylaniline hydrochloride, N, N-
Diethyl-p-phenylenediamine, 3-methyl-4-
Amino-N-ethyl-N-β- (methane-sulfoamido) ethylaniline, 3-methyl-4-amino-N-ethyl-N- (β-sulfoethyl) aniline, 3-ethoxy-4-amino-N-ethyl These are -N- (β-sulfoethyl) aniline and 4-amino-N-ethyl-N- (β-hydroxyethyl) aniline. Such a developer may be included in the alkaline processing composition (processing element) or in a suitable layer of the photosensitive element.

The developer may contain, as a preservative, sodium sulfite, potassium sulfite, ascorbic acid, reductones (eg piperidinohexose reductone) and the like.

The light-sensitive material of the present invention can directly obtain a positive image by developing with a surface developing solution. Surface developers are those in which the development process is substantially induced by latent images or fog nuclei on the surface of the silver halide grains. Although it is preferable that the silver halide dissolving agent is not contained in the developing solution, as long as the internal latent image does not substantially contribute until the development by the surface development center of the silver halide grains is completed, the silver halide dissolving agent (for example, sulfurous acid) is used. Salt).

The developer may contain an alkali agent and a buffer such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, trisodium phosphate, sodium metaborate and the like. The content of these agents is selected so that the pH of the developer is 10 to 13, preferably pH 11 to 12.5.

The developer may also include, for example, benzimidazoles such as 5 to minimize the minimum density of direct positive images.
-Nitrobenzimidazoles; benzotriazoles,
It is advantageous to include a compound usually used as an antifoggant such as benzotriazole and 5-methyl-benzotriazole.

〔Example〕

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited thereto.

Example An aqueous solution of silver nitrate and potassium bromide was added gently and mixed in the presence of 170 mg of potassium hexachloroiridate per mole of silver, and mixed to obtain 0.15 μm core silver halide grains. To this, 30 mg of lead acetate was added per mol of silver, and the mixture was heated to 70 ° C. An aqueous solution of silver nitrate and potassium bromide was added to this to grow crystals, and finally a core / shell type silver halide emulsion having an average edge length of 0.3 μm was prepared. (Emulsion I) In substantially the same procedure as in Emulsion I, core silver halide grains containing 120 mg of potassium hexachloroiridate having a core silver halide grain size of 0.3 μm per 1 mol of silver were obtained, and then 150 mg of lead acetate was added per 1 mol of silver. Then, an aqueous solution of silver nitrate and potassium bromide was added to prepare a 0.45 μm core / shell type silver halide emulsion.

(Emulsion II) Emulsions I and II were mixed in equal weights, and fog 1
-Formyl-2- {4- (3-phenylureido) phenyl] hydrazine (150 mg / mol of silver) was added and coated on a polyethylene terephthalate support so that the amount of silver would be 3000 mg / m ² , and further protected with gelatin. The layers were applied to directly prepare a positive photographic light-sensitive material (Sample A).

Sample A except that the amount of rash agent added was increased 1.5 times.
Sample B was prepared in the same manner as in.

Further, a 1 wt% methanol solution of 5-methylbenzotriazole was added to a gelatin aqueous solution, and the obtained coating solution was applied to the back side of the support of Sample B so that the coating amount of 5-methylbenzotriazole was 10 mg / m ^2. A direct positive photographic light-sensitive material (Sample C) of the present invention was prepared by coating.

