JPH03181938A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a row preservation property by incorporating 80mol% silver chloride into internal latent image type silver halide particles and sensitizing the particles with a specific sensitizing dye. CONSTITUTION:This photosensitive material is formed by incorporating >=80mol% silver chloride into the internal latent image type silver halide particles, forming the photosensitive layer of the same photosensitive region in such a manner that the particle distribution has at least two peaks as a whole and sensitizing the photosensitive layer with the sensitizing dye expressed by, for example, formula I. In the formula I, Z<11> denotes a sulfur atom or selenium atom; Z<12> denotes the nonmetal atom group necessary for forming a benzothiazole ring, benzoselenazole ring, etc.; R<11>, R<12> respectively denote an alkyl group or substd. alkyl group; R<13> denote an alkyl group, aryl group, furyl group, etc.; X1 denotes anion; l1 denotes 1 or 2. The increase in fogging in the case of preservation without exposing is lessened and the softening of the gradation at leg parts is lessened as well. The deterioration of the contents in the case of row preservation over a long period of time is eliminated.

Description

Detailed Description of the Invention [Industrial Field of Application] The present invention relates to a direct positive halide photosensitive material that directly forms a positive image by imagewise exposing a silver halide photographic material and then developing it, including fogging treatment. This invention relates to silver oxide photographic materials.

[Background of the Invention] Conventionally, as a method for directly obtaining a positive image, an internal latent image type silver halide emulsion that has not been fogged in advance is used, and after image exposure, capri processing (development nucleation processing) is performed, and then surface development is performed. Alternatively, after image exposure, a method is known in which surface development is performed while performing fogging treatment (development nucleation treatment).

The above fogging treatment (development nucleation treatment) may be carried out by exposing the entire surface to light, or may be carried out chemically using a fogging agent, or may be carried out using a strong developer. Heat treatment or the like may also be used.

The above-mentioned method for forming a positive image has the following advantages compared to the conventional method of using a silver halide emulsion having fog nuclei and directly obtaining a positive image after development using solarization or the Barschel effect. High sensitivity within the shell;
Suitable for applications requiring high sensitivity.

Ordinarily produced silver halide emulsions are sensitive to short wavelength light such as ultraviolet rays and blue light, but are not sensitive to longer wavelength light, so they are made using panchromatic sensitizing dyes. This extends the photosensitive wavelength range to longer wavelengths, extending the photosensitive wavelength range to the entire visible light range.

Internal latent image type silver halide emulsions can also have their sensitive wavelength range extended to longer wavelengths by the same means as above, but if a panchromatic sensitizing dye with a specific structure is used,
When a photosensitive material is stored for a long period of time, there is a problem in that fog increases and the gradation of the legs becomes softer. In particular, softening the gradation of the legs increases the density of the background and significantly degrades the image.

[Object of the Invention] Accordingly, an object of the present invention is to provide a direct positive silver halide photographic light-sensitive material with improved shelf life.

[Structure of the Invention] The above object of the present invention is to provide a direct positive silver halide photograph having on a support at least one silver halide emulsion layer for direct positive image formation containing internal latent image type silver halide grains. In a light-sensitive material, the internal latent image type silver halide grains contain at least 80 mol% of silver chloride as a whole, and the internal latent image type silver halide grains are contained in a photosensitive layer in the same photosensitive area. The overall particle distribution is at least 2
In addition, the internal latent image type silver halide grains have the following general formula [I], general formula [II], general formula [
This was achieved by a photographic light-sensitive material characterized in that it is sensitized with at least one sensitizing dye selected from the sensitizing dyes represented by II[] and general formula [IV].

The following Kanayama general formula [I] [In the formula, Zll represents a sulfur atom or a selenium atom, and Z
12 is a benzothiazole ring, a benzoselenazole ring, a naphtho(1,2-d]thiazole ring, or a naphtho(12-
dl Represents a group of nonmetallic atoms necessary to form a selenazole ring.

R'' and R'' each represent an alkyl group or a substituted alkyl group, and at least one of R'' and R12 has a sulfo group.

R13 represents an alkyl group, an aryl group, a furyl group or a thienyl group.

Xl represents an anion. g represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ] General formula [] [In the formula, R2° R21 each represents an alkyl group or a substituted alkyl group.

Z20 and Z21 each represent a group of nonmetallic atoms necessary to form a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, a naphthoxazole ring, or a quinoline ring.

Q20 is a pyrazolone ring, indanedione ring, 5(4H)
-isoxacilone ring, 2,4-chromandione ring, 4
．． 6- (LH,5H)pyrimidinedione ring, barbital acid ring, 2-thiobarbital acid ring, 1.3-dioxane-4,6-dione ring, 3.5-pyrazolidinedione ring, 3H-naf 0 1- (2,1-bl pyran-1,3(2H)-
dione ring, 5(4H)-isoxacilone ring, rhodanine ring, hydantoin ring, thiohydantoin ring or 1,
represents a nonmetallic atom group necessary to form a 3-cyclobutanedione ring, A'' represents an oxygen atom or a sulfur atom,
n 2 , d 2 and m2 each represent 1 or 2. ] General formula [III] [In the formula, R30 and R31 each represent an alkyl group or a substituted alkyl group.

D3Q represents a group of nonmetallic atoms necessary to form a 6-membered ring consisting of three methylene groups.

z30 and z31 represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle.

X represents an anion.

1 p3 and q3 represent O or l5n3 represents 1 or 2.

13 represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ] General formula [IV] In formula E, Y" and Y" each represent a group of nonmetallic atoms necessary to form a heterocycle.

R40 and R41 each represent an aliphatic group.

R'' represents a halogen atom or an alkyl group.

X4 represents an anion.

m, , R4 represents 1 or 2.

ρ4 represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ] Hereinafter, the present invention will be explained in detail.

First, a silver halide emulsion for direct positive image formation containing internal latent image type silver halide grains used in the present invention will be explained.

Internal latent image type silver halide grains mainly form latent images inside the silver halide grains.

A preferred silver halide emulsion for direct positive image formation containing internal latent image type silver halide grains of the present invention is a sample in which a silver halide emulsion is coated on a transparent support.
Exposure to a light intensity scale for a defined period of time up to about 1 second for 4 minutes at 20° C. using Surface Developer A, described below, which contains substantially no silver halide solvent and develops only the surface of the grains. When developed, the maximum density is not greater than 175, which is the maximum density obtained when the same sample is exposed in the same manner as above and developed for 4 minutes at 20°C using the following internal developer B that can develop the inside of the particles. This indicates the maximum concentration.

Particularly preferred is one in which the maximum density obtained using surface developer A is l// of the maximum density obtained using internal developer B.
10 or less.

