JP2835627B2 - Direct positive silver halide photographic material - Google Patents

Description

The present invention relates to a direct positive silver halide photographic material,
More specifically, the present invention relates to a direct positive silver halide photographic material capable of rapid processing and having little deterioration in photographic performance even after long-term storage.

[Background of the Invention]

Conventionally, there are mainly two types of methods for forming a direct positive image. One type is a method in which fog nuclei are generated in advance in silver halide, and solarization or Herschel is applied to the silver halide having the fog nuclei. This is a method of forming a positive image by obtaining a development nucleus by destroying a fog nucleus or a latent image by utilizing the effect and the like, and developing this nucleus. Another type uses an internal latent image type silver halide emulsion that has not been fogged in advance, and after image exposure, fog processing (development nucleation processing) and then surface development, or after image exposure. This is a method of forming a positive image by performing surface development while performing fogging processing (development nucleation processing).

Among the two methods for forming a positive image as described above, the latter type is generally higher in sensitivity than the former type and is suitable for applications requiring high sensitivity. I have.

Various techniques are known in this technical field. For example, U.S. Pat.Nos. 2,592,250 and 2,466,9
No. 57, No. 2,497,875, No. 2,588,982, No. 3,761,266
Nos. 3,761,276 and 3,796,577 and British Patent 1,151,
No. 363 is known.

The above fogging treatment (development nucleus generation treatment) may be performed by giving an entire surface exposure, may be performed chemically using a fogging agent, or may use a strong developing solution.
It is also known that heat treatment or the like may be used.

By using these known techniques, photographic light-sensitive materials capable of forming a positive image can be produced. However, in order to apply these photographic light-sensitive materials to various photographic fields, photographic performance is further improved and production is further increased. It is desired to solve the above problems.

The incorporation of silver chloride in the internal latent image type halide grains to provide rapid processing is described in, for example, JP-B-63-64776.
JP-A-63-254451, JP-A-64-65544, JP-A-1-1-1
Although described in 23227, etc., there is a drawback that the performance fluctuation when a raw sample is stored for a long time is large, especially the minimum density increases, and the gradation balance of the legs which is very important for image quality is impaired . In addition, when a positive color image is formed by performing a development process, a phenomenon in which other layers are originally caused to develop where only a specific layer should be developed occurs.
It has been found that it is easy to cause a phenomenon called so-called color turbidity that causes unnecessary color development.

On the other hand, color photographic light-sensitive materials are required to have higher and higher image quality, and it is necessary to improve image structures such as sharpness and granularity and to improve overall photographic characteristics such as color reproduction. In particular, it is desired to faithfully reproduce hues from a high-brightness subject to a low-brightness subject.

In order to obtain more faithful color reproduction, studies such as masking, overlay effect, and spectral sensitivity have been made.

For an explanation of the multi-layer effect, see, for example, Hanson et al., "Journal of the Optical Society.
of America), Vol. 42, pp. 663-669.

U.S. Pat. No. 3,672,898 discloses a color photographic light-sensitive material having a spectral sensitivity distribution such that the change in color balance with respect to various light sources such as daylight, fluorescent light, and tungsten light is small.

It is also 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.

Further, as an attempt to improve color reproducibility, a technique of improving color reproducibility by incorporating a dye absorbing a wavelength region between green and red into a silver halide photographic light-sensitive material has been disclosed in, for example, Nos. 52-20830 and JP-A-1-106047, all of which have disadvantages such as softening of the leg gradation when a raw sample is stored, and use of these water-soluble dyes. When color turbidity occurs due to this, there are still many problems to be solved.

(Object of the present invention)

Therefore, an object of the present invention is to provide excellent rapid processing, good color reproducibility, and property deterioration even when a raw sample is stored for a long period of time.
In particular, there is no increase in minimum density or deterioration in leg tone balance,
It is another object of the present invention to provide a direct positive silver halide photographic light-sensitive material having less color mixture.

[Configuration of the invention]

An 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 on a support, and an edge-sensitive emulsion layer containing at least one layer of internal latent image type silver halide grains. And a direct positive silver halide photographic material having a blue-sensitive emulsion layer containing at least one internal latent image type silver halide grain, wherein at least one layer of the internal latent image type silver halide grain contains at least 30 silver chloride. Mol%
And the direct positive silver halide photographic material has an absorption maximum wavelength of 57
This is achieved by a silver halide photographic light-sensitive material containing a water-soluble dye having a wavelength of from 0 to 620 nm.