These samples were exposed to a 1KW tungsten lamp at a color temperature of 2854 ° K for 1 second through a step wedge, and a developing solution D prepared by mixing the following replenishing solution A1 and starter B20 ml was used.
Development was carried out at 36 ° C. for 1 minute with an automatic processor (FMCP-4800 type camera processor: manufactured by Fuji Photo Film Co., Ltd.), and then the usual methods of stopping, fixing, washing with water, and drying were carried out. The maximum concentration (Dmax) and sensitivity of each sample were measured, and the results are shown in Table 1. Replenisher A Sodium sulfite 100g Potassium carbonate 20g 1-phenyl-4-methyl-4-hydroxymethyl-3
-Pyrazolidone 3g Hydroquinone 45g 5-Methylbenzotriazole 40mg Water is added to adjust the pH to 11.8 with potassium hydroxide Starter B Sodium bromide 175g Glacial acetic acid 63ml Water is added 1 On the other hand, all the above samples A, B and C are added. 70% of the coated silver amount is exposed so that it is blackened by the development,
Using D5, and automatically adding 6.25 ml of replenisher A per sample (105 mm x 145 mm size) with the automatic processor
800 sheets were continuously developed.

Samples A and B exposed using a developing solution fatigued by this running process with a tungsten lamp of 1 kW at a color temperature of 2854 ° K for 1 hour through a step wedge as described above.
And C respectively, and then the usual stop, fixing,
It was washed with water and dried. The maximum concentration (Dmax) and sensitivity of each sample were measured, and the results are shown in Table-1.

Also, the concentration of 5-methylbenzotriazole in each developer was measured by liquid chromatography (using an eluent consisting of acetonitrile and triethylamine) using a PEG column (developing solution / polyethylene glycol), and the results are shown in Table-2. Indicated.

As shown in Tables 1 and 2, stable photographic characteristics were obtained in the photosensitive material-automatic development system in which the sample A was automatically developed by the developer D (and the replenisher A). That is, this system was established.

Where developer D (and replenisher A) of the above system
In an attempt to create a photosensitive material-automatic development system in which the sample B was used in combination with the new sample B, when the sample B was developed with a fatigue solution after processing 800 sheets of the sample B, Dmax was increased and the sensitivity was increased. It dropped significantly. That is, stable photographic characteristics were not obtained, and this system was not established.

On the other hand, in the photosensitive material-automatic developing system in which the sample C in which 5-methylbenzotriazole is coated on the back side of the support having no relation to the photographic performance and the developer D (and the replenisher A) are combined as in the present invention, Even after treating 800 sheets of sample C, the concentration of 5-methylbenzotriazole was almost unchanged even in the fatigue solution, and its photographic performance was almost the same as that when the new solution was used. Therefore, it can be seen that the system in which the sample C and the developing solution D of the present invention are combined can provide stable photographic performance.

Example 2 Core / shell type emulsions III, IV and V were prepared by the following method.

Emulsion III An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to a gelatin aqueous solution under vigorous stirring at the same time for about 20 minutes while controlling the pAg to 7.90 at 40 ° C, and cubic monodisperse with an average particle size of 0.08 μm. A silver bromide emulsion was obtained. 580 mg of sodium thiosulfate chloroauric acid (tetrahydrate) per mol of silver was added to this emulsion, and the mixture was heated at 75 ° C. for 80 minutes for chemical sensitization. Using the thus obtained silver bromide grain emulsion as a core, grains were grown in the same manner as in the first precipitation environment to finally obtain a core / shell monodisperse cubic silver bromide emulsion having an average grain size of 0.18 μm. After washing with water and desalting, 6.2 mg of sodium thiosulfate and chloroauric acid (4 mol per mol of silver) were added to this emulsion.
Aqueous salt) was added and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization to obtain Emulsion III.

Emulsion IV An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous gelatin solution under vigorous stirring for about 40 minutes while controlling the pAg to 9.70 at 45 ° C, and the average particle size was 0.2 μm. To obtain an octahedral silver bromide emulsion.
Chemical sensitization treatment was carried out by adding 5 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver to this emulsion and heating at 75 ° C. for 80 minutes. The silver bromide particles thus obtained are used as a core to further grow by further treating in the same precipitation environment for 40 minutes, and finally an octahedral monodispersed core / shell silver bromide emulsion having an average particle diameter of 0.35 μm I got To this emulsion was added 4.5 mg of sodium thiosulfate and 1 mol of silver chloroauric acid (tetrahydrate) per mole of silver, and the mixture was heated at 65 ° C.
The mixture was heated for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion IV.

