JPH03219241A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve a green preservable property and white ground balance by incorporating silver chloride into internal latent image type silver halide particles and providing a magenta coupler-contg. silver halide emulsion layer between a cyan coupler-contg. silver halide emulsion layer and a substrate. CONSTITUTION:The silver chloride is incorporated into the internal latent image type silver halide particles and the magenta coupler-contg. silver halide emulsion layer is provided between the cyan coupler-contg. silver halide emulsion layer and the substrate. The preferable silver halide emulsion contg. the internal latent image type silver halide particles is the emulsion exhibiting the max. density not larger than 1/5 the max. density obtd. when the same sample is developed by using an internal developing soln. in the case of exposing of the sample formed by applying the silver halide emulsion on a transparent substrate for a prescribed period of time and developing of the same by using the surface developing soln. The green preservable property and the white ground balance are improved in this way.

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, fogging treatment (development nucleation treatment) 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.

Furthermore, in recent years, there has been a demand for silver halide photographic materials that can be rapidly processed.

It is known that high silver chloride emulsions can be used as silver halide emulsions for rapid processing. When a silver halide emulsion is used, Dmin
In addition, there was a problem in that the Dmin increase was unbalanced between each layer, the white background was colored, and the white background balance was deteriorated.

Upon investigation, the present inventors have found that the above-mentioned drawbacks can be improved by making the layer structure of the silver halide photographic light-sensitive material specific.

[Object of the Invention] Accordingly, an object of the present invention is to provide a direct positive silver halide photographic light-sensitive material which has improved storage stability and good white background balance.

[Structure of the Invention] The above object is to have a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support, and in at least one of the emulsion layers, an internal latent image type silver halide is formed. In the direct positive silver halide photographic light-sensitive material containing grains, the internal latent image type silver halide grains contain silver chloride, and between at least one layer of the cyan coupler-containing silver halide emulsion layer and the support. This can be achieved by a photographic material having at least one silver halide emulsion layer containing the magenta coupler.

The present invention will be explained in detail below.

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 described.

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 115, which is the maximum density obtained when the same sample is exposed in the same manner as above and developed at 20°C for 4 minutes 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 1/1/1 of the maximum density obtained using internal developer B.
10 or less.

(Surface developer A) Metol 2.5gL-ascorbic acid 10gNaBO2・4H203
5g KB r Add 1g water l[(Internal developer B) Metol 2.0g Sodium sulfite (anhydrous) 90.0g Hydroquinone
8.0g carbonated soda water salt
52.5g KBr
5. OgK I
O, 5 g with water added 1 g The internal latent image type silver halide emulsion of the present invention can be prepared by various methods. For example, the conversion silver halide emulsions described in U.S. Pat. No. 2,592,250, U.S. Pat.
Silver halide emulsions having internally chemically sensitized silver halide grains as described in US Pat. No. 16, US Pat. No. 3,317,322 and US Pat. Specification No. 3,271.157, No. 3.
447,927 and 3,531,291, silver halide emulsions having silver halide grains incorporating polyvalent metal ions, U.S. Pat. No. 3,761,276 Silver halide emulsions in which the grain surfaces of silver halide grains containing a dopant are weakly chemically sensitized as described in the specifications of JP-A-50-8524, JP-A-50-38525 and JP-A-53-2408 There are silver halide emulsions comprising grains having a layered structure as described in the above publication, and silver halide emulsions described in Jikai-Mei No. 52-156614 and Jikai-Mei No. 55-127549.

By containing silver chloride in the internal latent image type silver halide grains, the objects of the present invention can be achieved.

The silver chloride content is preferably 20 mol% or more,
More preferably, the content is 50 mol% or more.

Further, the higher the silver chloride content, the better the results can be obtained.

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

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

The silver halide grains having a layered structure means that the silver halide grains have two or more layers adjacent to each other with different halogen compositions, and more preferably, the layered structure is clearly defined. It is formed with a boundary.

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 by 20 mol% or more in silver chloride content.

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.

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 halide layer is simply added to the grain surface. Not only does silver grow, but the silver halide grains themselves are redissolved and recrystallized, creating a transition layer in which the silver halide content changes continuously and tends to obscure the boundaries.

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.

It is also preferable to control pH and the like to suppress the layer structure from becoming unclear due to recrystallization. Furthermore, in the preparation of silver halide using a silver halide solvent, the optimum conditions can be selected by selecting the type and amount of the silver halide solvent and controlling usage conditions such as pH. .