3 (Surface developer A) Metol 2.5gL-ascorbic acid logNaBOz ”4H20
35g KBr 1, add water B (internal developer B) Metol 2.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone 8.0g Sodium carbonate hydrate 52.5gK B r
5.0g K I
Add 0.5g water
11) The internal latent image type silver halide emulsion of the present invention can be prepared by various methods. For example, conversion silver halide emulsions described in U.S. Pat. No. 2,592,250, U.S. Pat. No. 3,208,318, U.S. Pat. No. 3,317,
Silver halide emulsions having internally chemically sensitized silver halide grains as described in U.S. Pat. No. 322 and U.S. Pat. No. 3,387,778;
Specification No. 3.447.927 and No. 3.531,
A silver halide emulsion having silver halide grains containing polyvalent metal ions as described in No. 291;
A silver halide emulsion in which the grain surface of silver halide grains containing a dopant is weakly chemically sensitized as described in U.S. Pat. No. 3,761.278, JP-A-50-852
Publication No. 4, Publication No. 50-8525 and Publication No. 53-240
There are silver halide emulsions comprising grains having a layered structure as described in Japanese Patent Publication No. 8, and other silver halide emulsions described in Japanese Patent Application Laid-open Nos. 52156-14 and 55-127549.

The object of the present invention can be achieved by setting the silver chloride content in the silver halide grains to 80 mol% or more, more preferably 90 mol% or more.

Internal latent image type silver halide grains containing silver chloride have poor developability and can be processed quickly.

One example of preferable internal latent image type silver halide grains according to the present invention is one having a laminated structure.

The expression "silver halide grains have a laminated structure" means that the silver halide grains have two or more adjacent layers having different halogen compositions, and more preferably, the laminated structure has clear boundaries. It is formed by having.

The laminated structure of silver halide grains is formed, for example, by forming a core/shell type consisting of a core and a shell each having a different halogen composition.

It is preferable that the silver halide compositions of two adjacent layers differ in silver chloride content by 20 mol % or more.

Silver halide grains having a laminated structure can be obtained by further growing and coating silver halide on the surface of a silver halide core grain.

In this case, the surface of the core grain is preferably covered with the grown silver halide to cover 50% or more of the surface area of the core grain, more preferably completely.

6 Generally, when growing a layer with a different silver halide composition on the surface of a silver halide grain, for example, when growing a layer by adding a water-soluble silver ion solution and a water-soluble halide ion solution, a new layer is simply added to the grain surface. Not only does the silver halide grow, but the silver halide grains themselves tend to redissolve and recrystallize, creating a transition layer in which the silver halide content changes continuously and making the boundary surface unclear. There is.

In the silver halide grains of the present invention, it is preferable to obtain a clear layered structure by minimizing the transition layer of the silver halide content due to the obscuring of the layered structure due to redissolution or the like as described above.

In order to suppress the transition layer and obtain a well-defined layered structure, for example, the supply rate of the silver halide forming raw material is varied according to grain growth to reduce recrystallization.

Also, silver halide growth conditions, temperature, pAg, pH
It is also preferable to control the following to suppress the layer structure from becoming unclear due to recrystallization. Furthermore, in the preparation of silver halide using a silver halide solvent (7), the optimum conditions can be achieved by controlling the type and amount of the silver halide solvent, as well as the usage conditions such as pH. You can choose.

In the case of a well-defined layer structure, the diffraction peak due to the layer with high silver chloride content and the diffraction peak due to the layer with low silver chloride content are generally separated in the curve of diffraction intensity versus diffraction angle in X-ray diffraction. and there is a minimum part in between, and the intensity of the minimum part is 80% or less of the smaller of the peak of the layer with high silver chloride content and the peak of the layer with low silver chloride content. It has become.

The total silver chloride content in the silver halide grains may be 80 mol % or more. The upper limit of silver chloride content is 1
It can be brought as close as possible to 00%.

The silver halide grains may have a layer with a high content of silver chloride on the inside and a layer with a low content of silver chloride on the surface, or a layer with a low content of silver chloride on the inside and a layer with a low silver chloride content on the surface. It may be a layer having a high silver chloride content.

Further, the silver halide grains may have a layer structure of three or more layers.

Each layer may have a structure in which the silver halide composition changes continuously, but it is necessary that a boundary surface such as a transition layer be formed between the layers.

The laminated silver halide grains of the present invention may contain silver chloride in at least one of its constituent layers. Silver halides in other constituent layers may be appropriately selected from silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride, etc., which are usually used in silver halide emulsions. Can be used. However, it is preferable that each emulsion layer constituting the photographic material contains silver chloride.

Further, as another example of preferable internal latent image type silver halide grains according to the present invention, cores containing polyvalent metal ions or chemically sensitized cores are coated with silver halide shells. /shell type silver halide grains.

In this case, the core and shell may have the same silver halide composition, or may have different silver halide compositions. At least 80 mol% of the particles as a whole
The silver halide compositions of the core and shell are arbitrary as long as these conditions are met. , silver chloroiodide, silver iodobromide, and silver chloroiodobromide.

The silver chloride content of the core and shell may be the same or different.

The shapes of the particles are cubic, octahedral, ('100) and (i
ll) Any shape, such as a tetradecahedron consisting of a mixture of faces, a shape with (110) faces, a spherical shape, a flat shape, a shape with a protrusion on the surface, a shape with a depression on the surface, or a mixture of these. good.

The core of the silver halide grains of the present invention may be chemically sensitized or doped with metal ions. Many methods are known for chemical sensitization. That is, sensitization methods include sulfur sensitization, gold sensitization, reduction sensitization, noble metal sensitization, and combinations of these sensitization methods. As the sulfur sensitization method, thiosulfates, 0 thioureas, thiazoles, rhodanines, and other compounds can be used. Such methods are described, for example, in US Pat. No. 1,574.944, US Pat. No. 1,623,499, US Pat. l1t5B, 955
It is stated in the number etc.

The core of the silver halide grains used in the present invention is, for example, US Pat.
No. 2,642.3 [! As described in No. 1, etc., sensitization can be carried out with a water-soluble gold compound or with a reduction sensitizer. Such methods are described, for example, in U.S. Pat. No. 2,487.850;
518. Reference can be made to the descriptions in No. f198, No. 2,983,610, etc.

Furthermore, noble metal sensitization can also be carried out using noble metal compounds such as platinum, iridium, palladium, and the like. Such methods are described, for example, in U.S. Pat.
8.080 and British Patent No. 818,081.

The core of the silver halide grains in the present invention can be doped with metal ions. To dope the core with metal ions, it can be added as a water-soluble salt of the metal ion, for example, during any process of forming the core particle. Preferred specific examples of metal ions include metal ions such as iridium, lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions are preferably used in an amount of IX 10-8 to 1 mole of silver.
IX is used at a concentration of 10-4 molar.

In the direct positive silver halide photographic material of the present invention, the grain distribution curve of the silver halide grains contained in the photosensitive layer in the same photosensitive region has at least two peaks as a whole. It is necessary.

The method for measuring particle size distribution will be described in detail below.

In the case of spherical silver halide grains, the grain size of silver halide emulsion grains referred to here refers to the diameter of the silver halide grains, and in the case of silver halide grains having shapes other than spherical, the projected image of the same area is It means the diameter when converted into a circular image. The grain size can be obtained, for example, by photographing silver halide grains with an electron microscope at a magnification of 10,000 to 50,000 times, and actually measuring the grain diameter or projected area on the print.

