JPH0833605B2 - Direct positive type silver halide color photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a direct positive type silver halide color photographic light-sensitive material. INDUSTRIAL APPLICABILITY The present invention can be utilized as a direct positive type silver halide color photographic light-sensitive material for reproducing a high quality original image having image information such as characters and paintings.

[Conventional technology]

Direct positive type silver halide color photographic light-sensitive materials are expected to be widely used in the field of obtaining direct positive images directly from color copying machines and other positive images. In some applications, the reproducibility of fine lines is not sufficient, and the reproducibility of the image information remains a problem. In addition, the color reproducibility may be insufficient, such as when reproducing from a printed matter with halftone dots. In order to solve this problem, it is possible to provide an antihalation layer for a direct positive type photosensitive material. This is because the above-mentioned photosensitive material having an antihalation layer is expected to be improved in the above points. However, according to the knowledge of the present inventors, the provision of the antihalation layer is effective in solving the above-mentioned problems, but there is a point that it is insufficient to deal with the rapidity of the treatment. That is, an antihalation dye is added to the antihalation layer to prevent halation, but an antihalation layer is formed by a mordant layer of the dye so that the dye does not elute during color development processing, and a series of If the processing step (1) is accelerated, decolorization of the dye in the step after color development may be insufficient and the dye may remain in the image. To avoid this, weakening the mordanting to facilitate the decolorization of the dye makes it easier for the dye to elute during color development, which may cause fluctuations in color development processability due to the elution, such as fluctuations in the amount of light fog due to elution. This leads to fluctuations in photographic performance.

On the other hand, when a means for forming an antihalation layer by adding an inorganic substance such as colloidal silver is used, the above problem does not occur and rapid processability can be dealt with, but in this case, deterioration of the contrast of the highlight part due to stain is caused. However, there is a problem in that it may cause an increase in the minimum concentration.

[Object of the Invention]

An object of the present invention is to solve the above problems of the direct positive type silver halide color photographic light-sensitive material from the viewpoint of the film thickness of the antihalation layer, and particularly to obtain a light-sensitive material excellent in halftone dot reproducibility.

[Structure and Action of Invention]

The present invention has a silver halide emulsion layer having different color sensitivities containing a cyan coupler, a magenta coupler and a yellow coupler, respectively, on a support, and all three silver halide emulsion layers having different color sensitivities are provided. In a silver halide light-sensitive material in which an intermediate layer and an antihalation layer are formed on the side closer to the support than the direct positive type silver halide emulsion layer which directly forms a positive image by light fog, Also, the above-mentioned object was achieved by making the total thickness of the intermediate layer and the antihalation layer on the side closer to the support 4 μm or less and the total film thickness of the photographic constituent layers on the support 15 μm or less. The present invention provides a direct positive type silver halide color photographic light-sensitive material.

In the direct positive type silver halide color photographic light-sensitive material of the present invention, the total thickness of the photographic constituent layers on the support is 15 μm or less. By doing so, dot reproducibility can be improved.

In the direct positive type silver halide color photographic light-sensitive material of the present invention, the total thickness of the intermediate layer and the antihalation layer on the side closer to the support than the silver halide emulsion layer is 4 μm or less. That is, the film thickness of the antihalation layer (generally an antihalation layer formed on the support) closer to the support than the silver halide emulsion layer and the first intermediate layer as an auxiliary layer coated on the antihalation layer. The total film thickness of the layers is 4 μm or less. Such a film thickness is 4
The thickness is preferably μ or less, more preferably 3 μ or less and 1 μ or more. When the film thickness is in this range, the shadow portion in the characteristic curve of the photograph can control the increase of the minimum density (Dmin) without lowering gamma-1 (γ1). Therefore, the contrast of the shadow portion can be increased, and the white background can be maintained in a good state. As a more remarkable effect, the reproducibility of halftone dots can be significantly improved.

However, when the film thickness is 4 μm or more, γ1 becomes small and Dmin tends to increase, which is not preferable. On the contrary, when the film thickness is 1 μm or less, the contrast of the shadow portion is improved, but there is a slight problem in forming the coating film.

