JPH03192251A - Direct positive silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the rapid processability and color reproducibility of a direct positive silver halide photographic sensitive material and to prevent the deterioration of gradation balance at a leg part and the rise of min. density during storage over a long period of time by incorporating silver chloride into internal latent image type silver halide particles in at least one layer of the sensitive material and a specified water soluble dye into the sensitive material. CONSTITUTION:Silver chloride is incorporated into internal latent image type silver halide particles in at least one layer of a direct positive silver halide photographic sensitive material by at least 30mol% and a water soluble dye having absorption max. at 570-620nm wavelength in a binder coating film is incorporated into the sensitive material. The internal latent image type silver halide particles may have any halogen compsn. contg. at least 30mol% silver chloride and may be made of silver chloride, silver chlorobromide, silver chloroiodobromide or silver chloroiodide. The pref. silver chloride content of the internal latent image type silver halide particles is >=50mol%, especially >=70mol%. The rapid processability and color reproducibility of the sensitive material are improved and the deterioration of gradation balance at a leg part and the rise of min. density during storage over a long period of time are prevented.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a direct positive silver halide photographic light-sensitive material, and more specifically, to a direct positive silver halide photographic material that can be rapidly developed and has little deterioration in photographic performance even after long-term storage. This invention relates to silver oxide photographic materials.

[Background of the invention]

There are two main types of conventionally known methods for forming direct positive images. One type is to generate fog nuclei in silver halide in advance, and then apply a solarization layer to the silver halide containing the fog nuclei. Alternatively, there is a method in which development nuclei are obtained by destroying fog ridges or latent images using the Burschel effect and the like, and these are developed to form a positive image. Another type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and after image exposure,
This is a method of forming a positive image by performing fogging (development generation treatment) and then surface development, or after image exposure, performing surface development while applying fogging (development nucleus generation treatment).

Of the two methods for forming a positive image as described above, the latter type of method is numerically more sensitive than the former type and is suitable for applications requiring high sensitivity. Are suitable.

Various techniques are known in this technical field. For example, U.S. Patent Nos. 2,592.250, 2,466.957, 2,497,875, and 2
, No. 588.982, No. 3,761.266, No. 3,
The methods described in No. 761.276, No. 3,796.577, British Patent No. 1,151.363, etc. are known.

The above capri processing (development nucleation processing) may be performed by exposing the entire surface to light, chemically using a capri agent, using a strong developer, and It is known that it can also be caused by hot air.

By using these known techniques, it is possible to produce photographic materials that form positive images, but in order to apply these photographic materials to various photographic fields, further improvements in photographic performance and manufacturing are required. A solution to the above problems is desired.

The inclusion of silver chloride in internal latent image type halide grains in order to impart rapid processability is disclosed in Japanese Patent Publication No. 63-647, for example.
No. 76, JP-A-63-254451, JP-A No. 64-655
No. 44, JP-A No. 1-123227, etc.,
There are drawbacks such as large fluctuations in performance when raw samples are stored for long periods of time, particularly an increase in minimum density, and loss of gradation balance in the legs, which is very important for image quality. Furthermore, when a positive color image is formed through development processing, a phenomenon occurs in which other layers are also developed when originally only a specific layer should be developed, resulting in unnecessary color development, a phenomenon called color turbidity. It was found that it is easy to cause

On the other hand, color photographic materials are required to have higher and higher image quality.
There is a need to improve overall photographic properties such as microstructure such as sharpness and graininess, and color reproduction.

In particular, it is desired to faithfully reproduce hues from objects with high brightness to objects with low brightness.

In order to obtain more faithful color reproduction, masking, multilayer effects, spectral sensitivity, etc. were investigated.

Regarding the multilayer effect, for example, Hanson
et al., “Journal of the Optical Society of America”
eOptical 5ociety of Aster
ica)', Vol. 42, pp. 663-669.

Further, U.S. Pat. No. 3,672,898 discloses a color photographic material having a spectral sensitivity distribution such that changes in color balance are small against various light sources such as daylight, fluorescent lamps, and tungsten light. ing.

Furthermore, it is known that the saturation of primary colors such as red, green, and blue can be improved by sharpening the spectral sensitivity distribution of the red-sensitive layer, green-sensitive layer, and blue-sensitive layer.

Furthermore, as an attempt to improve color reproducibility, a technique was developed, for example, in Japanese Patent Application Laid-Open No. 2002-100001, in which a dye that absorbs a wavelength region intermediate between green and red is incorporated into a silver halide photographic light-sensitive material. No. 52/20830, JP-A-1-10
No. 6047, however, all of them have drawbacks such as softening of the leg gradation when raw samples are stored, and color turbidity occurs due to the use of these water-soluble dyes. There are still many problems that need to be resolved.

[Object of the present invention]

Therefore, the object of the present invention is to provide a material that has excellent rapid processing properties, good color reproducibility, does not cause characteristic deterioration even when raw samples are stored for a long period of time, and in particular does not cause an increase in minimum density or deterioration of leg gradation balance. An object of the present invention is to provide a direct positive silver halide photographic material with little color mixture.