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

Furthermore, 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 boundaries 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, a core/shell comprising a polyvalent metal ion-containing or chemically sensitized core coated with a silver halide 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. It is sufficient that the grains as a whole contain silver chloride, and as long as this condition is met, the silver halide composition of the core and shell can be arbitrary. Examples include silver oxide, 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 (11).
1) Any shape, such as a tetradecahedron consisting of a mixture of faces, a shape with (l l O) faces, a sphere, a flat plate, a shape with protrusions on the surface, a shape with depressions on the surface, or a mixture of these. You can.

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, thioureas, thiazoles, rhodanines, and other compounds can be used. Such methods are described, for example, in U.S. Pat. No. 1,574,944;
No. 623,499, No. 2,410.689, No. 3,6
No. 56,955, etc.

The core of the silver halide grains used in the present invention is, for example, US Pat. No. 2,399,083, US Pat.
As stated in No. 2,842.361, 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;
Reference can be made to the descriptions in No. 18.698, 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.
Reference may be made to the descriptions in No. 8.060 and British Patent No. 618.061.

The core of the silver halide grains in the present invention can be doped with metal ions. To dope the core with metal ions, the metal ions can be added as water-soluble salts, for example, during any process of forming the core particle. Preferred specific examples of metal ions include iridium,
There are metal ions such as lead, antimony, bismuth, gold, osmium, and rhodium. These metal ions preferably range from IX 10-8 to IX to-
'Used in molar concentrations.

In the present invention, silver halide emulsions having any grain size distribution can be used.

Emulsions with a wide grain size distribution (referred to as polydisperse emulsions)
Alternatively, an emulsion with a narrow particle size distribution (referred to as a monodisperse emulsion) may be used alone, or a mixture of several types thereof 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 a liquid in which the other is present.

Alternatively, silver halide grains may be generated by sequentially and simultaneously adding halide ions and silver ions while controlling the pH and 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
) A shape having a surface, a spherical shape, a flat plate shape, etc. may be used. 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 colloids such as, for example, can also be used.

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

In the present invention, it is necessary that at least one silver halide emulsion layer containing a magenta coupler is provided between at least one silver halide emulsion layer containing a cyan coupler and the support.

When a silver halide emulsion layer containing a yellow coupler is provided in the silver halide photographic light-sensitive material of the present invention, the silver halide emulsion layer containing a yellow coupler can be arranged at any position as long as the above conditions are satisfied. , but is not particularly limited.

The magenta coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer of the present invention need not each be one layer, but may each be two or more layers. In this case, it is sufficient that the silver halide emulsion layer containing the magenta coupler is present between one layer of the silver halide emulsion layer containing the cyan coupler and the support. However, it is preferred that all magenta coupler-containing silver halide emulsion layers are present between all cyan coupler-containing silver halide emulsion layers and the support.

The magenta coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer of the direct positive silver halide photographic light-sensitive material of the present invention can be embodied as having any color sensitivity. Of course, it can also be preferably applied as a full-color photosensitive material. For full-color applications, the yellow coupler-containing silver halide emulsion layer is usually a blue-sensitive layer;
The silver halide emulsion layer containing a magenta coupler is used as a green-sensitive layer, and the silver halide emulsion layer containing a cyan coupler is used as a red-sensitive layer.

Yellow coupler, magenta coupler, and cyan coupler used in the present invention are not particularly limited, and any cyan coupler can be used.

As the yellow coupler, for example, an acetanilide coupler can be used. This includes benzoylacetanilide couplers, pivaloylacetanilide couplers, etc.

As the magenta coupler, for example, 5-pyrazolone couplers, pyrazolopenzimidazole couplers, pyrazolotriazole couplers, and open-chain acylacetonitrile couplers 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.

The above-mentioned high boiling point organic solvent is preferably a compound having a dielectric constant of 6.5 or less, such as esters such as phthalates and phosphoric esters, organic acid amides, ketones, and hydrocarbon compounds having a dielectric constant of 6.5 or less. be.

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 mmHg 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 IO to 10 (1% by weight, based on the coupler).

The silver halide photographic light-sensitive material used in the present invention can be, for example, a positive film, color photographic paper, etc., but the effect of the method of the present invention is especially effective when applied to color photographic paper used for direct viewing. Effectively demonstrated.