Next, the support used in the present invention will be described. The support usable in the present invention may be any support as long as it supports the emulsion layer and the like, and the material thereof can be arbitrarily selected. As a typical support, a polyethylene terephthalate film, a polycarbonate film, a polystyrene film, a polypropylene film, a cellulose acetate film, glass, which is subjected to an undercoating process if necessary.
Examples include baryta paper and polyethylene laminated paper.

A reflective support can be preferably used in the practice of the present invention. For example, polyolefin laminated paper can be used. For example, when a molten polyolefin is extrusion-coated on a paper substrate by extrusion coating to form a water resistant surface, a polyolefin laminated paper having excellent flatness can be obtained.

When a reflective support is used in the present invention, it is preferable that it has excellent water resistance on the surface, but a support having good water resistance can be obtained, for example, by forming a water resistant surface on a substrate.

The water resistant surface in this case can be formed by coating a substrate, for example a paper substrate, with a hydrophobic resin. In the embodiment in which such a water-resistant surface is formed, it is possible to prevent the substrate from being watered even when the silver halide photographic light-sensitive material is immersed in a bath used for the development processing.

As the resin used for the hydrophobic resin coating layer coated on the surface, for example, polyethylene, polypropylene, polyolefin such as polybutene, ethylene, propylene,
Copolymers of olefins such as butene with monomers such as vinyl acetate, vinylidene chloride, maleic anhydride (eg ethylene-vinyl acetate copolymers, propylene-vinylidene chloride copolymers, propylene-maleic anhydride copolymers, etc. ), Or homopolymers or co-polymers such as polystyrene, polyvinyl chloride, polyacrylate, saturated polyester, polycarbonate, etc.,
Alternatively, blended substances of these may be used. The thickness of the hydrophobic resin coating layer is not particularly limited, but generally 15 to
About 50 μm is preferable.

When polyethylene resin is used, its molecular weight is not particularly limited as long as extrusion coating is possible,
Usually, polyethylene having a molecular weight of 20,000 to 200,000 is used. The polyethylene resin used for the hydrophobic resin coating layer in this case may be any of low density, medium density and high density polyethylene resins, and these may be used alone or in combination of two or more kinds.

Further, fine particle powder having higher heat resistance than the above resin, for example, white pigment such as BaSO ₄ , ZnO, TiO ₂ may be mixed with the resin, whereby an opaque support can be obtained. In this case, an opaque white support having a low transmission density can be obtained by mixing and then extruding or stretching to form voids to whiten or by adhering them.

Further, in the light-sensitive material of the present invention, as an antihalation layer, each side of the red light-sensitive emulsion layer, the green light-sensitive emulsion layer and the blue light-sensitive emulsion layer corresponds to the side closer to the support than the silver halide emulsion layer. A layer containing a substance that absorbs light is formed. This substance does not elute in the color developing solution during the development processing of the light-sensitive material. This substance is
It is preferable that it absorbs the light transmitted through the emulsion layer, has the function of preventing halation by the support, and does not elute into the color developer during development processing. Since the substance does not elute, unevenness in the concentration distribution of the substance does not occur, and therefore an image with high sharpness can be formed, and thus an image without unevenness in development can be formed.

As the substance that absorbs light, various inorganic substances and organic substances that exhibit this action can be used.

As the inorganic substance, for example, colloidal metal can be used. As the organic substance, it is possible to use, for example, various dyes bonded to a polymer or the like and fixed (so-called mordant) so as not to be eluted in a color developing solution. When an antihalation dye is used by fixing it with a polymer mordant, it is not always easy to make the coating uniform, or if it is difficult to remove this substance after color development, decolorization may become necessary. Therefore, it is preferable to take measures against them.

Colloidal silver, colloidal manganese, and the like are preferable as the inorganic compound used when carrying out the present invention. Since these have good decolorizing properties, they are also effective when the present invention is applied to a color photographic light-sensitive material. As colloidal silver, for example, gray colloidal silver is prepared by reducing silver nitrate in gelatin in a gelatin in the presence of a reducing agent such as hydroquinone, phenidone, ascorbic acid, pyrogallol, or dextrin, and then neutralizing and cooling. It is obtained by setting gelatin and removing the reducing agent and unnecessary salts by the noodle washing method. When the colloidal silver particles are prepared in the presence of an azaindene compound or a mercapto compound when reducing with alkaline, a colloidal silver dispersion liquid having uniform particles can be obtained.