Emulsion V An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were added to an aqueous solution of gelatin with vigorous stirring while controlling the pAg to 8.60 at 75 ° C over a period of about 40 minutes, and the average particle size was 0.4 µm. An octahedral monodisperse silver bromide emulsion was obtained. Chemical sensitization treatment was carried out by adding 4 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) per mol of silver to this emulsion and heating at 75 ° C. for 80 minutes. The silver bromide grains thus obtained are used as cores for further growth for 40 minutes in the same precipitation environment as the first time.
Finally, an octahedral monodispersed core / shell silver bromide emulsion having an average particle diameter of 0.6 μm was obtained. After washing with water and desalting, 0.9 mg of sodium thiosulfate per mol of silver was added to this emulsion and the mixture was heated at 65 ° C. for 60 minutes for chemical sensitization to obtain an internal latent image type silver halide emulsion V.

Anti-halation dyes A, B, on a support made of 100 μm thick undercoated polyethylene terephthalate
Antihalation layer coated with C at 65 mg / m ² , 80 mg / m ² , 40 mg / m ² and gelatin at 5 g / m ² and barium strontium sulfate with an average particle size of 1.0 μm as a matting agent and an average Coating aid D is 30 mg / m ² and charge control agent E is 1 mg / m on poly (methyl methacrylate) having a particle size of 1.3 μm.
² and further, a protective layer (upper layer) consisting of 100 mg / m ^{2 of} hardener F and 1 g / m ^{2 of} gelatin was applied to complete a pack layer of 2 layers.

Sensitizing dye G was added to core / shell emulsions III, IV and V in amounts of 150 mg, 200 mg and 180 mg, respectively, relative to 1 mol of silver, and a foggant H was added to 110 mg and 83 mg, respectively, of 1 mol of silver.
mg and 150 mg were further added, and sodium dodecylbenzenesulfonate as a coating aid and a thickener were added to balance the surface tension and the viscosity, to prepare coating solutions for the first to third layers.

Further, a charge controlling agent E, a coating aid sodium dodecylbenzenesulfonate and a thickener were added to gelatin to prepare a coating solution for the fourth protective layer.

With respect to the back layer, the first to
Four layers sequentially coated silver amount of the first layer 1 g / m ² of the second layer 0.8 g / m ^2, third layer 1.5 g / m ^2, also the coating amount of gelatin first layer 1.3 g / m ^2, the The emulsion layers were multi-layered so that the second layer was 1.3 g / m ² , the third layer was 2.4 g / m ² , and the fourth layer was 1.7 g / m ^2, and the direct positive photographic light-sensitive material of the comparative example (Sample D) was used. It was made.

A direct positive photographic light-sensitive material (Sample E) of the present invention was prepared in the same manner as Sample D except that 12 mg / m ² of 5-methylbenzotriazole was added to the antihalation layer of the back layer.

These samples D and E were exposed, developed, fixed and washed with water in the same manner as in Example 1, and 800 sheets of each of the photosensitive materials were continuously developed in the same manner as in Example 1 with a fatigued developer. It was exposed, developed, fixed and washed again with water. The maximum concentration and sensitivity of each sample were measured, and the results are shown in Table-3.

From Table 3, it is understood that stable photographic performance can be obtained in the system in which the photosensitive material E of the present invention, the developing solution D, and the replenishing solution A are combined.

(Effect of the Invention) According to the present invention, a direct positive photographic light-sensitive material which can obtain stable photographic characteristics even when an existing developer is used in a running process by an automatic processor is obtained.

Claims (1)

(57) [Claims] 1. A support is coated on one side with an inner nucleus of silver halide doped with metal ions, chemically sensitized, or both, and at least a photosensitive site of the inner nucleus. A direct positive photographic light-sensitive material having at least one inner latent image type silver halide emulsion layer containing a core / shell type silver halide grain consisting of an outer shell and a binder. A photographic material for direct positive use, having at least one layer containing benzotriazoles on the side opposite to the silver halide emulsion layer.