(The number of particles to be measured is assumed to be 1000 or more indiscriminately.) The product n1X of the frequency n of particles with particle size r and r, 3
When r,' is plotted against r, n1Xr13
The peak of the particle distribution curve in the present invention is defined as the peak of the particle distribution curve in the present invention.

The silver halide grains contained in the green photosensitive layer according to the present invention need to have a grain size distribution curve with at least two peaks, but more preferably have a grain size distribution curve with at least three peaks. It has the following.

In the present invention, the peaks in the grain size distribution curve are silver halide grains within a grain size range of ±20% around the grain size of each peak, although the size of each peak is not particularly limited. The weight of the silver halide grains is preferably at least 5% of the total weight of the silver halide grains. More preferably 10%
That's all.

In the grain size distribution curve 3 of the silver halide grains in the present invention, there is no particular restriction on how far apart adjacent peaks are in terms of grain size, but at least the grain size is based on the larger grain size. It is preferable that the peak particle sizes are separated by 0% or more of the particle size.

The photosensitive layer according to the present invention preferably contains at least two types of silver halide emulsions having different average grain sizes. When the photosensitive layer is a single layer, in one preferred embodiment, the core layer contains at least two types of silver halide emulsions having different average grain sizes. In addition, when there are multiple photosensitive layers, even if the particle size distribution is the same in each layer,
Although they may be different, it is sufficient that the particle size distribution curve as a whole has at least two peaks.

A silver halide emulsion in which the grain distribution curve of silver halide grains has at least two peaks as a whole is, for example, a silver halide emulsion in which the grain distribution curve has one peak having two or more different average grain sizes. It can be obtained by mixing emulsions.

4 In addition, when two or more photosensitive layers in the same photosensitive region, for example, red-sensitive layers, are provided, a silver halide emulsion having at least two peaks in the grain distribution curve may be used in each layer. However, it is also possible to use silver halide emulsions with different average grain sizes and one peak in the grain distribution curve in each layer, and to reduce the total silver halide grains including two or more photosensitive layers. The distribution curve may have at least two peaks.

The average grain size of the silver halide emulsion with the largest average grain size among the two or more silver halide emulsions having one peak in the grain distribution curve used in the above mixture or in each layer is the average grain size. is preferably 10% or more, more preferably 20% or more larger than the average grain size of the smallest silver halide emulsion.

As the silver halide emulsion whose grain distribution curve has one peak, any grain size distribution can be used.

An emulsion with a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion with a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone. A mixture of several types of these may be used. Further, a mixture of a polydisperse emulsion and a monodisperse emulsion may be used. However, it is preferred to use monodisperse emulsions.

A monodisperse emulsion is one in which the coefficient of variation in the grain size distribution of silver halide grains contained in the emulsion is 22% or less, preferably 15% or less.

The size of a silver halide grain is expressed by its diameter in the case of a spherical particle, and by the diameter of a circle with an area equal to the projected area of the particle in the case of particles of other shapes. These can be measured by observation using an electron microscope.

The silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Further, a silver halide emulsion containing the silver halide grains may be prepared by simultaneously mixing halide ions and silver ions, or by mixing one of them in an acid in which the other is present.

6 Silver halide grains may also be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pHS pAg in the mixing pot, taking into account the critical growth rate of silver halide crystals. . By this method, silver halide grains with regular crystals and nearly uniform grain size can be obtained.

It is also possible to change the halogen composition of the particles using a conversion method after growth.

The shapes of silver halide grains are cubic, octahedral, (100
A tetradecahedron consisting of a mixture of ) and (ill) faces, (110
) It may have a shape with a surface, a spherical shape, a flat shape, etc. The average particle size is preferably from 0.05 μm to 3 μm.

As the binder (or protective colloid) for the silver halide emulsion of the present invention, it is advantageous to use gelatin, but other materials include gelatin derivatives, graft polymers of gelatin and other polymers, proteins, sugar derivatives, cellulose. Derivatives, synthetic hydrophilic polymer substances (single or copolymers)
Hydrophilic core oids such as the like can also be used.

The silver halide emulsion in the present invention can be chemically sensitized by a sulfur bottle sensitization method, a selenium sensitization method, a reduction sensitization method, a noble metal sensitization method, or the like.

Next, general formula [■] used in the present invention, general formula [II
], the sensitizing dyes represented by the general formula [I[r] and the general formula [IV] will be sequentially explained.

General formula [I] 13 [wherein 2+1 represents a sulfur atom or a selenium atom, z
I2 is a benzothiazole ring, a benzoselenazole ring, a naphtho[I,2-d]thiazole ring, or a naphtho(1,2
-d) Represents a group of nonmetallic atoms necessary to form a selenazole ring.

R11 and R12 each represent an alkyl group or a substituted alkyl group, and at least one of R and R12 has a sulfo group.

R13 represents an alkyl group, an aryl group, a furyl group or a thienyl group.

XI represents an anion. p represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ] In the above general formula [I], a benzothiazole ring, a benzoselenazole ring, a naphtho(1,2-d)thiazole ring or a naphtho(1,2-
The dl selenazole ring may have a substituent.

Examples of the substituents contained in the rings formed by these z12 include, for example, a halogen atom, an alkyl group, an alkoxy group, a carboxyl group, an acyl group, a hydroxyl group, a cyano group, and an aryl group.

Specific examples of these rings include, for example, benzothiazole, 5-chlorobenzothiazole, 5-bromobenzothiazole, 5-methylbenzothiazo9yl, 5-methoxybenzothiazole, 5-ethoxybenzothiazole, 6-methyl Benzothiazole, 6-chlorobenzothiazole, 5-carboxybenzothiazole, 5-acetylbenzothiazole, 5-methoxycarbonylbenzothiazole, 5-hydroxybenzothiazole, 5-trifluoromethylbenzothiazole, 5-
Cyanobenzothiazole, 5,6-dimethylbenzothiazole, 5-acetylaminobenzothiazole, 6methoxybenzothiazole, 5-ethoxy-6-methylbenzothiazole, 5,6-simethoxybenzothiazole,
5-hydroxy-6-methylbenzothiazole, 5.6
- benzothiazole rings such as dichlorobenzothiazole and 5-phenylbenzothiazole, benzoselenazole,
Benzoselenazole rings such as 5-chlorobenzoselenazole, 5-bromobenzoselenazole, 5-methylbenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, 5.6-dimethylbenzoselenazole, etc. can be mentioned.

Examples of the alkyl group represented by 0 R'' and R'' include methyl group, ethyl group, propyl group, i-propyl group, butyl group, and pentyl group.

These alkyl groups include substituents such as halogen atoms, hydroxy groups, alkoxy groups, carboxy groups, carbalkoxy groups, and sulfo groups, but R'' and R
At least one of t2 has a sulfo group.

Further, R-th and R12 may be the same or different.

Examples of the alkyl group represented by RI3 include methyl group,
Examples include lower alkyl groups such as ethyl group, propyl group, l-propyl group, and butyl group.

Examples of the aryl group represented by R1'l include a phenyl group.

The alkyl group, aryl group, furyl group or thienyl group represented by R'' includes those having substituents.