Furthermore, each color-sensitive layer of the present invention, on the support described above,
Red-sensitive direct positive silver halide emulsion layer containing cyan coupler, green-sensitive direct positive silver halide emulsion layer containing magenta coupler, yellow filter layer if necessary, and blue-sensitive direct positive halogenated containing yellow coupler. It has a silver emulsion layer.

The layer order of these layers is arbitrary, but they may be formed by coating in order from the support side in the order described above.

As the coupler contained in each of the color-sensitive layers, first, a yellow dye-forming coupler is a benzoylacetanilide type, a pivaloylacetanilide type, or a so-called split in which a carbon atom at the coupling position can be released during coupling. 2 substituted with an off group
Equivalent yellow couplers and the like are useful.

As the magenta dye-forming coupler, a 5-pyrazolone type, a pyrazolotriazole type, a pyrazolinobenzimidazole type, an indazolone type, or a 2-equivalent type magenta coupler having a split-off group is useful.

Further, as the cyan dye-forming coupler, a phenol type, naphthol type, pyrazoquinazolone type, or 2-equivalent type cyan coupler having a split-off group is useful.

These dye-forming couplers can be arbitrarily selected, and the usage method, usage amount, etc. are not particularly limited.

Further, it is possible to use an ultraviolet absorber in order to prevent fading of the dye image due to short wavelength actinic rays, and examples thereof include thiazolidone, benzotriazole, acrylonitrile, and benzophenone compounds.
The use of 120, 320, 326, 327, and 328 (all manufactured by Ciba Geigy) alone or in combination is advantageous.

As the direct positive type silver halide emulsion used in the light-sensitive material of the present invention, for example, an internal latent image type silver halide emulsion can be used. For example, a so-called conversion type silver halide emulsion by the conversion method described in U.S. Pat.No. 2,592,250, or internally chemically sensitized silver halide grains described in U.S. Pat.Nos. 3,206,316, 3,317,322 and 3,367,778 are used. Silver halide emulsion having, or U.S. Patents 3,271,157, 3,447,927 and 3,531,291
Weakening the grain surface of a silver halide emulsion having a silver halide grain containing a polyvalent metal ion described in U.S. Pat. No. 3,761,276 or containing a dopant described in U.S. Pat. Chemically sensitized silver halide emulsions, or so-called core-shell type silver halide emulsions by the laminating method described in JP-A Nos. 50-8524, 50-38525 and 53-2408, and others. 52-1566
The silver halide emulsions described in Nos. 14, 55-127549 and 57-79940 can be used.

In this case, the internal latent image type silver halide is particularly preferably made of laminated grains.

Such a silver halide can be produced in the same manner as a usual laminated silver halide. For example, Japanese Patent Laid-Open No. 50-
No. 8524, No. 50-38525, No. 53-60222, No. 55-1524 and U.S. Pat.No. 3,206,313, silver chloride grains are formed and then converted to silver bromide grains by adding bromide. Further, a method in which a halide is added to silver nitrate and laminated, or a method in which silver iodobromide grains are formed in a state in which excess halogen is small and silver chloride and silver bromide are sequentially laminated can be used.

Regarding the composition of the silver halide grains inside the laminated type or core / shell type, silver iodobromochloride grains having a high silver bromide content (60 to 100 mol%) are suitable. The composition of the silver halide laminated on the outside is preferably silver chlorobromide, and it is desirable that the silver chloride ratio is high (70 mol% or more) from the viewpoint of developability.

As the grain size of the silver halide, a grain size of 0.2 to 1.7 μm can be used. When high contrast is required, a narrow grain size distribution is preferable, and when low contrast is required, the grain size is small. Good with a wide size distribution.