[Configuration of the invention]

The above object of the present invention is to provide a red-sensitive emulsion layer containing at least one layer of internal latent image type silver halide grains and a green-sensitive emulsion layer containing at least one layer of internal latent image type silver halide grains on a support. and a direct positive silver halide photographic light-sensitive material having at least one layer of internally latent image type silver halide grains containing at least one layer of internally latent image type silver halide grains. 30 mol%
and the direct positive silver halide photographic light-sensitive material has a maximum absorption wavelength of 5 in the binder coating film.
This is achieved using a silver halide photographic material containing a water-soluble dye having a wavelength of 70 to 620 nm.

The internal latent image type silver halide grains of the present invention contain at least 3
Any halogen composition may be used as long as it contains 0 mol% silver chloride. Examples of the A-isomer include silver chloride, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide.

The silver chloride content of the silver halide grains containing the internal latent image of the present invention is preferably 50 mol % or more, more preferably 70 mol % or more.

The particle shapes are cubic, octahedral, (100), and (11).
1) Any shape such as a tetradecahedron consisting of a mixture of faces, a shape having (110) faces, a spherical shape, a flat shape, or a mixture thereof may be used. The average particle size is preferably 0.05 to 3 μm.

The radial distribution may be a monodisperse emulsion with uniform grain size and crystal habit, or an emulsion with irregular grain size or crystal habit.

The silver halide emulsion used in the present invention may be a mixture of two or more emulsions having different grain sizes.

Furthermore, two or more types of silver halide emulsions having different sensitivities can be applied separately in a plurality of layers.

Examples of the internal latent image direct positive emulsion of the present invention include, for example, U.S. Pat. No. 2,590.250, U.S. Pat.
No. 3,761,266, No. 3,761.276, No. 3,796.577 and British Patent No. 1,151°363
No. 62-215269, etc.

The internal latent image type silver halide photographic light-sensitive material of the present invention comprises at least one layer of internal latent image type silver halide emulsion.

The internal latent image type silver halide emulsion in the present invention is an emulsion having silver halide grains which form a latent image mainly inside the silver halide grains and have most of the photosensitive nuclei inside the grains, and which has arbitrary Silver halides such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and the like are included.

Particularly preferably, the emulsion is prepared by exposing a portion of a sample coated on a transparent support to a light intensity scale for a defined period of time up to about 1 second to obtain surface images of grains substantially free of silver halide solvent. The following surface developer A to develop
Another part of the same emulsion sample is exposed in the same way and developed for 4 minutes at 20°C with internal developer B, which develops the image inside the grains. It indicates the maximum density not greater than 115 of the maximum density obtained. Preferably, the maximum density obtained with surface developer A is 1/1/1 of the maximum density obtained with internal developer B.
not greater than 10.

(Surface developer A) Meter 2.5g L-Ascorbic acid 10g Sodium metaborate (tetrahydrate) 35g Potassium bromide 1g Add water If (Internal developer B) Meter 2.0g Sodium sulfite (anhydrous) 90. 0 g Hydroquinone 8.0 g Sodium carbonate 52.5 g Potassium bromide
5.0g potassium iodide
Add 0.5g water
Further, internal latent image type silver halide emulsions that can be preferably used in the present invention include those prepared by various methods.

For example, the conversion silver halide emulsions described in U.S. Pat. No. 2,592,250, or U.S. Pat.
206.316, 3,317,322 and 3,
367.778, or U.S. Pat. Nos. 3,271.157, 3,447.927 and 3,531.291. Silver halide emulsions having silver halide grains incorporating polyvalent metal ions as described in US Pat. Silver halide emulsion whose grain surface is weakly chemically sensitized or
No. 0-8524, No. 50-38525 and No. 53-2
Silver halide emulsion consisting of grains having a layered structure as described in No. 408, and other JP-A-52-156614
and JP-A-55-127549.

One of the following formulas CI), (II) or (
The compound represented by III) will be explained.

Hereinafter - Formula (I) In the formula, R8 and R4 each represent an aliphatic group, an aromatic group or a heterocyclic group. Ll, L, and each represent a methine group.

In the above formula (I), examples of the aliphatic group represented by R1 and R1 include an alkyl group, a cycloalkyl group, and an alkenyl group. Further, typical aromatic groups include aryl groups, such as phenyl groups and naphthyl groups. Furthermore, representative examples of the heterocyclic group include a benzothiazolyl group and a benzoxacylyl group.

The aliphatic group, aromatic group, and heterocyclic group represented by R8 and R4 further include a hydroxyl group, an amino group, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), an alkoxy group (e.g., methoxy, ethoxy, etc.), and a carboxyl group. It may be substituted with a carbamoyl group, a sulfo group, a sulfamoyl group, an aryl group (eg, phenyl, 4-sulfophenyl, etc.), an aryloxy group (eg, phenoxy, 4-sulfophenoxy, etc.), or the like. Further, the aryl group may be substituted with an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, etc.).