The internal latent image type silver halide grains of the present invention have at least
Any halogen composition may be used as long as it contains 30 mol% silver chloride. Specifically, they are silver chloride, silver chlorobromide, silver chloroiodobromide, and silver chloroiodide.

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

Particles are cubic, octahedral, {100} and {111}
It may be any one of a tetrahedron composed of a mixture of planes, a shape having {110} planes, a sphere, a flat plate, or a mixture thereof. The average particle size is preferably from 0.05 to 3 μm.

The size distribution may be a monodisperse emulsion having a uniform particle size and crystal habit or an emulsion having no uniform particle size and crystal habit.

The silver halide emulsion used in the present invention may be a mixture of two or more emulsions having different grain sizes. Further, two or more kinds of silver halide emulsions having different sensitivities can be separately used in a plurality of layers.

As the internal latent image type direct positive emulsion of the present invention, for example,
U.S. Pat.Nos. 2,590,250, 2,466,957, 2,497,875
Nos. 2,588,982, 3,761,266, 3,761,276,
No. 3,796,577 and British Patent 1,151,363, JP-A-62-21
No. 5269.

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

The internal latent image type silver halide emulsion in the present invention is an emulsion having a silver halide grain mainly forming a linear image inside the silver halide grain and having most of the photosensitive nucleus inside the grain, 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, wherein only a surface image of grains substantially free of silver halide solvent is obtained. When developing at 20 ° C. for 4 minutes using the following surface developing solution A, another part of the same emulsion sample is similarly exposed to develop an image inside the grains. Shows the maximum density not more than 1/5 of the maximum density obtained when developing at 20 ° C. for 4 minutes. Preferably, the maximum density obtained with the surface developer A is not more than 1/10 of the maximum density obtained with the internal developer B.

(Surface developer A) Meter 2.5 g L-Ascorbic acid 10 g Sodium metaborate (tetrahydrate) 35 g Potassium bromide 1 g Add water 1 (Internal developer B) Meter 2.0 g Sodium sulfite (anhydrous) 90.0 g Hydroquinone 8.0 g Sodium carbonate water salt 52.5 g Potassium bromide 5.0 g Potassium iodide 0.5 g Water is added. 1 The internal latent image type silver halide emulsion preferably used in the present invention can be prepared by various methods. Things included.

For example, a conversion type silver halide emulsion described in U.S. Pat.No. 2,592,250, or U.S. Pat.
Nos. 3,317,322 and 3,367,778, and silver halide emulsions having internally chemically sensitized silver halide grains or U.S. Pat.Nos. 3,271,157, 3,447,927 and 3,531,291. Silver halide emulsions having silver halide grains containing valent metal ions, or silver halide grains having weakly chemically sensitized grain surfaces of silver halide grains containing a doping agent described in U.S. Pat. No. 3,761,276 Emulsion, or JP-A-50-8524, 50
Silver halide emulsions comprising grains having a laminated structure described in JP-A-38525 and JP-A-52-2408,
And silver halide emulsions described in JP-A-52-156614 and JP-A-55-127549.

The compound represented by the following general formula (I), (II) or (III) which is preferably used as a water-soluble dye having a spectral absorption maximum wavelength in the range of 570 to 620 nm in the binder coating film according to the present invention will be described. I do.

In the formula, R ₃ and R ₄ each represent an aliphatic group, an aromatic group, or a heterocyclic group. L ₁ , L ₂ and L ₃ each represent a methine group.

In the general formula [I], examples of the aliphatic group represented by R ₃ and R ₄ include an alkyl group, a cycloalkyl group, and an alkenyl group. The aromatic group typically includes an aryl group, for example, a phenyl group, a naphthyl group and the like. Further, as the heterocyclic group, for example, a benzothiazolyl group and a benzooxazolyl group can be exemplified.

The aliphatic group, aromatic group and heterocyclic group represented by R ₃ and R ₄ further include a hydroxyl group, an amino group, a halogen atom (eg, fluorine, chlorine, bromine, etc.) and an alkoxy group (eg, methoxy, ethoxy, etc.) , A carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, an aryl group (eg, phenyl, 4-sulfophenyl), an aryloxy group (eg, phenoxy, 4-sulfophenoxy). The aryl group has 1 carbon atom.
And may be substituted with an alkyl group (e.g., methyl, ethyl, etc.).