There is no particular limitation on the crystal form or crystal habit of the silver halide grains used at this time. As crystal habit, cubic crystal, octahedron, tetradecahedral,
Twinned or tabular crystals can be preferably used.

The emulsion may be prepared by any of the acid method, neutral method, alkali method, ammonia method and the like. The forward mixing method, the back mixing method,
Any of the simultaneous mixing methods can be used, and a pAg controlled double jet method or a laminated emulsion by a conversion method may be used.

Various photographic additives can be added to the internal latent image type silver halide emulsion. For example, various optical sensitizers can be added. Also, supersensitization can be performed.

When an internal latent image type silver halide emulsion is used, the emulsion usually has a surface sensitivity as low as possible, a stabilizer usually used for imparting a lower minimum density and more stable properties, for example, a compound having an azaindene ring. And a heterocyclic compound having a mercapto group can be contained.

Besides, a wetting agent can be used depending on the purpose.
Other photographic additives include gelatin plasticizers, surfactants, ultraviolet absorbers, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, moldants, whitening agents, and developing agents. The use of speed regulators, matting agents, etc. is optional.

The silver halide color photographic light-sensitive material of the present invention may contain appropriate gelatin (including oxidized gelatin) and its derivatives depending on the purpose. Examples of this preferable gelatin derivative include acylated gelatin, guanidylated gelatin, carbamylated gelatin, cyanoethanolated gelatin, esterified gelatin and the like.

Further, in the silver halide color photographic light-sensitive material of the present invention, in addition to gelatin in the hydrophilic colloid layer,
Other hydrophilic binders can be included.

This hydrophilic binder can be added to a photographic constituent layer such as an emulsion layer or an intermediate layer, a protective layer, a filter layer and a backing layer according to the purpose. Further, the hydrophilic binder is appropriately plasticized according to the purpose. Agents, lubricants, etc. can be contained.

The photographic constituent layers of the light-sensitive material of the present invention can be hardened with any suitable hardener.

Further, in the practice of the present invention, as the coating method of the photographic constituent layer, dip coating, air doctor coating, extrusion coating, slide hopper coating, curtain flow coating and the like can be used.

The color-sensitive emulsion layers in the present invention are all due to light fog,
It directly forms a positive image. In this case, the main step is generally to perform surface development on an internal latent image type silver halide photographic light-sensitive material which has not been fogged in advance, after fog treatment after image exposure or while performing fog treatment. is there. The fog process can be performed by uniformly exposing the entire surface. In this case, the entire surface uniform exposure may be performed by immersing or moistening the image-exposed internal latent image type silver halide color photographic light-sensitive material in a developing solution or another aqueous solution, and then uniformly exposing the entire surface. preferable.

The light source used here may be any light within the photosensitive wavelength range of the internal latent image type silver halide color photographic light-sensitive material, and may be irradiated with high illuminance light such as flash light for a short time, or You may irradiate weak light for a long time. The time for uniform exposure over the entire surface can be varied within a wide range so as to finally obtain the best positive image, depending on the internal latent image type silver halide color photographic light-sensitive material, the development processing conditions, the type of light source used and the like.

When the present invention is applied to an internal latent image type silver halide color photographic light-sensitive material, a positive image is directly formed by subjecting it to imagewise exposure as described above, followed by development processing. As the development processing method, any development processing method is adopted, and a surface development processing method is preferable. This surface development processing method means processing with a developing solution which does not substantially contain a silver halide solvent.

In carrying out the present invention, a positive image (visual image) corresponding to the original image can be formed by subjecting the exposed silver halide photographic light-sensitive material to a treatment with a processing solution having developing and fixing abilities.

The primary aromatic amino-based color developing agent used in the color developing processing in the present invention includes various kinds widely used in various color photographic processes. These developers include conventionally known aminophenol-based and p-phenylenediamine-based derivatives. These compounds are generally used in the form of salts, such as the hydrochloride or sulphate, for their stability in the free state. Further, these compounds generally have a concentration of about 0.1 g to about 30 g for color developer 1, and more preferably about 1 g to about 1 g for color developer 1.
Use at a concentration of about 15g.