The silver halide photographic material of the present invention, including this color photographic paper, may be one for monochrome use or one for multicolor use.

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.

A matting agent is added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the silver halide photosensitive material of the present invention for the purpose of reducing the gloss of the photosensitive material, increasing the ease of writing, and preventing the photosensitive materials from sticking to each other. can be added.

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. Antistatic agents are sometimes used in the antistatic layer on the side of the support on which the emulsion is not laminated, or they are used to protect the emulsion layer and/or the side other than the emulsion layer on which the emulsion layer is laminated with respect to the support. It may also be used in colloid layers.

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.

In the photographic emulsion layer and other hydrophilic colloid layers used in the silver halide photographic material of the present invention, a hardening agent is used alone or in combination to crosslink inder (or protective colloid) molecules and increase film strength. It is hardened by. It is desirable to add the hardening agent in an amount that can harden the photosensitive material to the extent that it is not necessary to add the hardening agent to the processing solution, but it is also possible to add the 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. Moreover, it can also be applied to a thin reflective support with a thickness of 120 to 160 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 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 property, dimensional stability, etc. of the support surface). degree 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 light-sensitive 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.

The compounds used in the following examples are shown below.

Margin below D-1 D-2 (L:th14b03N! (nith14b(J3 MC-1 YC-1 0 A-1 C3H7(i) I O-1 O-2 O Hi CH3 O-4 S H H O- 1 A-1 2H5 Kuzu CH2C00CH2CHC4H9 Iku A-2 NIOiS CHCOOCHz (ChCF2) JCH
2GOOCH2(CF2CF2)2HA-1 T-1 1 MC-A MC-D 1 MC-B (1 Below margin Caf17(+) MC-C Example 1 Preparation of Emulsion E M-1 A gelatin aqueous solution was vigorously stirred, While maintaining the temperature at °C, an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride were added simultaneously, and the average particle size was 0.21.cz m.
of tetradecahedral particles (AgBr: Ag(J!=
An emulsion having a molar ratio of 70:30 was obtained. To this obtained emulsion, 4 mg of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver were sequentially added.
Chemical sensitization was performed by 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 with a monodisperse dodecahedral structure having an average grain size of 0.45 μm.

The coefficient of variation in particle size was 10%.

To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver, and 6
Chemical sensitization was performed by heating at 0° C. for 45 minutes to obtain an internal latent image type silver halide emulsion (EM-1).

Preparation of Emulsion EM-2 An aqueous gelatin solution was vigorously stirred, and an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide were simultaneously added while maintaining the temperature at 40°C to obtain an emulsion having tetradecahedral grains with an average grain size of 0.21 μm. .

To this obtained emulsion, 4 g of sodium thiosulfate and 7 mg of chloroauric acid (tetrahydrate) per mole of silver were sequentially added.
Chemical sensitization was performed by 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 bromide emulsion with a monodispersed tetradecahedral structure having an average grain size of 0.degree. 45 .mu.m.

The coefficient of variation in particle size was 10%.

To this emulsion were added 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) per mole of silver, and 6
Chemical sensitization was performed by heating at 0° C. for 45 minutes to obtain an internal latent image type silver halide emulsion (EM-2).

Preparation of Emulsion EM-3 A gelatin aqueous solution was vigorously stirred, and while maintaining the temperature at 40°C, an aqueous solution of silver nitrate and an aqueous solution containing potassium bromide and sodium chloride were simultaneously added.
Tetrahedral silver chlorobromide particles [AgBr:AgCl-7
A monodispersed emulsion having a molar ratio of 0:80 was obtained.

The coefficient of variation in particle size was 9%.

To this obtained emulsion, 1.5 mg of sodium thiosulfate and 2.0 mg of chloroauric acid (tetrahydrate) were added per mole of silver.
Chemical sensitization was carried out by adding and heating at 60° C. for 90 minutes to obtain a surface latent image type silver halide emulsion (EM-3).

Paper support laminated on both sides with polyethylene (thickness 2
A color photographic material (sample 1) was prepared by coating the following layers from the first layer to the ninth layer on the front side of the sample (20 μm).

Note that titanium white is contained as a white pigment in the polyethylene layer on the first layer coating side.