Examples of the aryl group represented by R ₃ and R ₄ having a sulfo group include 4-sulfophenyl, 3-sulfophenyl, 2-methyl-4-sulfophenyl, and 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-phenoxy-3-sulfophenyl, 2-chloro-6-methyl-4-sulfophenyl, 3-carboxy-2-hydroxy-5-sulfophenyl, 3,6-disulfo-α -Naphthyl, 8-hydroxy-3,6-disulfo-α-naphthyl, 5-hydroxy-7
-Sulfo-β-naphthyl, 6,8-disulfo-β-naphthyl and the like.

Examples of the case where the heterocyclic group of R ₃ and R ₄ are substituted with a sulfo group include groups such as 2- (6-sulfo) benzothiazolyl and 2- (6-sulfo) benzoxazolyl. it can.

Further, the sulfo group may be bonded to the aryl group via a divalent organic group, for example, 4- (4-sulfophenoxy) phenyl, 4- (2-sulfoethyl) phenyl,
Groups such as-(sulfomethylamino) phenyl and 4- (2-sulfoethoxy) phenyl can be exemplified.

Examples of the aryl group represented by R ₃ and R ₄ substituted with a carboxyl group include 4-carboxyphenyl, 3,5-dicarboxyphenyl and 3,5-disulfophenyl-3-carboxy- And groups such as 4-hydroxy-5-sulfophenyl.

The methine group represented by L ₁ , L ₂ and L ₃ is an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl, isopropyl, t-butyl, etc.) or an aryl group (eg, phenyl, tolyl, etc.) May be substituted.

Of R ₃ and R ₄ , an aromatic group is preferable, and a 4-sulfophenyl group and a 2,5-disulfophenyl group are particularly preferable.

Hereinafter, typical specific examples of the dye of the present invention represented by the general formula [I] are shown, but the dye of the present invention is not limited thereto.

These samples can be synthesized by the method described in JP-A-58-111640.

Wherein R ₅ and R ₆ are each a hydroxyl group, an alkoxy group or (However, R ′ and R ″ each represent a hydrogen atom or an alkyl group.) L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group. R ₇ and R ₈ Each represents an aliphatic group, an aromatic group, or a heterocyclic group.

In the general formula (II), examples of the alkoxy group represented by R ₅ and R ₆ include groups such as methoxy, ethoxy, i-propoxy, and butoxy; Examples of the amino group include an amino group, an ethylamino group, a dimethylamino group, a diethylamino group and the like.

R ₇ , R _{8 and} L ₁ , L ₂ , L ₃ , L ₄ and L ₅ are represented by the general formula (I)
Has the same meaning as R ₃ , R _{4 and} L ₁ , L _2, and L ₃ .

Hereinafter, typical specific examples of the dye of the present invention represented by the general formula [II] are shown, 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.

In the formula, R ₉ , R ₁₀ , R ₁₁ and R ₁₂ each represent a hydrogen atom, an alkyl group or an aryl group. L ₁ , L ₂ , L ₃ , L ₄ and L ₅ each represent a methine group.

In the general formula [III], the alkyl group and the aryl group represented by R ₉ , R ₁₀ , R ₁₁ and R ₁₂ include those having a substituent.

Examples of the alkyl group include methyl, ethyl, hydroxyethyl, carboxymethyl, cyanoisopropyl,
And benzyl and the like.

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

The methine groups represented by L ₁ , L ₂ , L ₃ , L ₄ and L ₅ have the same meanings as L ₁ , L ₂ and L ₃ represented by the general formula [I].

Hereinafter, typical specific examples of the dye of the present invention represented by the general formula [I] are shown, but the dye of the present invention is not limited thereto.

The water-soluble dye having a spectral absorption maximum wavelength in the range of 570 to 620 nm in the binder coating film according to the present invention may be contained in any photographic constituent layer, i.e., a silver halide emulsion layer and a non-photosensitive layer. It is preferably contained in a green light-sensitive silver halide emulsion layer or a non-light-sensitive layer adjacent to the green light-sensitive silver halide emulsion layer. The content of these dyes is 5 × 10 ^-4
5 × 10 ⁻² g / m ² , preferably 1 × 10 ⁻³ to 1 × 10 ⁻² g / m ² .

The spectral absorption maximum wavelength in the binder coating film according to the present invention is
As the dye at 570 to 620 nm, the following compounds can also be preferably used.