As the p-phenylenediamine-based developer, a primary aromatic amino-based color developer is particularly useful, and N, N-
A dialkyl-p-phenylenediamine compound,
The alkyl group and phenyl group may be substituted or unsubstituted. Among them, examples of particularly useful compounds include N, N-diethyl-p-phenylenediamine hydrochloride.

The alkaline color developer that can be used in the present invention is
In addition to the first aromatic amino color developer, various components that are usually added to color developers, such as alkali agents such as sodium hydroxide, sodium carbonate and potassium carbonate, alkali metal bisulfites, An alkali metal thiocyanate, an alkali metal halide, benzyl alcohol, a water softening agent, a thickening agent and the like can be optionally contained. The pH value of this color developing solution is preferably usually 7 or more, most commonly about 10 to about 13, and preferably about 10.

The fixing processing solution in the case of carrying out the present invention is a processing solution containing a soluble complexing agent which is solubilized as a silver halide complex salt, and not only a general fixing solution but also a bleach-fixing solution, a one-bath development fixing solution, A one-bath development bleach-fix solution is also included, but a bleach-fix solution is preferred. Typical examples of the soluble complexing agent include thiosulfates such as potassium thiosulfate, thiocyanates such as potassium thiocyanate, thiourea, thioether, high concentration bromide and iodide. In particular, the inclusion of a thiosulfate is desirable from the standpoint of stabilizing the dye image over time, chemical stability, and the ability to form a soluble complex with silver halide.

After the color development processing, it is processed with a processing solution having a fixing ability. In color processing, when the processing solution having a fixing ability is a fixing solution, a bleaching process is usually performed before the processing solution. As the bleaching agent used in the bleaching solution or the bleach-fixing solution used in the bleaching step, a metal complex salt of an organic acid is used, and the metal complex salt oxidizes the metal silver produced by development to convert it into silver halide. It has a function of coloring the uncolored portion of the color former, and its structure is such that an organic acid such as aminopolycarboxylic acid or oxalic acid or citric acid is coordinated with a metal ion such as iron, cobalt or copper. The most preferable organic acid used for forming such a metal complex salt of an organic acid includes polycarboxylic acid or aminopolycarboxylic acid. These polycarboxylic acids or aminopolycarboxylic acids may be alkali metal salts, ammonium salts or water-soluble amine salts.

The bleaching solution used contains the above-mentioned metal complex salt of an organic acid as a bleaching agent and can also contain various additives. As the additive, it is particularly preferable to contain an alkali halide or an ammonium halide, for example, a rehalogenating agent such as potassium bromide, sodium bromide, sodium chloride, ammonium bromide, a metal salt, a chelating agent and the like. In addition, borate, oxalate, acetate, carbonate, phosphate and other pH buffers, alkylamines, polyethylene oxides and the like, which are known to be added to ordinary bleaching solutions, can be appropriately added. .

Further, the fixing solution and the bleach-fixing solution may contain conventionally used various pH buffering agents such as sulfite salts, boric acid, borax, alkaline agents and acetic acid, either alone or in combination.

When processing is performed while replenishing the bleach-fixing solution (bath) with a bleach-fixing replenishing solution, the bleach-fixing solution (bath) may contain thiosulfate, thiocyanate, sulfite or the like,
The bleach-fixing replenisher may contain these salts to replenish the processing solution (bath).

Further, in order to increase the activity of the bleach-fixing solution, air or oxygen may be blown in the bleach-fixing bath and the storage tank for the bleach-fixing replenisher, if desired, or a suitable oxidizing agent such as peroxide may be used. Hydrogen, bromate, persulfate and the like may be added appropriately.

After the treatment with the treatment liquid having the fixing ability, a usual washing treatment may be carried out. However, particularly when carrying out the present invention, it is preferable to carry out a stabilizing treatment which substantially does not include a washing process.

Stabilization treatment that does not substantially include a water washing step means immediately after the treatment with a processing solution having a fixing ability, the stabilization treatment by a single-tank or multi-tank countercurrent method. Treatment steps other than general washing with water such as washing with water and a known washing accelerating bath may be included.