Examples of the anion represented by Xl include chloride ion, bromide ion, iodide ion, perchlorate ion, 1-paratoluenesulfonate ion, and ethyl sulfate ion.

When the dye represented by the general formula [I] forms an inner salt, g is 1, that is, X is not necessary.

General Formula [I1] [In the formula, R2° and R2+ each represent an alkyl group or a substituted alkyl group.

Z20 and z21 each represent a group of nonmetallic atoms necessary to form a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, a naphthoxazole ring, or a quinoline ring.

Q20 is a pyrazolone ring, indanedione ring, 5(4H)
-Isoxacylone ring, 2.4-chromanedione ring, 4.6-(IH,5H)pyrimidinedione ring, barbylic acid ring, 2-thiobarbyl ring formation, 1
, 3-dioxane-4,6-dione ring, 3,5-pyrazolidinedione ring, 3H-naphtho [2,1-bl pyran-1,3(2H)-dione ring, 5 (4H)-isoxacilone ring , represents a nonmetallic atom group necessary to form a rhodanine ring, hydantoin ring, thiohydantoin ring, or 1,3-cyclobutanedione ring, A'' represents an oxygen atom or a sulfur atom, and n2, d2, and m are Each represents 1 or 2.] R20 and R2+ may be the same or different, and the alkyl group has 1 to 8 carbon atoms, and the substituted alkyl group has 1 to 10 carbon atoms. is preferable. Examples of the substituent of the substituted alkyl group include a halogen atom, a hydroxyl group, an alkoxy group, an aryl group,
Examples include dialkylamino group, alkoxycarbonyl group, acyloxy group, cyano group, and acyl group.

Particularly preferred R20SR21 is an alkyl group having no substituent 3 group or an alkyl group having an alkoxy group.

The ring formed by z20 and Z21 includes a ring having a substituent.

Examples of substituents include halogen atoms, alkoxy groups,
alkoxycarbonyl group, alkyl group, acyl group, acyloxy group, hydroxyl group, trifluoromethyl group,
Examples include cyano group, sulfamoyl group, and carbamoyl group. When these substituents have carbon atoms, those having 1 to 8 carbon atoms are preferred.

At least one of the rings formed by Z20 and Z21 is a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, or a naphthoxazole ring (which contains a halogen atom, an alkoxy group, alkoxycarbonyl group,
It may be substituted with an alkyl group, an acyl group, an acyloxy group, a hydroxyl group, a trifluoromethyl group, a cyano group, a sulfamoyl group, a carbamoyl group, or the like. ) Tea 4 It is preferable.

Examples of the ring formed by Q20 include a barbyl ring, a 2-thiobarbylic acid ring, an indanedione ring, 2.
A 4-chromandione ring is preferred, and a barbituric acid ring is particularly preferred.

The ring formed by Q20 also includes a ring having a substituent.

Examples of substituents include those described for the ring formed by z20 and z2I.

It is preferable that n2, d2 and m2 are each 1.

General Formula [III] [In the formula, R30 and R31 each represent an alkyl group or a substituted alkyl group.

D30 forms a 6-membered ring consisting of three methylene groups 5 Represents the nonmetallic atomic group necessary to

Z30 and zil represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle.

X3 represents an anion.

1) 3, qj represents 0 or 1, and n3 represents 1 or 2.

p3 represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ] Examples of the substituent of the substituted alkyl group represented by R", R" include a hydroxyl group, an alkoxy group, a carboxyl group, a sulfo group, and a carbalkoxy group.

Examples of the alkyl group and substituted alkyl group represented by R3° and R31 include methyl group, ethyl group, propyl group, 2
-Hydroxyethyl group, 2-methoxyethyl group, carboxymethyl group, 2-carboxyethyl group, 3-carboxypropyl group, 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, carboethoxymethyl group,
Examples include 2-carbomethoxyethyl group and 2-carboethoxyethyl group 6 .

The nonmetallic atom group required to form a 6-membered ring consisting of three methylene groups represented by D'O may have a substituent such as an alkyl group (for example, a methyl group).

z30. The nitrogen-containing heterocycle formed by zil also includes one having a substituent.

Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxyl group↓ z30. The nitrogen-containing heterocycle formed by zil includes, for example, a benzothiazole ring (e.g., benzothiazole ring, 5-chlorobenzothiazole ring, 6-chlorobenzothiazole ring, 4-methylbenzothiazole ring, 5-chlorobenzothiazole ring,
-Methylbenzothiazole ring, 6-methylbenzothiazole ring, 5-phenylbenzothiazole ring, 6-methoxybenzothiazole ring, 4-ethoxybenzothiazole ring, 5-methoxybenzothiazole ring, 5-hydroxybenzothiazole ring, 6- Hydroxybenzothiazole ring, 5.6-simethoxybenzothiazole ring,
5.6-dimethylbenzothiazole ring), naphthothiazole ring (e.g. α-naphthothiazole ring, β-naphthothiazole), benzoselenazole ring (e.g. benzoselenazole ring, 5-chlorobenzoselenazole ring, 6-methyl benzoselenazole ring, 6-methylbenzoselenazole ring, zole ring, β-naphthoselenazole ring), benzoxazole ring (e.g. benzoxazole ring, 5-methylbenzoxazole ring, 6-methoxybenzothiazole ring, 5-phenylbenz oxazole ring), naphthoxazole ring (e.g. α-naphthoxazole ring, β
-naphthoxazole ring), 2-quinoline ring (e.g. 2
-quinoline ring, 6-methyl-2-quinoline ring, 6-chloro-2-quinoline ring, 5-ethoxy-2-quinoline ring),
4-quinoline ring (e.g. 4-quinoline ring, 6-methyl-
4-quinoline ring, 8-methyl-4-quinoline ring), 3.
Examples include 3-dialkylindolenine rings (Example 8, 3,3-dimethylindolenine ring, 3.3dimethyl-5-methylindolenine ring).

The nitrogen-containing heterocycles formed by Z30.231 may be the same or different.

Examples of the anion represented by X3 include chloride ion, bromide ion, iodide ion, perchlorate ion, paratoluenesulfonate ion, and ethylsulfate ion.

When the dye represented by the general formula [m] forms an inner salt, R3 is 1, that is, X3 is unnecessary.

General formula [IV] [wherein y40. y41 each represents a nonmetallic atomic group necessary to form a heterocycle.

three R'' and R'' each represent an aliphatic group.

R'' represents a halogen atom or an alkyl group.

X4 represents an anion.

m4 and n4 represent 1 or 2.

R4 represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ]Y40, the heterocycle formed by Y'' includes those having a substituent.