The ingredients and coating amount of each layer (mg/dm') are shown below.
) is shown. Note that silver halide emulsions are expressed in terms of silver.

1st layer (red-sensitive layer) Red-sensitive emulsion gelatin cyan coupler (CC-1) obtained by spectrally sensitizing emulsion EM-1 with red-sensitive sensitizing dyes (RD-1 and RD-2) Solvent (SO-2) 2nd layer (intermediate layer) Gelatin color mixing inhibitor (AS-1) Solvent (So-2) 3rd layer (green-sensitive layer) Green color obtained by spectrally sensitizing emulsion EM-1 with a green-sensitive sensitizing dye (GD-1) Sensitive emulsion gelatin magenta coupler (MC-1) Solvent (So-2) 4th layer (intermediate layer) 3.0 13.8 4.0 4.0 7.5 0.55 0.72 3, O 13,8 3,5 4,0 5th layer (blue-sensitive layer) same as 2nd layer Blue-sensitive emulsion made by spectrally sensitizing emulsion EM-1 with blue-sensitizing dye (BD-1) 3.0 Gelatin 13.8 Yellow Coupler (YC-1) 7.0 Solvent (SO-2)
4.0 6th layer (UV absorption layer) Gelatin 5.4 Ultraviolet absorber (UV-1) 1.0 Ultraviolet absorber (UV-2) 2.8 Solvent (So-3
) 1.2 7th layer (protective layer) Gelatin 12.3 In addition, 5A-1 and 5A-2 were used as coating aids, and 6 sag of HA-1 was added as a hardening agent per 1 g of gelatin. I did it.

Next, Samples 2 to 9 were prepared using the emulsion and coupler shown in Table 1 in place of the emulsion (EM-1) and coupler in the first, third and fifth layers of Sample 1.

In addition, 800 mg of 5T-1 was added as a stabilizer to the silver halide emulsion of each sample per mole of silver halide. Further, in Samples 1 to 7 containing internal latent image type silver halide emulsions, FA-1 was added as a fogging agent to each emulsion layer at a rate of 2.0 x 1 to 6 mol per mol of silver halide.

A portion of each sample obtained was heated for 5 minutes at a temperature of 50°C and a RH of 80%.
It was stored for 1 day, and another portion was stored in a refrigerator (5°C) for the same period.

Each sample was exposed through an optical wedge in a conventional manner and processed under the following processing conditions.

Processing process> Color development, bleaching, fixing, stabilization, drying Processing solution composition> Time Processing temperature 2 minutes 30 seconds 38°C 60 seconds 35°C 1 minute 30 seconds 25-30'°C 1 minute 75-80°C (color developing solution) Benzyl alcohol 10ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide
1.5 Sodium chloride
0.2g potassium carbonate
30.0g Hydroxylamine sulfate 3
．． 0g polyphosphoric acid (TPPS) 2.
5g 3-Methyl-4-amino-N-ethyl-N-(β-methanesulponamidoethyl)aniline sulfate 5.5g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 1.0g hydroxide Add 2.0 g of potassium water to bring the total amount to 1 g, and adjust the pH to 10.20.

(Bleach-fix solution) Ferric ammonium ethylenediaminetetraacetic acid dihydrate 60g ethylenediaminetetraacetic acid 3g ammonium thiosulfate (70% solution) 100ml ammonium sulfite (40% solution) 27.5ml Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid. , add water to bring the total volume to 1fI.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol logl-hydroxyethylidene-1,1-diphosphonic acid 2.5 g bismuth chloride 0.2 and magnesium chloride 0.1 g Ammonium hydroxide (2
8% aqueous solution) 2.0g sodium nitrilotriacetate Add 1.0g water to bring the total volume to 1fI, and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

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

Sensitometry was performed on the obtained positive or negative image to evaluate variations in white background.

ΔDmin+″; Sample stored in refrigerator and temperature 50°C
, variation of Dmin measured with red light between samples stored at RH 80% ΔDmin′; samples stored in a refrigerator and temperature 50°C, R
The fact that the variation in Dmin measured with green light between samples stored at H80% and the white background is close to 1 means that the variation in the color balance of the white background is small.

The results are shown in Table-1.