Further, examples in which the aryl group represented by R8 and R1 have a sulfo group include 4-sulfophenyl, 3-sulfophenyl, 2-methyl-4-sulfophenyl, 2-chloro-4-sulfophenyl, 4- Chloro-3-sulfophenyl, 2-chloro-5-sulfophenyl, 2-methoxy-
4-sulfophenyl, 2-hydroxy-4-sulfophenyl, 2.5-dichloro-4-sulfophenyl, 2.6
-dimethyl-4-sulfophenyl, 2.5-disulfophenyl, 3.5-disulfophenyl, 4-”'dituxy-3-sulfophenyl, 2-chloro-6-methyl-4-
Sulfophenyl, 3-carboxy-2-hydroxy-5
-sulfophenyl, 3,6-disulfo-a-naphthyl,
8-hydroxy-3,6-disulfo-a-naphthyl, 5
-Hydroxy-7-sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl and the like can be mentioned.

Examples of the heterocyclic groups R1 and R4 being substituted with a sulfo group include groups such as 2-(6-sulfo)benzothiazolyl and 2-(6-sulfo)benzoxasilyl.

Further, the sulfo group may be bonded to an aryl group via a divalent organic group, for example, 4-(4-sulfophenoxy)
Phenyl, 4-(2-sulfoethyl)phenyl, 3-(
Examples include groups such as sulfomethylamino)phenyl and 4-(2-sulfoethoxy)phenyl.

Further, examples of the aryl groups represented by R1 and R4 being substituted with a carboxyl group include 4-carboxyphenyl, 3.5-dicarboxyphenyl and (/3゜5-disulfophenyl-3-carboxy- 4-hydroxy-5-
Examples include groups such as sulfophenyl.

L,,L! The methine group represented by and has 1 to 1 carbon atoms.
It may be substituted with an alkyl group (eg, methyl, ethyl, isopropyl, t-butyl, etc.) or an aryl group (eg, phenyl, tolyl, etc.).

Among R1 and R6, an aromatic group is preferred, and a 4-sulfophenyl group and a 2.5-disulfophenyl group are particularly preferred.

Typical specific examples of the dye of the present invention represented by the general formula CI) are shown below.These samples of the dye of the present invention can be synthesized by the method described in JP-A-58-111640. I can do it.

- Formula (II) where RS and R1 are each a hydroxyl group, and R''
each represents a hydrogen atom or an alkyl group. L
l, L3, Ll, L, and each represent a methine group. R7 and R1 each represent an aliphatic group, an aromatic group or a heterocyclic group.

In general formula (n), examples of the alkoxy group represented by R11 and R1 include groups such as methoxy, ethoxy, i-propoxy, butoxy, thylamino group,
Examples include dimethylamino group and diethylamino group.

R1, R, and 6, L3, L3, L, and
- It is synonymous with R8, R6, and 1, L3, and L3 in Formula (1).

Typical specific examples of the dye of the present invention represented by general formula (n) are shown below, but the dye of the present invention is not limited thereto.

These dyes can be synthesized by the method described in JP-A-52-20330.

General formula (II+) where R1, R4°, R+i and R1! each represents a hydrogen atom, an alkyl group or an aryl group, L6, Ll, L
l, L4 and ri each represent a methine group.

- In formula (m), R,, R11, R11 and R1
The alkyl group and aryl group represented by ff1 include those having a substituent.

Examples of the alkyl group include groups such as methyl, ethyl, hydroxyethyl, carboxymethyl, cyanoisopropyl, and benzyl.

Examples of the aryl group include phenyl, tolyl, ethylphenyl, chlorophenyl, methoxyphenyl, sulfophenyl, and carboxyphenyl.

The methine groups represented by Ll, L1, L, and Ll have the same meanings as Lx, Lx, and Lx represented by formula CI) above.

Typical specific examples of the dye of the present invention represented by the general formula CI) are shown below, and the dye of the present invention has a maximum spectral absorption wavelength of 570 to 620 in the binder coating film according to the present invention.
A water-soluble dye in the nm range may be contained in any photographic constituent layer, i.e., a silver halide emulsion layer and a non-light-sensitive layer, but is preferably contained in a green-sensitive silver halide emulsion layer or a green-sensitive silver halide emulsion layer. It is contained in a non-photosensitive layer adjacent to the silver halide emulsion layer. The content of these dyes ranges from 5810-' to 5
X 10-"g/ll", preferably I X 10-
= I X 10-"g/-'

The maximum spectral absorption wavelength in the binder coating film according to the present invention is 5
As the dye in the range of 70 to 620 am, the following compounds can also be preferably used.

rl/-1 V-3 V-4 V-5 ■-6 V-2 shi=h@shi1- EV-7 IV-8 In the present invention, the binder forming the photographic constituent layer of the photographic light-sensitive material is used as a binder. It is preferable that the amount used is 8.5 g/m" or less. When carrying out the present invention, in order to further speed up color development, the amount used is 8.0 g/wr. "The following is more preferable, particularly preferably 7.5 g/m" or less. By setting the binder amount to 8.5 g/U3 or less in this way, the amount of binder applied to the photographic constituent layer of a processing solution such as a color developing solution is It is possible to shorten the immersion time and speed up the processing time, and at the same time improve the whiteness of raw samples during long-term storage.

Further, when carrying out the present invention, the amount of binder can be further reduced, but in order to maintain image quality, it is preferable not to reduce the amount of binder too much.

By reducing the amount of binder to 8.5 g/wr" or less, it is possible to shorten the immersion time in processing solutions such as color developer, speeding up the color development process, and at the same time reducing the time required for long-term storage of raw samples. The white background can be improved.