Examples of the substituent include an alkyl group, an aryl group, and an alkoxy group.

y40. Examples of the nitrogen-containing heterocycle formed by y41 include thiazole ring, benzothiazole ring (e.g. benzothiazole ring, 5-chlorobenzothiazole ring, 6-chlorobenzothiazole ring, 4-methylbenzothiazole ring, 5 -Methylbenzothiazole ring, 6-methylbenzothiazole ring, 5-phenylbenzothiazole ring, 6-methoxybenzothiazole ring, 4-ethoxybenzothiazole ring, 5-methoxybenzothiazole ring,
5-hydroxybenzothiazole ring, 6-hydro-oxybenzothiazole ring, 5,6-simethoxybenzothiazole ring, 5,6-dimethylbenzothiazole ring),
Naphthothiazole ring (e.g. α-naphthothiazole ring,
β-naphthothiazole ring), selenazole ring, benzoselenazole ring (e.g. benzoselenazole ring, 5-chlorobenzoselenazole ring, 6-methylbenzoselenazole ring, 6methoxybenzoselenazole ring), naphthoselenazole ring ( For example, α-naphthoselenazole ring, β-naphthoselenazole ring), oxazole ring, benzoxazole ring (for example, benzoxazole ring, 5-methylbenzoxazole ring, 6-methoxybenzothiazole ring, 5-phenylbenzoxazole ring), Naphthoxazole ring (e.g. α-naphthoxazole ring, β-naphthoxazole ring), 2-quinoline ring (e.g. 2-quinoline ring, 6-methyl-2-quinoline ring, 6-chloro-2
-quinoline ring, 5-ethoxy-2-quinoline ring), 4-
Quinoline ring (e.g. 4-quinoline ring, 6-methyl-4-
quinoline ring, 8-methyl-4-1 quinoline ring), and 3.3-dialkylindolenine ring (for example, 3,3-dimethylindolenine ring, 3°3-dimethyl-5-methylindolenine ring).

The nitrogen-containing heterocycles formed by Y'' and Y4+ may be the same or different.

Examples of the aliphatic groups represented by R40 and R41 include alkyl groups, alkenyl groups, alkynyl groups, and aralkyl groups. These aliphatic groups may be linear or branched. These aliphatic groups also include those having substituents.

Examples of the substituent include a hydroxyl group, an alkoxy group, a carboxyl group, a sulfo group, and a carboxyalkoxy group.

Examples of the aliphatic group represented by R'' and R41 include methyl group, ethyl group, propyl group, 2-hydroxyethyl group, 2-methoxyethyl group, carboxymethyl group, 2-carboxyethyl group, and 3-carboxypropyl group. group, 4-carboxybutyl group, 22-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, carbomethoxymethyl group, carboethoxymethyl group, carbomethoxyethyl group, carboethoxyethyl group, and allyl group.

These aliphatic groups represented by R40 and R'' may be the same or different.

Examples of the halogen atom represented by R42 include fluorine atom, chlorine atom, and bromine atom, and examples of the alkyl group include methyl group, ethyl group, and propyl group.

Examples of the anion represented by x4 include chloride ion, bromide ion, iodide ion, perchlorate ion, paratoluenesulfonate ion, and ethylsulfate ion.

When the dye represented by the general formula [IV] forms an inner salt, p4 is 1, that is, X4 is unnecessary.

Below, general formula [I], general formula [II], general formula [I[
Typical examples of the sensitizing dyes represented by the general formula [I] and the general formula [IV] are shown below.
], the sensitizing dyes represented by the general formula [■] and the general formula [IV] are not limited to these.

Margin below 4 -1 -2 -3 CI(3 5 ■ ■ ■ 6 ■ 7 ■ ■ ■ 0 -11 ■ 2 ■ 3 ■ 4 9 ■ ■ ■ 0 II-4 11-5 -6 ■ 1-8 -9 ■-10 ■-11 ■-12 3 ■ 3 ■ 4 ■-15 4 ■ 16 ■ 7 ■ 8 ■ one ■ 0 H3 ■ ■ ■ 7 ■ -5 ■ 8 ■ 7 ■ ■ ■ 0 ■ 1 ■ 2 ■ 3 ■-14 ■-15 2H5 1 ■ 2H5 ■ 6 ■ 7 ■-18 2 ■ one ■ ■ ■ ■ ■ V-6 CH.

5 V-7 V-8 ■ 6 Compounds represented by the general formula [I], the general formula [II], the general formula [■], and the general formula [IV] are known, for example, as described in U.S. Patent No. 3.486, Specification No. 902, No. 2,704.
715 Specification, British Patent No. 2,739,9 [I4 Specification, British Patent No. 595,784 Specification, British Patent No. 774,779]
Issue Specification, F.M. Hemer, "The Chemistry of Heterocyclic Combinations," Volume 18.

"Cyanine Dio and Related Compounds" (Interscience Publishers' Nyny York, 1964) (P. M. Haier: "
The Chemistry of Heterology
cllc Compounds.

Vol, 18. Cyanine Dyes and
Re1ated Compounds”fntersc
ience publjsyers, New Yor
K., 1984) and D.M. Starmer (D.
M. Sturmer), Volume 30 (1977)
It can be easily synthesized by referring to the known method described on page 411, etc.

When adding the sensitizing dyes represented by general formula [I], general formula [II], general formula [m], and general formula [IV] to a silver halide emulsion, the amount to be added depends on the type of emulsion and the structure of the compound. Although it may vary depending on factors such as halo 7, generally 3xt rho 6 to 2.5x 10-2 per 1 mole of halo 7 silver
mol, preferably from 3 x 10-5 to 9XLO-3 mol, particularly preferably from 3 x 10-5 to 3 x 10-'
It is in the molar range.

Among the sensitizing dyes represented by the general formula [I], the general formula [II], the general formula [III], and the general formula [rV], the most preferable dyes for achieving the effects of the present invention are the general formula [I ], and the second most preferred is the general formula [
It is a sensitizing dye represented by [I1].

The direct positive silver halide photographic material of the present invention can be applied as a monochrome photographic material, but can also preferably be applied as a full-color photographic material.

For full color applications, there is usually a blue-sensitive layer, a green-sensitive layer,
A red-sensitive layer is provided, and a yellow coupler is provided in the blue-sensitive layer.
The green-sensitive layer contains a magenta coupler, and the red-sensitive layer contains a cyan coupler.

There are no particular limitations on the yellow, magenta, and cyan couplers that can be used in the present invention, and any arbitrary ones can be used.

As the yellow coupler, for example, an acetani-8-lide coupler can be used. These include benzoylacetanilide couplers, pivaloylacetanilide couplers, and the like.

As the magenta coupler, for example, a 5-pyrazolone coupler, a pyrazolobenzimidazole coupler, a pyrazolotriazole coupler, or an open-chain acylacetonitrile coupler can be used.

As the cyan coupler, for example, a phenol coupler or a naphthol coupler can be used.

The compounds such as dye-forming couplers used in the direct positive silver halide photographic material of the present invention usually have a boiling point of about 150
Dissolve in a high boiling point organic solvent or water-insoluble polymer at ℃ or higher, using a low boiling point and/or water-soluble organic solvent as necessary, and emulsify it in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. After being dispersed, it is added into the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent may be included after or simultaneously with the dispersion.

6 The above-mentioned high boiling point organic solvent is preferably a compound with a dielectric constant of 6.5 or less, such as esters such as phthalates and phosphoric esters, organic acid amides, ketones, and hydrocarbons with a dielectric constant of 6.5 or less. It is a compound.