In the present invention, the binder forming the photographic component layer of the photographic light-sensitive material can function as a binder, and the amount used is preferably 8.5 g / m ² or less. In practicing the present invention, further the amount used to accelerate the color development is more preferably 8.0 g / m ² or less, particularly preferably 7.5
g / m ² or less. By reducing the amount of binder to 8.5 g / m ² or less in this way, the immersion time of a processing solution such as a color developing solution in the photographic constituent layer is shortened, and the processing time is shortened. White background can be improved.

In practicing the present invention, the amount of binder can be further reduced, but it is preferable that the amount of binder is not too small in order to maintain image quality. By setting the amount of the binder to 8.5 g / m ² or less in this manner, the immersion time in a processing solution such as a color developing solution can be shortened, and the color developing process can be accelerated, and at the same time, a white background can be obtained during long-term storage of a raw sample. Can be improved.

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

Further, the photographic light-sensitive material of the present invention may contain other binders according to 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 to 20%, vinyl containing urethanecarboxylic acid groups or cyanoacetyl groups such as polyacrylamide, imidized polyacrylamide, casein, vinyl alcohol, and vinylaminoacetate copolymer. Alcohol polymers, polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, polymers obtained by polymerization of proteins or saturated acylated proteins with monomers having a vinyl group, polyvinylpyridine, polyvinylamine, polyaminoethyl methacrylate, polyethyleneimine, etc. are included. , Emulsion layer or intermediate layer,
It can be added to a photographic component layer such as a protective layer, a filter layer, and a backing layer according to the purpose, and the hydrophilic binder can further contain an appropriate plasticizer, a lubricant, and the like according to the purpose. .

The photographic constituent layer of the photographic material of the present invention has a swelling degree of 170.
% Is preferred. In practicing the present invention, the speed can be further increased by setting the content to 160% or less, and particularly preferably, the content can be further increased by setting the content to 150% or less. Here, the degree of swelling is defined by the following equation.

In the above formula, Wl is the weight per unit area of the photographic constituent layer to be measured, and Wω is impregnated in the photographic constituent layer when the photographic photosensitive material having the photographic constituent layer is immersed in pure water at 38 ° C for 3 minutes. Of pure water per unit area. That is, the degree of swelling is a measure of the amount of immersion of a processing solution such as a color developing solution into the photographic constituent layer.

Therefore, in the photosensitive material of the present invention, if the degree of swelling is 170% or less, a good image can be obtained. More preferably
It is 160% or less, particularly preferably 150% or less. By reducing the degree of swelling in this way, it is possible to achieve further rapid color development processing. However, if it is less than 100%, there may be problems with the image quality, so it is practically 100%
The above is preferred.

Various hardeners can be used to adjust the degree of swelling when practicing the present invention. For example, use of a hardening agent described in TH James, "The Theory of the Photographic Process" (4th edition), pp. 77-87, or "Research Disclosure", No. 17643. Can be. Specific examples of these hardeners include inorganic hardeners such as chrome alum, aldehyde hardeners such as formaldehyde, glutaraldehyde, and mucohalic acid, and α-diketones such as 2,3-butanedione. Hardeners, s-triazine hardeners such as 2,4-dichloro-6-hydroxy-s-triazine, epoxy or aziridine hardeners, active olefin hardeners such as divinyl ketone, dialdehyde starch And the like. However, the present invention is not limited to the above-mentioned hardeners.

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

The photographic constituent layer in the light-sensitive material of the present invention comprises 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 practice, the above-mentioned light-sensitive material can be further provided with an intermediate layer, a protective layer, a backing layer, and the like.

Further, the internal latent image type silver halide emulsion which can be used in the present invention includes stabilizers which are usually used, for example, a compound having an azaindene ring and a nitrogen-containing heterocyclic compound having a mercapto group (typically 4- Hydroxy-
6-methyl-1,3,3a, 7-tetrazaindene and 1-phenyl-5-mercaptotetrazole) in an amount of 1 mg to 10 g per 1 mol of silver halide, thereby lowering the minimum density. Can give more stable results.

In addition, in the present invention, for example, a mercury compound, a triazole-based compound, an azaindene-based compound, a benzothiazolium-based compound, a zinc compound, or the like can be used as the antifoggant or the stabilizer.

Various photographic additives can be optionally 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, horopora cyanines, hemicyanines, oxonols And hemioxonols, these optical sensitizers, as a nitrogen-containing heterocyclic nucleus, a part of the structure of a basic group such as thiazoline and thiazole,
Or rhodanine, thiohydantoin, oxazolidinedione, barbituric acid, thiobarbituric acid, those containing nuclei such as pyrazolone are preferred, such nuclei are alkyl,
It can be substituted with each group such as hydroxyalkyl, sulfoalkyl, carboxyalkyl, halogen, phenyl, cyano, alkoxy and the like, and it is optional to condense with a carbocyclic or heterocyclic ring.