In the practice of the present invention, the washing treatment may not be carried out before and after the stabilizing treatment, but the surface is washed with a rinse or sponge by washing with a small amount of water within a short time and the stabilization of the image and the silver halide photographic light-sensitive material are carried out. It is optional to provide a treatment tank for adjusting the surface physical properties of. Activators such as formalin and its derivatives, siloxane derivatives, polyethylene oxide compounds, and quaternary salts are used to stabilize the image and adjust the surface properties of the silver halide photographic material.

In practicing the present invention, it is optional to provide additional processing steps in addition to the above processing steps. In addition to the above-mentioned stabilizing solution, silver may be recovered by a known method from a processing solution containing a soluble silver complex salt such as a fixing solution or a bleach-fixing solution.

Further, if the stabilizing treatment as described above is carried out, there is an advantage that the water washing step is substantially unnecessary, and thus the piping facility for the water washing treatment is not necessary and the apparatus itself can be easily installed at any place.

Example An antihalation layer prepared as described below and a first intermediate layer as an auxiliary layer were simultaneously coated and dried on a backing-supported support made of polyethylene laminated paper having a thickness of 110 μm.

[Anti-halation layer (first layer)] A coating solution (S
-2) was added in a small amount to prepare a coating solution, and this coating solution was coated so that the amount of colloidal silver was 0.15 g / m ² . At this time,
Samples Nos. 2 to 8 having different thicknesses of the antihalation layer (first layer) were prepared as those according to the present invention by changing the amount of gelatin applied to the support. Sample No. 1 is a comparative sample having no antihalation layer (first layer).

[First intermediate layer (second layer)] A coating solution (S-2) and a hardener (H-
3) was added and each sample was adjusted so that the amount of gelatin added to each sample was the amount shown in Table 1, and the sample was coated on the support in the same manner as described above.

On the support coated with the antihalation layer and the intermediate layer as described above, the following red light-sensitive emulsion layer (third layer) is further prepared.
Layers) to the protective layer (11th layer) were sequentially coated according to the following formulation and dried. For the comparative sample, the emulsion was directly coated on the support and dried as described above.

[Red Photosensitive Emulsion Layer (Third Layer)] A 2.0% inactive gelatin solution was kept at 50 ° C., and the following solutions A and B were simultaneously added with stirring and the mixture was injected over 3 minutes. Ten
After that, the following liquid C was added by injection over 3 minutes. After aging for 40 minutes, excess salt was removed by a precipitation water washing method, and then the following solutions D and E were used.
The solution was added, and silver chlorobromide consisting of 95 mol% AgCl and 5 mol% AgBr was laminated on the surface. The excess water-soluble salt was removed again by the precipitation washing method, and a small amount of gelatin was added and dispersed.

Thereafter, a solution containing a sensitizing dye [D-1], a sensitizing dye [D-4], 2,5-dioctylhydroquinone protected and dispersed with dibutyl phthalate, and a cyan coupler [CC-1] in this silver halide emulsion, 4-hydroxy-6-
Methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-
5-Mercaptotetrazole, gelatin, and coating aid [S-1] are added in appropriate amounts. The amount of silver applied was 0.4 g / m ² .

[Second intermediate layer (fourth layer)] A gelatin solution containing 2,5-dioctylhydroquinone dispersed in dioctyl phthalate, an ultraviolet absorber Tinuvin 328 (manufactured by Ciba Geigy), and a coating aid [S-1] is prepared. Then, it was applied so that the applied amount of TINUVIN 328 would be 0.15 g / m ² .

[Green photosensitive emulsion layer (fifth layer)] Silver halide grains were prepared in the same manner as the red photosensitive emulsion. A liquid containing sensitizing dye [D-2], 2,5-dioctylhydroquinone protected and dispersed by dibutyl phthalate, and magenta coupler [MC-1], 4-hydroxy-6-methyl-1,3,3a, 7 -Tetrazaindene, 1-phenyl-5-mercaptotetrazole, further gelatin,
An appropriate amount of coating aid [S-2] is added. The amount of silver applied was 0.4 g / m ² .