More preferably, the dielectric constant is 8.5 or less and 1.9 or more and 100
It is a high boiling point organic solvent with a vapor pressure of 0.5 m+*Hg or less at °C. Among these, phthalate esters and phosphoric esters are more preferred.

The most preferred are dialkyl phthalates having an alkyl group having 9 or more carbon atoms. Furthermore, the high boiling point organic solvent is 2
It may be a mixture of more than one species.

Note that the dielectric constant indicates the dielectric constant at 30°C.

These high boiling point organic solvents are generally used in a proportion of 0 to 400% by weight based on the coupler and the like. Preferably it is 10 to 100% by weight based on the coupler.

The silver halide photographic material used in the present invention can be, for example, a positive film, color photographic paper, etc., but the method of the present invention is particularly effective when applied to color photographic paper used for direct viewing. The results will be effectively demonstrated.

Hydrophilic colloid layers such as the protective layer and intermediate layer of the silver halide photographic light-sensitive material of the present invention may contain an ultraviolet absorber in order to prevent deterioration of images due to ultraviolet light.

The silver halide photographic material of the present invention may be provided with auxiliary layers such as a filter layer, an antihalation layer and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that flow out of the color light-sensitive material or are bleached during development.

The silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide light-sensitive material of the present invention is intended to reduce the gloss of the light-sensitive material, increase the ease of writing, and prevent the light-sensitive materials from sticking to each other. A solute agent can be added as a solute.

A lubricant can be added to the silver halide photographic material of the present invention in order to reduce sliding friction.

An antistatic agent can be added to the silver halide photographic material of the present invention for the purpose of preventing static electricity. When charging 1. A stopper is sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or on the side other than the emulsion layer and/or the emulsion layer on the side on which the emulsion layer is laminated with respect to the support. It may also be used as a protective colloid layer.

The photographic emulsion layer and/or the silver halide photographic light-sensitive material of the present invention
Alternatively, other hydrophilic colloid layers may contain various interfaces for the purpose of improving coating properties, preventing static electricity, improving slipperiness, emulsifying and dispersing, preventing adhesion, and improving photographic properties (such as accelerating development, increasing contrast, sensitization, etc.). An activator is used.

As the binder (or protective colloid) used in the silver halide photographic material of the present invention, gelatin is advantageously used, but gelatin derivatives, graft polymers of gelatin and other polymers, proteins, Hydrophilic colloids such as sugar derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances (single or copolymers) can also be used.

The photographic emulsion layer and other hydrophilic colloid layers used in the silver halide photographic light-sensitive material of the present invention cross-link binder (or protective colloid) molecules, and 2. A hardening agent is used alone or in combination to increase film strength. It is hardened. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to such an extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add a hardening agent to the processing solution.

The photographic emulsion layer and other layers of the silver halide photographic light-sensitive material of the present invention are made of baryta paper, paper laminated with α-olefin polymer, etc., paper laminated so that the layer of α-olefin polymer etc. can be easily peeled off, or synthetic paper. Flexible reflective supports such as paper, films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, polyamide, and reflective supports coated with white pigments. It can be applied to rigid bodies such as glass, metal, and ceramics. It is also possible to coat a thin reflective support with a thickness of 120 to 180 μm.

The support used in the present invention may be either a reflective support or a transparent support.

In order to impart reflective properties to the support, a white pigment 3 may be contained in the support, or a layer of a hydrophilic colloid, synthetic polymer, or the like containing the white pigment may be applied.

As the white pigment, inorganic or organic pigments can be used. Preferred are inorganic pigments, such as alkaline earth metal sulfates such as barium sulfate, alkaline earth metal carbonates such as calcium carbonate, silicas such as finely divided silicic acid and synthetic silicates, calcium silicate, alumina, Examples include alumina hydrate, titanium oxide, zinc oxide, talc, and clay. Among these, preferred are barium sulfate and titanium oxide.

The silver halide photosensitive material of the present invention can be prepared by subjecting the surface of the support to corona discharge, ultraviolet irradiation, flame treatment, etc., if necessary, and then directly or applying an undercoat layer (adhesiveness, antistatic properties, etc. of the support surface). Dimensional stability, abrasion resistance, hardness, anti-halation properties,
1 for improving frictional properties and/or other properties
or two or more undercoat layers).

When coating a photographic material using the silver halide emulsion of the present invention, a thickener may be used to improve coating properties. Eftrusion coating and curtain coating, which allow two or more layers to be applied simultaneously, are particularly useful as coating methods.The color developing agent used in the color developer in the present invention is widely used in various color photographic processes. The commonly used ones are included.

In the present invention, after color development, the material is immediately treated with a processing solution having a bleaching ability, but the processing solution having a bleaching ability may also be a processing solution having a fixing ability (a so-called bleach-fix solution).

As the bleaching agent used in the bleaching step, a metal complex salt of an organic acid is used.

[Examples] Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Preparation of emulsion EM-1 5 A gelatin aqueous solution was vigorously stirred, and an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride were simultaneously added while maintaining the gelatin solution at 40°C.
Hedron particle (AgBr: Ag(J! = LO:
90 (molar ratio)] was obtained. Chemical sensitization was carried out by sequentially adding 4 μm of sodium thiosulfate and 7 μg of chloroauric acid (tetrahydrate) per mole of silver to the emulsion obtained, and heating at 75° C. for 25 minutes. Using the obtained grains as cores, the grains were further grown under the above conditions to finally obtain a core/shell type silver chlorobromide emulsion having a monodispersed tetradecahedral structure and having an average grain size of 0.60 μm.

The coefficient of variation in particle size was 10%.

To this emulsion were added 1.5 μ of sodium thiosulfate and 1.5 μ of chloroauric acid (tetrahydrate) per mole of silver, and the mixture was heated at 60°C.
A chemical sensitization treatment was carried out by heating for 45 minutes to obtain an internal latent image type silver halide emulsion EM-1.

Preparation of emulsions EM-2, EM-3 and EM-4 Except for changing the halogen composition and grain size as shown in Table 1, EM-1
Emulsions EM-2, 6, EM-3 and EM-4 were prepared in the same manner as above.

Table-1 Paper support laminated on both sides with polyethylene (thickness 2
A photosensitive material sample 1 was prepared by coating the following layers from the first layer to the ninth layer on the front side of the photosensitive material (20 μm). The polyethylene on the front side of the paper support contains titanium white as a white pigment.

The numbers below indicate the coating amount (■/dm'). However, silver halide emulsions are expressed in terms of silver.