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 Supersensitization Mechanism” (Review of Supersensitization)
zation), Photogaphic Science and Engineering (PS
E) Vol. 18, p. 4418 (1974).

In addition, in the internal latent image type silver halide emulsion that can be used in the present invention, additives used according to the purpose include wetting agents such as dydroxyalkane and the like, and further as film physical property improving agents such as alkyl acrylate or Water-dispersible particulate polymer obtained by emulsion polymerization of alkyl methacrylate and acrylic acid or methacrylic acid copolymer, styrene-maleic acid copolymer, styrene-maleic anhydride half-alkyl ester copolymer, etc. And saponin, polyethylene glycol lauryl ether, and the like, for example, are included as coating aids. Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, and development speeds. The use of regulators, matting agents and the like is optional.

The silver halide emulsion prepared as described above is coated on a support via an undercoat layer, an antihalation layer, a filter layer and the like, if necessary, to obtain an internal latent image type silver halide photographic material.

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

Further, it is useful to use an ultraviolet absorber, for example, thiazolidone, benzotriazole, acrylonitrile, a benzophenone-based compound, in order to prevent fading due to actinic rays having a short wavelength of the dye image, and particularly useful is Tinuvin PS, 320,
It is advantageous to use 326, 327, and 328 (all manufactured by Ciba-Geigy) alone or in combination.

As the support of the silver halide photographic light-sensitive material to which the present invention is applied, any one can be used, and as a representative support, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, and a polypropylene film, which are optionally subjected to an undercoating process, may be used. Film, cellulose acetate film, glass, baryta paper, polyethylene laminated paper and the like are included.

Further, the silver halide photographic light-sensitive material to which the present invention is applied,
Many photographic constituent layers such as an emulsion layer, a filter layer, an intermediate layer, a protective layer, an undercoat layer, a backing layer, and an antihalation layer can be provided on the support.

The silver halide photographic light-sensitive material to which the present invention is applied is effectively applied to various uses such as general use, X-ray, color, false color, printing, infrared, micro, and silver dye bleaching. And Rogers U.S. Patents 3,087,817, 3,185,567 and 2,983,60.
No. 6, U.S. Pat.No. 3,253,915 to Weyers et al., U.S. Pat.No. 3,227,550 to Whitemore et al., U.S. Pat.
No. 27,551, Whitemore U.S. Pat.No. 3,227,552 and Rand U.S. Pat.Nos. 3,415,644, 3,415,645 and 3,41
It can be applied to a color image transfer method, a color diffusion transfer method, an absorption transfer method, and the like as described in 5,646.

〔Example〕

Hereinafter, the present invention will be illustrated by way of examples, but embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Emulsion EM-1) While stirring an aqueous gelatin solution vigorously and keeping it at 75 ° C,
An aqueous potassium bromide solution and an aqueous silver nitrate solution were simultaneously added over 15 minutes to obtain an octahedral silver bromide emulsion having an average particle size of 0.30 μm. 0.1 g of 3,4-dimethyl- per mole of silver was added to this emulsion.
Chemical sensitization was performed by sequentially adding 1,3-thiazoline-2-thione, 4 mg of sodium thiosulfate, and 7 mg of chloroauric acid (tetrahydrate) and heating at 75 ° C. for 25 minutes. The obtained grains were used as a core to further grow them under the same grain growth conditions as the first time, and finally an octahedral monodispersed core / shell silver bromide emulsion having an average grain size of 0.55 μm was obtained. The variation in particle size was 10%. 1.5 mg of sodium thiosulfate and 1.5 mg of chloroauric acid (tetrahydrate) were added per mole of silver in this emulsion,
The mixture was heated for 5 minutes to carry out a chemical sensitization treatment to obtain an 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 for emulsion EM-1.
EM-2 to EM-5 have halogen compositions as shown in Table 1.

The following first layer (lowest layer) to ninth layer (top layer) were applied on a double-sided polyethylene laminated paper support.

In addition, SA-1 and SA-2 were used as coating aids, and HA-1 and HA-2 were used as hardeners.

The components and the coating amounts in g / m ² are shown below. For silver halide, it is a silver conversion value.