From the results in Margin Table 1 below, it can be seen that in a direct positive silver halide photographic light-sensitive material containing internal latent image type silver halide grains in the emulsion layer, a cyan coupler-containing silver halide emulsion layer and a magenta coupler-containing silver halide emulsion layer Let be the array of the present invention,
Samples 4 to 6 of the present invention having a halogen composition according to the present invention
It can be seen that only in this case, it is possible to obtain results with small fluctuations in white background and excellent shelf life.

Furthermore, as is clear from Samples 8 and 9, the effect of specifying the arrangement order and halogen composition of the cyan coupler-containing silver halide emulsion layer and the magenta coupler-containing silver halide emulsion layer is clear from samples 8 and 9. This cannot be obtained with negative light-sensitive materials using emulsions.

Example 2 Preparation of Emulsions EM-4, EM-5 and EM-6 Emulsion E of Example 1 except that the halogen composition was changed as shown in Table 2.
Internal latent image type silver halide emulsion E was prepared in the same manner as M-1.
M-4, EM-5 and EM-6 were prepared.

Table 2 Samples 10 to 14 were prepared in the same manner as Sample 5 of Example 1, except that the emulsions and sensitizing dyes in the first, third, and fifth layers were changed as shown in Table 3.

In the same manner as in Example 1, variations in white background were evaluated between a sample stored in a refrigerator (5° C.) for 5 days and a sample stored at a temperature of 50° C. and RH 80% for 5 days.

The results are shown in Table-3.

From the results shown in Margin Table 3 below, it can be seen that only Samples 11 to 14 of the present invention, in which the halogen composition was the composition of the present invention, were able to obtain excellent results. Further, it can be seen that these effects are better as the silver halide has a halogen composition with a higher silver chloride content.

Example 3 Preparation of Emulsion EM-7 An aqueous solution containing ossein gelatin was controlled at 55°C, and while stirring vigorously, an aqueous silver nitrate solution and an aqueous solution containing potassium bromide and sodium chloride [KBr: Na
Cjl-40: 80 (molar ratio)] were simultaneously added using a controlled double jet method to obtain an average particle size of 0.
An emulsion having cubic silver chlorobromide grains of 3 μm was obtained. Using the obtained particles as core particles, a silver nitrate aqueous solution and a sodium chloride aqueous solution were added to the core particles at 55°C by a double jet method.
Ag was added at the same time while keeping it at 6, and the average particle size was 0.
6 μm cubic monodisperse core/shell emulsion (EM-7)
I got it.

The coefficient of variation in particle size was 8%.

Preparation of Emulsion EM-8 A cubic monodisperse core/shell type emulsion (EM-8) with an average grain size of 0.8 μm and a coefficient of variation of 10% per grain size was obtained in the same manner as Emulsion-7.

Paper support laminated on both sides with polyethylene (thickness 2
A color photographic material (sample 15) was prepared by coating the following layers from the first layer to the ninth layer on the front side of the sample (20 μm).

Note that titanium white is contained as a white pigment in the polyethylene layer on the first layer coating side.

The components and coating amount (-g/dm') of each layer are shown below. Note that silver halide emulsions are expressed in terms of silver.

1st layer (green-sensitive layer) Green-sensitive emulsion made by spectrally sensitizing emulsions EM-7 and EM-8 (1:1 in molar ratio) with a green-sensitive sensitizing dye (GD-1) 2.7 Gelatin 13.0 Magenta coupler (MC-1) 2.4 Image stabilizer (AO-
1) Solvent (So-4) 2nd layer (intermediate layer) Gelatin color mixing inhibitor (AS-1) Solvent (So-2) 3rd layer (red-sensitive layer) Emulsions EM-7 and EM-8 (in molar ratio Red-sensitive emulsion gelatin cyan coupler (CC-1) Cyan coupler (CC-2) Image stabilizer (AO-2) spectrally sensitized with red-sensitive sensitizing dyes (RD-1 and RD-2) Solvent (So-1) 4th layer (intermediate layer) 5th layer (yellow filter layer) same as 2nd layer Gelatin 2.0 3.15 7.5 0.55 0.72 4.0 13.8 2° ■ 2.1 2.2 3.3 4.2 Yellow colloidal silver ultraviolet absorber (UV-1) Ultraviolet absorber (UV-2) Color mixing inhibitor (AS-1) Solvent (So-3) 6th layer ( Color mixture prevention layer) Gelatin color mixture prevention agent (AS-1) Solvent (So-2) 7th layer (blue-sensitive layer) Emulsions EM-7 and EM-8 (molar ratio 1:1) were mixed with blue-sensitive sensitizing dye ( Blue-sensitive emulsion gelatin yellow coupler (YC-1) spectrally sensitized with BD-1) Image stabilizer (AO-2) Solvent (SO-1) 8th layer (ultraviolet absorption layer) Gelatin ■, 0 0.5 1 .4 0.4 0.8 4.0 0.27 0.36 5.0 13.5 8.4 3.0 5.2 5.4 Ultraviolet absorber (UV-1) 1.0 Ultraviolet absorber ( UV-2) 2.8 Solvent (S
O-3) 1.2 7th layer (protective layer) Gelatin 12.3 In addition,
Coating was carried out by using 5A-1 and 5A-2 as coating aids and adding 6 mg of HA-1 per 1 g of gelatin as a hardening agent.