1st layer (red-sensitive layer) Red-sensitive emulsion obtained by spectrally sensitizing emulsion EM-1 with red-sensitive sensitizing dye 7 (1-14) Gelatin cyan coupler (CC-1) Cyan coupler (CC-2) Image stabilizer (AO-2) Solvent (So-1) Second layer (intermediate layer) Gelatin color mixing inhibitor (AS-1) Solvent (So-2) Third layer (green-sensitive layer) Green-sensitized emulsion EM-1 Green-sensitive emulsion gelatin magenta coupler (MC-1) spectrally sensitized with dye (GD-1) Image stabilizer (AO-1) Solvent (So-4) 4th layer (intermediate layer) 0.55 0.72 2 .7 13.0 2.4 2.0 3.15 8 Same as 2nd layer 5th layer (yellow filter layer) Gelatin yellow Colloidal silver UV absorber (UV-1) Ultraviolet absorber (UV-2) Color mixture Inhibitor (AS-1,) Solvent (So-3) 6th layer (color-mixing prevention layer) Gelatin color-mixing inhibitor (AS-1) Solvent (So-2) 7th layer (blue-sensitive layer) Emulsion EM-1 Blue-sensitive emulsion gelatin yellow coupler (YC-1) spectrally sensitized with blue-sensitive sensitizing dye (BD-1) Image stabilizer (AO-2) Solvent (So-1) 9 0 0.27 0.36 8 layers (ultraviolet absorbing layer) Gelatin 54 ultraviolet absorber (UV-1) 1. ．． 0 Ultraviolet absorber (UV-2) 2.8 Solvent (So-
3) 1.2 9th layer (protective layer) Gelatin 12.3 In addition,
Coating was carried out using 5A-1, 5A-2t- as a coating aid and 6 µm of HA-1 as a hardening agent per Ig of gelatin.

Below margin 0 BD (CH2), 5O3Na (CHz)tsOi BD (CH2)45OJa (CH2)4SO1 1 YC YC YC I 0 2 O 2 O Ht H3 o-4 S-1 H H O-1 3 O A 4 5OJi CJs A-2 bOJ CHCOOCH2(CF2CF2)2HCH2COOC
H2(ChCFz)J Below blank space 5 Samples 2 to 6 were prepared by changing the red-sensitive emulsion in the first layer of Sample 1 as shown in Table 2.

Table 2 The amount of sensitizing dye added in each emulsion was 1.0 IO 4 moles per 1 mole of silver halide.

6 Instead of the first layer of sample 1, from the support side, add the first layer shown below.
Sample 7 was obtained in the same manner as sample i except that the A layer and the first B layer were provided.

1st A layer (first red-sensitive layer) Red-sensitive emulsion obtained by spectrally sensitizing emulsion E M-1 with red-sensitive sensitizing dye (I-14) 2.5 gelatin 6,9 cyan coupler (CC-1) 1. 05 Cyan coupler (CC-2') 1.05 Image stabilizer (
AO-2) 1.1 Solvent (SO-1
) 1.65 1st B layer (second red-sensitive layer) Red-sensitive emulsion obtained by spectrally sensitizing emulsion EM-1 with red-sensitizing dye (1-14) 1.5 Gelatin
6.9 cyan coupler (CC-
1) 1.05 cyan coupler (CC-2
) 1.05 Image stabilizer (AO-2)
1.1 Solvent (SO-1)
Parts of samples 1 to 77 prepared as described above were stored for 5 days at a temperature of 50° C. and a relative temperature of 80% (storage conditions 1). In addition, a part of the same sample was heated at 5°C.
The samples were stored for the same period of time in a refrigerator maintained at

Each of the obtained samples was exposed to light through an optical wedge according to a conventional method, and subjected to the following processing steps, and sensitometry was performed on each of the obtained samples.

Minimum density Dmin and leg tone G- for cyan image
1 was measured, and the magnitude of the variation in the minimum density Dmin and the leg gradation G-1 was evaluated when the storage conditions were changed, such as storage under storage condition 1 and storage condition 2.

Leg gradation G-1=Absolute value of the slope of the straight line connecting the density point of Dmin+0.5 and the density point of Dmin+O,15 in the characteristic curve.

Variation of minimum density Dmin A value obtained by subtracting the minimum density 8 value under storage condition 2 from the minimum density value under storage condition 1 for a Nisian image.

Variation of Dmin - (Dmin of storage condition 1) (Dmin of storage condition 2) Leg gradation (, -1 variation: Leg gradation G-1 when saved under storage condition 1 (Dmin of storage condition 1) Leg gradation G when G-1) is saved under storage condition 2
The value obtained by dividing by the value of -1 (61 of storage condition 2) and multiplying by 100.

Processing process〉 Immersion Exposure Color Development Bleach-Fixing Super Stabilizer Drying Processing Solution Composition〉 (Color Developer) Processing Temperature 38°C 38°C (1 lux) 38°C 35°C 25-30°C 75-80°C 9 Benzyl alcohol 10g Ethylene glycol 8.55 g Jetanolamine 50g Ce2 (SO4)
3 0.015g potassium sulfite
2.5g sodium bromide
0.1g sodium chloride
2.5g diethylhydroxylamine (85%)
5.0g Sodium diethylenetriaminepentaacetate 2.0g CI)
-37.0g Fluorescent brightener (4,4'-diaminostilbendisulfonic acid derivative) I, Og
Potassium carbonate 30.0g Potassium hydroxide 2.0g Add water to bring the total amount to 1D, and add potassium hydroxide or sulfuric acid to I) HlO,L
Adjust to o.

(Bleach-fix solution) Ferric ammonium diethylenetriaminepentaacetate 90°0 Diethylenetriaminepentaacetic acid 3g Ammonium thiosulfate (70% solution) 180ml Ammonium sulfite (40% solution) 27,5 m13-mercapto-1,2,4 triazole (1 , 15g of potassium carbonate or glacial acetic acid to adjust to pa 7.t, and add water to bring the total volume to lit.

(Stabilizing liquid) Ortho-phenylphenyl 0.3g Potassium sulfite (50% solution) 12ml Ethylene glycol 10゜1-hydroxyethylidene-1,1-diphosphonic acid 2.5g Bismuth chloride 0.2g Zinc sulfate heptahydrate 0 .7g ammonium hydroxide (2
8% aqueous solution) 2.0g polyvinylpyrrolidone (K
-17) 0.2g optical brightener (4,4' -
Diaminostilbendisulfonic acid derivative) Add 2 g of water to bring the total volume to 14), and adjust the pH to 7.5 with ammonium hydroxide or sulfuric acid.

Note that the stabilization treatment was performed using a countercurrent method with a two-tank configuration.

The results are shown in Table-3.

Table 3 As is clear from Table 3, the samples of the present invention showed small fluctuations in Dmin even under forced aging conditions (storage conditions 1).
In addition, the variation in G-1 is small, which is effective for preserving freshness.

Example 2 Preparation of emulsions EM-5, EM-6, EM-7 and emulsion EM-8 2 Emulsion EM-1 was prepared in the same manner as EM-1 except that the halogen composition and grain size were changed as shown in Table 4. -5, EM-5, EM
-7 and emulsion EM-8 were prepared.

Table 4 In each of the first, third and seventh emulsion layers of Sample 6 of Example 1, fogging agents FA-1 and FA-
2 per mole of silver halide, respectively.2. OX10
Sample 8 was prepared in exactly the same manner as Sample 6 except that -5 mol was added.

Furthermore, emulsions EM-1 and EM-2 in the first layer of sample 8
Sample 11 was prepared from Sample 9 by changing the parameters as shown in Table 5.

3 In addition, the following 5T-1 was added to the first layer of sample 9 to make sample 1.
2 (The amount of ST-1 added is 50 per mole of silver halide.
The following ST~2 was added to the first layer of Sample 9 to give Sample 1B (the amount of ST-2 added was 3/3 mole of silver halide).
0■) was created.