Gelatin is a binder that can be used in the present invention, and in addition to gelatin, appropriate gelatin derivatives can be used depending on the purpose. Suitable gelatin derivatives include, for example, acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, and esterified gelatin.

Further, the photographic material of the present invention may contain other binders depending on the purpose, such as colloidal albumin,
Agar, gum arabic, dextran, alginic acid, cellulose derivatives such as cellulose acetate hydrolyzed to an acetyl content of 10-20%, polyacrylamide, imidized polyacrylamide, casein, urethane carboxylic acids such as vinyl alcohol vinyl amino acetate copolymer. Vinyl alcohol polymers containing groups or cyanoacetyl groups Polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerization of proteins or saturated acylated proteins with monomers having vinyl groups polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, Contains polyethyleneimine, etc., and can be added to photographic constituent layers such as emulsion layers, intermediate layers, protective layers, filter layers, backing layers, etc., depending on the purpose.Additionally, the hydrophilic binder mentioned above can contain additives suitable for the purpose. It is possible to contain plasticizers, lubricants, etc.

The photographic constituent layer of the light-sensitive material of the present invention has a swelling degree of 170
% or less is preferable. When carrying out the present invention, the speed can be further increased by reducing the speed to 160% or less, particularly preferably 150% or less. Here, the degree of swelling is defined by the following formula.

WQ Swelling degree c s W ) - -X ioo%Q In the above formula, WQ is the weight per unit area of the photographic constituent layer to be measured, and Wtm is the weight of the photographic light-sensitive material having the photographic constituent layer described above in pure water at 38°C. It represents the weight per unit area of pure water impregnated into the photographic constituent layer when immersed in water for 3 minutes. In other words, the degree of swelling is used as a measure of the amount of penetration of a processing solution such as a color developer into the photographic constituent layer.

Therefore, in the light-sensitive material of the present invention, if the degree of swelling is 170% or less, good images can be obtained. It is more preferably 160% or less, particularly preferably 150% or less, and by lowering the degree of swelling in this manner, further speeding up of the color development process can be achieved. However, 100
If it is less than 100%, problems may remain in image quality, so it is practically preferable to set it to 100% or more.

Various hardeners can be used to adjust the degree of swelling when carrying out the present invention. For example, T.

H. James, “The Theory of the Photographic Process” (4th edition), pp. 77-87,
Or “Research Disclosure” magazine 1764
Hardeners described in No. 3 can be used. Specific examples of these hardeners include inorganic hardeners such as chrome alum, formaldehyde, glutaraldehyde,
Aldehyde hardeners such as mucohalogenic acid, a-diketone hardeners such as 2,3-butanedione, S-) lyazine hardeners such as 2,4-dichloro-6-hydroxy-5-triazine, Examples include epoxy or aziridine hardeners, active olefin hardeners such as divinyl ketone, and polymer hardeners such as dialdehyde starch. However, the present invention is not limited to the above-mentioned hardening agents.

Furthermore, in addition to adjusting the degree of swelling with a hardening agent, a hardening accelerator such as resorcinol can be used. or,
It can also be adjusted by adjusting the pH of the gelatin layer. Furthermore, the photographic light-sensitive material on which the photographic constituent layers are formed can be adjusted by controlling the degree of heating and/or humidification.

The photographic constituent layers in the light-sensitive material of the present invention include a blue-sensitive silver halide emulsion layer, a green-sensitive silver halide emulsion layer, a red-sensitive silver halide emulsion layer, and a colloidal silver layer.

In actual practice, the above-mentioned photosensitive material can be further provided with an intermediate layer, a protective layer, a backing layer, etc.

Further, in the internal latent image type silver halide emulsion that can be used in the present invention, commonly used stabilizers, such as compounds having an azaindene ring and nitrogen-containing heterocyclic compounds having a mercapto group (typically, 4- hydroxy-6
-methyl-1,3,3a,7-chitrazaindene and l
-Phenyl-5-mercaptotetrazole), etc., in an amount of 1 mg" to 1 mole of silver halide, provides more stable results with a lower minimum concentration. In addition, in the present invention, fogging As the inhibitor or stabilizer, for example, mercury compounds, triazole compounds, azaindene compounds, benzothiazolium compounds, zinc compounds, etc. can be used.

Various photographic additives may optionally be added to the silver halide emulsion used in the present invention. For example, optical sensitizers that can be used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holoporacyanines, hemicyanines, and oxonols. These optical sensitizers contain basic groups such as thiazoline and thiazole as a nitrogen-containing heterocyclic nucleus, or rhodanine, thiohydantoin, oxazolidinedione, barbyl, etc. Those containing a nucleus of acid, thiobarbylic acid, pyrazolone, etc. are preferable, and such a nucleus can be substituted with a polygroup such as alkyl, hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, alkoxy, etc., and carbon Fusing with a ring or heterocycle is optional.

The internal latent image type silver halide emulsion used in the present invention can be supersensitized. Regarding the method of supersensitization, for example, "Review of the mechanism of supersensitization J (Review of 5u
peoplesitization), Photog
aphic 5science and Engineer
ing (PSE) Vol, 18.4418 pages (19
1974).