First layer (red-sensitive layer) EM spectrally sensitized with red-sensitive sensitizing dyes (SD-1, SD-2)
-1 ... 0.35 Gelatin ... 1.3 Cyan coupler (C-1) ... 0.26 Cyan coupler (C-2) ... 0.26 Solvent (SO-1) ... 0.16 Stabilizer (ST-1, ST-2, ST-3, ST-) 4) Second layer (intermediate layer) Color mixture inhibitor (AS-1) ... 0.08 Solvent (SO-2) ... 0.18 Gelatin ... 0.8 Third layer (green sensitive layer) Spectral sensitization with green sensitizing dye (SD-3) Felt EM-1 ... 0.30 Gelatin ... 1.1 Magenta coupler (M-1) ... 0.22 Image stabilizer (AO-1, AO-2 equivalent) ... 0.30 Solvent (SO-3) ... 0.15 Stain inhibitor (AS-) 2) ... 0.01 Stabilizer (ST-1, ST-2, ST-3, ST-4) 4th layer (intermediate layer) Same as 2nd layer.

Fifth layer (yellow filter layer) Yellow colloidal silver ... 0.10 Gelatin ... 0.95 Color mixture inhibitor (AS-1) ... 0.06 Solvent (SO-2) ... 0.15 6th layer Same as 2nd layer.

7th layer (blue-sensitive layer) EM-1 spectrally sensitized with a blue-sensitive sensitizing dye (SD-4) 0.57 gelatin 1.1 yellow coupler (Y-1) 0.60 solvent (SO-1) 0.15 stain Inhibitor (AS-1) 0.005 Stabilizer (ST-1, ST-2, ST-3, ST-4) 8th layer (ultraviolet absorbing layer) Ultraviolet absorbing agent (UV-1, UV-2 equivalent) 1.0 Solvent (SO-3) 0.15 Gelatin 1.0 Water-soluble dye (Table 2) 0.02 Ninth layer (protective layer) Silica (average particle size 4 μm) 0.02 Gelatin 1.0 The obtained sample is designated as material No. 1.

Sample Nos. 2 to 12 were prepared in the same manner as Sample No. 1. Sample No.1
Table 2 shows the differences.

The silver halide color photographic light-sensitive materials (samples Nos. 1 to 12) prepared as described above were exposed with a sensitometer through an optical wedge, and then processed in the following processing steps, 1, 2, and 3
And the sensitometric maximum density in the blue measurement Minimum density Is shown in Table-3.

In addition, another part of Sample Nos. 1 to 12, after giving green light and red light to the entire surface so that the M concentration and the C concentration are each the minimum concentration, exposed to blue light through an optical wedge, Processing-
3 was performed, and the M density at an exposure amount at which the Y density was 1.0 was measured as color turbidity. (D indicated by ^G) Further, another part of the sample No.1~12, 50 ℃, after storage at 80% 3 days after exposure with a sensitometer through an optical wedge, Senshito applies processing -3 The metrology was performed.

Table 3 also shows the gamma balance B / G and R / G of the leg. Here, the gamma of the leg is represented by the absolute value of the slope of a straight line connecting each density of (minimum density + 0.15) and (minimum density + 0.5) on the characteristic curve. The value obtained by dividing by the gamma value of the measurement and multiplying by 100 was shown as gamma balance B / G. Similarly, the ratio to gamma in red light measurement is gamma balance R / G.

Processing step-2 Only processing time differs from processing step-1.

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

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

(Color developing solution) Benzyl alcohol 10 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 1.5 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfate 3.0 g Polyphosphoric acid (TPPS) 2.5 g 3-Methyl-4-amino-N -Ethyl-N-β-methanesulfonamidoethylaniline sulfate 5.5 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 1.0 g Potassium hydroxide 2.0 g Water was added to make the total amount 1 and pH = Adjust to 10.20.

(Bleaching / fixing solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Add water to make the total volume 1 and add potassium carbonate or ice Adjust to pH 7.1 with acetic acid.

(Stabilizing solution) 5-chloro-2-methyl-4-isothiazoline-3-
ON 1.0 g Ethylene glycol 10 g 1-Hydroxyethylidene-1,1-diphosphonic acid 2.5 g Bismuth chloride 0.2 g Magnesium chloride 0.1 g Ammonium hydroxide (28% aqueous solution) 2.0 g Sodium nitrilotriacetate 1.0 g Adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

 In addition, the stabilization process was a countercurrent system having a two-tank configuration.