[Third intermediate layer (sixth layer)] With the same formulation as the second intermediate layer, the amount of Tinuvin 328 applied is 0.2 g / m ²
And

[Yellow filter layer (seventh layer)] Yellow colloidal silver and dioctyl phthalate dispersed by oxidation under a weak alkaline reducing agent (weak reducing agent removed by a noodle washing method after neutralization) 2,5- Dioctyl hydroquinone solution, coating aid [S-2] and film hardener [H-1] (added just before coating) were added, and the amount of silver coated
It was applied so as to be 0.15 g / m ² .

[4th intermediate layer (8th layer)] The same formulation as the 2nd intermediate layer, Tinuvin 328 coating amount 0.15 g / m ²
It applied so that it might become.

[Blue Sensitive Emulsion Layer (Ninth Layer)] A 1.5% inactive gelatin solution was kept at 60 ° C. and stirred, and the following solutions A and B were added at the same time and the mixture was injected over 15 minutes. Fifteen
After that, the following solution C was injected over 2 minutes and aged for 40 minutes.
After that, excess salt is removed by precipitation water washing method, and then D solution and E solution are added to form a surface layer of 97 mol% AgCl and 3 mol% AgBr, and then excess salt is removed again by precipitation water washing method to disperse gelatin for dispersion. Was added.

A yellow coupler [YC-] dispersed with a sensitizing dye [D-3] and dioctyl phthalate in this silver halide emulsion.
1], 2-mercaptobenzothiazole, 4-
Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, gelatin, coating aid [S-3] and hardener [H-
2] (added just before coating), using 0.5g of coated silver
It was applied so as to be / m ² .

[Fifth Intermediate Layer (10th Layer)] The same as the second intermediate layer, it was applied so that the coating amount of Tinuvin 328 would be 0.3 g / m ² . However, the hardener [H-2] was added immediately before coating.

[Protective layer (11th layer)] Amorphous silica having an average particle size of 3 µm, coating aid [S-
3], a gelatin solution containing hardeners [H-2] and [H-3] (added immediately before coating), and a gelatin coating amount of 1.0 g / m ²
It applied so that it might become. Each sample was prepared in this way.

KS-7 type sensitometer (Konishi Roku Photo Industry Co., Ltd.)
Was used to perform wedge exposure, and development processing was performed according to the following steps.

I. Processing process (processing temperature and processing time) [1] Immersion (color developing solution) 38 ° C 8 seconds [2] Fog exposure 1 lux 10 seconds [3] Color development 38 ° C 2 seconds [4] Bleach fixing 35 ° C 60 seconds [5] Stabilization treatment 25-30 ° C for 1 minute 30 seconds [6] Drying 75-80 ° C for 1 minute b. Composition of processing solution (color developer) Benzyl alcohol 10ml Ethylene glycol 15ml Potassium sulfite 2.0g Potassium bromide 1.5g 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-methanesulfonamidoethyl) -aniline sulfate 5.5g Optical brightener (4,4'-diaminostil benzsulfonic acid derivative) 1.0g Potassium hydroxide 2.0g Add water Adjust the total amount to 1 and adjust to pH 10.20.

(Bleach-fixing solution) Ethylenediaminetetraacetic acid ferric ammonium dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% solution) 100ml Ammonium sulfite (40% solution) 27.5ml Water adjusted to pH 7.1 with potassium carbonate or glacial acetic acid Is added to bring the total amount to 1.

(Stabilizing liquid) 5-chloro-2-methyl-4-isothiazolin-3-one 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) 2.0g Sodium nitrilotriacetate 1.0g Add water to make the total amount 1 and adjust the pH to 7.0 with ammonium hydroxide or sulfuric acid.

Table 2 shows gamma- ₁ (γ1) and minimum density (Dmin) of blue light (B), green light (G), red light (R) of No. _{1 to 8} samples obtained by the above treatment. In the table shown in Table ₁ , the value of γ ₁ is the tangent of the angle of the density origins of 0.15 to 0.5 on the characteristic curve with the horizontal axis representing the image contrast.