In addition, in the internal latent image type silver halide emulsion that can be used in the present invention, additives used depending on the purpose include, for example, dihydroxyalkane as a wetting agent, and furthermore, as a film property improver, for example, alkyl acrylate or Water-dispersible particulate polymeric substances obtained by emulsion polymerization of copolymers of alkyl methacrylate and acrylic acid or methacrylic acid, styrene-maleic acid copolymers, styrene-maleic anhydride bar 7 alkyl ester copolymers, etc. etc., and coating aids include, for example, saponin, polyethylene glycol lauryl ether, and the like. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speed. The use of conditioning agents, matting agents, etc. is optional.

The silver halide emulsion prepared as described above is coated on a support via a subbing layer, an antihalation layer, a filter layer, etc., if necessary, to obtain a silver halide photographic light-sensitive material with an internal latent image.

It is useful to use the silver halide photographic light-sensitive material to which the present invention is applied as a color photographic material, and in this case it is preferable to include cyan, magenta and yellow dye image-forming couplers in the silver halide photographic emulsion.

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

Any support can be used for the silver halide photographic light-sensitive material to which the present invention is applied, but typical supports include polyethylene terephthalate film, polycarbonate film, polystyrene film, and polypropylene, which are subbed-treated as necessary. Film, cellulose acetate film, glass, baryta paper, polyethylene laminate paper, etc.

Further, the silver halide photographic light-sensitive material to which the present invention is applied has various photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, a subbing layer, a backing layer, and an antihalation layer on a support. It is possible to install many.

Silver halide photographic materials to which the present invention is applied include general use, X-ray use, color use, false color use, printing use, infrared use,
It can be effectively applied to various uses such as microscopic use and silver dye bleaching, and it can also be applied to colloid transfer method, US Pat. No. 3,087.817, US Pat. No. 606, U.S. Patent No. 3,253,915 to Weyertz et al., U.S. Patent No. 3 to Whitemore et al.
, 227.550, U.S. Pat. No. 3,227.551 to Barr et al., U.S. Pat. No. 3,227,552 to Whitemore.
U.S. Pat. No. 3,415.644 and Rand, No. 3,
415,645 and 3,415.646, color diffusion transfer methods,
It can also be applied to absorption transfer methods, etc.

〔Example〕

The present invention will be illustrated below with reference to Examples, but the embodiments of the present invention are not limited thereto.

Example-1 (Preparation of emulsion EM-1) While vigorously stirring an aqueous gelatin solution and keeping it at 75°C,
A potassium bromide aqueous solution and a silver nitrate aqueous solution were added simultaneously over 15 minutes to obtain an octahedral silver bromide emulsion with an average grain size of 0.30 μm. This emulsion contains 0.1 g of 3,4 per mole of silver.
-dimethyl-1,3-thiazoline-2-thione, 4 g
of sodium thiosulfate, 711 g of chloroauric acid (tetrahydrate)
Chemical sensitization was performed by sequentially adding and heating at 75° C. for 25 minutes. The obtained particles were used as cores and further grown under the same particle growth conditions as the first time, until the average particle size was finally 0.
．． A monodisperse core/shell silver bromide emulsion of 55 μm octahedron was obtained. The variation in particle size was 10%. 1.5 g of sodium thiosulfate per mole of silver in this emulsion;
5 mg of chloroauric acid (tetrahydrate) was added and chemical sensitization was performed by heating at 60° C. for 45 minutes to obtain internal latent image type silver halide emulsion EM-1.

(Preparation of Emulsions EM-2 to EM-5) EM-2 to EM-5 were prepared in the same manner as Emulsion EM-1 and have halogen compositions as shown in Table-1.

Table 1 The following first layer (
The bottom layer) to the ninth layer (top layer) were applied.

In addition, 5A-1 and 5A-2 were used as coating aids, and
Coating was performed using HA-1 and HA-2 as hardeners.

Below are the ingredients and g/l! Indicates the amount of coating expressed in units.

Silver halide is a silver equivalent value.

1st layer (red-sensitive layer) EM-1 spectrally sensitized with red-sensitive sensitizing dyes (so-1, 5D-2)...0.35 Gelatin...1.3 cyan coupler (c-i > ...0.2
6 cyan coupler (c-2)...0
．． 26 Solvent (so-t)...
0.16 stabilizer (ST-1,5T-2,5T-3,5T
-4) Second layer (intermediate layer) Color mixing prevention agent (AS-1) ...0.0
8 Solvent (SO-2)...0.
18 Gelatin...0.
8 Third layer (green sensitive layer) EM-1 spectrally sensitized with green sensitizing dye (SD-3)
...0.30 Gelatin ...1.1 Magenta Power Puller CM-1) ...0.22
Image stabilizer (AO-1, AO-2 equivalent) ・0.30 Solvent (S O-3) ・0.15 Stain inhibitor (As-2) ...0. O1
Stabilizer (ST-1, 5T-2, 5T-3, 5T-4) 4th layer (intermediate layer) Same as 2nd layer.

5th layer (yellow filter layer) Yellow Colloy F Silver-0,10 Gelatin...0.95
Color mixing inhibitor (AS-1) -0,06 solvent (30-2) -0,15 No. 6
Same as layer 2.