As is evident from Table 3, samples Nos. 6, 7, 8, and
It can be seen that 9, 11, and 12 obtained higher maximum densities than the comparative sample even if the color development processing time was short, and that the absorption of green color when yellow was developed was small and the color turbidity was small.

Furthermore, the sample of the present invention has a small variation in leg gamma balance from a fresh sample even when the raw sample is stored at high temperature and high humidity, and is favorable.

Example 2 A paper support (thickness: 17) laminated on both sides with polyethylene
5 μm) on the front side, the following first to twelfth layers, and on the back side, the first
A color photographic light-sensitive material in which three to fourteenth layers were applied in layers was prepared. The white side of the first layer of polyethylene contains titanium white as a white pigment.

(Composition of photosensitive layer) The components and the coating amounts in g / m ² are shown below. In addition,
Silver halide is shown in terms of silver. Emulsions used in each layer were prepared according to the method of preparing the following emulsion EM-11. However, the emulsion of the twelfth layer is not chemically sensitized and has substantially no photosensitivity.

(Preparation of Emulsion EM-11) Monodisperse silver chlorobromide EM-11 was prepared in the following manner.

An aqueous solution containing silver nitrate and an aqueous solution containing potassium bromide are added simultaneously by the control double jet method while controlling the aqueous solution containing ossein gelatin at 50 ° C, and at an addition rate that does not generate new silver halide nuclei. Thus, an emulsion comprising silver bromide cubic grains of 0.25 μm was obtained.
An aqueous solution containing silver nitrate and an aqueous solution containing sodium chloride are simultaneously added to the obtained silver bromide emulsion by a control double jet method at an addition rate that does not generate new silver halide nuclei. I got The grain shape was a cubic monodispersed emulsion having a uniform shape and size. (Distribution area: 8%, silver chloride content: 52%) The photosensitive silver halide emulsions used in Example-2 all have a silver chloride content of 52%.

First layer (low-sensitivity red-sensitive layer) Silver chlorobromide spectrally sensitized with red sensitizing dyes (SD-4, SD-5, SD-6) (average particle size 0.3 μm, particle size distribution [coefficient of variation] ]
8%) ... 0.06 Silver chlorobromide spectrally sensitized with red sensitizing dyes (SD-5, SD-6, SD-7) (average particle size 0.45 µm, particle size distribution 10%) ... 0.10 Gelatin ... Table- 4 Cyan coupler (C-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 (SO- 0.06 Second layer (high-sensitivity red-sensitive layer) Silver chlorobromide spectrally sensitized with red sensitizing dyes (SD-5, SD-6, SD-7) (average particle size 0.60 μm) 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-1) ... 0.03 Coupler solvent (SO-1, SO-4) ... 0.10 Third layer (intermediate layer) Gelatin ... Table 4 Color mixture inhibitor (AS-1) ... 0.08 Solvent (SO-1, SO) -5) ... 0.16 4th layer (low-sensitivity green-sensitive layer) Silver chlorobromide spectrally sensitized with a color sensitizing dye (SD-7) (average particle size 0.25 μm, particle size distribution 8%) ... 0.04 Spectral sensitized with a green sensitizing dye (SD-7, SD-8) Silver chlorobromide (average particle size 0.45 µm, particle size distribution 11%) ... 0.06 Gelatin ... Table 4 Magenta coupler (M-2) ... 0.11 Anti-fading agent (AO-3) ... 0.10 Coupler solvent (SO-5) 0.15 Fifth layer (high-sensitivity green-sensitive layer) Silver chlorobromide spectrally sensitized with green sensitizing dyes (SD-7, SD-8) (average particle size 0.8 μm, particle size) 0.10 Gelatin ... Table-4 Magenta coupler (M-2) ... 0.11 Anti-fading agent (AO-4) ... 0.10 Coupler solvent (SO-5, SO-6 equivalent) ... 0.15 6th layer (intermediate) Layer) Same as the third layer 7th layer (yellow filter layer) Yellow colloidal silver ... 0.20 gelatin ... Table 4 Color mixture inhibitor (AS-1) ... 0.06 Solvent (SO-1, SO-5) ... 0.15 8th layer (Intermediate layer) 3rd Same as ninth layer (low-sensitivity blue-sensitive layer) Silver chlorobromide spectrally sensitized with blue sensitizing dyes (SD-9, SD-10) (average particle size 0.45 μm, particle size distribution 8%)… 0.07 blue Silver chlorobromide spectrally sensitized with sensitizing dyes (SD-9, SD-10) (average particle size: 0.60 μm, particle size distribution: 14%) ... 0.10 Gelatin ... 0.50 Yellow coupler (Y-2) ... 0.20 Anti-fading Agent (AO-4) ... 0.20 Coupler solvent (SO-4) ... 0.05 Layer 10 (High-sensitivity blue-sensitive layer) Silver chlorobromide spectrally sensitized with blue-sensitizing dyes (SD-9, SD-10) (Average particle size: 1.2 μm, particle size distribution: 21%) 0.25 Gelatin Table-4 Yellow coupler (Y-2) 0.38 Anti-fading agent (AO-4) 0.10 Coupler solvent (SO-4) 0.10 No. 11 Layer (UV absorbing layer) Gelatin ... Table-4 UV absorber (UV-3, UV-4, UV-5 equivalent) ... 1.0 Color mixture inhibitor (AS-1, AS-3 equivalent) ... 0.15 Solvent (SO -4)… 0.15 Anti-irradiation dye (A I-1, AI-2 equivalent) ... 0.02 Anti-irradiation dye (AI-3, AI-4 equivalent) ... 0.02 Water-soluble dye (I-1) ... 0.02 12th layer (protective layer) Fine particle chlorobromide Silver (97 mol% silver chloride, average particle size 0.2μ)
m) ... 0.05 Acrylic-modified copolymer of polyvinyl alcohol (modification degree 17%) ... 0.02 Polymethyl methacrylate particles (average particle size 2.4μ)
m), silicon oxide (average particle size 5 μm) equivalent: 0.05 gelatin ... Table 4 Gelatin hardener (HA-3) ... Table 4 13th layer (back layer) Gelatin ... 2.50 14th layer (backside protective layer) Polymethyl methacrylate particles (average particle size 2.4
μm), silicon oxide, (average particle size 5 μm) equivalent: 0.05 gelatin: 2.00 gelatin hardener (HA-3): 0.11 In each photosensitive layer, FA-11, FA-12 and FA were used as fogging agents.
-13 each with 2.0 × 10 ^-6 mol per mol of silver halide,
Further, 4.5 × 10 ^-4 mol of each of the fogging inhibitors ST-11 and ST-12 were added.