Samples 16 to 18 were prepared in the same manner except that the magenta coupler (MC-1) in the first layer of sample 15 was changed to the magenta coupler and coating amount shown in Table 4.

In addition, the cyan couplers (CC-1) and (CC-2) used in the third layer of sample 15 were replaced with the cyan couplers shown in Table 4 alone, and the amount of coating shown in Table 4 was changed. Samples 19 and 20 were prepared in the same manner except for the following changes.

Below is a margin table-4 A part of each sample obtained was heated to
It was stored for 1 day, and another portion was stored in a refrigerator (5°C) for the same period.

Each sample was exposed through an optical wedge in a conventional manner and processed under the following processing conditions.

Processing process> Time Processing temperature Immersion 2 seconds 38℃ exposure (Lux) 5 seconds 38℃ color development 25 seconds 38℃ bleach-fixing
45 seconds super stabilizer 90 seconds dry
45 seconds <Processing liquid composition> (Color developer) Benzyl alcohol ethylene glycol diethylene glycol Ce2 (SO4).

Potassium sulfite Sodium bromide Sodium chloride Diethylhydroxylamine (85%) Diethylenetriamine Sodium pentaacetate 3-Methyl-4-amino-N Ethyl-N-(β-methanesulfonamidoethyl)aniline sulfate Optical brightener (4,4 '-Diaminosph 5-80°C 25-30°C 35°C 0g 8.55g 0g 0.015g 2.5g 0.1g 2.5g 5, Og 2, Og 7.0g Tilbendisulfonic acid derivative) 1.0g Potassium carbonate
30g potassium hydroxide
Add 2.0 g of water to bring the total volume to lII, and adjust the pH to 10.10 with potassium hydroxide or sulfuric acid.

(Bleach-fix solution) Ferric ammonium diethylenetriaminepentaacetate 90g Diethylenetriaminepentaacetic acid 8g Ammonium thiosulfate (70% solution) 180ml Ammonium sulfite (40% solution) 27.5ml 13-Mercapto-1
, 2,4 Triazole 0.15g Adjust the pH to 7.1 with potassium carbonate or glacial acetic acid, and add water to bring the total amount to 1g.

(Stabilizing liquid) 0-Phenylphenol 0.3g Potassium sulfite (50% solution) 12ml Ethylene glycol 10g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5g Bismuth chloride 0.2g Zinc sulfate (7 hydrate) 0. 7g ammonium hydroxide (28% aqueous solution) 2.0g polyvinylpyrrolidone (K-17) 0.2g optical brightener (4,4'-diaminostilbendisulfonic acid derivative) 2g Add water to bring the total amount to lII, and hydroxylate Adjust pH to 7.5 with ammonium or sulfuric acid.

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

When each sample was evaluated for variations in white background in the same manner as in Example 1, samples 15 to 20, which are samples of the present invention, all showed good results.

[Effects of the Invention] The direct positive silver halide photographic light-sensitive material using the internal latent image type silver halide grains of the present invention has improved storage stability and good white background balance.

Claims (1)

[Claims] Direct positive silver halide comprising a silver halide emulsion layer containing a magenta coupler and a silver halide emulsion layer containing a cyan coupler on a support, and containing internal latent image type silver halide grains in at least one of the emulsion layers. In the photographic light-sensitive material, the internal latent image type silver halide grains contain silver chloride,
A photographic light-sensitive material further comprising at least one silver halide emulsion layer containing a magenta coupler between the at least one silver halide emulsion layer containing a cyan coupler and a support.