7th layer (blue-sensitive layer) EM-1 spectrally sensitized with blue-sensitive sensitizing dye (SD-4) Gelatin...0.57...1.1 Yellow coupler (Y-1'')...・0.
60 solvent (30-1) ...0
．． 15 Stain inhibitor (As-1)...
0.005 stabilizer (ST-1,5T-2,5T-3,5
T-4) 8th layer (ultraviolet absorption layer) Ultraviolet absorber (UV-1, UV-2 equivalent) -1.0 solvent (SO-3) ...0.15 gelatin ...1.0 water soluble Sex dye (Table-2) ...0.02 No. 9
Layer (protective layer) Silica (average particle size 4 μm) ...0.02
Gelatin...1.0D
-4 -1 Shimu -2 -1 Y-1 0-1 o-2 T-2 A-1 A-2 ■ C0CR-CO! S- u S-2 l O-1 O-2 A-2 The obtained sample is designated as material No. 1.

Sample No. 1 Samples Nos. 2 to 12 were prepared in the same manner.

Sample No. 1 Table 2 shows the differences between the two.

*Comparative Dye A The silver halide color photographic light-sensitive material prepared as above (sample No. 1 = 12) was exposed with a light-sensitive needle through an optical wedge, and then subjected to the following processing steps -1, 2 and 1. 3 was applied, and sensitometry was performed. Maximum density (Dsax) and minimum density (D
ain) are shown in Table-3.

In addition, another part of sample No. l = 12 has an M concentration,
and green light on the entire surface so that the C concentration is the minimum concentration, respectively.
After applying red light, it was exposed to blue light through an optical wedge, processing-3 was performed, and the M density at the exposure amount at which the Y density was 1.0 was measured as color turbidity. (Denoted as DO) Furthermore, another part of sample No. 1=12 was heated at 50°C and 80°C.
% for 3 days, and then exposed to light with a photosensitive needle through an optical wedge, followed by treatment-3 and sensitometry.

The gamma balance B/G and R/G of the legs are also shown in Table 3. Here, the gamma of the leg is expressed as the absolute value of the slope of the straight line connecting the densities (minimum density + 0.15) and (minimum density + 0.5) on the characteristic curve, and the gamma value of the blue light measurement is The result obtained by dividing the gamma value of optical measurement and multiplying by 100 is shown as gamma balun XB/G. Similarly, the ratio to gamma in red light measurement is the balance R/G.

Processing process-1 (temperature and air flow time) (1) Immersion (color developer) 38°C 8 seconds [2] Fog exposure -1 lux'clO second [3] Color development 38°C 60 seconds [4] Bleach-fixing
35℃ 60 seconds [5] Stabilization geography 25-3
0℃ 1 minute 30 seconds [6] Drying 75-80
℃ 1 minute processing step-2 Only the color development time is different from processing step-1.

[3] Color development 90 seconds processing step -
3 Only the time of color development differs from that of processing step-1.

[3] Color development 120 seconds processing solution composition is as follows.

(Color developer) Benzyl alcohol ethylene glycol 15m! Potassium sulfite 2.0g Potassium bromide 1.5g Sodium chloride Potassium carbonate Hydroxylamine sulfate Polyphosphoric acid (TPPS) 3-Methyl-4-amino-N-ethyl-N-β-methanesulfonamide ethylaniline sulfate Fluorescent whitening Agent (4.4'-diaminostilbendisulfonic acid derivative) Add aqueous potassium hydroxide to bring the total amount to 1 g.

(bleach-fix solution) Ferric ethylenediaminetetraacetic acid ammonium dihydrate Ethylenediaminetetraacetic acid Ammonium thiosulfate (70% solution) Ammonium sulfite (40% solution) Add water to bring the total volume to la, carbonate power Adjust the pH to 7.1 with hydroacetic acid.

Adjusted to pH-10.20 Soot 0.2g 3Q. O g 3,0 g 2,5g 5,5g 1,0g 2,0g 0g 3g 100■4 27,5s4 Rum or (stabilizing liquid) 5-chloro・2-methyl-4-isothiazolin・3・one 1. 0 g ethylene glycol 10 g hydroxyethylidene-1, todiphosphonic acid 2.5 g bismuth chloride 0.2 g magnesium chloride 0.1 g ammonium hydroxide (
28% aqueous solution) 2.0g sodium nitrilotriacetate Add 1.0g water to make a total volume of 1ffi, and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

As is clear from Table 3, sample No. of the present invention.

6.7.8.9.11 and 12 obtained a higher maximum density than the comparative sample even though the color development time was short, and when yellow color was developed, green absorption was small and the color became cloudy. It can be seen that is small.

Furthermore, the sample of the present invention is good, with small fluctuations in leg gamma balance from a fresh sample even when the raw sample is stored at high temperatures.

Example-2 Paper support laminated on both sides with polyethylene (thickness 17
A color photographic material was prepared in which the following 1st to 12th layers were coated on the front side of the film (5 μm), and 13th to 14th layers were coated on the back side. The first layer coating side of the polyethylene contains titanium white as a white pigment.