A part of the silver halide color photographic light-sensitive materials Nos. 13 to 17 prepared as described above was stored at 55 ° C. and 80% RH for 6 days. Another part is the same period, refrigerator (5 ℃)
Saved in. After exposing each sample through an optical wedge, processing-A (described later) was performed to measure the minimum density and the maximum density.

 Table 5 shows the obtained results.

The method of replenishing the washing water is to replenish the washing bath (3), guide the overflow of the washing bath (3) to the washing bath (2), and guide the overflow of the washing bath (2) to the washing bath (1). A so-called countercurrent replenishment system was used. At this time, the amount of the bleach-fix solution brought into the washing bath (1) from the bleach-fix bath using the photosensitive material was 35.
ml / m ² , and the ratio of the replenishment amount of the washing water to the carry-in amount of the bleach-fix solution was 9.1 times.

 The composition of each processing solution was as follows.

Tap water is passed through a mixed-bed column filled with an H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and an OH-type anion exchange resin (Amberlite IR-400) to obtain calcium. And the magnesium ion concentration was adjusted to 3 mg / or less, and subsequently, 20 mg / sodium isocyanurate dichloride and 1.5 g / sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5.

As can be seen from Table 5, from the results of storage of the raw sample under particularly severe conditions, the increase in the minimum concentration was smaller when the total amount of gelatin was smaller than 8.5 g / m ² , and the degree of swelling was 170%.
The smaller the value, the smaller the increase in the minimum density.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-123227 (JP, A) JP-A 64-65544 (JP, A) JP-A 1-1121850 (JP, A) JP-A 52- 20830 (JP, A) JP-A-63-249141 (JP, A) JP-A-1-106047 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03C 1/83 G03C 1 / 40 G03C 1/485

Claims (1)

(57) [Claims] An at least one red-sensitive emulsion layer containing at least one internal latent image type silver halide grain on a support.
A direct positive silver halide photographic material having at least one edge sensitive emulsion layer containing internal latent image type silver halide grains and at least one blue sensitive emulsion layer containing internal latent image type silver halide grains. One layer of the internal latent image type silver halide grains contains at least 30 mol% of silver chloride, and the direct positive silver halide photographic material has a maximum absorption wavelength of 570 to 620 nm in the binder coating film. A direct positive silver halide photographic material characterized by containing a water-soluble dye.