Further, a halftone dot wedge (150 lines / inch) is set on the surface of the sample using the above sample, and it is separately exposed to blue light (B), green light (G), and red light (R), and the above development is performed. After processing, the reproducibility of halftone dots was tested. Sakura Area Duck 1000 (manufactured by Konishi Rokusha Kogyo Co., Ltd.) was used for measuring the dot reproducibility at this time.

As is clear from the results shown in Table 2, the dot reproducibility was as sharp as 30% to 5-10% in Sample Nos. 2 to 8 in which the antihalation layer (first layer) was formed below the emulsion layer. It turns out that it will be greatly improved. This is particularly remarkable for green light (G) and red light (R). Furthermore, deterioration of γ ₁ and (Dmin) caused by providing the antihalation layer is caused by the antihalation layer (first layer).
It is also clear from the fact that the thickness of the first intermediate layer (second layer) can be improved by controlling the thickness to 4 μm or less, preferably 3 μm or less, and the contrast of the shadow portion is improved.

On the contrary, if the film thickness of the antihalation layer is 1 μm or less, there are some problems in coating property and the like, so it is desirable that the film thickness be 1 μm or more. Therefore, the thickness of the antihalation layer (first layer) and the first intermediate layer (second layer) is 4
It is desirable that the thickness is less than or equal to μ, preferably 1.0 μ to 3.0 μ.

Example-2 An antihalation layer (first layer) and a first intermediate layer (second layer) were prepared according to the formulation of Sample No. 4 of Example-1,
Further, by changing the binder amount (gelatin amount) from the red photosensitive emulsion layer (third layer) to the protective layer (11th layer), sample Nos. 2-1 to 2-4 shown in Table 3 below were prepared. did. However, silver,
The amount of the coupler and other additives was kept constant, and the hardener was prepared by changing the amount of the hardener so as to match the level of the hardener.

The sample Nos. 2-1 to 2-4 prepared as described above were subjected to post-wedge exposure development processing using a sensitometer in the same manner as in Example 1, and γ ₁ and Dmin of each of the obtained samples were determined as follows. Shown in the table.

As is clear from the results of Table 4 above, the samples of Table 2
Compared with the sample of No. 8, for γ ₁ and Dmin, the antihalation layer (first layer) and the first intermediate layer (second layer)
The total thickness of the emulsion layer side is not only γ ₁ , Dm
It was also found from the results shown in Table 3 that it affects in. Therefore, it is desirable that the thickness of the antihalation layer (first layer) and the first intermediate layer (second layer) be 4 μm or less, and the total thickness be 15 μm or less. In particular, it was found that the dot reproducibility can be greatly improved and the photographic performance can be improved, as is clear from Table 2 when the thickness is in the above range.

Further, it has been confirmed that the curl balance between the front and the back, the drying property and the developing property are advantageously exerted by setting the total thickness to 15 μm or less.

[Effect of the Invention] According to the present invention, an antihalation layer is provided directly on a positive type silver halide color photographic light-sensitive material, and the thickness of this antihalation layer is set to 4 μm or less to increase the sharpness of a developed image. Therefore, the contrast of the shadow portion can be improved. Moreover, the light-sensitive material of the present invention has good dot reproducibility.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Bunzo Ueda 28 Horinouchi, Odawara-shi, Kanagawa Konishi Rokusha Shin Kogyo Co., Ltd. (56) Reference JP 58-60739 (JP, A) JP 57 -109950 (JP, A) JP 61-27539 (JP, A) JP 47-38035 (JP, A)

Claims (1)

[Claims] 1. A silver halide emulsion layer having different color sensitivities containing a cyan coupler, a magenta coupler and a yellow coupler, respectively, is provided on a support, and three silver halide emulsion layers having different color sensitivities are provided. A silver halide which is composed of a direct positive type silver halide emulsion layer which directly forms a positive image by light fog, and in which an intermediate layer and an antihalation layer are formed closer to the support than the silver halide emulsion layer. In the light-sensitive material, the total thickness of the intermediate layer and the antihalation layer on the side closer to the support than the silver halide emulsion layer is 4 μm or less, and the total thickness of the photographic constituent layers on the support is 15 μm or less. A direct positive type silver halide color photographic light-sensitive material characterized by the following.