(Photosensitive layer composition) The components and the coating amount expressed in g/m 311 are shown below.

Note that silver halide is shown in terms of silver equivalent value.

The emulsions used in each layer were prepared according to the manufacturing method for emulsion EM-11 below. However, the emulsion in the twelfth layer is not chemically sensitized and has substantially no photosensitivity.

(Preparation of emulsion EM-11) Monodisperse silver chlorobromide EM-11 was prepared as follows.

While controlling the aqueous solution containing ossein gelatin at 50°C, an aqueous solution containing silver nitrate and an aqueous solution containing potassium bromide were added simultaneously by a controlled double jet method at a rate that did not generate new silver halide nuclei. ,0
．． An emulsion consisting of 25 micron silver bromide cubic grains was obtained. To the obtained silver bromide emulsion, an aqueous solution containing silver nitrate and an aqueous solution containing sodium chloride were added simultaneously by a controlled double jet method at a rate that did not generate new silver halide nuclei to obtain a grain size of 0.32μ■. An emulsion was obtained.

The grain shape was cubic and a monodispersed emulsion with uniform shape and size. (Width of distribution: 8%, silver chloride content: 52%) The photosensitive silver halide emulsion used in Example-2 was as follows:
All have a silver chloride content of 52%.

111 layer (low sensitivity red sensitive layer) Silver chlorobromide (average particle size 0.3 μm, particle size distribution [
Coefficient of variation] 8%) ... Silver chlorobromide spectrally sensitized with 0.06 red sensitizing dye (SD-5, 5D-6, 5D-7) (average particle size o, 45 μm 1 particle size distribution lO% )-o,
i.

Gelatin...Table-4 Cyan coupler CC-3)...0.11 Cyan coupler (C-4)...0.11 Anti-fading agent (UV-3, UV-4 equivalent)...0 .12 Coupler dispersion medium (P-1) ...0.03
Coupler solvent (30-1,5O-4)...0.06 2nd layer (high sensitivity red sensitive layer) Salt spectrally sensitized with red sensitizing dye (SD-5, 5D-6, 5D-7) Silver bromide (average particle size O, aOμ ugly, particle size distribution 1
5%) ...0.14 gelatin
°...Table-4 Cyan coupler (C-3)...0.15 Cyan coupler (C-4)...0.15 Anti-fading agent (
UV-3, UV-4 equivalent)...0.15 Coupler dispersion medium (p-i)...0.03 Coupler solvent (So-1,5O-4)...0.10 Third layer (Intermediate layer) Gelatin color mixing inhibitor (As-1”) Solvent (So-1,5O-5) 4th layer (low sensitivity green sensitive layer) Green sensitizing dye (SD-7) Silver oxide (average particle size 0 .25μm1...Table 4...0.08...0.16 Spectral sensitized packed grain size distribution 8%)...0.04 Spectral sensitized particle size distribution...0. 06...Table-4...0.11...0.10 .5O-a equivalent) Green sensitizing dye (SD-7, 3D-8) Sensed silver chlorobromide (average particle size 0 Gelatin magenta coupler (M-2) Antifading agent (AO-3) Coupler solvent (So-5...0.15 5th layer (high sensitivity green sensitive layer) Green sensitizing dye (SD-7) , 5D-8)-t' spectrally sensitized silver chlorobromide (average particle size 0.82 m1 particle size distribution 16%)
...0.10 gelatin
...Table-4 Magenta coupler (M-2) ...0.11 Antifading agent (AO
-4) -0,10 coupler solvent (So-
5,5O-6 equivalent)...0.15 6th layer (intermediate layer) 7th layer (yellow filter layer) same as the 3rd layer Yellow colloidal silver gelatin color mixing inhibitor (AS-1) Solvent (30- 1,5o-5) 8th layer (intermediate layer) 9th layer same as 3rd layer (low sensitivity blue sensitive layer) ...0.20 ...Table-4 ...0.06 ...0 .15 Blue sensitizing dye (SD-9, 5D-10) Spectrally sensitized silver chlorobromide (average particle size 0°45 μm, particle size distribution 8%)
...0.07 blue sensitizing dye (SD-9, SD-10) -C' spectrally sensitized silver chlorobromide (average particle size 0.602 m1 particle size distribution 14%
”) ・0.10 gelatia ・・・0゜5゜yellow coupler (Y-2) ・0.20 antifading agent (AO-4) ・0.20 coupler solvent (
So-4) ・0.05 1st θ layer (high sensitivity blue-sensitive layer) 1 [Silver chlorobromide spectrally sensitized with sensitized & prime (SD-9, 5D-10) (average grain size 1.2 μm 1 grain Diameter distribution 21%)
...0.25 Gelatin ...Table 4 Yellow coupler (Y-2) ...0.38 Anti-fading agent (
A o -4) -0,10 coupler solvent (So-4) ・0.10 11th layer (ultraviolet absorbing layer) Gelatin ...Table 4 Ultraviolet W & absorber (UV-3, UV-4, UV- 5 equivalents)
...1.0 Color mixing prevention agent (
AS-1, AS-3 equivalent)...0.15 Solvent (SO-4)...0.1
5 Irradiation prevention dye (Al-1, Al-2 equivalent) ...0.02 Irradiation prevention dye (AI-3, Al-4 equivalent)
...0.02 water-soluble dye (1-
1) ...0.02 12th layer (protective layer) Fine grain silver chlorobromide (silver chloride 97 mol%, average particle size 0.2p
m) ...acrylic modified copolymer of 0.05 polyvinyl alcohol (denaturation degree 17%)
) ... 0.02 Polymethyl methacrylate particles (average particle size 2.4 μm), silicon oxide (average particle size 5 μm) equivalent amount ... 0.05 Gelatin ... Table 4 Gelatin hardening agent ( HA-3) ...Table-4 No. 13
Layer (back layer) Gelatin...2.50 14th layer (back protective layer) Polymethyl methacrylate particles (average particle size 2.4
μm), silicon oxide, (average particle size 5, un) equivalent
...0.05 gelatin
...2.00 gelatin hardening agent (
HA-3)...0.11 Each photosensitive layer contains FA-11, FA-12 and FA-13 as capri agents at a concentration of 2.0% per mole of silver halide. OX No-'%
Also, 4.5X 10-' moles each of fog suppressants 5T-11 and 5T-12 were added.