Margin below 4 A 1 A T H T 5 Table Each sample obtained was stored under storage conditions 1 and 2 shown in Example 1, exposed through an optical wedge according to a conventional method, and processed through the following processing steps. and sensitometry was performed on each sample obtained.

As in Example 1, the minimum density Dmin for the cyan image
and leg gradation G-1 are measured, and the minimum density Dmin and the magnitude of the variation in leg gradation m(,-1) are obtained when storage conditions are changed, such as storage under storage condition 1 and storage condition 2. was evaluated.

[Processing steps] 6 Temperature color development 35.0±0.3°C Bleach-fixing 35.0±0.5°C Stabilization 30-34°C Drying 60-80°C [Color developer] Pure water triethanolamine N, N-diethylhydroxylamine Potassium chloride Potassium sulfite Potassium sulfite 1-Hydroxyethylidene-1,1-diphosphonic acid Ethylenediamine Tetraacetic acid catechol-3,5-disulfonic acid disodium salt N-ethyl-N-β-methanesulfonamidoethyl- 3-Methyl-4 aminoaniline sulfate Time 45 seconds 45 seconds 90 seconds 60 seconds 800 ml 1 mouth g g O, 02゜g 0.3 g t, og 1, og 1.0 g 7 Fluorescent brightener (4, 4'-diaminostilbendisulfonic acid derivative) l, O
g Potassium carbonate 27g Add pure water to bring the total amount to tU, and adjust the pH to 10.10.

[Bleach-fix solution] 1 g of bleach-fix solution contains 60 g of ferric ammonium ethylenediaminetetraacetic acid dihydrate, 3 g of ammonium thiosulfate (70% aqueous solution) room + 27.5 ml of ammonium sulfite (40% aqueous solution M).

Adjust the pH to 5.7 with potassium carbonate or glacial acetic acid.

[In Stabilizing Liquid Co-Stabilizing Liquid ID, 5-chloro-2-methyl-4 isothiazolin 3-one 1.0 g ethylene glycol 1. Contains ogl-hydroxyethylidene-1 8 1-diphosphonic acid ethylenediaminetetraacetic acid ammonium hydroxide (20% aqueous solution) ammonium sulfite fluorescent brightener (4,4'-diaminostilbene diphosphonic acid derivative). Adjust pH with sulfuric acid or potassium hydroxide.

The results are shown in Table-6. Also in 1), the variation in Dmin is small, and the variation in G-1 is also small, which is effective for shelf life.

That is, it can be seen that samples with a silver chloride content of less than 80% deteriorate significantly during storage, and in this case, no improvement can be achieved even by adding a conventionally known stabilizer.

Example 3 Table 7 shows the red sensitizing dye in the first layer of Sample 8 of Example 1.
Sample 14 was prepared in the same manner as sample 3 except for the following changes.
Sample 1B was prepared from.

Table 7 All amounts added are per mole of silver halide, lx to
−'Mole.

00 Each sample obtained was stored under the storage conditions 1 and 2 shown in Example 1, exposed through an optical wedge according to a conventional method, and processed in the same manner as in Example 1. Sensitometry was performed.

As in Example 1, the minimum density Dmin for the cyan image
and leg gradation G-1 are measured, and the minimum density Dmin and the magnitude of the variation in leg gradation G-1 brought about when storage conditions are changed such as storage under storage condition 1 and storage condition 2 are calculated. evaluated.

Table 8 As shown in Table 8, Sample 3.14. is a sample of the present invention.
Only 15.16 gave good results.

[Effects of the Invention] The direct positive silver halide photographic material of the present invention has less increase in fog when stored without exposure, less softening of gradation in the legs, and can be stored raw for a long period of time. There is no significant deterioration of the image even in this case.

Claims (1)

[Scope of Claims] A direct positive silver halide photographic light-sensitive material having on a support at least one silver halide emulsion layer for direct positive image formation containing internal latent image type silver halide grains. The image-type silver halide grains as a whole contain at least 80 mol % of silver chloride, and the grain distribution of the internal latent image-type silver halide grains contained in the photosensitive layer in the same photosensitive area as a whole is at least 80 mol %. In addition to having two peaks, the internal latent image type silver halide grains have the following general formula [
I ], general formula [II], general formula [III] and general formula [IV]
A photographic light-sensitive material characterized in that it is sensitized with at least one sensitizing dye selected from among the sensitizing dyes represented by: General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z^1^1 represents a sulfur atom or a selenium atom, and Z^1^2 is a benzothiazole ring, benzoselenazole ring, naphtho [ Represents a group of nonmetallic atoms necessary to form a 1,2-d]thiazole ring or a naphtho[1,2-d]selenazole ring. R^1^1 and R^1^2 each represent an alkyl group or a substituted alkyl group, and at least one of R^1^1 and R^1^2 has a sulfo group. R^1^3 represents an alkyl group, an aryl group, a furyl group or a thienyl group. X_1 represents an anion. l_1 represents 1 or 2,
It is 1 when the dye forms an inner salt (betaine-like structure). ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^2^0 and R^2^1 each represent an alkyl group or a substituted alkyl group. Z^2^0 and Z^2^1 are each a nonmetal necessary to form a benzothiazole ring, a naphthothiazole ring, a benzoselenazole ring, a naphthoselenazole ring, a benzoxazole ring, a naphthoxazole ring, or a quinoline ring. Represents a group of atoms. Q^2^0 is a pyrazolone ring, an indanedione ring, 5 (4
H)-Isoxazolone ring, 2,4-chromandione ring, 4,6-(1H,5H)pyrimidinedione ring, barbituric acid ring, 2-thiobarbituric acid ring, 1,3-dioxane-4,6 -dione ring, 3,5-pyrazolidinedione ring, 3H-naphtho[2,1-b]pyran-1,3(2
H)-dione ring, 5(4H)-isoxazolone ring, rhodanine ring, hydantoin ring, thiohydantoin ring or 1,3-cyclobutanedione ring, represents a group of nonmetallic atoms necessary to form A^2^ 0 represents an oxygen atom or a sulfur atom, and n_2, d_2 and m_2 are each 1
Or represents 2. ] General formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. are included ▼ [In the formula, R^3^0 and R^3^1 each represent an alkyl group or a substituted alkyl group. D^3^0 represents a group of nonmetallic atoms necessary to form a 6-membered ring consisting of three methylene groups. Z^3^0 and Z^3^1 represent a group of nonmetallic atoms necessary to form a nitrogen-containing heterocycle. X_3 represents an anion. p_3 and q_3 represent 0 or 1, and n_3 represents 1 or 2. l_3 represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ] General formula [IV] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [In the formula, Y^4^0 and Y^4^1 each represent a group of nonmetallic atoms necessary to form a heterocycle. R^4^0 and R^4^1 each represent an aliphatic group. R^4^2 represents a halogen atom or an alkyl group. X_4 represents an anion. m_4 and n_4 represent 1 or 2. l_4 represents 1 or 2, and is 1 when the dye forms an inner salt (betaine-like structure). ]