D-9 D-8 P-1 AO-3 AO-4 S-3 I-1 -2 -2 -3 -4 A-3 A-2 Silver halide color photographic light-sensitive material sample prepared as above Part of No. 13 to 17 was heated at 55°C, 80% R.
It was stored under H conditions for 6 days. Also, another part is the same period,
It was stored in the refrigerator (5°C). After each sample was exposed to light through an optical wedge, it was subjected to Process-8 (described later) and the minimum density and maximum density were measured.

The results obtained are shown in Table-5.

Processing process Time Temperature Volume Replenishment amount Color development
130 seconds 38℃ 3 m 300mQ/■1
Bleach fixing 40 seconds 35℃ 3ft 3OO
s2/m” water washing (1) 40 seconds 33℃ 3a water washing (2) 40 seconds 33℃ 312 water washing (3) 1
5 seconds 33℃ 0.5ff 320m12/m
``Drying 30 seconds 80℃ To replenish the washing water, refill the washing bath (3),
This is a so-called countercurrent replenishment method in which the overflow liquid of step 3) is led to the washing bath (2), and the overflow liquid of the washing bath (2) is led to the washing bath (1). At this time, the drift caused by the photosensitive material
The amount of bleach-fix solution carried from the white fixing bath to the washing bath (1) is 3.
5 m4/m', and the ratio of the amount of washing water replenishment to the amount of bleach-fix solution brought in is 9.1 times, t;.

The composition of each treatment liquid was as follows.

Ethylenediaminetetrakismethylenephosphonic aciddiethylene glycolbenzylalcoholpotassium bromideSodium sulfiteN, diethylhydroxydylaminetriethylenediamine (1゜4.diazabicyclo[2,2゜21octane) N.ethyl-N-β-methanesulfonamidoethyl-3・Methi 0.5 g 0.5 g 10 mm 12.0 mQ O, 65 g 2.4 g 4.0 g 10 all 14.4■a 2.9 g 4°8g 4.0 4.8g 5.6 6. 6g Luaniline sulfate potassium carbonate optical brightener (diaminomethylben type) Add water to pH (25℃) Bleach-fix solution 27.0g 1.0g iooo Tsuru a 10.50 25.0g 1.2g 000mQ 10.80 Mother liquor replenisher Ethylenediaminetetraacetic acid 4.0 g Same as mother liquor 2
Sodium dihydrate ethylenediaminetetraacetic acid 46.0 gFe(m) rare ammonium dihydrate ammonium thiosulfate 155 Q (700g
IQ) p-toluenesulfinic acid 20.0 g Sodium bisulfite 12.0 g Ammonium bromide 50.0 g Ammonium nitrate
Add 30.0 g of water to 1000 apH (25°C) 6.20 Table 5 Washing water Both mother liquor and replenisher are tap water H1! Calcium and magnesium ion concentrations were determined by passing water through a mixed bed column filled with strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). The concentration was adjusted to below 3 mg/l, and then 20 g/12 of sodium incyanurate dichloride and 1.5 g of sodium sulfate #1 were added. pti of this liquid
was in the range of 6.5 to 7.5.

As can be seen from Table 5, from the results of preserving raw samples under particularly severe conditions, the increase in the minimum concentration is smaller when the total amount of gelatin attached is less than 8.5 g/m'', and the degree of swelling is 1.
When the ratio is smaller than 70%, the increase in the minimum concentration is also smaller.

Claims (1)

[Claims] A red-sensitive emulsion layer containing at least one internal latent image type silver halide grains, at least one green sensitive emulsion layer containing internal latent image type silver halide grains, and at least one layer of internal latent image type silver halide grains on a support. In a direct positive silver halide photographic material having a blue-sensitive emulsion layer containing image-type silver halide grains, at least one layer of internal latent image-type silver halide grains contains at least 30 mol% of silver chloride; The direct-positive silver halide photographic light-sensitive material is characterized in that the direct-positive silver halide photographic light-sensitive material contains a water-soluble dye having a maximum absorption wavelength of 570 to 620 nm in the binder coating film.